WO2018105726A1 - リバースモードの液晶デバイス - Google Patents
リバースモードの液晶デバイス Download PDFInfo
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- WO2018105726A1 WO2018105726A1 PCT/JP2017/044174 JP2017044174W WO2018105726A1 WO 2018105726 A1 WO2018105726 A1 WO 2018105726A1 JP 2017044174 W JP2017044174 W JP 2017044174W WO 2018105726 A1 WO2018105726 A1 WO 2018105726A1
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- liquid crystal
- carbons
- hydrogen
- replaced
- fluorine
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- 0 *C(*)(c1ccc(*OC(C(*)=C)=O)cc1)c(cc1)ccc1S Chemical compound *C(*)(c1ccc(*OC(C(*)=C)=O)cc1)c(cc1)ccc1S 0.000 description 1
- ZKBUNGNDTCOGEU-UHFFFAOYSA-N Cc1cc(OC(c(cc2)ccc2OC(OCCCCOC(C=C)=O)=O)=O)ccc1OC(c(cc1)ccc1OC(OCCCCOC(C=C)=O)=O)=O Chemical compound Cc1cc(OC(c(cc2)ccc2OC(OCCCCOC(C=C)=O)=O)=O)ccc1OC(c(cc1)ccc1OC(OCCCCOC(C=C)=O)=O)=O ZKBUNGNDTCOGEU-UHFFFAOYSA-N 0.000 description 1
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- 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
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- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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- 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
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- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G02F1/133723—Polyimide, polyamide-imide
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
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- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
- C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
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- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
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- 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
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- 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
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- 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
- G02F1/13712—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 the liquid crystal having negative dielectric anisotropy
Definitions
- the present invention relates to a reverse mode type liquid crystal device that becomes transparent when no voltage is applied and scatters when a voltage is applied.
- the present invention relates to a liquid crystal device used for a dimming window and a smart window for blocking and transmitting outside light and field of view in a building window, a show window, an indoor partition, a car sunroof, a rear window, and the like.
- a reverse mode light scattering type liquid crystal device orients liquid crystal vertically with respect to a support substrate in order to obtain a transparent state when no voltage is applied.
- an alignment film made of polyimide or the like has been used so far.
- a solution in which a liquid crystal alignment material is dissolved in an organic solvent is applied to a substrate, and then the solvent is removed and the film is formed by heating the substrate.
- the alignment treatment is performed using the liquid crystal alignment film, there is a problem that the process becomes complicated and costs increase.
- the use of a solvent and a heat treatment are involved, the material of the substrate is limited, and there is a problem that causes the peeling of the sealing agent due to the contact between the sealing portion in the cell and the alignment film.
- Patent Document 4 discloses a PSA (Polymer Sustained Alignment) type liquid crystal display that uses a LC medium having negative dielectric anisotropy containing a self-aligning additive and exhibits vertical alignment without a polyimide alignment film. It is described that by forming a polymer thin film layer on a liquid crystal substrate, the temperature stability and electro-optical switching speed of the display are improved.
- the technique described in this document 4 discloses an application to a PSA-VA display, and a light scattering type liquid crystal device as in the present application and an appropriate material for use in the liquid crystal device. There is no description about the type and its composition. *
- Non-Patent Document 1 an example using a self-vertical alignment liquid crystal material without using an alignment film is disclosed in Non-Patent Document 1.
- the liquid crystal device manufactured by the method described in Non-Patent Document 1 has insufficient characteristics, and a higher-performance liquid crystal device is required for practical use.
- Devices can be provided. Since the vertical alignment agent and the polymerizable compound used in the device of the present application have high solubility in the liquid crystal composition, a liquid crystal material having high storage stability can be provided without phase separation or crystallization in the liquid crystal material.
- the problem to be solved by the present invention is to provide a reverse mode light scattering liquid crystal device that can withstand practical use, has a low driving voltage, exhibits a high haze when a voltage is applied, and a low haze when no voltage is applied. It is in.
- Another object of the present invention is to provide the above-mentioned liquid crystal device that can be manufactured with a simple process and high yield and low cost.
- the present inventors have provided a reverse mode light scattering liquid crystal device that achieves the above problems without using a liquid crystal alignment film, and the device. As a result, the present inventors have completed the present invention.
- a reverse mode liquid crystal device having a light control layer and at least a pair of electrodes,
- the light control layer is (A) a liquid crystal composition; (B) a vertical alignment agent; (C) at least one polymerizable compound selected from a polymer-forming monomer and a polymer-forming oligomer;
- a liquid crystal device comprising a polymer of a polymerizable material containing
- the reverse mode light scattering liquid crystal device of the present invention can be obtained without using a vertical alignment film using a polymer material such as polyimide. In addition, it has low voltage drivability and a large difference in haze between transmission and scattering states (high contrast).
- Such a liquid crystal device can electrically control the blocking and transmission of outside light and field of view, and it can be used for building windows and show windows, indoor partitions, car sunroofs, and rear windows. It can be used for various applications such as light control glass for blocking / transmitting light, a light guide plate (light guide), a display device for a computer terminal, and a display device for projection.
- light control glass for blocking / transmitting light
- a light guide plate light guide
- display device for a computer terminal a display device for projection.
- the liquid crystal device of the present invention is a reverse mode liquid crystal device having a light control layer and at least one pair of electrodes, (A) a liquid crystal composition; (B) a vertical alignment agent; (C) at least one polymerizable compound selected from a polymer-forming monomer and a polymer-forming oligomer; A polymer of a polymerizable material containing
- vertical alignment agent refers to a liquid crystal that is included in a liquid crystal to align the liquid crystal at an angle of 70 to 90 degrees with respect to the substrate in the liquid crystal state.
- the vertical alignment agent is preferably an organic compound having 8 or more carbon atoms having a polar group at the molecular end, and more preferably an organic compound having 10 or more carbon atoms.
- the content is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more with respect to the material of the entire light control layer.
- the content is preferably 10% by weight or less, and more preferably 5% by weight or less.
- the polar group at the molecular end of the vertical alignment agent includes —OR 2 , —N (R 2 R 3 ) 2 , —COR 2 , —CO 2 R 2 , —COOCH ⁇ CHR 2 , —NR 2 COMe, —CON (R 2 R 3 ) 2 , —SR 2 (R 2 and R 3 represent hydrogen or methyl group), ammonium salt, carboxylate and the like.
- the -N (R 2 R 3) 2 then in order to suppress the reaction between the product and other acrylic monomers of salts with acidic gases in the air, -N substituted on the aromatic (R 2 R 3) 2 It is preferable to use.
- the non-polymerizable vertical alignment agent shown below preferably has a polar group at one molecular end for vertical alignment, and —OH, —N (R 2 ) 2 (R 2 Preferably represents at least one of hydrogen and a methyl group, more preferably —OH.
- the polymerizable vertical alignment agent preferably has —OH and —COOCH ⁇ CHR 2 as polar groups at the molecular ends, and may further have both at the molecular ends. Furthermore, what contains only OH as a polar group is preferable.
- a non-polymerizable vertical alignment agent is preferably used as an example of the vertical alignment agent.
- a non-polymerizable vertical alignment agent include compounds represented by the following formulas (P-1) to (P-7).
- R3 is hydrogen, halogen, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, or 1 carbon in which at least one hydrogen is replaced by fluorine or chlorine. 1 to 18 alkyl, or alkenyl having 2 to 18 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine;
- R 4 is hydrogen, halogen, alkyl having 8 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, alkyl having 8 to 18 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen.
- Ring A and Ring B are independently 1,4-cyclohexylene and 1,4-phenylene, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, carbon An alkoxy of 1 to 12 or an alkyl of 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
- Z 3 is a single bond or — (CH 2 ) 2 —;
- Z 4 is a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—.
- At least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH—; c is 0, 1, 2 or 3. d is 0, 1, 2 or 3. c + d is 2, 3 or 4. E is 0, 1, 2; c + e is 1, 2 or 3; f is 0, 1, 2; c + f is 1 or 2; g is an integer of 0-6; h is an integer of 1-6.
- the carbon number of formula (P-1), formula (P-5), or R 4 is It is more preferable to select a compound having one OH group such as formula (P-6) having 10 or more alkyl groups.
- a polymerizable vertical alignment agent can also be preferably used in order to suppress a decrease in haze ratio when transparent due to a decrease in vertical alignment with time. Further, in order to suppress a decrease in haze ratio when transparent due to crystal precipitation or the like, a compound having a (meth) acryl group as a polymerization group is more preferable.
- the above-mentioned polymerizable vertical alignment agent has a high production cost, and therefore, for the purpose of reducing the cost of the liquid crystal device of the present invention, it is possible to use a non-polymerizable vertical alignment agent in applications where performance degradation over time is acceptable. ,preferable.
- polymerizable vertical alignment agent examples include polymerizable compounds represented by general formulas (1) to (3).
- R 1 is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
- Ring A and Ring B are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-
- Z 1 is a single bond, — (CH 2 ) 2 —, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, or —CF ⁇ CF—;
- Sp 1 and Sp 2 are each independently a single bond or alkylene having 1 to 7 carbon atoms, in which at least one —CH 2 — is replaced by —O—, —COO—, or —OCO—.
- at least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH—, in which at least one hydrogen may be replaced with fluorine; a is 0, 1, 2, 3, or 4;
- Examples of the compound (1) are (1-1) to (1-7).
- R 1 is alkyl having 1 to 10 carbons
- Sp 1 is a single bond or alkylene having 1 to 3 carbon atoms, in which at least one —CH 2 — may be replaced by —O—
- L 1 , L 2 , L 3 , L 4 , and L 5 are independently hydrogen, fluorine, methyl, or ethyl
- Y 1 and Y 2 are independently hydrogen or methyl.
- R 2 is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
- R 3 is hydrogen or methyl;
- Ring A and Ring B are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5 -Diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, in which at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 An alkyl of 1 to 12 carbons, or an alkyl of 1 to 12 carbons in
- At least one — (CH 2 ) 2 — may be replaced with —CH ⁇ CH—, in which at least one hydrogen may be replaced with fluorine; b is 0, 1, 2 or 3. l (el) is 1, 2, 3, 4 or 5. Examples of the compound (2) are (2-1) to (2-19).
- R 1 is alkyl having 1 to 10 carbons
- Sp 2 and Sp 3 are each independently an alkylene having 1 to 3 carbon atoms, in which at least one —CH 2 — may be replaced by —O—
- L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 , L 9 , L 10 , L 11 , and L 12 are independently hydrogen, fluorine, or methyl
- l is 1, 2, 3, or 4, and at least one —CH 2 — of the alkylene may be replaced by —O—.
- Ring A is 1,4-phenylene, naphthalene-2,6-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons Or at least one hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by fluorine or chlorine;
- R 4 and R 5 are each independently a hydrocarbon having 1 to 30 carbon atoms, and R 4 and R 5 may be linked to form a cyclic structure;
- Sp 5 is a single bond or alkoxy having 2 to 12 carbon atoms, and one CH 2 hydrogen of the alkoxy may be substituted with OH;
- R 3 is hydrogen or methyl.
- polymerizable vertical alignment agents represented by the general formulas (1) to (3) include Japanese Patent Application Nos. 2015-023330, 2015-181370, 2008-266550, 2008-266632, The compounds described in Application No. 2016-120581 and the like can be preferably used.
- the vertical alignment agent of the present invention may be used as a mixture of two or more thereof. As such two types, a polymerizable and non-polymerizable vertical alignment agent may be selected in combination.
- Polymerizable material in the present invention, at least one polymerizable compound selected from a polymer-forming monomer and a polymer-forming oligomer is used.
- a polymer obtained from a polymerizable material containing a polymerizable compound has an important role of forming a polymer network in the light control layer and increasing the haze ratio when a voltage is applied.
- Such a polymer-forming monomer or oligomer can be selected from all known polymer-forming monomers or oligomers, but it reduces the haze rate during transmission and at the same time increases the haze rate during scattering. Therefore, it is preferable to use a compound represented by the following formulas (6) to (8).
- the light control layer constitutes a polymer of a polymerizable material containing a polymerizable compound.
- a polymerizable vertical alignment agent and a polymerizable liquid crystal composition are included together with the polymerizable compound, A polymer may be constituted as the polymerizable material.
- ring X and ring Y are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran.
- At least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen having 1 to 12 carbons replaced by fluorine or chlorine.
- Z10, Z12, Z14, Z15, and Z19 are each independently a single bond, —O—, —COO—, —OCO—, or —OCOO—;
- Z 11 , Z 13 , Z 16 , and Z 18 Are independently a single bond, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —COS—, —SCO—, —OCOO—, —CONH—, —NHCO—, —CF 2.
- M 1 is hydrogen or methyl
- r is an integer of 1 to 20.
- Examples of compound (7) are formula (7-1) to formula (7-31).
- M 2 and M 3 are independently hydrogen or methyl, and t and v are independently an integer of 1 to 20.
- t and v are preferably 3 or more and 16 or less, and preferably 4 or more and 12 or less. More preferably.
- Examples of the compound (8) are the formulas (8-1) to (8-10).
- M 3 , M 5 , and M 6 are independently hydrogen or methyl, and w, k, and z are independently 1 to 20 It is an integer.
- the polymerizable group represented by the formula (6) is combined with the compounds represented by the formulas (7) and (8). It is preferable to use a compound having one of these together.
- the compound represented by the formula (6) is preferably 50% by weight or less, more preferably 30% by weight or less based on the compounds represented by the formulas (7) and (8). .
- Specific examples of the compounds represented by the above formulas (6) to (8) include polymerizable liquid crystal compounds described in Japanese Patent No. 4063873, Japanese Patent Application Laid-Open No. 2008-266550, Japanese Patent Application Laid-Open No. 2008-266632, and the like. In order to improve the contrast characteristics of the liquid crystal device and reduce the cost, the following compounds are most preferable.
- the content of the polymer derived from at least one polymerizable compound represented by the above formulas (6) to (8) maintains the contrast characteristics of the liquid crystal device. 5 to 50% by weight is preferred.
- the content of the component derived from the non-polymerizable vertical alignment agent in the light control layer is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight
- the content of the component derived from the polymerizable compound (C) is preferably 5 to 45% by weight, more preferably 6 to 20% by weight
- the content of the liquid crystal composition (A) is preferably It is in the range of 50% to 94.5% by weight, more preferably 76 to 93% by weight.
- the total content of the components derived from the polymerizable vertical alignment agent and the polymerizable compound (C) in the light control layer is preferably in the range of 5 to 50% by weight with respect to the entire light control layer. More preferably, it is 6 to 25% by weight, and the content of the liquid crystal composition (A) is in the range of 50 to 95% by weight, and more preferably 7 to 94% by weight.
- general compounds other than the above formulas (6) to (8) can also be used as the polymer-forming monomer or polymer-forming oligomer.
- examples of such compounds include compounds represented by the following general formulas (9), (10), and (11).
- P 1 -Z 20 -P 2 (9) In the formula (9), Z 20 is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen may be replaced with alkyl having 1 to 5 carbons, fluorine, chlorine, or P 3.
- At least one —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N (R 5 ) —, and at least one —CH 2 —CH 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, wherein at least one —CH 2 — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic A compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound, or a heterocyclic aromatic compound, produced by removing two hydrogens.
- a valent group In these divalent groups, the number of carbon atoms is from 35 to 5, at least one hydrogen may be replaced by R 5 or P 3, where R 5 is alkyl of 1 to 12 carbon atoms In this alkyl, at least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—; P 1 , P 2 , and P 3 are each independently a polymerizable group, and P 1 , P 2 , and P 3 are independently represented by formulas (P-1) to (P-6). It is a group selected from the group of polymerizable groups.
- M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with
- At least one of P 1 , P 2 and P 3 is acryloyloxy or methacryloyloxy.
- M 4 and M 5 are independently hydrogen or methyl;
- Z 5 is alkylene having 20 to 80 carbons, in which at least one hydrogen is 1 to 20 carbons
- at least one —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N (R 5 ).
- at least one —CH 2 —CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, wherein R 5 is from 1 to 12 carbon atoms.
- M 6 is hydrogen or methyl;
- Z 6 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced with fluorine or chlorine.
- At least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—;
- R 6 is alkyl having 1 to 40 carbons, At least one hydrogen may be replaced with fluorine or chlorine, and at least one —CH 2 — may be replaced with —O—, —CO—, —COO—, or —OCO—, and at least one of -CH 2 -, a saturated aliphatic compound carbocyclic, saturated aliphatic compounds heterocyclic, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbon May be replaced by a divalent group formed by removing two hydrogens from an aromatic compound of the formula, or a heterocyclic aromatic compound, in which the carbon
- Examples of the polymer-forming monomer or oligomer represented by the above formulas (9) to (11) include a polymerizable group having no liquid crystal group such as acryloyl group such as n-dodecyl acrylate.
- the amount of the compounds represented by the above formulas (9) to (11) may be 40% by weight or less based on the whole polymer-forming monomer or oligomer in order to reduce the haze ratio during transmission. Preferably, it is 20% by weight or less.
- liquid crystal composition used in the liquid crystal composition light control layer a liquid crystal composition that is generally recognized as a liquid crystal material in this technical field can be used.
- a liquid crystal composition any compound that is generally recognized as a liquid crystal material in this technical field can be used, and a compound having negative dielectric anisotropy can also be used.
- light control windows such as windows and show windows of buildings exposed to outside light, sunroofs of cars, and rear windows
- light resistance to ultraviolet rays is required.
- heat resistance is required because the body heats up due to sunlight in summer. Therefore, it is made of a compound having a structure stable to ultraviolet rays, and has an NI point (upper limit temperature) of 80 ° C.
- the transition temperature from the nematic phase (lower limit temperature) is ⁇ 10 ° C. or lower, preferably ⁇ 20 ° C. or lower, more preferably ⁇ 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower.
- a liquid crystal composition having ⁇ n of 0.15 or more, preferably 0.18 or more, more preferably 0.2 or more is used.
- a liquid crystal material in which the liquid crystal composition contains at least one liquid crystal selected from the compound represented by the general formula (4) as the first component is preferable.
- R5 and R6 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least 1 1 to 12 carbon alkyls in which two hydrogens are replaced by fluorine or chlorine;
- Ring G and Ring H are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen Chroman-2,6-diyl substituted with fluorine or chlorine; j is 1, 2 or 3, and k is 0 or 1; The sum of j is 1,
- R 5 and R 6 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.
- the ratio of the first component in the liquid crystal composition is in the range of 20% to 90% by weight, preferably 30% to 85% by weight, more preferably 40% to 60% by weight, based on the entire liquid crystal composition. Preferably there is. When it is contained in such an amount, the dielectric anisotropy of the liquid crystal composition is negatively increased.
- the liquid crystal composition contains at least one liquid crystal compound selected from the compounds represented by formula (5) as the second component.
- R 7 and R 8 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Substituted alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
- Ring M and Ring N are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
- Z 9 is a single bond, ethylene, or carbonyloxy; q is 1, 2 or 3.
- R 7 and R 8 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.
- the proportion of the second component in the liquid crystal composition (A) is 10% to 70% by weight, preferably 15% to 65% by weight, more preferably 40% to 60% by weight, based on the entire liquid crystal composition. % Range.
- the dielectric anisotropy of the liquid crystal composition can be made negative and the lower limit temperature can be lowered.
- a thermal polymerization initiator in order to polymerize a polymer-forming monomer or oligomer to form a polymer network, a thermal polymerization initiator, a photopolymerization initiator, or the like may be included. At this time, it is preferable to use a photopolymerization initiator from the viewpoint of ease of device preparation.
- Commercially available polymerization initiators such as thermal polymerization initiators and photopolymerization initiators can be used.
- the liquid crystal composition may contain other additives such as a chain transfer agent, a photosensitizer, and a dye crosslinking agent.
- the liquid crystal device of the present invention is a reverse mode liquid crystal device having a light control layer and at least one pair of electrodes, and the pair of electrode layers are disposed so that at least a part of the pair of electrode layers face each other with the light control layer interposed therebetween. .
- the electrode layer is not particularly limited as long as it has at least one pair of electrode layers for applying a voltage to the light control layer, and can be appropriately selected according to the shape of the light control layer, etc. It is.
- the electrode layers are provided on the opposing surfaces, and the opposing surfaces may be the surfaces having the largest area, or may be the thickness direction or the upper and lower end surfaces. .
- the electrode layer can also be curved. Electrodes may be provided on the same surface of the light control layer so as to be spaced apart from each other in parallel or non-parallel. Furthermore, even if the electrode is provided in the whole light control layer, it may be provided only in one part.
- electrodes may be provided on either the front or back surface of the light control layer and the side surface (end surface).
- the pair only needs to have at least one set of electrodes, and is not limited to 1: 1, but may be 1: 2 or more (one is plural), or two or more: 2 or more (both are plural).
- At least one of the electrode layers having two transparent substrates and a light control layer sandwiched between the substrates is one mode.
- the electrode layer is provided so that the electrode can apply a voltage to the liquid crystal material.
- the substrate used in the liquid crystal device may be a rigid material such as glass or metal, or may be a flexible material such as plastic. In the liquid crystal device, the two substrates are opposed to each other and are separated by an appropriate distance.
- At least one of them has transparency, but it does not require complete transparency. If the liquid crystal device is used to act on light passing from one side of the device to the other, the two substrates are both given appropriate transparency.
- This substrate may be provided with appropriate transparent or opaque electrodes depending on the purpose, either entirely or partially.
- a known conductive material such as ITO, copper, silver, gold, PEDOT (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) is used.
- the light control layer is preferably sandwiched between a pair of transparent substrates, and the transparent substrate has a transparent electrode.
- the transparent substrate is preferably a glass plate or an acrylic plate, and more preferably the transparent substrate is a plastic film.
- liquid crystal device of the present invention When the liquid crystal device of the present invention is used for a display device for a computer terminal, a projection display device, or the like, it is preferable to provide a TFT or the like on the electrode layer as an active element.
- an alignment film such as polyimide provided in a normal liquid crystal device is not necessarily required. It should be noted that a spacer for maintaining a gap can be usually interposed between the two substrates, as in a known liquid crystal device.
- liquid crystal cell materials such as Mylar, alumina, rod-type glass fiber, glass beads, and polymer beads can be used.
- the light control layer of the liquid crystal device of the present invention is sandwiched between two substrates, and a sealing material is applied around the substrate, like a normal liquid crystal display element. A method of bonding the two can be used.
- the liquid crystal device of the present invention does not require an alignment film, other materials such as the alignment film do not intervene between the sealing material and the substrate, so that the sealing agent does not easily peel off.
- the substrates can be fixed by interposing a polymer network.
- the content of the polymer derived from the compounds represented by the above formulas (7) and (8) serving as the material of the polymer network is determined with respect to the entire material of the light control layer 5 to 50% by weight is preferred.
- the transparent substance (polymer network) in the light control layer is made of a polymer of a polymerizable material.
- the transparent material dispersed in the form of fibers or particles, or the liquid crystal material described above is dispersed in droplets. It may be a film or a gel having a three-dimensional network structure.
- the light control layer preferably has a network structure in which the liquid crystal composition forms a continuous structure.
- the liquid crystal composition forms a continuous structure.
- the liquid crystal device of the present invention has a high contrast with a haze ratio of 20% or less when no voltage is applied and a haze ratio of 70% or more when a voltage is applied.
- the reverse mode liquid crystal device of the present invention can be manufactured, for example, as follows.
- At least one polymerizable compound selected from a liquid crystal composition, a vertical alignment agent, a polymer-forming monomer, and a polymer-forming oligomer is provided between two substrates having at least one electrode layer having transparency.
- a liquid crystal device can be produced by polymerizing the polymerizable material by irradiating ultraviolet rays through the transparent substrate or heating the transparent substrate through a composition containing the polymerizable material containing .
- FIGS. 1 and 2 Schematic diagrams are shown in FIGS. 1 and 2 as examples of the reverse mode type liquid crystal device of the present invention.
- FIG. 1 shows a state in which no voltage is applied, the orientation of the liquid crystal material is homeotropic, and light is transmitted, so that the panel is transparent.
- FIG. 2 shows a state in which a voltage is applied, and the liquid crystal composition tries to have a homogeneous alignment, but the presence of a peripheral network makes it impossible to obtain a uniform alignment, and light is scattered, so the panel becomes cloudy.
- the thickness of the light control layer having light scattering properties in the liquid crystal device of the present invention can be adjusted according to the purpose of use, but in order to obtain sufficient contrast between the opacity and transparency due to light scattering. It is 2 to 40 ⁇ m, more preferably 5 to 20 ⁇ m, and most preferably 7 to 15 ⁇ m. Generally, a higher voltage is required for switching as the substrate interval becomes thicker.
- a dye can be added to the light control layer in the liquid crystal device of the present invention.
- the dye at this time is preferably a dichroic dye in order to increase the light utilization efficiency during transmission.
- the concentration thereof is preferably 0.01% by weight to 10% by weight, and preferably 0.1% by weight to 5% by weight with respect to the whole liquid crystal composition in order to prevent the precipitation of the dye and to obtain sufficient color development. Further preferred.
- a protective film such as an ultraviolet absorbing film can be attached to the liquid crystal device of the present invention.
- the position of the protective film may be the same or opposite substrate side as the light control layer and other positions, and may be one sheet or a plurality.
- the liquid crystal device having a light control layer obtained in the present invention is used as a light control window, a light guide plate (light guide), a light modulation device, etc., for architectural use such as indoor interior, and for automobile use such as a leaf for automobiles. It can be used for various applications such as. Moreover, it can also be used in combination with a normal liquid crystal display element using a polarizing plate.
- a liquid crystal device that can be driven at a low voltage, has a small haze when no voltage is applied and has high transparency, and has a large haze and high scattering when a voltage is applied.
- room temperature means 15-30 ° C. Unless otherwise noted, the examples were performed at room temperature.
- (1) -1 used as the vertical alignment agent is represented by the following chemical formula.
- the transition temperature from the crystal phase of the compound (1) -1 to the smectic phase was 40.8 ° C.
- the transition temperature from the smectic phase of compound (1) -1 to the isotropic liquid was 109 ° C.
- M-1 used as a polymerizable monomer is represented by the following chemical formula.
- the transition temperature from the crystal phase of compound M-1 to the nematic phase was 83.6 ° C.
- the transition temperature from the nematic phase of compound M-1 to the isotropic liquid was 116.9 ° C.
- the extraordinary refractive index of Compound M-1 was 1.6627.
- the ordinary light refractive index of Compound M-1 was 1.5048.
- Compound M-1 is a polymer-forming monomer having two acrylate groups.
- the pure compound M-1 has a liquid crystal phase.
- M-2 used as a polymerizable monomer is represented by the following chemical formula.
- the transition temperature from the crystal phase of compound M-2 to the nematic phase was 60.3 ° C.
- the transition temperature from the nematic phase to the isotropic liquid of Compound M-2 was 124.4 ° C.
- the extraordinary refractive index of Compound M-2 was 1.6370.
- the ordinary light refractive index of Compound M-1 was 1.4924.
- Compound M-2 is a polymer-forming monomer having two acrylate groups.
- the pure compound M-2 has a liquid crystal phase.
- Transition temperature measurement method A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and heated at a specific speed. The temperature at which a part of the sample was changed from the nematic phase to the isotropic liquid was measured, and was defined as the “transition temperature from the nematic phase to the isotropic liquid” of the sample.
- a sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and cooled at a specific speed.
- the temperature at which a part of the sample was changed from the isotropic liquid to the nematic phase was measured, and was defined as the “transition temperature from the isotropic liquid to the nematic phase” of the sample.
- the average refractive index was determined by the following procedure. (1) The ordinary refractive index of the sample with respect to the white light source by a lamp was measured using an Abbe refractometer. (2) Using an Abbe refractometer, the extraordinary refractive index of the sample with respect to a white light source by a lamp was measured. (3) The average refractive index was calculated by ((normal light refractive index 2 + extraordinary light refractive index 2 ) / 2) 1/2 .
- the contrast ratio is a ratio between the transmitted light intensity under a specific situation and the situation transmitted light intensity under a different situation.
- ⁇ Measurement of ⁇ and ⁇ > ⁇ , ⁇ and ⁇ were determined by the following procedure. (1) A sample is put in a TN device in which the distance between two glass substrates is 10 ⁇ m and the twist angle is 80 degrees, (2) A 10 V, 1 kHz sine wave was applied to the device, and after 2 seconds, the dielectric constant in the major axis direction of the liquid crystal molecules was measured, and ⁇ (3) A 0.5 V, 1 kHz sine wave was applied to the device, and after 2 seconds, the dielectric constant in the minor axis direction of the liquid crystal molecules was measured, and ⁇ (4) The value of ⁇ is ⁇ .
- a cell was installed on a HAZE METER NDH5000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD so that the light source was perpendicular to the cell surface, and the haze and parallel light transmittance were measured at room temperature.
- a liquid crystal composition LC-1 was prepared by mixing the compounds shown in Table 1. Those skilled in the art can synthesize the compounds shown in Table 1 by referring to the methods described in JP02503443A, JP20008040A, Molecular Crystals and Liquid Crystals, Volume 195, Pages 221-37, 1991 and the like.
- Example 1 ⁇ Preparation of liquid crystal composition LC-1-1> Liquid crystal composition LC-1 and Irgacure (trademark) 651 were mixed at a weight ratio of 100 / 0.3 and named Liquid crystal composition LC-1-1.
- Irgacure TM 651 is 2,2-dimethoxy-1,2-diphenylethane-1-one.
- phase transition temperature from the nematic phase to the isotropic liquid of the liquid crystal composition LC-1 was 79.5 ° C. This transition temperature was measured while heating at a rate of 2.0 ° C./min.
- the physical property data of the liquid crystal composition (LC-1) is shown in Table 2.
- liquid crystal compositions LC-1-1, (1) -1, and M-1 were mixed at a weight ratio of 94/2/4 and named liquid crystal composition MLC-A.
- liquid crystal compositions LC-1-1, (1) -1, and M-2 were mixed at a weight ratio of 90/3/7, and named liquid crystal composition MLC-B.
- the polymer / liquid crystal composite material PDLC-A was prepared by the following procedure. (1) A glass substrate on which electrodes of two transparent conductive films not subjected to orientation treatment are attached is disposed so that the width between the glass substrates is 10 ⁇ m and the electrodes are inside, and the glass substrate A liquid crystal composition MLC-A was inserted between them to produce a cell. (2) The cell was heated until the liquid crystal composition MLC-A became isotropic, and then cooled to room temperature. At this time, it was confirmed by phase observation with a polarizing microscope that the liquid crystal in the cell was vertically aligned with respect to the substrate.
- the glass substrate is e. Etch. KSSZ-10 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-A between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm.
- a potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- ⁇ Preparation of polymer / liquid crystal composite PDLC-B> In the preparation of the polymer / liquid crystal composite material PDLC-B, the liquid crystal composition MLC-A was replaced with the liquid crystal composition MLC-B, and light with a wavelength of 365 nm was irradiated at 2.5 mWcm ⁇ 2 for 400 seconds. The liquid crystal composition was polymerized to prepare a polymer / liquid crystal composite material PDLC-B.
- the polymer / liquid crystal composite material PDLC-A was arranged so that the light source light was perpendicular to the cell surface, and the electro-optical characteristics of the polymer / liquid crystal composite material PDLC-A were measured with an electric field application unit and a bipolar power source. .
- the polarizing microscope used was Nikon, Eclipse, LV100POL.
- a white light source of a polarizing microscope was used as the light source.
- the electric field application unit used was a waveform generator 3320A manufactured by Keysight.
- As the bipolar power source ELECTRONIC INSTRUMENTS 4010 manufactured by NF was used.
- the voltage of the electrodes of the two transparent conductive films was increased from 0V to 60V.
- the transmitted light intensity for each applied voltage was measured.
- the applied voltage-transmittance curve between the electrodes of the polymer / liquid crystal composite material PDLC-A is shown in FIG.
- the transmittance with respect to the voltage is indicated by a black circle.
- the transmittance for the voltage when the voltage between the electrodes is decreased from 60 V to 0 V is indicated by white circles. The results are shown in FIG.
- PDLC-A is replaced with PDLC-B as a polymer / liquid crystal composite material, and the voltage of the electrodes of the two transparent conductive films is increased from 0 to 80 V, from 80 V to 0 V It was lowered until it became. At that time, the transmitted light intensity was measured for each applied voltage.
- the applied voltage-transmittance curve between the electrodes of the polymer / liquid crystal composite material PDLC-B is shown in FIG.
- the transmittance with respect to the voltage is indicated by a black circle.
- the transmittance for the voltage when the voltage between the electrodes is decreased from 80 V to 0 V is indicated by white circles. The results are shown in FIG.
- the contrast ratio was 19 when no voltage was applied between the electrodes of the polymer / liquid crystal composite material PDLC-B and when a voltage of 80 V was applied between the electrodes of the polymer / liquid crystal composite material PDLC-A. .
- the haze of the measurement cell when a voltage of 50 V was applied to the measurement cell was measured and is shown in B of Table 3.
- ⁇ Measurement of Haze and Parallel Light Transmittance of Polymer / Liquid Crystal Composite Material PDLC-B was placed in the haze meter so that the light source light was perpendicular to the cell surface. A voltage of 0 to 60 V was applied to the cell, and haze and parallel light transmittance were measured.
- the haze of the measurement cell when a voltage of 60 V was applied to the measurement cell was measured and described in B of Table 3.
- P-5-1, P-6-1, P-7-1, and C-2 can be purchased from Aldrich Partner Products or Tokyo Kasei Co., Ltd.
- M-3, M-4, M-5, and M-6 used as the polymerizable compound are represented by the following chemical formula.
- Those skilled in the art can synthesize these compounds by referring to the methods described in JP4036076, JP5295471, JP5162985, Molecular Crystals and Liquid Crystals, Volume 137, Issue 1-4, Pages 349-64, 1986, and the like.
- M-7, M-8, and M-9 can be purchased from Shin-Nakamura Chemical Co., Ltd. or Tokyo Kasei Co., Ltd.
- liquid crystal composition MLC-D The liquid crystal compositions LC-1-1, (2) -1, and M-1 were mixed at a weight ratio of 93/2/5 and named liquid crystal composition MLC-D.
- Liquid crystal compositions LC-1-1, P-3-1, M-2, and M-5 were mixed at a weight ratio of 93/1/5/1, and named liquid crystal composition MLC-S.
- Liquid crystal compositions LC-1-1, P-5-1 and M-1 were mixed at a weight ratio of 90/4/6 and named liquid crystal composition MLC-V.
- the liquid crystal compositions LC-1-1, C-2, and M-1 were mixed at a weight ratio of 93/2/5 and named liquid crystal composition MLC-C2.
- the polymer / liquid crystal composite material PDLC-D was prepared by the following procedure. (1) A glass substrate on which electrodes of two transparent conductive films not subjected to orientation treatment are attached is disposed so that the width between the glass substrates is 10 ⁇ m and the electrodes are inside, and the glass substrate A liquid crystal composition MLC-D was inserted between them to produce a cell. (2) The cell was heated until the liquid crystal composition MLC-D became an isotropic phase, and then cooled to room temperature.
- the glass substrate is e. Etch. KSSZ-10 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying the voltage between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-D between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm. A potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- Polymer / liquid crystal composite material PDLC-V, Reference Example 2 was prepared using liquid crystal composition MLC-V and liquid crystal composition MLC-C2 in the same manner as PDLC-D.
- the glass substrate is e. Etch. KSSZ-5 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying the voltage between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-D between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm. A potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- liquid crystal composition MLC-T liquid crystal composition MLC-U
- liquid crystal composition MLC-X liquid crystal composition MLC-X in the same manner as PDLC-S
- the polymer / liquid crystal composite materials PDLC-T, PDLC-U, and PDLC-X was prepared.
- the measurement cell haze and voltage haze applied when no voltage is applied to the PDLC-T, PDLC-U, and PDLC-X measurement cells when no voltage is applied and applied The haze and parallel light transmittance at the time were measured, and it was confirmed that there was a change in haze when a voltage was applied.
- Table 8 shows the alignment state when no voltage is applied and the presence or absence of a haze change due to voltage application.
- the measured cell haze when the applied voltage was not applied to the measurement cell and the haze when no voltage was applied were measured and listed in Table 9.
- the voltage at the time of voltage application was 40V.
- the haze and parallel light transmittance were measured when no voltage was applied to the PDLC-S measurement cell and when the voltage was applied, and it was confirmed that there was a change in haze when the voltage was applied.
- a liquid crystal composition LC-2 was prepared by mixing the compounds shown in Table 4. Those skilled in the art can synthesize the compounds shown in Table 4 by referring to the methods described in JP02503443A, JP20008040A, Molecular Crystals and Liquid Crystals, Volume 195, Pages 221-37, 1991 and the like.
- Liquid liquid crystal composition LC-2 and Irgacure (trademark) 651 were mixed at a weight ratio of 100 / 0.3 and named Liquid crystal composition LC-1-1.
- Irgacure TM 651 is 2,2-dimethoxy-1,2-diphenylethane-1-one.
- phase transition temperature from the nematic phase to the isotropic liquid of the liquid crystal composition LC-2 was 98.4 ° C. This transition temperature was measured while heating at a rate of 2.0 ° C./min.
- the physical property data of the liquid crystal composition (LC-2) is shown in Table 5.
- Liquid crystal compositions LC-2-1, (1) -1, and M-2 were mixed at a weight ratio of 94/2/4 and named liquid crystal composition MLC-C.
- Liquid crystal compositions LC-2-1, (2) -1, M-2, and M-3 were mixed at a weight ratio of 92/2/3/3 and named liquid crystal composition MLC-E.
- Liquid crystal compositions LC-2-1, P-1-3, M-1, and M-5 were mixed at a weight ratio of 92/2/3/3 and named liquid crystal composition MLC-I.
- Liquid crystal compositions LC-2-1, P-1-4, M-1, and M-6 were mixed at a weight ratio of 91/2/4/3 and named liquid crystal composition MLC-J.
- Liquid crystal compositions LC-2-1, P-1-5, and M-1 were mixed at a weight ratio of 91/2/7 and named liquid crystal composition MLC-K.
- Liquid crystal compositions LC-2-1, P-1-7, M-2, and M-7 were mixed at a weight ratio of 90/3/5/2 and named liquid crystal composition MLC-M.
- Liquid crystal compositions LC-2-1, P-1-9, M-2, and M-4 were mixed at a weight ratio of 84/5/6/5, and were named as liquid crystal composition MLC-P.
- Liquid crystal compositions LC-2-1, P-6-1 and M-2 were mixed at a weight ratio of 93/2/5 and named liquid crystal composition MLC-W.
- the polymer / liquid crystal composite material PDLC-C was prepared by the following procedure. (1) A glass substrate on which electrodes of two transparent conductive films not subjected to orientation treatment are attached is arranged such that the width between the glass substrates is 5 ⁇ m and the electrodes are on the inside, and the glass substrate A liquid crystal composition MLC-C was inserted between them to produce a cell. (2) The cell was heated until the liquid crystal composition MLC-C became an isotropic phase, and then cooled to room temperature. At this time, it was confirmed by phase observation with a polarizing microscope that the liquid crystal in the cell was vertically aligned with respect to the substrate.
- the glass substrate is e. Etch. KSSZ-5 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying the voltage between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-D between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm. A potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- a liquid crystal composition MLC-E, a liquid crystal composition MLC-J liquid crystal, a composition MLC-K, and a liquid crystal composition MLC-W were used in the same manner as in PDLC-C, and a polymer / liquid crystal composite material PDLC-E, PDLC-J, PDLC-K, and PDLC-W were prepared.
- ⁇ Preparation of PDLC-I of polymer / liquid crystal composite material> A glass substrate on which electrodes of two transparent conductive films not subjected to orientation treatment are attached is disposed so that the width between the glass substrates is 10 ⁇ m and the electrodes are inside, and the glass substrate A liquid crystal composition MLC-I was inserted between them to produce a cell. (2) The cell was heated until the liquid crystal composition MLC-I became isotropic, and then cooled to room temperature. At this time, it was confirmed by phase observation with a polarizing microscope that the liquid crystal in the cell was vertically aligned with the substrate.
- the glass substrate is e. Etch. KSSZ-10 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying the voltage between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-D between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm. A potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- liquid crystal composition MLC-M Using the liquid crystal composition MLC-M, the liquid crystal composition MLC-P, and the liquid crystal composition MLC-R in the same manner as PDLC-I, the polymer / liquid crystal composite materials PDLC-M, PDLC-P, and PDLC-R was prepared.
- PDLC-A is replaced with PDLC-C as a polymer / liquid crystal composite material, and the voltage of the electrodes of the two transparent conductive films is increased from 0 to 60 V, from 60 V to 0 V It was lowered until it became. At that time, the transmitted light intensity was measured for each applied voltage, and a rectangular wave of 20 V was applied to confirm that the polymer / liquid crystal composite material PDLC-C was driven in the reverse mode.
- PDLC-M of polymer / liquid crystal composite material ⁇ Electro-optical properties of PDLC-M of polymer / liquid crystal composite material>
- PDLC-A is replaced with PDLC-I as a polymer / liquid crystal composite material, and the voltage of the electrodes of the two transparent conductive films is increased from 0 to 60V, from 60V to 0V It was lowered until it became.
- the transmitted light intensity was measured for each applied voltage, and a rectangular wave of 20 V was applied to confirm that the polymer / liquid crystal composite material PDLC-D was driven in the reverse mode.
- Table 9 shows the measurement cell haze and the voltage haze when no voltage was applied to the measurement cell.
- the voltage at the time of voltage application was 40V.
- Table 9 shows the measurement cell haze and the voltage haze when no voltage was applied to the measurement cell.
- the voltage at the time of voltage application was 40V.
- a liquid crystal composition LC-3 was prepared by mixing the compounds shown in Table 6. Those skilled in the art can synthesize the compounds shown in Table 6 by referring to the methods described in JP02503443A, JP20008040A, Molecular Crystals and Liquid Crystals, Volume 195, Pages 221-37, 1991 and the like.
- Liquid liquid crystal composition LC-3 and Irgacure (trademark) 651 were mixed at a weight ratio of 100 / 0.3 and named Liquid crystal composition LC-1-1.
- Irgacure TM 651 is 2,2-dimethoxy-1,2-diphenylethane-1-one.
- phase transition temperature from the nematic phase to the isotropic liquid of the liquid crystal composition LC-3 was 122.8 ° C. This transition temperature was measured while heating at a rate of 2.0 ° C./min.
- Liquid crystal compositions LC-3-1, (2) -1, M-1, and M-4 were mixed at a weight ratio of 91/2/4/3 and named liquid crystal composition MLC-F.
- liquid crystal compositions LC-3-1, P-1-1 and M-2 were mixed at a weight ratio of 92/2/6 and named liquid crystal composition MLC-G.
- Liquid crystal compositions LC-3-1, P-1-2, M-1, and M-4 were mixed at a weight ratio of 88/2/6/4 and named liquid crystal composition MLC-H.
- Liquid crystal compositions LC-3-1, P-1-6, M-1, and M-4 were mixed at a weight ratio of 85/3/6/6 and named liquid crystal composition MLC-L.
- Liquid crystal compositions LC-3-1, P-1-8, M-4, and M-8 were mixed at a weight ratio of 89/3/5/3 and named liquid crystal composition MLC-N.
- Liquid crystal compositions LC-3-1, P-2-1, M-4, and M-7 were mixed at a weight ratio of 94/2/4/2 and named liquid crystal composition MLC-Q.
- liquid crystal compositions LC-3-1, C-3, and M-1 were mixed at a weight ratio of 93/2/5 and named liquid crystal composition MLC-C3.
- the glass substrate is e. Etch. KSSZ-10 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying the voltage between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-D between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm. A potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- the liquid crystal composition MLC-G, the liquid crystal composition MLC-H, the liquid crystal composition MLC-L, the liquid crystal composition MLC-N, the liquid crystal composition MLC-Q, and the liquid crystal composition MLC-C3 are obtained by the same operation as PDLC-F.
- the polymer / liquid crystal composite materials PDLC-G, PDLC-H, PDLC-L, PDLC-N, PDLC-Q, and Reference Example 3 were prepared.
- PDLC-F of polymer / liquid crystal composite material ⁇ Electro-optical properties of PDLC-F of polymer / liquid crystal composite material>
- PDLC-A is replaced with PDLC-F as a polymer / liquid crystal composite material, and the voltage of the electrodes of the two transparent conductive films is increased from 0 to 60 V. From 60 V to 0 V It was lowered until it became. At that time, the transmitted light intensity was measured for each applied voltage, and a rectangular wave of 20 V was applied to confirm that the polymer / liquid crystal composite material PDLC-F was driven in the reverse mode.
- PDLC-G, PDLC-H, PDLC-L, PDLC-N, and PDLC-Q were driven in the reverse mode by the same operation as PDLC-F.
- the measured cell haze when the applied voltage was not applied to the measurement cell and the haze when no voltage was applied were measured and listed in Table 9.
- the voltage at the time of voltage application was 60V.
- C-4 A person skilled in the art can synthesize (C-4) by a method described in WO2017-130566A or the like.
- C-5) can be purchased from Sigma Aldrich.
- Liquid crystal compositions LC-1-1, C-5, and M-1 were mixed at a weight ratio of 90 / 0.0009 / 10 and named liquid crystal composition MLC-C5.
- the glass substrate is e. Etch. KSSZ10 / A107P1NSS05 manufactured by Sea Co., Ltd. was used. By applying between the electrodes of the glass substrate, an electric field could be applied to the liquid crystal composition MLC-C4 between the glass substrates.
- the transparent conductive film is ITO.
- the dimension of the transparent conductive film is 10 mm ⁇ 10 mm.
- a potential difference is generated between the two substrates, and an electric field can be applied to the inserted liquid crystal composition.
- a polymer / liquid crystal composite material of Reference Example 5 was prepared using the liquid crystal composition MLC-C5 in the same manner as in Reference Example 4.
- ⁇ Measurement of Haze and Parallel Light Transmittance of Polymer / Liquid Crystal Composite Reference Example 4 The polymer / liquid crystal composite material reference example 4 was placed in the haze meter so that the light source light was perpendicular to the cell surface. A voltage of 0 to 60 V was applied to the cell, and haze and parallel light transmittance were measured. When the applied voltage was not applied to the measurement cell, the haze of the measurement cell and the haze when no voltage was applied were measured, but no change in haze of the measurement cell could be confirmed by applying a voltage between 0 and 60V.
- the haze and parallel light transmittance of the measurement cell of Reference Example 5 when no voltage was applied and when the voltage was applied were measured in the same manner as in Reference Example 4.
- the cell of Reference Example 5 did not show a vertical alignment state when no voltage was applied, and no haze change of the measurement cell could be confirmed by applying a voltage between 0 and 60V .
Abstract
Description
調光層および少なくとも一対の電極を有するリバースモードの液晶デバイスであって、
上記調光層が、
(A)液晶組成物と、
(B)垂直配向剤と、
(C)高分子形成性モノマーおよび高分子形成性オリゴマーから選ばれる少なくとも1つの重合性化合物と、
を含む重合性材料の重合物を含むことを特徴とする液晶デバイス。
(A)液晶組成物と、
(B)垂直配向剤と、
(C)高分子形成性モノマーおよび高分子形成性オリゴマーから選ばれる少なくとも1つの重合性化合物と、
を含む重合性材料の重合物を含む。
垂直配向剤
本明細書において、「垂直配向剤」とは、液晶中に含ませることで、液晶を、液晶状態において、基板に対して70度から90度の角度で配向させる(垂直配向性を与える)化合物とする。
R4は、水素、ハロゲン、炭素数8から18のアルキル、炭素数8から18のアルケニル、少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数8から18のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数8から18のアルケニルであり;
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-フェニレンであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;
Z3は、単結合または-(CH2)2-であり;Z4は、単結合または炭素数1から6のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく;
cは、0、1、2または3である。dは、0、1、2または3である。c+dは、2、3または4である。;eは、0、1、2である。c+eは、1、2または3であり;
fは0、1、2である。c+fは、1または2であり;gは、0~6の整数であり;hは1~6の整数である。
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-1,2-ジイル、ナフタレン-1,3-ジイル、ナフタレン-1,4-ジイル、ナフタレン-1,5-ジイル、ナフタレン-1,6-ジイル、ナフタレン-1,7-ジイル、ナフタレン-1,8-ジイル、ナフタレン-2,3-ジイル、ナフタレン-2,6-ジイル、ナフタレン-2,7-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、フルオレン-2,7-ジイル、フェナントレン-2,7-ジイル、アントラセン-2,6-ジイル、ペルヒドロシクロペンタ[a]フェナントレン-3,17-ジイル、または2,3,4,7,8,9,10,11,12,13,14,15,16,17-テトラデカヒドロシクロペンタ[a]フェナントレン-3,17-ジイルであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z1は、単結合、-(CH2)2-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、または-CF=CF-であり;
Sp1、Sp2は独立して、単結合または炭素数1から7のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素で置き換えられてもよく;
aは、0、1、2、3、または4である。
化合物(1)の例は(1-1)~(1-7)である。
R1は、炭素数1~10のアルキルであり;
Sp1は、単結合または炭素数1から3のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-で置き換えられてもよく;
L1、L2、L3、L4、およびL5は独立して、水素、フッ素、メチル、またはエチルであり;
Y1およびY2は独立して、水素またはメチルである。
R3は水素またはメチルであり;
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-フェニレン、ナフタレン-2,6-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、フルオレン-2,7-ジイル、であり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;
Z2は、単結合、-(CH2)2-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、または-CF=CF-であり;
Sp3、Sp4は独立して、単結合または炭素数1から7のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素で置き換えられてもよく;
bは、0、1、2または3である。l(エル)は、1,2,3,4または5である。
化合物(2)の例は(2-1)~(2-19)である。
R1は炭素数1から10のアルキルあり;
Sp2、およびSp3は独立して、炭素数1から3のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-で置き換えられてもよく;
L1、L2、L3、L4、L5、L6、L7、L8、L9、L10、L11、およびL12は独立して、水素、フッ素、またはメチルであり;
lが、1、2、3、または4であり、このアルキレンの少なくとも1つの-CH2-は、-O-で置き換えられてもよい。
R4およびR5はそれぞれ独立して炭素数1から30までの炭化水素であり、R4およびR5が繋がって環状構造となっていても良く;
Sp5は単結合または炭素数2から12のアルコキシであり、このアルコキシの1つのCH2の水素はOHで置換されていても良く;
R3は水素またはメチルである。
本発明では、高分子形成性モノマーおよび高分子形成性オリゴマーから選ばれる少なくとも1つの重合性化合物が使用される。重合性化合物を含む重合性材料から得られた重合物は、調光層中でポリマーネットワークを形成し、電圧印加時のヘーズ率を増加させる重要な役割を持つ。このような高分子形成性モノマーまたはオリゴマーとしては、公知のすべての高分子形成性モノマーまたはオリゴマーから選択する事が出来るが、透過時のヘーズ率を低下させると同時に散乱時時のヘーズ率を増大させるため、以下の式(6)から(8)で示される化合物を用いる事が好ましい。本発明では、調光層中に、重合性化合物を含む重合性材料の重合物を構成しているが、重合性化合物とともに、重合性垂直配向剤、重合性液晶組成物を含む場合、これらが重合性材料として、重合物を構成していることもある。
xおよびyは独立して、0から3の整数であり;
xおよびyの和は1から4であり;
r,t,w,v,kおよびzは独立して、0から20の整数であり;
M1からM6は独立して、水素またはメチルである。
化合物(6)の例は式(6-1)~式(6-24)である。
化合物(8)の例は式(8-1)~式(8-10)である。
P1-Z20-P2 (9)
式(9)において、Z20は炭素数1から20のアルキレンであり、このアルキレンにおいて、少なくとも1つの水素は、炭素数1から5のアルキル、フッ素、塩素、またはP3で置き換えられてもよく、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、-OCO-、-NH-、または-N(R5)-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、少なくとも1つの-CH2-は、炭素環式の飽和脂肪族化合物、複素環式の飽和脂肪族化合物、炭素環式の不飽和脂肪族化合物、複素環式の不飽和脂肪族化合物、炭素環式の芳香族化合物、または複素環式の芳香族化合物、から2つの水素を除くことによって生成した二価基で置き換えられてもよく、これらの二価基において、炭素数は5から35であり、少なくとも1つの水素は、R5またはP3で置き換えられてもよく、ここでR5は、炭素数1から12のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく;
P1、P2、およびP3は独立して、重合性基であり
P1、P2、およびP3が独立して、式(P-1)から式(P-6)で表される重合性基の群から選択された基である。
アルキレングリコール=ジアクリレート(アルキレンの炭素数は1~10)、ポリエチレングリコール=ジアクリレート(ポリエチレンの繰り返し数1~10)、ポリプロピレングリコール=ジ(メタ)アクリレート(ポリプロピレンの繰り返し数1~10)、ポリ(メチル)エチレングリコール=ジ(メタ)アクリレート(ポリエチレンの繰り返し数1~10)、トリメチロールプロパントリ(メタ)アクリラート、テトラエチレングリコール=ジ(メタ)アクリレート、1,10-デカンジオール=ジ(メタ)アクリレート、などの液晶性を示す基を有さず重合性基を2以上有する高分子形成性モノマーまたはオリゴマーなどが挙げられる。
調光層に使用する液晶組成物には、通常この技術分野で液晶材料と認識される液晶組成物を使用できる。かかる液晶組成物としては、通常この技術分野で液晶材料として認識されるものであればよく、負の誘電率異方性を有する化合物を用いることもできる。外光にさらされる建物の窓やショーウインドウ、車のサンルーフ、リアウインドウなどの調光窓の場合、紫外線に対する耐光性が求められる。車などに掲載される場合は、さらに夏場など太陽光で車体が高熱になるので耐熱性が求められる。そのため紫外線に対して安定な構造を有する化合物からなり、耐熱性を持たせるためNI点(上限温度)が80℃以上の好ましくは90℃以上さらに好ましくは100℃以上であり、冬場など低温の環境下で耐寒性を持たせるために、ネマチック相からの転移温度(下限温度)が-10℃以下好ましくは-20℃以下より好ましくは-30℃以下、さらに好ましくは-40℃以下であり、電界印加時の高へーズ化のためにΔnが0.15以上好ましくは0.18以上さらに好ましくは0.2以上の液晶組成物が用いられる。電界スイッチングON/OFFを繰り返しても散乱と透過の特性(ヘーズ)が初期の状態から変わらないようするためには、Δεは-1以上-30以下、好ましくは-2以上-20以下が用いられる。
環Gおよび環Hは独立して、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、ナフタレン-2,6-ジイル、少なくとも1つの水素がフッ素または塩素で置き換えられたナフタレン-2,6-ジイル、クロマン-2,6-ジイル、または少なくとも1つの水素がフッ素または塩素で置き換えられたクロマン-2,6-ジイルであり;
jは1、2、または3であり、kは0または1であり;
そしてjとkとの和は3以下である。
式(4)の化合物の例を下記式(4-1)~式(4-22)に示す。
環Mおよび環Nは独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;
Z9は、単結合、エチレン、またはカルボニルオキシであり;
qは1、2、または3である。
(転移温度の計測方法)
偏光顕微鏡を備えた融点測定装置のホットプレートに試料を置き、特定の速度で加熱した。試料の一部がネマチック相から等方性液体に変化したときの温度を計測して、当該試料の「ネマチック相から等方性液体への転移温度」とした。
<平均屈折率の測定方法>
平均屈折率は、以下の手順で、求めた。
(1)アッベ屈折計を用いて、ランプによる白色光源に対する、試料の常光屈折率を測定した。
(2)アッベ屈折計を用いて、ランプによる白色光源に対する、試料の異常光屈折率を測定した。
(3)((常光屈折率2+異常光屈折率2)/2)1/2 で平均屈折率を算出した。
コントラスト比とは、特定の状況下の透過光強度と、異なる状況下の状況透過光強度の比である。
ε∥、ε⊥およびΔεを以下の手順で求めた。
(1)2枚のガラス基板の間隔が10μmであり、そしてツイスト角が80度であるTN素子に試料を入れ、
(2)該素子に10V、1kHzのサイン波を印加し、2秒後に液晶分子の長軸方向における誘電率を測定し、ε∥とし、
(3)該素子に0.5V、1kHzのサイン波を印加し、2秒後に液晶分子の短軸方向における誘電率を測定し、ε⊥とし、
(4)ε∥-ε⊥の値をΔεとした。
NIPPON DENSHOKU INDUSTRIES Co., LTD製 HAZE METER NDH5000に、光源光がセル面に対して垂直となるようにセルを設置し、室温でヘーズおよび平行光線透過率を計測した。
液晶組成物LC-1を、表1に記載の化合物を混ぜて作製した。当業者はJP02503443A、 JP20008040A、 Molecular Crystals and Liquid Crystals ,Volume195,Pages221-37,1991などに記載の方法を参考とすることで、表1に記載の化合物を、合成できる。
<液晶組成物LC-1-1の調製>
液晶組成物LC-1とイルガキュアー(商標)651を、重量比100/0.3で混ぜて、液晶組成物LC-1-1と名づけた。イルガキュアー(商標)651は、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オンである。
液晶組成物LC-1-1、(1)-1、M-1を重量比=94/2/4で、混合し、液晶組成物MLC-Aと名づけた。
液晶組成物LC-1-1、(1)-1、M-2を重量比=90/3/7で、混合し、液晶組成物MLC-Bと名づけた。
高分子/液晶複合材料PDLC-Aは、以下の手順で作成した。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が10μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Aを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Aが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を400秒間、2.5mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
<高分子/液晶複合材料のPDLC-Bの調製>
高分子/液晶複合材料PDLC-Bの作製において、液晶組成物MLC-Aを、液晶組成物MLC-Bに置き換えて、波長365nmの光を400秒間、2.5mWcm-2で照射し、セル内の液晶組成物を重合反応させ、高分子/液晶複合材料PDLC-Bを作成した。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Aを配置し、高分子/液晶複合材料PDLC-Aの電気光学特性を電界印加ユニットとバイポーラー電源で測定した。
PDLC-Bの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Bにおきかえて2枚の透明導電膜の電極の電圧を0から80Vになるまで上昇、80Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測した。
<高分子/液晶複合材料PDLC-Aのヘーズおよび平行光線透過率の測定>
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Aをヘーズメーター内に配置した。セルに0~50Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
<高分子/液晶複合材料PDLC-Bのヘーズおよび平行光線透過率の測定>
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Bをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
<高分子/液晶複合材料のPDLC-Dの調製>
高分子/液晶複合材料PDLC-Dは、以下の手順で作成した。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が10μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Dを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Dが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が5μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Sを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Sが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
PDLC-Dの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Bにおきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加し、高分子/液晶複合材料PDLC-Dがリバースモードで駆動することを確認した。PDLC-Dと同様な操作でPDLC-Vがリバースモードで駆動することを確認した。PDLC-Dと同様な操作で参考例2がリバースモードで駆動することは確認できなかった。
PDLC-Sの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Sにおきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加し、高分子/液晶複合材料PDLC-Sがリバースモードで駆動することを確認した。PDLC-Sと同様な操作でPDLC-T、PDLC-U、PDLC-Xがリバースモードで駆動することを確認した。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Dをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Vをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
液晶組成物LC-2を、表4に記載の化合物を混ぜて作製した。当業者はJP02503443A、JP20008040A、 Molecular Crystals and Liquid Crystals ,Volume195,Pages221-37,1991などに記載の方法を参考とすることで、表4に記載の化合物を、合成できる。
<液晶組成物LC-2-1の調製>
液液晶組成物LC-2とイルガキュアー(商標)651を、重量比100/0.3で混ぜて、液晶組成物LC-1-1と名づけた。イルガキュアー(商標)651は、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オンである。
高分子/液晶複合材料PDLC-Cは、以下の手順で作成した。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が5μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Cを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Cが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcM-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が10μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Iを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Iが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
PDLC-Cの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Cにおきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加し、高分子/液晶複合材料PDLC-Cがリバースモードで駆動することを確認した。
PDLC-Iの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Iにおきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加し、高分子/液晶複合材料PDLC-Dがリバースモードで駆動することを確認した。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Cをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
と電圧無印加時のへーズを計測し表9に記載した。電圧印加時の電圧は40Vであった。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Mをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
と電圧無印加時のへーズを計測し表9に記載した。電圧印加時の電圧は40Vであった。
液晶組成物LC-3を、表6に記載の化合物を混ぜて作製した。当業者はJP02503443A、JP20008040A、 Molecular Crystals and Liquid Crystals ,Volume195,Pages221-37,1991などに記載の方法を参考とすることで、表6に記載の化合物を、合成できる。
<液晶組成物LC-3-1の調製>
液液晶組成物LC-3とイルガキュアー(商標)651を、重量比100/0.3で混ぜて、液晶組成物LC-1-1と名づけた。イルガキュアー(商標)651は、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オンである。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が10μmであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-Fを挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-Fが等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
PDLC-Fの電気光学特性の測定において、高分子/液晶複合材料としてPDLC-AをPDLC-Fにおきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加し、高分子/液晶複合材料PDLC-Fがリバースモードで駆動することを確認した。
光源光がセル面に対して垂直となるように高分子/液晶複合材料PDLC-Fをヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
<液晶材料>
液晶組成物LC-1-1、C-4、M-10を重量比=97.8/1.7/0.5で、混合し、液晶組成物MLC-C4と名づけた。
液晶組成物LC-1-1、C-5、M-1を重量比=90/0.0009/10で、混合し、液晶組成物MLC-C5と名づけた。
(1)配向処理を施していない2枚の透明導電膜の電極がついているガラス基板を、ガラス基板の間の幅が10・/SUB>mであり、かつ、電極が内側になるように配置し、該ガラス基板間に液晶組成物MLC-C4を挿入し、セルを作製した。
(2)該セルを液晶組成物MLC-C4が等方相になるまで加熱したのち、室温まで冷却した。このときセル内の液晶は基板に対して垂直配向していることを偏光顕微鏡による相観察により確認した。
(3)波長365nmの光を60秒間、18mWcm-2で照射し、セル内の液晶組成物を重合反応させた。
(4)重合反応後ガラス基板の間の物質がネマチック液晶相を維持することを確認した。
参考例4と同様な操作で液晶組成物MLC-C5を用いて、高分子/液晶複合材料の参考例5の調製を行った。
参考例4の電気光学特性の測定において、高分子/液晶複合材料としてPDLC-Aを参考例4におきかえて2枚の透明導電膜の電極の電圧を0から60Vになるまで上昇、60Vから0Vになるまで下降させた。その際印加電圧ごとの、透過光強度を計測し、20Vの矩形波を印加したが、高分子/液晶複合材料参考例4はリバースモードで駆動することが確認できなかった。参考例4と同様な操作で参考例5もリバースモードで駆動することが確認できなかった。
光源光がセル面に対して垂直となるように高分子/液晶複合材料参考例4をヘーズメーター内に配置した。セルに0~60Vの電圧を印加しヘーズおよび平行光線透過率を測定した。
印加電圧を、計測セルにかけなかったときの、計測セルのへーズと電圧無印加時のへーズを計測したが、0~60Vの間の電圧印加により計測セルのヘーズ変化は確認できなかった。
2 液晶材料
3 透明物質
Claims (28)
- 調光層および少なくとも一対の電極を有するリバースモードの液晶デバイスであって、
上記調光層が、
(A)液晶組成物と、
(B)垂直配向剤と、
(C)高分子形成性モノマーおよび高分子形成性オリゴマーから選ばれる少なくとも1つの重合性化合物と、
を含む重合性材料の重合物を含むことを特徴とする液晶デバイス。 - 調光層中の前記垂直配向剤(B)に由来する成分の含有量が、調光層全体に対して0.1~10重量%の範囲であることを特徴とする請求項1に記載の液晶デバイス。
- 垂直配向剤(B)が、その分子末端に極性基を有する炭素数8以上の有機化合物である請求項1に記載の液晶デバイス。
- 垂直配向剤(B)の分子末端の極性基として、-OH、-N(R2)2 (R2は水素あるいはメチル基を示す)の少なくとも一方を有することを特徴とする請求項3に記載の液晶デバイス。
- 前記垂直配向剤(B)が、非重合性垂直配向剤であることを特徴とする請求項1~4のいずれかに記載の液晶デバイス。
- 前記非重合性垂直配向剤が、一般式(P-1)~(P-7)から選ばれる少なくとも1つの化合物である請求項5に記載の液晶デバイス;
R4は、水素、ハロゲン、炭素数8から18のアルキル、炭素数8から18のアルケニル、少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数8から18のアルキル、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数8から18のアルケニルであり;
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-フェニレンであり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z3は、単結合または-(CH2)2-であり;
Z4は、単結合または炭素数1から6のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく;
cは、0、1、2または3である。dは、0、1、2または3である。c+dは、2、3または4であり;
eは、0、1、2である。c+eは、1、2または3であり;
fは0、1、2である。c+fは、0,1または2であり;gは、0~6の整数であり;hは1~6の整数である。 - 調光層中の、前記非重合性垂直配向剤に由来する成分の含有量が0.5~5重量%であり、前記重合性化合物(C)に由来する成分の含有量が5から45重量%であり、液晶組成物(A)の含有量が50重量%から94.5重量%の範囲である、請求項5または6に記載の液晶デバイス。
- 前記垂直配向剤(B)が、重合性垂直配向剤(ただし重合性化合物(C)と異なる)である請求項1~4のいずれかに記載の液晶デバイス。
- 前記重合性垂直配向剤が、一般式(1)で表される化合物から選ばれる少なくとも1つであることを特徴とする請求項8に記載の液晶デバイス;
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-フェニレン、ナフタレン-2,6-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、フルオレン-2,7-ジイル、であり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;
Z1は、単結合、-(CH2)2-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、または-CF=CF-であり;
Sp1、Sp2は独立して、単結合または炭素数1から7のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素で置き換えられてもよく;
aは、0、1、2、または3である。
- 前記重合性垂直配向剤が、一般式(2)で表される化合物から選ばれる少なくとも1つの化合物である請求項8に記載の液晶デバイス;
R3は水素またはメチルであり;
環Aおよび環Bは独立して、1,4-シクロへキシレン、1,4-フェニレン、ナフタレン-2,6-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、フルオレン-2,7-ジイル、であり、これらの環において、少なくとも1つの水素は、フッ素、塩素、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または少なくとも1つの水素がフッ素または塩素で置き換えられた炭素数1から12のアルキルで置き換えられてもよく;
Z2は、単結合、-(CH2)2-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、または-CF=CF-であり;
Sp3、Sp4は独立して、単結合または炭素数1から7のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-(CH2)2-は、-CH=CH-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素で置き換えられてもよく;
bは、0、1、2または3である。l(エル)は、1,2,3,4または5である。 - 前記重合性垂直配向剤が、一般式(3)で表される化合物から選ばれる少なくとも1つの化合物である請求項8に記載の液晶デバイス;
R4およびR5はそれぞれ独立して炭素数1から30までの炭化水素であり、R4およびR5が繋がって環状構造となっていても良く;
Sp5は単結合または炭素数2から12のアルコキシであり、このアルコキシの1つのCH2の水素はOHで置換されていても良く;
R3は水素またはメチルである。 - 調光層中の、前記重合性垂直配向剤と前記重合性化合物(C)に由来する成分の含有量の合計が、調光層全体に対して5重量%から50重量%の範囲であり、液晶組成物(A)の含有量が50重量%から95重量%の範囲にあることを特徴とする請求項8~11のいずれかに記載の液晶デバイス。
- 液晶組成物(A)に含まれる液晶材料の誘電率異方性が、負であることを特徴とする請求項1~12のいずれかに記載の液晶デバイス。
- 液晶組成物(A)が、第一成分として一般式(4)で表される化合物から選ばれる少なくとも1つの液晶を含む液晶材料である請求項1~13のいずれかに記載の液晶デバイス;
環Gおよび環Hは独立して、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、ナフタレン-2,6-ジイル、少なくとも1つの水素がフッ素または塩素で置き換えられたナフタレン-2,6-ジイル、クロマン-2,6-ジイル、または少なくとも1つの水素がフッ素または塩素で置き換えられたクロマン-2,6-ジイルであり;
Z7およびZ8は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり;
jは1、2、または3であり、kは0または1であり;
そしてjとkとの和は3以下である。 - 液晶組成物(A)中の前記第一成分の割合が、液晶組成物(A)全体に対して、20重量%から90重量%の範囲である、請求項14に記載の液晶デバイス。
- 液晶組成物(A)が、その第二成分として一般式(5)で表される化合物から選ばれる少なくとも1つの液晶化合物を含むことを特徴とする請求項14または15に記載の液晶デバイス;
環Mおよび環Nは独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;
Z9は、単結合、エチレン、またはカルボニルオキシであり;
qは1、2、または3である。 - 液晶組成物(A)中の前記第二成分の割合が液晶組成物全体に対して、10重量%から70重量%の範囲である、請求項16に記載の液晶デバイス。
- 重合性化合物(C)が式(6)、式(7)、および式(8)で表される化合物の群から選択された少なくとも1種である、請求項1~17のいずれかに記載の液晶デバイス。
Z10、Z12、Z14、Z15、およびZ19は独立して、単結合、-O-、-COO-、-OCO-、または-OCOO-であり;
Z11、Z13、Z16、およびZ18は独立して、単結合、-OCH2-、-CH2O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、-NHCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-OCOCH2CH2-、-CH=CH-、-N=CH-、-CH=N-、-N=C(CH3)-、-C(CH3)=N-、-N=N-、または-C≡C-であり;
Z17は単結合、-O-または-COO-であり;
Xは水素、フッ素、塩素、トリフルオロメチル、トリフルオロメトキシ、シアノ、炭素数1から20のアルキル、炭素数2から20のアルケニル、炭素数1から20のアルコキシ、または炭素数1から20のアルコキシカルボニルであり;
sおよびuは1から3の整数であり;
xおよびyは独立して、0から3の整数であり;
xおよびyの和は1から4であり;
r,t,w,v,kおよびzは独立して、0から20の整数であり;
M1からM6は独立して、水素またはメチルである。 - 一対の電極が調光層を挟んで対向した構成である請求項1~18のいずれかに記載の液晶デバイス。
- 調光層が一対の透明基板により挟持され、透明基板が透明電極を有する、請求項1~19のいずれかに記載の液晶デバイス。
- 透明基板がガラス板またはアクリル板である、請求項20に記載の液晶デバイス。
- 透明基板がプラスチックフィルムである、請求項20に記載の液晶デバイス。
- 電圧無印加時のヘーズ率が20%以下でかつ電圧印加時のヘーズ率が70%以上であることを特徴とする請求項1~22のいずれかに記載の液晶デバイス。
- 請求項1~18のいずれかに記載の、
(A)液晶組成物と、
(B)垂直配向剤と、
(C)高分子形成性モノマーおよび高分子形成性オリゴマーから選ばれる少なくとも1つの重合性化合物と、
を含む重合性材料を含む液晶デバイス用材料。 - 光重合開始剤を含有する、請求項24に記載の液晶デバイス用材料。
- 請求項1~19のいずれかに記載の液晶デバイスの調光素子への使用。
- 請求項20~22のいずれかに記載の液晶デバイスの調光窓への使用。
- 請求項20~22のいずれかに記載の液晶デバイスのスマートウィンドウへの使用。
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KR20190089940A (ko) | 2019-07-31 |
JP7070429B2 (ja) | 2022-05-18 |
KR102490072B1 (ko) | 2023-01-17 |
US20200183203A1 (en) | 2020-06-11 |
CN110050226A (zh) | 2019-07-23 |
CN110050226B (zh) | 2022-01-18 |
JPWO2018105726A1 (ja) | 2019-10-24 |
EP3553595A1 (en) | 2019-10-16 |
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