WO2016204066A1 - 液晶表示素子及びその製造方法 - Google Patents
液晶表示素子及びその製造方法 Download PDFInfo
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- WO2016204066A1 WO2016204066A1 PCT/JP2016/067217 JP2016067217W WO2016204066A1 WO 2016204066 A1 WO2016204066 A1 WO 2016204066A1 JP 2016067217 W JP2016067217 W JP 2016067217W WO 2016204066 A1 WO2016204066 A1 WO 2016204066A1
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134345—Subdivided pixels, e.g. for grey scale or redundancy
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13775—Polymer-stabilized liquid crystal layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/12—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
- G02F2201/122—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode having a particular pattern
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/12—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
- G02F2201/123—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode pixel
Definitions
- the present invention relates to a liquid crystal display element useful as a constituent member for a liquid crystal TV or the like and a method for manufacturing the same.
- Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
- Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using TFT (thin film transistor), and IPS. (In-plane switching) type.
- the liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. It is required to be viscous and have a low driving voltage.
- the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize dielectric anisotropy ( ⁇ ), refractive index anisotropy ( ⁇ n), etc. for each liquid crystal display element. It is composed of
- a liquid crystal composition having a negative ⁇ is used, which is widely used for liquid crystal TVs and the like.
- low voltage driving, high-speed response, and a wide operating temperature range are required. That is, the absolute value of ⁇ is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (T NI ) is required.
- T NI nematic phase-isotropic liquid phase transition temperature
- T NI nematic phase-isotropic liquid phase transition temperature
- ⁇ n ⁇ d which is the product of ⁇ n and the cell gap (d)
- it is necessary to adjust ⁇ n of the liquid crystal composition to an appropriate range according to the cell gap when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low rotational viscosity ( ⁇ 1 ) is required.
- an MVA (multi-domain vertical alignment) type that divides the alignment direction of liquid crystal molecules in a pixel into a plurality of parts by providing a protrusion structure on the substrate.
- Liquid crystal display elements have been widely used.
- the MVA type liquid crystal display element is excellent in view angle characteristics, the response speed of liquid crystal molecules is different between the vicinity of the protrusion structure on the substrate and the part away from the protrusion structure, and the liquid crystal having a slow response speed away from the protrusion structure. Due to the influence of the molecules, there is a problem that the overall response speed is insufficient, and there is a problem of a decrease in transmittance due to the protruding structure.
- PSA is a method for providing a uniform pretilt angle in a divided pixel without providing a non-transparent protrusion structure in a cell, unlike a normal MVA liquid crystal display element.
- Liquid crystal display elements including polymer sustained alignment: polymer sustaining alignment and PS liquid crystal display elements (polymer stabilized)
- a PSA liquid crystal display element is obtained by adding a small amount of a polymerizable compound to a liquid crystal composition, introducing the liquid crystal composition into a liquid crystal cell, and then applying active energy rays while applying a voltage between the electrodes. It is produced by polymerizing the polymerizable compound. Therefore, an appropriate pretilt angle can be given in the divided pixels, and as a result, it is possible to achieve an improvement in contrast by improving the transmittance and a high-speed response by giving a uniform pretilt angle (for example, Patent Documents). 1).
- a vertical alignment film is formed on two substrates. By omitting such a vertical alignment film formation process, the manufacturing process is simplified, the yield is improved, and the result is low.
- a liquid crystal display element that can be reduced in cost has also been proposed. (For example, refer to Patent Document 2).
- this type of liquid crystal display element can improve the transmittance since it can improve the transmittance, like the PSA liquid crystal display element, and can also be expected to have high-speed response.
- the manufactured element generates display unevenness due to the manufacturing process, and a method using a specific liquid crystal material is disclosed as an improvement method (see Patent Document 3).
- a polymerizable compound in the liquid crystal composition is polymerized, and the polymer does not form a vertical alignment film. Since it is formed directly on the electrode substrate as an alignment control layer, it is required that the alignment control layer itself is stable and does not change for a long time from the viewpoint of alignment uniformity and alignment stability of liquid crystal molecules in the liquid crystal element. It was.
- the present invention has been made in view of the above circumstances, simplifying the process of forming a vertical alignment film on an electrode substrate, polymerizing a polymerizable compound in a liquid crystal composition, and aligning the alignment control layer on the electrode substrate
- a liquid crystal display device manufactured by forming a liquid crystal display device the alignment control layer formed on the electrode substrate is improved in adhesion to the electrode substrate, and the alignment stability of the liquid crystal molecules is increased by suppressing the change in the alignment control layer over time.
- the present inventors have studied various liquid crystal compositions and polymerizable compounds in the liquid crystal composition.
- the liquid crystal composition contains the polymerizable compound, and the liquid crystal composition is contained in the liquid crystal cell.
- the polymerizable compound in the liquid crystal composition is polymerized by irradiation with active energy rays while applying a voltage between the electrodes while applying a voltage between the electrodes, on one or both substrates on the substrate constituting the liquid crystal cell. It has been found that the above-mentioned problems can be solved by combining a specific compound as a liquid crystal compound and a polymerizable compound without providing a vertical alignment film, and the present invention has been completed.
- the present invention provides a liquid crystal layer containing a liquid crystal composition between a first substrate having a common electrode and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels.
- a sandwiched liquid crystal display element having no alignment film on one or both of the first substrate and the second substrate, and one or more trifunctional or higher functional (meth) acrylate compounds; Having an orientation control layer formed from one or more bifunctional or monofunctional (meth) acrylate compounds;
- the liquid crystal composition has the following general formula (I)
- R 1 ⁇ and R 2 ⁇ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms
- 8 represents an alkenyloxy group
- Q 1 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- l 1 represents 1 or 2
- Q 1 may be the same or different.
- R 3 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms
- R 4 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms
- Q 2 And Q 3 each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- G 1 and G 2 present are each independently a single bond, —CH 2 CH 2 — , —CH 2 O—, —OCH 2 —, —CF 2 O— or —OCF 2 —, where l 2 represents 0, 1 or 2, but when l 2 is 2, two Q 2 and G 2 is represented by may be the same or different.
- the present invention also provides a liquid crystal composition between a first substrate having a common electrode and a color filter layer and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels.
- R 1 ⁇ and R 2 ⁇ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms
- 8 represents an alkenyloxy group
- Q 1 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- l 1 represents 1 or 2
- Q 1 may be the same or different.
- R 3 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms
- R 4 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms
- Q 2 And Q 3 each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- G 1 and G 2 present are each independently a single bond, —CH 2 CH 2 — , —CH 2 O—, —OCH 2 —, —CF 2 O— or —OCF 2 —, where l 2 represents 0, 1 or 2, but when l 2 is 2, two Q 2 and G 2 is represented by may be the same or different.
- a liquid crystal display element having good alignment stability over time and a method for manufacturing the same are provided by an alignment control layer that has good adhesion to the substrate and that is substantially prevented from changing over time.
- the liquid crystal display element of the present invention is a liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal layer to displace the liquid crystal molecules in the liquid crystal layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.
- FIG. 1 is a schematic perspective view showing an embodiment of the liquid crystal display element of the present invention.
- the liquid crystal display element 10 of the present embodiment includes a first substrate 11, a second substrate 12, and a liquid crystal layer that is sandwiched between the first substrate 11 and the second substrate 12 and contains a liquid crystal composition. 13, a common electrode 14 provided on the surface of the first substrate 11 facing the liquid crystal layer 13, a pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal layer 13, A color filter 18 provided between one substrate 11 and the common electrode 14 is schematically configured.
- the first substrate 11 and the second substrate 12 for example, a glass substrate or a plastic substrate is used.
- a substrate made of a resin such as acrylic resin, methacrylic resin, polyethylene terephthalate, polycarbonate, or cyclic olefin resin is used as the plastic substrate.
- the common electrode 14 and the pixel electrode 15 are usually made of a transparent material such as indium-added tin oxide (ITO).
- ITO indium-added tin oxide
- the pixel electrodes 15 are arranged in a matrix on the second substrate 12.
- the pixel electrode 15 is controlled by a drain electrode of an active element typified by a TFT switching element (not shown).
- the TFT switching element has a gate line as an address signal line and a source line as a data line in a matrix. is doing.
- the pixel electrode 15 has two or more regions having different pretilt directions of liquid crystal molecules in the pixel. In this way, by defining the pretilt direction of the liquid crystal molecules and dividing the direction in which the liquid crystal molecules fall within the pixel into several regions, the viewing angle characteristics are improved.
- a pixel electrode having a slit (a portion where no electrode is formed) having a stripe-like or V-shaped pattern may be provided in each pixel.
- FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of a pixel is divided into four regions.
- the slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application.
- the liquid crystal molecules are directed in four different directions, approaching horizontal alignment. As a result, the alignment direction of the liquid crystal molecules in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.
- the pixel electrode 15 has a slit (is a slit electrode).
- a method of providing a structure such as a linear protrusion in the pixel, a method of providing an electrode other than the pixel electrode and the common electrode, and the like are applied (not shown). And a method of providing the structure is preferable.
- the said structure should just have at least one of the 1st board
- a configuration using a slit electrode is preferable from the viewpoint of transmittance and ease of manufacture. Since the slit electrode does not have a driving force for the liquid crystal molecules when no voltage is applied, the slit electrode cannot give a pretilt angle to the liquid crystal molecules. However, in the present invention, a pretilt angle can be imparted by providing an alignment control layer described later, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.
- having a pretilt angle means that in a state where no voltage is applied, the direction perpendicular to the substrate surface (the surface adjacent to the liquid crystal layer 13 in the first substrate 11 and the second substrate 12) and the liquid crystal molecules This means that the direction of the director is slightly different.
- the liquid crystal display element of the present invention is a vertical alignment (VA) type liquid crystal display element
- the director of the liquid crystal molecules is aligned substantially perpendicular to the substrate surface when no voltage is applied.
- VA vertical alignment
- polyimide, polyamide, polysiloxane, or the like is provided between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer, respectively.
- a vertical alignment film is disposed, in the liquid crystal display element of the present invention, at least one substrate does not have such a vertical alignment film.
- a vertical alignment film is provided on one substrate, for example, a transparent organic material such as polyimide, polyamide, BCB (Penzocyclobutene Polymer), or polyvinyl alcohol can be used.
- a voltage is applied between the electrodes and the liquid crystal molecules are slightly tilted and irradiated with active energy rays such as ultraviolet rays.
- An appropriate pretilt angle is imparted by polymerizing the polymerizable compound in the liquid crystal composition.
- the polymerizable compound specifically, a polymerizable compound described later is polymerized to form the alignment control layer.
- the liquid crystal molecules are substantially vertically aligned means a state in which the director of the vertically aligned liquid crystal molecules is slightly tilted from the vertical direction to give a pretilt angle.
- the angle formed by the direction completely parallel to the substrate surface and the direction of the director of the liquid crystal molecules is 90 °, and the liquid crystal molecules are completely homogeneously aligned (
- the angle is preferably 89 to 85 °, more preferably 89 to 87 °. It is.
- the polymerizable compound at least as the first polymerizable compound, one or more trifunctional or more (meth) acrylate compounds, and the second As the polymerizable compound, one or more difunctional or monofunctional (meth) acrylate compounds are used together.
- the trifunctional or higher functional (meth) acrylate compound used as the first polymerizable compound means a polymerizable compound having three or more (meth) acryloyloxy groups, for example, the general formula (X0a)
- Z is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen having 1 to 8 carbon atoms.
- l and n each independently represents an integer of 0, 1, 2, or 3, and l + n represents 3 or more
- Z represents the formula (R-1) to the formula (R -15) and when n represents 0, R 1 represents any one of the formulas (R-1) to (R-15)
- m represents an integer of 0 to 4, and when a plurality of R 1 , R 2 , Z, S 1 and S 2 are present, they may be the same or different, and a plurality of L 1 and M 2 are present. In this case, they may be the same or different, but at least one of L 1 represents a single bond.
- (meth) acrylate means both acrylate and methacrylate
- (meth) acryloyl group means acryloyl group (H 2 C ⁇ CH—CO Both-) and methacryloyl groups (H 2 C ⁇ C (CH 3 ) —CO—) are meant.
- —COO— means “—C ( ⁇ O) —O—” and “—OCO—” means “—O—C ( ⁇ O) —”.
- Z represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or the number of carbon atoms.
- halogenated alkoxy group 1 to 8 halogenated alkoxy group, halogen, cyano group, nitro group or R 2 , but hydrogen atom, alkyl group having 1 to 3 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, carbon atom It is preferably an alkoxy group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, a halogen, a cyano group or R 2 , and each of S 1 and S 2 independently represents 1 to 12 carbon atoms.
- alkylene group having 1 to 3 carbon atoms, one or adjacent have not more than one -CH 2 in the alkylene group - is 1-3 carbon atoms replaced with -O- 10 carbon alkylene group Or preferably a single bond, more preferably a single bond, and R 1 and R 2 each independently represents a hydrogen atom or any one of formulas (R-1) to (R-15).
- a single bond, —O—, —CH 2 —, —OCH 2 —, —CH 2 O—, —C 2 H 4 —, —COO—, —OCO—, —CH ⁇ CH—COO— , —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH ⁇ CH—COO—, —COO—CH ⁇ CH—OCO—, —OCO—CH ⁇ CH-COO -, - OCO- CH CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - preferably C 2 H 4 OCO- or -C ⁇ C-, M 1 And M 3 each independently represents an aromatic ring or an aliphatic ring, preferably an aromatic ring, and M 2 represents 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl Group, pyrimidine
- L and n each independently represents an integer of 0, 1, 2 or 3, and l + n represents 3 or more, and when l represents 0, Z is represented by formulas (R-1) to ( R-15) represents any one group, and when n represents 0, R 1 represents any one group of formula (R-1) to formula (R-15), and l and n are Preferably it is not zero.
- Preferable trifunctional or higher functional (meth) acrylate compounds include compounds represented by the following formulas (X2a-101) to (X2a-150).
- the bifunctional or monofunctional (meth) acrylate compound used as the second polymerizable compound is used together.
- the above-mentioned bifunctional or monofunctional (meth) acrylate compound means a polymerizable compound having two (meth) acryloyloxy groups or one (meth) acryloyloxy group, for example, the general formula (X1a)
- a 1 represents a hydrogen atom or a methyl group
- a 2 represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group.
- a 3 and A 6 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 18 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
- a 4 and A 7 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 9 carbon atoms).
- B 1 , B 2 and B 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are
- each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more of the alkyl groups may be substituted.
- Each hydrogen atom may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms), or the following general formula (Ib)
- a 9 represents a hydrogen atom or a methyl group
- a 8 represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group.
- a group represented by formula (1) However, among the total of 2 k + 1 B 1 , B 2 and B 3 , the number of the group represented by the general formula (Ib) is 0 or 1.
- R 7 represents a hydrogen atom or a methyl group
- 6-membered rings T 1 , T 2 and T 3 are each independently
- R 70 represents a hydrogen atom or a methyl group
- R 71 represents a hydrocarbon group having a condensed ring
- the “alkylene group” is a divalent group obtained by removing one hydrogen atom from each terminal carbon atom of an aliphatic linear or branched hydrocarbon. If there is a substitution from a hydrogen atom to a halogen atom or an alkyl group or a substitution from a methylene group to an oxygen atom, -CO-, -COO- or -OCO-, to that effect Shall be specifically refused.
- the “alkylene chain length” means, for example, n in the general formula “— (CH 2 ) n — (where n represents an integer of 1 or more)” in the case of a linear alkylene group. It shall be.
- the alkyl group having 1 to 18 carbon atoms in A 3 and A 6 may be linear, branched or cyclic, but may be linear or branched.
- examples of the halogen atom in A 3 and A 6 include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
- the alkyl group having 1 to 17 carbon atoms in which the hydrogen atom of the alkyl group in A 3 and A 6 is substituted is the same as the alkyl group in A 3 and A 6 except that the number of carbon atoms is different. Is mentioned.
- examples of the halogen atom of the hydrogen atoms of the alkyl group in A 3 and A 6 are substituted, include those similar to the aforementioned halogen atom in A 3 and A 6.
- the alkylene group having 1 to 15 carbon atoms in A 2 is a divalent group obtained by removing one hydrogen atom from the alkyl group having 1 to 15 carbon atoms in A 3 and A 6 .
- the group of is mentioned.
- examples of the alkyl group having 1 to 10 carbon atoms in A 4 and A 7 include the same groups as the alkyl groups in A 3 and A 6 except that the number of carbon atoms is different.
- the alkyl group having 1 to 9 carbon atoms in which the hydrogen atom of the alkyl group in A 4 and A 7 is substituted is different from the alkyl group in A 3 and A 6 except that the number of carbon atoms is different. The same can be mentioned.
- examples of the halogen atom of the hydrogen atoms of the alkyl group in A 4 and A 7 are substituted, include those similar to the aforementioned halogen atom in A 3 and A 6.
- a linear or branched alkyl group having 1 to 10 carbon atoms in B 1 , B 2 and B 3 is a straight chain having 1 to 10 carbon atoms in A 3 and A 6 .
- the same thing as a chain-like or branched alkyl group is mentioned.
- the trialkoxysilyl group having 3 to 6 carbon atoms in which the hydrogen atom of the alkyl group in B 1 , B 2 and B 3 is substituted includes any one of a methoxy group and an ethoxy group as the alkoxy group. 3 may be bonded to the same silicon atom, and the three alkoxy groups bonded to the same silicon atom may all be the same or only two may be the same. Specifically, a trimethoxysilyl group, a triethoxysilyl group, an ethoxydimethoxysilyl group, a diethoxymethoxysilyl group, and the like can be given.
- examples of the halogen atom in which the hydrogen atom of the alkyl group in B 1 , B 2, and B 3 is substituted include the same halogen atoms as those in A 3 and A 6 .
- B 1 , B 2 and B 3 are present in total 2k + 1, of which the number of the groups represented by the general formula (Ib) is 0 or 1.
- the group represented by the general formula (Ib) may be any of B 1 , B 2 and B 3 , but is preferably B 1 .
- B 1 , B 2 or B 3 is a group represented by the above general formula (Ib), and preferred examples thereof include the following general formula (X1a -1)
- a 11 and A 19 each independently represent a hydrogen atom or a methyl group;
- a 12 and A 18 are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other).
- Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom, Which may be substituted with a methyl group or an ethyl group)
- a 13 and A 16 each independently represents a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups in the linear alkyl group have an oxygen atom Each of which may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as a non-direct bond.
- a 14 and A 17 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other).
- Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom or Which may be substituted with an alkyl group of 1 to 9 carbon atoms)
- a 15 represents an alkylene group having 9 to 16 carbon atoms (in at least 1 to 5 methylene groups in the alkylene group, one hydrogen atom in the methylene group independently represents 1 to 10 carbon atoms).
- one or two or more methylene groups may be independently selected as those in which oxygen atoms are not directly bonded to each other. And may be substituted with an oxygen atom, —CO—, —COO— or —OCO—.
- X1a-2 A compound represented by The following general formula (X1a-2)
- a 31 and A 32 each independently represent a hydrogen atom or a methyl group, b, c and d each independently represents an integer of 1 to 10, and e represents an integer of 0 to 6).
- a 41 and A 42 each independently represents a hydrogen atom or a methyl group, and m, n, p and q each independently represents an integer of 1 to 10). Examples include compounds selected from the group.
- the linear alkyl group having 2 to 20 carbon atoms in A 13 and A 16 is the same as the linear alkyl group in A 3 and A 6 ; Nonadecyl group, icosyl group, etc. are mentioned.
- examples of the alkyl group having 1 to 10 carbon atoms in A 14 and A 17 include the same alkyl groups as those in A 3 and A 6 except that the number of carbon atoms is different. It is done.
- examples of the alkylene group having 1 to 15 carbon atoms for A 12 and A 18 include the same alkylene groups as those described above for A 2 .
- the alkylene group having 9 to 16 carbon atoms in A 15 is obtained by removing one hydrogen atom from the alkyl group having 9 to 16 carbon atoms in A 3 and A 6 A divalent group is mentioned.
- Examples of the chain or branched alkyl group include the same alkyl groups as those described above for A 3 and A 6 except that the number of carbon atoms is different.
- examples of the halogen atom of the hydrogen atoms of the alkyl group in A 14 and A 17 are substituted, include those similar to the aforementioned halogen atom in A 3 and A 6.
- the compound represented by the general formula (X1a-1) is such that A 11 and A 19 are both hydrogen atoms in that the polymerization rate is faster than that in which both A 11 and A 19 are methyl groups. Those are preferred.
- a 12 and A 18 are each independently a single bond or an alkylene group having 1 to 3 carbon atoms.
- the distance between two polymerizable groups can be adjusted by changing the length of carbon number independently for A 12 and A 18 and A 15 .
- the feature of the compound represented by the general formula (X1a-1) is that the distance between the polymerizable groups (distance between the crosslinking points) is long, but if this distance is too long, the polymerization rate becomes extremely slow. There is an upper limit on the distance between the polymerizable groups because it adversely affects the phase separation. On the other hand, the distance between the two side chains of A 13 and A 16 also affects the mobility of the main chain.
- the lengths of these side chains are preferably as follows.
- a 13 and A 14 are bonded to the same carbon atom in the main chain, but when their lengths are different, the longer side chain is referred to as A 13 ( If the length and the length of a 14 of a 13 are equal, one to one and a 13). Similarly, when the length of the length and A 17 of A 16 are different, if the length and the length of A 17 in the longer side chain of is referred to as A 16 (A 16 are equal, either the one and a 16).
- such A 13 and A 16 are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more present in the linear alkyl group). These methylene groups are each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, assuming that oxygen atoms are not directly bonded to each other.
- An alkyl group (the linear alkyl One or more methylene groups present in the group may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, assuming that the oxygen atoms are not directly bonded to each other. Good.)
- the side chain Since the side chain has higher mobility than the main chain, its presence contributes to improvement of the mobility of the polymer chain at low temperature, but as mentioned above, spatial interference occurs between the two side chains. On the contrary, motility decreases. In order to prevent such spatial interference between side chains, it is effective to increase the distance between the side chains and to shorten the side chain length within a necessary range.
- a 14 and A 17 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group are oxygen atoms). Are each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— so that they are not directly bonded to each other, and one or more hydrogen atoms present in the alkyl group Are each independently substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms.), But preferably each independently an hydrogen atom or an alkyl having 1 to 7 carbon atoms.
- a group (one or two or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, —COO— or —OCO—, as oxygen atoms are not directly bonded to each other); More preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (one or two or more methylene groups present in the alkyl group are Oxygen atoms may be independently substituted with oxygen atoms, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other, and more preferably each independently a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms (one or two or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, It may be substituted with —COO— or —OCO—.
- a 14 and A 17 the it is too long length it is not preferred to induce spatial interference between side chains.
- a 14 and A 17 is an alkyl chain of short length, high to motility can become a side chain having, and is considered to have a function of inhibiting the approach of adjacent main chain between
- the action of preventing the interference between the polymer main chains is considered to increase the mobility of the main chains, and it is possible to suppress the anchoring energy from increasing at low temperatures, and the polymer stabilized liquid crystal This is effective in improving the display characteristics of the display element in a low temperature range.
- a 15 located between the two side chains is preferably longer in terms of changing the distance between the side chains and also in increasing the distance between the crosslinking points to lower the glass transition point.
- a 15 is too long, the general formula becomes too large molecular weight of the compound represented by (X1a-1), the compatibility with the liquid crystal composition is lowered, and the polymerization rate decreases
- There is an upper limit on the length of the length for example, because the phase separation is adversely affected.
- a 15 represents an alkylene group having 9 to 16 carbon atoms (in at least 1 to 5 methylene groups in the alkylene group, each hydrogen atom in the methylene group independently represents 1 carbon atom). May be substituted with 10 to 10 linear or branched alkyl groups, and one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other. And may be substituted with an atom, —CO—, —COO— or —OCO—.
- the alkylene chain length of A 15 is preferably 9 to 16 carbon atoms.
- the number of substitution of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and more preferably 2 or 3 More preferably.
- the number of carbon atoms in the substituted alkyl group is preferably 1 to 5, more preferably 1 to 3.
- the compounds represented by the general formula (X1a-1) are “Tetrahedron Letters, Vol. 30, pp 4985”, “Tetrahedron Letters, Vol. , Vol. 34, pp 217-225 "and the like.
- a compound in which A 14 and A 17 are hydrogen includes a compound having a plurality of epoxy groups and a polymer such as acrylic acid or methacrylic acid having active hydrogen capable of reacting with the epoxy group. It can be obtained by reacting with a functional compound to synthesize a polymerizable compound having a hydroxyl group and then reacting with a saturated fatty acid.
- radical polymerizable compound is, for example, A 14 and A 17 in the general formula (X1a-1) are alkyl groups and A 12 and A 18 are methylene groups having 1 carbon atom, an oxetane group
- a method of reacting a fatty acid chloride or a fatty acid capable of reacting with an oxetane group with a polymerizable compound having active hydrogen such as acrylic acid, or a compound having one oxetane group It can be obtained by a method of reacting a polyvalent fatty acid chloride or a fatty acid capable of reacting with an oxetane group and further reacting a polymerizable compound having active hydrogen such as acrylic acid.
- a 12 and A 18 in the general formula (X1a-1) are an alkylene group having 3 carbon atoms (propylene group, —CH 2 CH 2 CH 2 —), a furan group is used instead of the oxetane group. It can be obtained by using a compound having a plurality of. Further, when A 12 and A 18 in the general formula (X1a-1) are an alkylene group having 4 carbon atoms (butylene group, —CH 2 CH 2 CH 2 CH 2 —), instead of the oxetane group It can be obtained by using a compound having a plurality of pyran groups.
- a 11 and A 19 each independently represent a hydrogen atom or a methyl group;
- a 12 ′ and A 18 ′ each represent a methylene group;
- a 13 and A 16 are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups present in the linear alkyl group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-)
- a 14 ′ and A 17 ′ each independently represents an alkyl group having 1 to 10 carbon atoms,
- a 15 represents an alkylene group having 9 to 16 carbon atoms (in the alkylene group, at least 1 to 5 methylene groups, each hydrogen atom in the methylene group independently represents one having 1 to 10 carbon atoms).
- Examples of the alkyl group for A 14 ′ and A 17 ′ include the same alkyl groups as those for A 14 and A 17 .
- the total number of —COO— and —OCO— in A 15 is 2 or less, and —COO— and —OCO in A 13 and A 16 Particularly preferred are those in which each of-is 1 or less, and specific examples include compounds represented by the following formulas (X1a-101) to (X1a-109).
- the hydrocarbon group having 1 to 18 carbon atoms in R 8 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is linear These may be branched or cyclic, and may be any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.
- the cyclic hydrocarbon group may be either monocyclic or polycyclic.
- the hydrocarbon group having 1 to 18 carbon atoms in R 8 is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, and carbon atoms in A 3 and A 6 Examples thereof include the same alkyl groups having 1 to 18 atoms, and a linear or branched saturated aliphatic hydrocarbon group is particularly preferable.
- Preferred examples of the compound represented by the general formula (X1b) include those in which the 6-membered rings T 1 , T 2 and T 3 are all hydrocarbon rings.
- the hydrocarbon group of R 71 may be any one having a condensed ring, may be composed only of a condensed ring, or may be a condensed ring and other hydrocarbon groups. You may have.
- the condensed ring may be either an aliphatic ring or an aromatic ring.
- the aliphatic ring may be either a saturated aliphatic ring or an unsaturated aliphatic ring, and may have both a saturated aliphatic ring and an unsaturated aliphatic ring.
- the number of rings constituting the condensed ring may be two or more, but preferably 2 to 7.
- the hydrocarbon group other than the condensed ring may be linear, branched or cyclic, and may have both a linear (linear and / or branched) structure and a cyclic structure.
- the chain structure and cyclic structure hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the cyclic structure hydrocarbon group may be an aliphatic ring hydrocarbon group or an aromatic hydrocarbon group. Either is acceptable.
- R 71 include a monovalent group obtained by removing one hydrogen atom from a steroid, and a monovalent group obtained by removing a hydroxyl group from cholesterol is preferred.
- the polymerizable compound used for forming the orientation control layer is a bifunctional or monofunctional (meth) acrylate as the first polymerizable compound and at least one trifunctional or higher functional (meth) acrylate compound and the second polymerizable compound.
- One or more acrylate compounds may be used, but it is excellent in the effect that it is difficult to generate dripping marks at the time of manufacturing the liquid crystal display element without deteriorating various characteristics as the liquid crystal display element and the image sticking characteristics of the liquid crystal display element. Therefore, a total of 2 to 5 types is preferable.
- the ratio of at least one trifunctional or higher functional (meth) acrylate compound and bifunctional or monofunctional (meth) acrylate compound used for forming the orientation control layer is appropriately adjusted depending on how many polymerizable compounds are used.
- the ratio of the tri- or higher functional (meth) acrylate compound to the liquid crystal composition is preferably 0 to 5% by mass, and more preferably 1.0 to 4.0% by mass.
- the ratio of the bifunctional or monofunctional (meth) acrylate compound is preferably 0 to 5% by mass, and more preferably 1.0 to 4.0% by mass.
- the liquid crystal composition used in the present invention has the general formula (I)
- R 1 ⁇ and R 2 ⁇ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms
- 8 represents an alkenyloxy group
- Q 1 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- l 1 represents 1 or 2
- Q 1 may be the same or different.
- R 3 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms
- R 4 ⁇ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms
- Q 2 And Q 3 each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group
- G 1 and G 2 present are each independently a single bond, —CH 2 CH 2 — , —CH 2 O—, —OCH 2 —, —CF 2 O— or —OCF 2 —, where l 2 represents 0, 1 or 2, but when l 2 is 2, two Q 2 and G 2 is represented by may be the same or different.
- the alkyl group having 1 to 8 carbon atoms in R 1 ⁇ and R 2 ⁇ may be linear, branched or cyclic, but may be linear or branched.
- the alkyl group in R 1 ⁇ and R 2 ⁇ preferably has 1 to 6 carbon atoms.
- examples of the alkenyl group having 2 to 8 carbon atoms in R 1 ⁇ and R 2 ⁇ include ethenyl group (vinyl group), 2-propenyl group (allyl group), etc., and carbon atoms in R 1 ⁇ and R 2 ⁇
- Examples of the alkyl group represented by Formulas 2 to 8 include monovalent groups in which one single bond (C—C) between carbon atoms is substituted with a double bond (C ⁇ C).
- the alkenyl group in R 1 ⁇ and R 2 ⁇ preferably has 2 to 6 carbon atoms, and more preferably has the following structure.
- the alkoxy group having 1 to 8 carbon atoms in R 1 ⁇ and R 2 ⁇ is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 8 carbon atoms in R 1 ⁇ and R 2 ⁇ is oxygen.
- a monovalent group formed by bonding to an atom is exemplified.
- the alkoxy group in R 1 ⁇ and R 2 ⁇ preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
- the alkenyloxy group R l [alpha] and R 2.alpha having 2 to 8 carbon atoms in, ethenyloxy group, 2-propenyloxy group, wherein the R l [alpha] and 2 to 8 carbon atoms in R 2.alpha
- examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.
- the alkenyloxy group in R 1 ⁇ and R 2 ⁇ preferably has 2 to 6 carbon atoms.
- Preferred compounds represented by the general formula (I) include those in which the combination of R 1 ⁇ and R 2 ⁇ is the alkyl group, the alkyl group and the alkoxy group, the alkyl group and the alkenyl group. Some are listed.
- preferred examples of the compound represented by the general formula (I) include those represented by the following general formulas (I-1) to (I-4).
- the content of the compound represented by the general formula (I) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.
- R 3 ⁇ is the same as R 1 ⁇ and R 2 ⁇ .
- examples of the alkyl group and alkoxy group having 1 to 8 carbon atoms in R 4 ⁇ include the same as the alkyl group and alkoxy group having 1 to 8 carbon atoms in R 1 ⁇ and R 2 ⁇ . .
- the alkenyl group having 4 to 8 carbon atoms and the alkenyloxy group having 3 to 8 carbon atoms in R 4 ⁇ are the same as those in R 1 ⁇ and R 2 ⁇ except that the number of carbon atoms is different. The same thing as an alkenyl group and an alkenyloxy group is mentioned.
- the alkyl groups in R 3 ⁇ and R 4 ⁇ preferably each independently have 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the alkoxy groups in R 3 ⁇ and R 4 ⁇ preferably each independently have 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.
- Preferred compounds represented by the general formula (II) are those in which R 3 ⁇ is the alkyl group, R 4 ⁇ is the alkoxy group, l 2 is 0 or 1, and G 1 is simple. And a bond, —CH 2 CH 2 — or —CH 2 O—, and G 2 is a single bond or —CH 2 CH 2 —.
- preferred examples of the compound represented by the general formula (II) include those represented by the following general formulas (II-1) to (II-8).
- the content of the compound represented by the general formula (II) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.
- [content of compound represented by general formula (II)] / [content of compound represented by general formula (I)] (mass ratio) is 8/2 to 2/8. Is preferable, 7/3 to 3/7 is more preferable, and 6/4 to 4/6 is particularly preferable.
- liquid crystal composition includes the following general formula (III)
- R 5 ⁇ and R 6 ⁇ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 alkenyloxy groups (one or two or more methylene groups in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group independently represent oxygen atoms or -CO- may be substituted with one or two or more hydrogen atoms in the alkylene group represents may be substituted by a fluorine atom.
- Q 3 is 1,4-phenylene group or Represents a tetrahydropyran-2,5-diyl group, l 3 represents 0 or 1
- G 2 represents a single bond, —CH 2 O—, —OCH 2 —, —CF 2 O— or —OCF 2 —.
- L 1 ⁇ L 6 is, Represents a respectively independently a hydrogen atom or a fluorine atom, at least two L 1 ⁇ L 6 represents a fluorine atom, if and G 2 l 3 represents 0 represents a single bond, L 5 and L 6 may not contain a fluorine atom.) May be contained.
- R 5 ⁇ and R 6 ⁇ are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 2 to 8 carbon atoms.
- the alkenyloxy group is the same as in R 1 ⁇ and R 2 ⁇ .
- Preferred examples of the compound represented by the general formula (III) include, for example, the following general formula (III-1)
- liquid crystal composition includes the following general formula (IV) which does not correspond to the compounds other than the compounds represented by the general formulas (I) and (II).
- R 7 ⁇ and R 8 ⁇ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). It may contain the compound.
- the alkyl group having 1 to 10 carbon atoms in R 7 ⁇ and R 8 ⁇ may be linear, branched or cyclic, but may be linear or branched.
- the alkyl group in R 1 ⁇ and R 2 ⁇ preferably has 1 to 6 carbon atoms.
- the alkenyl group in R 7 ⁇ and R 8 ⁇ preferably has 2 to 6 carbon atoms, and examples thereof include the same as those in R 1 ⁇ and R 2 ⁇ .
- the alkoxy group having 1 to 10 carbon atoms in R 7 ⁇ and R 8 ⁇ is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 10 carbon atoms in R 7 ⁇ and R 8 ⁇ is oxygen.
- a monovalent group formed by bonding to an atom is exemplified.
- R 9 ⁇ and R 10 ⁇ are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 18 represents an alkenyloxy group, Q 4 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and l 4 represents 0 or 1. Good.
- the alkyl group having 1 to 18 carbon atoms in R 9 ⁇ and R 10 ⁇ may be linear, branched or cyclic, but may be linear or branched.
- the alkyl group in R 9 ⁇ and R 10 ⁇ preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- Examples thereof include a monovalent group in which a single bond (C—C) is substituted with a double bond (C ⁇ C).
- the alkenyl group in R 9 ⁇ and R 10 ⁇ preferably has 2 to 6 carbon atoms, and examples thereof include the same ones as in R 1 ⁇ and R 2 ⁇ .
- the alkoxy group having 1 to 18 carbon atoms in R 9 ⁇ and R 10 ⁇ is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 18 carbon atoms in R 9 ⁇ and R 10 ⁇ is oxygen.
- a monovalent group formed by bonding to an atom is exemplified.
- the alkoxy group in R 9 ⁇ and R 10 ⁇ preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- examples of the alkenyloxy group having 2 to 18 carbon atoms in R 9 ⁇ and R 10 ⁇ include an ethenyloxy group, a 2-propenyloxy group, etc., and those having 2 to 18 carbon atoms in R 9 ⁇ and R 10 ⁇ Examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.
- Preferred examples of the compound represented by the general formula (V) include, for example, the following general formula (V-1)
- the content of the components other than the compounds represented by the general formulas (I) and (II) such as the compounds represented by the general formulas (III), (IV), and (V) in the liquid crystal composition is 25.
- the content is preferably at most mass%, more preferably at most 20 mass%.
- the liquid crystal display element 10 may further include a passivation film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13 ( (Not shown). As described above, the surface of the first substrate 11 or the second substrate 12 in the vicinity is protected by having the passivation film.
- the liquid crystal display element 10 may further include a planarization film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13. (Not shown). When the flatness of the surface of this film is high, such a passivation film may be handled as a flattening film.
- passivation film and the planarizing film known ones can be used as appropriate.
- the liquid crystal display element of the present invention includes a liquid crystal composition using a specific compound represented by general formulas (I) and (II) as liquid crystal molecules, an alignment control layer formed from two or more polymerizable compounds, and By using in combination, unlike a conventional liquid crystal display element, an alignment film may not be provided between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer. When no voltage is applied, the liquid crystal molecules are aligned substantially perpendicular to the substrate surface. Further, image sticking and generation of dripping marks during production are suppressed without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity ( ⁇ 1 ) and the like.
- ⁇ Method for manufacturing liquid crystal display element The liquid crystal display element 10 shown in FIG. 1 can be manufactured by the following method, for example.
- the liquid crystal-containing polymerization composition is It contains the compound represented by the general formula (I), the compound represented by the general formula (II), and two or more kinds of the polymerizable compounds as essential components.
- spacer protrusions for securing a cell gap are sprayed on the facing surfaces of either the first substrate 11 or the second substrate 12.
- the seal portion is printed (formed) by screen printing using an epoxy adhesive or the like.
- the surface of the first substrate 11 facing the second substrate 12 is the surface having the common electrode 14 and the color filter 18, and the surface of the second substrate 12 facing the first substrate 11 is The surface having the pixel electrode 15.
- the first substrate 11 and the second substrate 12 are made to face each other, and these are bonded together via the spacer protrusion and the seal portion, and then the liquid crystal-containing polymerization composition is injected into the formed space. To do. Then, the liquid crystal-containing polymerization composition is sandwiched between the first substrate 11 and the second substrate 12 by curing the seal portion by heating or the like.
- a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means.
- the voltage at this time is 5 to 30 V, for example.
- substrate 12 surface which opposes the composition for liquid crystal containing polymerization
- An electric field having a predetermined angle is generated with respect to the liquid crystal-containing polymerization composition, and the liquid crystal molecules in the liquid crystal-containing polymerization composition (compound represented by general formula (I), general formula The compound (II) (19) is oriented in a predetermined direction with respect to the normal direction of the first substrate 11 and the second substrate 12, and as shown in FIG. Is granted.
- the magnitude of the pretilt angle ⁇ can be controlled by appropriately adjusting the magnitude of the voltage.
- the two or more polymerizable compounds are polymerized by irradiating an active energy ray such as ultraviolet rays from the outside of the first substrate 11 to the liquid crystal-containing polymerization composition while the voltage is applied.
- an active energy ray such as ultraviolet rays from the outside of the first substrate 11 to the liquid crystal-containing polymerization composition while the voltage is applied.
- the active energy ray may be irradiated from the outside of the second substrate 12 or may be irradiated from both the outside of the first substrate 11 and the outside of the second substrate 12.
- liquid crystal-containing polymerization composition By irradiation with active energy rays, two or more kinds of the polymerizable compounds in the liquid crystal-containing polymerization composition react, and the liquid crystal-containing polymerization composition becomes a liquid crystal composition having a desired composition to form the liquid crystal layer 13. At the same time, an alignment control layer is formed between the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13.
- the formed alignment control layer imparts a pretilt angle ⁇ to the liquid crystal molecules 19 located in the vicinity of the first substrate 11 and in the vicinity of the second substrate 12 in the liquid crystal layer 13 in a non-driven state.
- the irradiation intensity of the active energy ray may or may not be constant, and when changing the irradiation intensity, the irradiation time at each irradiation intensity can be arbitrarily set, but two or more stages
- the irradiation intensity of the irradiation process after the second stage is preferably weaker than the irradiation intensity of the irradiation process of the first stage, and the total irradiation time of the irradiation process after the second stage is It is preferable that the irradiation time is longer than the first stage irradiation time and the total irradiation energy amount is large.
- the average irradiation light intensity in the first half of the entire irradiation process time is preferably stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More preferably, the irradiation intensity always decreases to a certain value as the irradiation time elapses.
- the irradiation intensity of the active energy ray in this case is preferably 2 to 100 mW / cm 2 , but it is the highest in all irradiation processes in the first stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously.
- the irradiation intensity is 10 to 100 mW / cm 2
- the minimum irradiation intensity is 2 to 50 mW / cm 2 after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. It is more preferable.
- the total irradiation energy amount is preferably 10 to 300 J, more preferably 50 to 250 J, and further preferably 100 to 250 J.
- the applied voltage may be alternating current or direct current.
- the irradiated active energy rays preferably have a plurality of spectra, and ultraviolet rays having a plurality of spectra are preferable.
- active energy rays having a plurality of spectra two or more kinds of the polymerizable compounds can be polymerized by active energy rays having a spectrum (wavelength) suitable for each type, and in this case, the orientation control layer Is formed more efficiently.
- the alignment control layer is composed of a polymer of the polymerizable compound.
- the first substrate 11 and the liquid crystal layer 13 are not clearly separated and formed between them.
- the first substrate 11 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13).
- the alignment control layer is not necessarily formed between the second substrate 12 and the liquid crystal layer 13 by clearly dividing the second substrate 12.
- the second substrate 12 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13).
- the two or more kinds of polymerizable compounds are preferentially polymerized with each other having similar structures to align liquid crystal molecules in the vicinity region of the substrate, and the direction of the pretilt. It is presumed that the orientation is controlled by defining the value in a predetermined direction.
- Tni, ⁇ n, ⁇ , ⁇ , ⁇ 1 respectively are defined as follows.
- T ni Nematic phase-isotropic liquid phase transition temperature (° C.)
- ⁇ n refractive index anisotropy at 25 ° C.
- ⁇ dielectric anisotropy at 25 ° C.
- ⁇ viscosity at 20 ° C. (mPa ⁇ s)
- ⁇ 1 rotational viscosity at 25 ° C. (mPa ⁇ s)
- image sticking, dripping marks and pretilt stability of liquid crystal display elements were evaluated by the following methods.
- the burn-in evaluation of the liquid crystal display element is based on the following four-level evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. went. ⁇ : No afterimage ⁇ : Level of afterimage is slightly acceptable but acceptable ⁇ : Level of afterimage is unacceptable ⁇ : Image retention is quite poor (drop mark) Evaluation of the drop marks of the liquid crystal display device was performed by the following four-stage evaluation of the drop marks that appeared white when the entire surface was displayed in black.
- pretilt stability The pretilt stability of the liquid crystal display device was evaluated by measuring the amount of pretilt shift before and after voltage application after applying a predetermined voltage in the display area.
- the sealing material was cured to form a liquid crystal composition layer.
- a spacer having a thickness of 3.2 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.2 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby the liquid crystal display element of Example 1 was obtained.
- an alignment control film including a polymer of a polymerizable compound having a reactive group is formed, and a pretilt angle is imparted to the liquid crystal molecules in the liquid crystal composition layer.
- the pretilt angle is defined as follows. In the case of complete vertical alignment, the pretilt angle ( ⁇ ) is 90 °, and when the pretilt angle is given, the pretilt angle ( ⁇ ) is smaller than 90 °.
- the liquid crystal display element of Example 1 had a pretilt angle in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.3 °.
- the liquid crystal display element of Example 1 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Example 2 In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.5 wt% of the liquid crystal composition LC-1
- the sealing material was cured to form a liquid crystal composition layer.
- a spacer having a thickness of 3.2 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.2 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element of Example 2.
- the liquid crystal display element of Example 2 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.7 °.
- the liquid crystal display element of Example 2 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- a transparent electrode layer comprising a transparent common electrode, a color filter layer, and a first substrate (common electrode substrate) having a protrusion for controlling the orientation direction of the liquid crystal material, and a transparent pixel electrode driven by an active element
- a second substrate (pixel electrode substrate) provided with protrusions for controlling the orientation direction of the pixel electrode layer and the liquid crystal material was manufactured.
- a vertical alignment film material was applied to each of the common electrode substrate and the pixel electrode substrate by a spin coating method, and the applied film was heated at 200 ° C., thereby forming a vertical alignment film of 100 nm on the surface of each substrate.
- the liquid crystal composition LC-1 was sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film was formed, and then the sealing material was cured to form a liquid crystal composition layer. At this time, a spacer having a thickness of 3.2 ⁇ m was used, and the thickness of the liquid crystal composition layer was set to 3.2 ⁇ m.
- the liquid crystal display element of Comparative Example 1 thus obtained was found to be inferior in contrast to Example 1 in terms of contrast, response speed, drop marks and image sticking, as shown in the following table. .
- Example 3 In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-2 containing a compound selected from general formula (I) and a compound selected from general formula (II).
- the constituent compounds and the ratios contained are as follows.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby the liquid crystal display element of Example 3 was obtained.
- the liquid crystal display element of Example 3 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.5 °.
- the liquid crystal display element of Example 3 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Example 4 In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.38 wt% of the liquid crystal composition LC-2
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby a liquid crystal display element of Example 4 was obtained.
- the liquid crystal display element of Example 4 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.6 °.
- the liquid crystal display element of Example 4 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Comparative Example 2 In the same experiment as in Comparative Example 1, a liquid crystal composition layer was formed using the liquid crystal composition LC-2. At this time, the thickness of the liquid crystal composition layer was set to 3.8 ⁇ m using a spacer having a thickness of 3.8 ⁇ m.
- the liquid crystal display element of Comparative Example 2 obtained in this way was found to be inferior in contrast, contrast speed, response speed, drop marks, and image sticking. .
- Example 5 In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-3 containing a compound selected from general formula (I) and a compound selected from general formula (II).
- the constituent compounds and the ratios contained are as follows.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element of Example 5.
- the liquid crystal display element of Example 5 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.7 °.
- the liquid crystal display element of Example 5 obtained in this way shows an excellent contrast and response speed, hardly causes dripping marks, and is also excellent in terms of image sticking. became.
- Example 6 In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-3
- a photopolymerization initiator Igacure 651 was added and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-3a.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby a liquid crystal display element of Example 6 was obtained.
- the liquid crystal display element of Example 6 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.4 °.
- the liquid crystal display element of Example 6 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Comparative Example 3 In the same experiment as in Comparative Example 1, a liquid crystal composition layer was formed using the liquid crystal composition LC-3. At this time, the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the liquid crystal display element of Comparative Example 2 thus obtained was found to be inferior in contrast, response speed, drop marks and image sticking as compared to Example 3, as shown in the following table. .
- Example 7 In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-4 containing a compound selected from general formula (I) and a compound selected from general formula (II).
- the constituent compounds and the ratios contained are as follows.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element of Example 7.
- the liquid crystal display element of Example 7 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.8 °.
- the liquid crystal display element of Example 7 obtained in this way shows excellent contrast and response speed, hardly causes dripping marks, and is also excellent in terms of image sticking. became.
- Example 8 In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.05 wt% of the liquid crystal composition LC-4
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- the liquid crystal display element of Example 8 was obtained by irradiating the liquid crystal display element with ultraviolet rays at 100 mW for 10 minutes using USH-250BY manufactured by USHIO ELECTRIC CO., LTD.
- the liquid crystal display element of Example 8 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.3 °.
- the liquid crystal display element of Example 8 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Comparative Example 4 In the same experiment as in Comparative Example 1, a liquid crystal composition layer was formed using the liquid crystal composition LC-4. At this time, the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the liquid crystal display element of Comparative Example 4 thus obtained was found to be inferior in contrast, response speed, drop marks and image sticking as compared to Example 4. .
- Example 9 In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-5 containing a compound selected from general formula (I) and a compound selected from general formula (II).
- the constituent compounds and the ratios contained are as follows.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby a liquid crystal display element of Example 9 was obtained.
- the liquid crystal display element of Example 9 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 88.9 °.
- the liquid crystal display element of Example 9 obtained in this way shows excellent contrast and response speed, hardly causes drop marks, and is also excellent in terms of image sticking. became.
- Comparative Example 5 In the same experiment as in Comparative Example 1, a liquid crystal composition layer was formed using the liquid crystal composition LC-5. At this time, the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the liquid crystal display element of Comparative Example 5 obtained in this way was found to be inferior in contrast, response speed, drop marks and image sticking as compared to Example 9, as shown in the following table. .
- Example 10 In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-6 containing a compound selected from general formula (I) and a compound selected from general formula (II).
- the constituent compounds and the ratios contained are as follows.
- the sealing material was cured to form a liquid crystal composition layer.
- the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group.
- USH-250BY manufactured by USHIO INC. Was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes, whereby the liquid crystal display element of Example 10 was obtained.
- the liquid crystal display element of Example 10 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. .
- the pretilt angle maintained was 89.0 °.
- the liquid crystal display element of Example 10 obtained in this way shows excellent contrast and response speed, hardly causes dripping marks, and is also excellent in terms of image sticking. became.
- Comparative Example 6 In the same experiment as Comparative Example 1, a liquid crystal composition layer was formed using the liquid crystal composition LC-6. At this time, the thickness of the liquid crystal composition layer was set to 3.5 ⁇ m using a spacer having a thickness of 3.5 ⁇ m.
- the liquid crystal display element of Comparative Example 6 thus obtained was found to be inferior to Example 10 in terms of contrast, response speed, drop marks and image sticking, as shown in the following table. .
- Example 11 Comparative Examples 7 to 10.
- the polymerizable compound shown below with respect to the liquid crystal composition LC-1 (98.3 mass%) prepared in Example 1
- a liquid crystal display element CLCD-1b was obtained in the same manner as in Example 1 except that this liquid crystal-containing polymerization composition CLC-1b was used.
- a liquid crystal display element CLCD-3b was obtained in the same manner as in Example 1 except that this liquid crystal-containing polymerization composition CLC-3b was used.
- a liquid crystal display element CLCD-5b was obtained in the same manner as in Example 1 except that this liquid crystal-containing polymerization composition CLC-5b was used.
- a liquid crystal display element CLCD-10b was obtained in the same manner as in Example 1 except that this liquid crystal-containing polymerization composition CLC-6b was used.
- Liquid crystal display element CLCD-1b (Comparative Example 7), CLCD-3b (Comparative Example 8), CLCD-5b (Comparative Example 9), CLCD-10b (Comparative Example 10), and Liquid Crystal Display Element CLCD of Example 1 1 (Example 11), the liquid crystal display element CLCD-3 (Example 12) of Example 5, the liquid crystal display element CLCD-5 (Example 13) of Example 9, and the liquid crystal display element CLCD-10 of Example 10 (
- the pretilt stability evaluation performed using the liquid crystal display element of Example 14) revealed that the pretilt shift amount was small and the stability was excellent as shown in the following table. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
Abstract
Description
前記液晶組成物が、下記一般式(I)
前記画素電極と前記共通電極との間に、前記液晶含有重合用組成物中の液晶分子にプレチルト角を付与するための電圧を印可した状態で活性エネルギー線を照射することにより、前記2種以上の重合性化合物を重合させると共に、前記液晶含有重合用組成物を前記液晶組成物として、前記第一の基板及び第二の基板と前記液晶層との間に、配向制御層を形成することを特徴とする液晶表示素子の製造方法を提供する。
<液晶表示素子>
本願発明の液晶表示素子は、一対の基板の間に、液晶組成物を含有する液晶層が挟持された液晶表示素子であって、液晶層に電圧を印加し、液晶層中の液晶分子をフレデリクス転移させることにより、光学的なスイッチとして働かせる原理に基づくものであり、この点では周知慣用技術を用いることができる。
(式中、Zは、水素原子、炭素原子数1~8のアルキル基、炭素原子数1~8のハロゲン化アルキル基、炭素原子数1~8のアルコキシ基、炭素原子数1~8のハロゲン化アルコキシ基、ハロゲン、シアノ基、ニトロ基又はR2を表し、S1及びS2はそれぞれ独立して、炭素原子数1~12個のアルキレン基又は単結合を表し、該アルキレン基中の1個の-CH2-又は隣接していない2個以上の-CH2-は、-O-、-COO-、-OCO-又は-OCOO-に置き換えられても良く、
R1及びR2はそれぞれ独立して、水素原子又は式(R-1)から式(R-15)
L1はおよびL2はそれぞれ独立して、単結合、-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-(CH2)j-C(=O)-O-、-(CH2)j-O-(C=O)-、-O-(C=O)-(CH2)j-、-(C=O)-O-(CH2)j-、-CH2OCO-、-COOCH2-、-OCOCH2-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-又は-C≡C-(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、jは1~4の整数を表す。)を表し、
M1およびM3はお互い独立して、芳香環、脂肪族環を表わし、
M2は、1,4-フェニレン基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、ナフタレン-1,4-ジイル基、テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表し、
M1、M2及びM3はそれぞれ独立して、無置換であっても、炭素原子数1~8のアルキル基、炭素原子数1~8のハロゲン化アルキル基、炭素原子数1~8のアルコキシ基、ハロゲン、シアノ基、又はニトロ基で置換されていても良く、
lおよびnはそれぞれ独立して、0、1、2又は3の整数を表し、かつ、l+nが3以上を表すが、lが0を表す場合、Zは式(R-1)~式(R-15)のいずれか一つの基を表し、nが0を表す場合、R1は式(R-1)~式(R-15)のいずれか一つの基を表し、
mは、0から4の整数を表し、R1、R2、Z、S1及びS2が複数存在する場合は、同一であっても異なっていても良く、L1及びM2が複数存在する場合は、同一であっても異なっていても良いが、L1の少なくとも一つは単結合を表す。)
なお、本明細書において、「(メタ)アクリレート」とは、アクリレート及びメタクリレートの両方を意味するものとし、同様に、「(メタ)アクリロイル基」とは、アクリロイル基(H2C=CH-CO-)及びメタクリロイル基(H2C=C(CH3)-CO-)の両方を意味するものとする。
3官能以上の(メタ)アクリレート化合物で好ましいものとしては、下記式(X2a-101)~(X2a-150)で表される化合物が挙げられる。
A2は単結合又は炭素原子数1~15のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子はそれぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)を表し、
A3及びA6はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~18のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~17のアルキル基で置換されていてもよい。)を表し、
A4及びA7はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~10のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~9のアルキル基で置換されていてもよい。)を表し、
kは1~40を表し、
B1、B2及びB3は、それぞれ独立して水素原子、炭素原子数1~10の直鎖状若しくは分岐鎖状のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数3~6のトリアルコキシシリル基で置換されていてもよい。)、又は下記一般式(I-b)
A8は単結合又は炭素原子数1~15のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子は、それぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)で表される基を表す。ただし、合計で2k+1個あるB1、B2及びB3のうち、前記一般式(I-b)で表される基となるものの個数は0又は1個である。)で表される化合物、
一般式(X1b)
6員環T1、T2及びT3はそれぞれ独立して
n4は0又は1を表し、
Y1及びY2はそれぞれ独立して単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-(CH2)4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2=CHCH2CH2-又は-CH2CH2CH=CH-を表し、
Y3は単結合、-COO-又は-OCO-を表し、
R8は炭素原子数1~18の炭化水素基を表す。)で表される化合物、
及び一般式(X1c)
からなる群より選ばれる化合物であることが好ましい。
A12及びA18は、それぞれ独立して単結合又は炭素原子数1~15のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子は、それぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)を表し、
A13及びA16は、それぞれ独立して炭素原子数2~20の直鎖状のアルキル基(該直鎖状のアルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよい。)を表し、
A14及びA17は、それぞれ独立して水素原子又は炭素原子数1~10のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~9のアルキル基で置換されていてもよい。)を表し、
A15は炭素原子数9~16のアルキレン基(該アルキレン基中の少なくとも1~5個のメチレン基において、該メチレン基中の1個の水素原子は、それぞれ独立して炭素原子数1~10の直鎖状又は分岐鎖状のアルキル基で置換されていてもよく、該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよい。)を表す。)で表される化合物、
下記一般式(X1a-2)
下記一般式(X1a-3)
及び下記一般式(X1a-4)
A12’及びA18’はそれぞれメチレン基を表し、
A13及びA16はそれぞれ独立して炭素原子数2から20の直鎖アルキル基(該直鎖アルキル基中に存在する1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよい。)を表し、
A14’及びA17’はそれぞれ独立して炭素原子数1から10のアルキル基を表し、
A15は炭素原子数9から16のアルキレン基(該アルキレン基中の少なくとも1~5個のメチレン基において、該メチレン基中の1個の水素原子はそれぞれ独立して炭素原子数1から10の直鎖又は分岐のアルキル基で置換されていてもよく、該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよい。)を表す。)で表される化合物が好ましい。
及び一般式(II)
一般式(I)中、R1α及びR2αにおける炭素原子数1~8のアルコキシ基としては、メトキシ基、エトキシ基等、R1α及びR2αにおける炭素原子数1~8の前記アルキル基が酸素原子に結合してなる一価の基が挙げられる。
前記液晶組成物の一般式(I)で表される化合物の含有量は、30~65質量%であることが好ましく、35~55質量%であることがより好ましい。
前記液晶組成物の一般式(II)で表される化合物の含有量は、30~65質量%であることが好ましく、35~55質量%であることがより好ましい。
<液晶表示素子の製造方法>
図1に示す液晶表示素子10は、例えば、以下の方法で製造できる。
前記一般式(I)で表される化合物、前記一般式(II)で表される化合物、及び2種以上の前記重合性化合物を必須成分として含有するものである。
Tni :ネマチック相-等方性液体相転移温度(℃)
Δn :25℃における屈折率異方性
Δε :25℃における誘電率異方性
η :20℃における粘度(mPa・s)
γ1 :25℃における回転粘度(mPa・s)
以下の実施例及び比較例における液晶表示素子の焼き付き、滴下痕及びプレチルト安定性について下記の方法により評価した。
(焼き付き)
液晶表示素子の焼き付き評価は、表示エリア内に所定の固定パターンを1000時間表示させた後に、全画面均一な表示を行ったときの固定パターンの残像のレベルを目視にて以下の4段階評価で行った。
◎:残像無し
○:残像ごく僅かに有るも許容できるレベル
△:残像有り許容できないレベル
×:残像有りかなり劣悪
(滴下痕)
液晶表示装置の滴下痕の評価は、全面黒表示した場合における白く浮かび上がる滴下痕を目視にて以下の4段階評価で行った。
◎:滴下痕無し
○:滴下痕ごく僅かに有るも許容できるレベル
△:滴下痕有り許容できないレベル
×:滴下痕有りかなり劣悪
(プレチルト安定性)
液晶表示装置のプレチルト安定性の評価は、表示エリア内に所定の電圧を印加下後に、電圧印加前後でのプレチルトシフト量を測定した。
(実施例1)
透明な共通電極からなる透明電極層及びカラーフィルター層を具備した第一の基板(共通電極基板)と、アクティブ素子により駆動される透明画素電極を有する画素電極層を具備した第二の基板(画素電極基板)とを作製した。
一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-1を調製した。構成する化合物及び含有する比率は下記の通りである。
実施例1の液晶表示素子は、画素電極のスリットに従って、4つの区画において異なった方向にプレチルト角を有し、前記重合性化合物の硬化後、交流電場を切った状態でもプレチルト角が維持された。維持されたプレチルト角は88.3°であった。
実施例1と同様の実験において、液晶組成物LC-1 98.5wt%に対して、以下に示される重合性化合物
実施例2の液晶表示素子は、画素電極のスリットに従って、4つの区画において異なった方向にプレチルト角を有し、前記重合性化合物の硬化後、交流電場を切った状態でもプレチルト角が維持された。維持されたプレチルト角は88.7°であった。
透明な共通電極からなる透明電極層及びカラーフィルター層及び液晶材料の配向方向を制御するための突起を具備した第一の基板(共通電極基板)と、アクティブ素子により駆動される透明画素電極を有する画素電極層及び液晶材料の配向方向を制御するための突起を具備した第二の基板(画素電極基板)とを作製した。
実施例1と同様の実験において、使用する液晶組成物を一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-2に変更した。構成する化合物及び含有する比率は下記の通りである。
実施例1と同様の実験において、液晶組成物LC-2 98.38wt%に対して、以下に示される重合性化合物
比較例1と同様の実験において、液晶組成物LC-2を使用して液晶組成物層を形成した。この際、厚さ3.8μmのスペーサを用いて、液晶組成物層の厚さを3.8μmとした。
実施例1と同様の実験において、使用する液晶組成物を一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-3に変更した。構成する化合物及び含有する比率は下記の通りである。
実施例1と同様の実験において、液晶組成物LC-3 98.0wt%に対して、以下に示される重合性化合物
比較例1と同様の実験において、液晶組成物LC-3を使用して液晶組成物層を形成した。この際、厚さ3.5μmのスペーサを用いて、液晶組成物層の厚さを3.5μmとした。
実施例1と同様の実験において、使用する液晶組成物を一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-4に変更した。構成する化合物及び含有する比率は下記の通りである。
実施例1と同様の実験において、液晶組成物LC-4 98.05wt%に対して、以下に示される重合性化合物
比較例1と同様の実験において、液晶組成物LC-4を使用して液晶組成物層を形成した。この際、厚さ3.5μmのスペーサを用いて、液晶組成物層の厚さを3.5μmとした。
実施例1と同様の実験において、使用する液晶組成物を一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-5に変更した。構成する化合物及び含有する比率は下記の通りである。
比較例1と同様の実験において、液晶組成物LC-5を使用して液晶組成物層を形成した。この際、厚さ3.5μmのスペーサを用いて、液晶組成物層の厚さを3.5μmとした。
実施例1と同様の実験において、使用する液晶組成物を一般式(I)から選ばれる化合物、及び一般式(II)から選ばれる化合物を含有した液晶組成物LC-6に変更した。構成する化合物及び含有する比率は下記の通りである。
比較例1と同様の実験において、液晶組成物LC-6を使用して液晶組成物層を形成した。この際、厚さ3.5μmのスペーサを用いて、液晶組成物層の厚さを3.5μmとした。
実施例1で調製した液晶組成物LC-1(98.3質量%)に対して、以下に示される重合性化合物
上記、液晶表示素子CLCD-1b(比較例7)、CLCD-3b(比較例8)、CLCD-5b(比較例9)及びCLCD-10b(比較例10)と実施例1の液晶表示素子CLCD-1(実施例11)、実施例5の液晶表示素子CLCD-3(実施例12)、実施例9の液晶表示素子CLCD-5(実施例13)及び実施例10の液晶表示素子CLCD-10(実施例14)の液晶表示素子を用いて行った、プレチルト安定性評価は、以下の表に示すように、プレチルトシフト量が小さく、安定性が優れていることが明らかとなった。つまり、経時的な変化が大幅に抑制された配向制御層により配向の経時安定性が良好な液晶表示素子を得られることが明らかである。
Claims (9)
- 共通電極を有する第一の基板と、複数の画素を有しかつ各前記画素毎に画素電極を有する第二の基板との間に、液晶組成物を含有する液晶層が挟持された液晶表示素子であって、
前記第一の基板及び第二の基板の、一方又は両方の基板上に配向膜を有さず、
1種以上の3官能以上の(メタ)アクリレート化合物と、1種以上の2官能あるいは単官能(メタ)アクリレート化合物から形成された配向制御層を有し、
前記液晶組成物が、下記一般式(I)
- 前記の3官能以上の(メタ)アクリレート化合物が、一般式(X0a)
R1及びR2はそれぞれ独立して、水素原子又は式(R-1)から式(R-15)
L1はおよびL2はそれぞれ独立して、単結合、-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-(CH2)j-C(=O)-O-、-(CH2)j-O-(C=O)-、-O-(C=O)-(CH2)j-、-(C=O)-O-(CH2)j-、-CH2OCO-、-COOCH2-、-OCOCH2-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-又は-C≡C-(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、jは1~4の整数を表す。)を表し、
M1およびM3はお互い独立して、芳香環、脂肪族環を表わし、
M2は、1,4-フェニレン基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、ナフタレン-1,4-ジイル基、テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表し、
M1、M2及びM3はそれぞれ独立して、無置換であっても、炭素原子数1~8のアルキル基、炭素原子数1~8のハロゲン化アルキル基、炭素原子数1~8のアルコキシ基、ハロゲン、シアノ基、又はニトロ基で置換されていても良く、
lおよびnはそれぞれ独立して、0、1、2又は3の整数を表し、かつ、l+nが3以上を表すが、lが0を表す場合、Zは式(R-1)~式(R-15)のいずれか一つの基を表し、nが0を表す場合、R1は式(R-1)~式(R-15)のいずれか一つの基を表し、
mは、0から4の整数を表し、R1、R2、Z、S1及びS2が複数存在する場合は、同一であっても異なっていても良く、L1及びM2が複数存在する場合は、同一であっても異なっていても良いが、L1の少なくとも一つは単結合を表す。)
で表される化合物であり、
前記の2官能あるいは単官能(メタ)アクリレート化合物が、
一般式(X1a)
A2は単結合又は炭素原子数1~15のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子はそれぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)を表し、
A3及びA6はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~18のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~17のアルキル基で置換されていてもよい。)を表し、
A4及びA7はそれぞれ独立して水素原子、ハロゲン原子又は炭素原子数1~10のアルキル基(該アルキル基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数1~9のアルキル基で置換されていてもよい。)を表し、
kは1~40を表し、
B1、B2及びB3は、それぞれ独立して水素原子、炭素原子数1~10の直鎖状若しくは分岐鎖状のアルキル基(該アルキル基中の1個若しくは2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキル基中の1個又は2個以上の水素原子は、それぞれ独立してハロゲン原子又は炭素原子数3~6のトリアルコキシシリル基で置換されていてもよい。)、又は下記一般式(I-b)
A8は単結合又は炭素原子数1~15のアルキレン基(該アルキレン基中の1個又は2個以上のメチレン基は、酸素原子が相互に直接結合しないものとして、それぞれ独立して酸素原子、-CO-、-COO-又は-OCO-で置換されていてもよく、該アルキレン基中の1個又は2個以上の水素原子は、それぞれ独立してフッ素原子、メチル基又はエチル基で置換されていてもよい。)で表される基を表す。ただし、合計で2k+1個あるB1、B2及びB3のうち、前記一般式(I-b)で表される基となるものの個数は0又は1個である。)で表される化合物、
一般式(X1b)
6員環T1、T2及びT3はそれぞれ独立して
n4は0又は1を表し、
Y1及びY2はそれぞれ独立して単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-(CH2)4-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2=CHCH2CH2-又は-CH2CH2CH=CH-を表し、
Y3は単結合、-COO-又は-OCO-を表し、
R8は炭素原子数1~18の炭化水素基を表す。)で表される化合物、
及び下記一般式(X1c)
R71は縮合環を有する炭化水素基を表す。)で表される化合物
からなる群より選ばれる化合物である請求項1に記載の液晶表示素子。 - 前記画素電極がスリットを有する請求項1又は2に記載の液晶表示素子。
- 前記第一の基板及び第二の基板の少なくとも一方が、プレチルトの方向を規定する構造物を有する請求項1又は2に記載の液晶表示素子。
- 前記第一の基板と前記液晶層との間、及び前記第二の基板と前記液晶層との間、の少なくとも一方に、パッシベーション膜を有する請求項1~4のいずれか一項に記載の液晶表示素子。
- 前記第一の基板と前記液晶層との間、及び前記第二の基板と前記液晶層との間、の少なくとも一方に、平坦化膜を有する請求項1~5のいずれか一項に記載の液晶表示素子。
- 共通電極及びカラーフィルタ層を有する第一の基板と、複数の画素を有し、かつ各前記画素毎に画素電極を有する第二の基板との間に、液晶組成物を含有する液晶層が挟持され、前記画素中にプレチルトの方向が異なる2以上の領域を有する液晶表示素子の製造方法であって、
前記第一の基板と前記第二の基板の、一方又は両方の基板上に配向膜を設けず、下記一般式(I)
前記画素電極と前記共通電極との間に、前記液晶含有重合用組成物中の液晶分子にプレチルト角を付与するための電圧を印可した状態で活性エネルギー線を照射することにより、前記2種以上の重合性化合物を重合させると共に、前記液晶含有重合用組成物を前記液晶組成物として、前記第一の基板及び第二の基板と前記液晶層との間に、配向制御層を形成することを特徴とする液晶表示素子の製造方法。 - 前記活性エネルギー線が複数のスペクトルを有する紫外線である請求項7に記載の液晶表示素子の製造方法。
- 前記画素電極がスリットを有するか、又は前記第一の基板及び第二の基板の少なくとも一方が、プレチルトの方向を規定する構造物を有する請求項7又は8に記載の液晶表示素子の製造方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019069911A1 (ja) * | 2017-10-02 | 2019-04-11 | 富士フイルム株式会社 | 液晶組成物、反射層、反射層の製造方法、及び共重合体 |
JPWO2020121639A1 (ja) * | 2018-12-12 | 2021-02-15 | Dic株式会社 | 重合性化合物含有液晶組成物及び液晶表示素子ならびに重合性化合物 |
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TWI606113B (zh) * | 2013-02-06 | 2017-11-21 | Dainippon Ink & Chemicals | Liquid crystal display element and its manufacturing method |
JP7173130B2 (ja) * | 2018-03-30 | 2022-11-16 | Jsr株式会社 | 表示装置及びその作製方法、並びに液晶配向剤及び硬化性組成物 |
TWI794515B (zh) * | 2018-07-03 | 2023-03-01 | 日商Dic股份有限公司 | 液晶顯示元件及液晶顯示元件之製造方法 |
WO2020065713A1 (ja) * | 2018-09-25 | 2020-04-02 | 堺ディスプレイプロダクト株式会社 | 液晶表示装置 |
US10861209B1 (en) * | 2018-11-08 | 2020-12-08 | Michael Bruce | Unmanned aerial monitoring vehicle |
CN111748356B (zh) * | 2020-07-24 | 2023-03-14 | 京东方科技集团股份有限公司 | 液晶组合材料及显示面板 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120169980A1 (en) * | 2010-12-31 | 2012-07-05 | Au Optronics Corporation | Method for fabricating polymer stabilized alignment liquid crystal display panel |
US20130287970A1 (en) * | 2012-04-28 | 2013-10-31 | Shenzhen China Star Optoelectronics Technology Co., Ltd | Liquid Crystal Medium Composition and Liquid Crystal Display Using Same |
WO2013161669A1 (ja) * | 2012-04-24 | 2013-10-31 | Dic株式会社 | 重合性化合物を含有する液晶組成物及びそれを使用した液晶表示素子 |
WO2014024648A1 (ja) * | 2012-08-08 | 2014-02-13 | Jnc株式会社 | 液晶組成物および液晶表示素子 |
US20140085591A1 (en) * | 2012-09-21 | 2014-03-27 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Mixture for Liquid Crystal Medium and Liquid Crystal Display Using the Same |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6690441B2 (en) * | 2000-09-22 | 2004-02-10 | Dai Nippon Printing Co., Ltd. | Multi-domain vertical alignment mode liquid crystal display having spacers formed over zigzag like alignment-controlling projection |
JP5437993B2 (ja) * | 2008-04-01 | 2014-03-12 | 株式会社Adeka | 三官能(メタ)アクリレート化合物及び該化合物を含有する重合性組成物 |
CN102220140A (zh) * | 2010-04-16 | 2011-10-19 | 统炀企业有限公司 | 液晶配向组合物及制造液晶显示装置的方法 |
US9120970B2 (en) * | 2010-07-15 | 2015-09-01 | Merck Patent Gmbh | Liquid crystalline media and liquid crystal displays with a polymer-stabilized homeotropic orientation |
EP2670818B1 (de) * | 2011-02-05 | 2016-10-05 | Merck Patent GmbH | Flüssigkristallanzeigen mit homöotroper ausrichtung |
KR101380192B1 (ko) * | 2012-03-30 | 2014-04-02 | 디아이씨 가부시끼가이샤 | 액정 표시 소자 및 그 제조 방법 |
US20130299741A1 (en) * | 2012-05-09 | 2013-11-14 | Shenzhen China Star Optoelectronics Technology Co. Ltd. | Liquid crystal medium composition |
TWI606113B (zh) * | 2013-02-06 | 2017-11-21 | Dainippon Ink & Chemicals | Liquid crystal display element and its manufacturing method |
CN103484131B (zh) * | 2013-08-29 | 2016-08-10 | 深圳市华星光电技术有限公司 | 液晶介质组合物 |
CN104597661B (zh) * | 2014-11-21 | 2017-06-27 | 深圳市华星光电技术有限公司 | 垂直配向液晶显示器及其制作方法 |
-
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- 2016-06-09 WO PCT/JP2016/067217 patent/WO2016204066A1/ja active Application Filing
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- 2016-06-09 EP EP16811541.8A patent/EP3312667B1/en active Active
- 2016-06-09 CN CN201680032505.3A patent/CN107615149B/zh active Active
- 2016-06-09 JP JP2016555852A patent/JP6132123B1/ja active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120169980A1 (en) * | 2010-12-31 | 2012-07-05 | Au Optronics Corporation | Method for fabricating polymer stabilized alignment liquid crystal display panel |
WO2013161669A1 (ja) * | 2012-04-24 | 2013-10-31 | Dic株式会社 | 重合性化合物を含有する液晶組成物及びそれを使用した液晶表示素子 |
US20130287970A1 (en) * | 2012-04-28 | 2013-10-31 | Shenzhen China Star Optoelectronics Technology Co., Ltd | Liquid Crystal Medium Composition and Liquid Crystal Display Using Same |
WO2014024648A1 (ja) * | 2012-08-08 | 2014-02-13 | Jnc株式会社 | 液晶組成物および液晶表示素子 |
US20140085591A1 (en) * | 2012-09-21 | 2014-03-27 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Mixture for Liquid Crystal Medium and Liquid Crystal Display Using the Same |
Non-Patent Citations (2)
Title |
---|
See also references of EP3312667A4 * |
SU , CHUN-WEI ET AL.: "Analysis and Implementation of PI Less Technology Applied in TFT LCD Displays", IDW'10 - PROCEEDINGS OF THE 17TH INTERNATIONAL DISPLAY WORKSHOPS, vol. 1, 2010, pages 17 - 20, XP009507892 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019069911A1 (ja) * | 2017-10-02 | 2019-04-11 | 富士フイルム株式会社 | 液晶組成物、反射層、反射層の製造方法、及び共重合体 |
US11634638B2 (en) | 2017-10-02 | 2023-04-25 | Fujifilm Corporation | Liquid crystal composition, reflective layer, method for producing reflective layer, and copolymer |
JPWO2020121639A1 (ja) * | 2018-12-12 | 2021-02-15 | Dic株式会社 | 重合性化合物含有液晶組成物及び液晶表示素子ならびに重合性化合物 |
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KR20180019534A (ko) | 2018-02-26 |
US20180142155A1 (en) | 2018-05-24 |
JP6132123B1 (ja) | 2017-05-24 |
EP3312667B1 (en) | 2019-08-21 |
JPWO2016204066A1 (ja) | 2017-06-29 |
CN107615149B (zh) | 2020-10-27 |
EP3312667A4 (en) | 2019-01-23 |
TWI697548B (zh) | 2020-07-01 |
TW201716552A (zh) | 2017-05-16 |
EP3312667A1 (en) | 2018-04-25 |
CN107615149A (zh) | 2018-01-19 |
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