WO2009139330A1 - 光学的に等方性の液晶媒体及び光素子 - Google Patents
光学的に等方性の液晶媒体及び光素子 Download PDFInfo
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- WO2009139330A1 WO2009139330A1 PCT/JP2009/058680 JP2009058680W WO2009139330A1 WO 2009139330 A1 WO2009139330 A1 WO 2009139330A1 JP 2009058680 W JP2009058680 W JP 2009058680W WO 2009139330 A1 WO2009139330 A1 WO 2009139330A1
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- 0 *c1ccc(*c2ccc(*[C@]3C4OC[C@](*c5ccc(*c6ccc(*)cc6)cc5)[C@]4OC3)cc2)cc1 Chemical compound *c1ccc(*c2ccc(*[C@]3C4OC[C@](*c5ccc(*c6ccc(*)cc6)cc5)[C@]4OC3)cc2)cc1 0.000 description 18
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- C07—ORGANIC CHEMISTRY
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
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- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
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- C09K19/58—Dopants or charge transfer agents
- C09K19/586—Optically active dopants; chiral dopants
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- C09K19/00—Liquid crystal materials
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- C09K19/58—Dopants or charge transfer agents
- C09K19/586—Optically active dopants; chiral dopants
- C09K19/588—Heterocyclic compounds
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—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
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—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
- C09K2019/0466—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 linking chain being a -CF2O- chain
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K2019/546—Macromolecular compounds creating a polymeric network
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- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
Definitions
- the present invention relates to a liquid crystal medium useful as a material for an optical element. Specifically, the present invention relates to a liquid crystal medium having a wide liquid crystal phase temperature range, large dielectric anisotropy, and refractive index anisotropy. In addition, the present invention relates to an optical element using the liquid crystal medium. Specifically, the present invention relates to an optical element that can be used in a wide temperature range, can be driven at a low voltage, and can obtain a high-speed electro-optical response.
- Liquid crystal display elements using a liquid crystal composition are widely used in displays such as watches, calculators, word processors and the like. These liquid crystal display elements utilize the refractive index anisotropy and dielectric anisotropy of liquid crystal compounds.
- PC phase change
- TN twisted nematic
- STN super twisted nematic
- BTN Battery twisted nematic
- ECB mainly using one or more polarizing plates
- OCB electrically controlled birefringence
- OCB optically compensated bend
- IPS in-plane switching
- VA vertical alignment
- wavelength tunable filters, wavefront control elements, liquid crystal lenses, aberration correction elements, aperture control elements, optical head devices, etc. using electrical birefringence in the blue phase, which is one of the optically isotropic liquid crystal phases have been proposed.
- Patent Documents 10 to 12 The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal).
- liquid crystal display elements contain a liquid crystal composition having appropriate physical properties.
- the liquid crystal composition preferably has appropriate physical properties.
- General physical properties necessary for the liquid crystal compound which is a component of the liquid crystal composition are as follows. (1) being chemically stable and physically stable; (2) having a high clearing point (liquid crystal phase-isotropic phase transition temperature); (3) The lower limit temperature of the liquid crystal phase (such as an optically isotropic liquid crystal phase such as a nematic phase, a cholesteric phase, a smectic phase, or a blue phase) is low.
- liquid crystal composition containing a chemically and physically stable liquid crystal compound as in (1) When a liquid crystal composition containing a chemically and physically stable liquid crystal compound as in (1) is used for a liquid crystal display element, the voltage holding ratio can be increased.
- the temperature range of a nematic phase or an optically isotropic liquid crystal phase is set. It can be expanded and used as a display element in a wide temperature range.
- the liquid crystal compound is generally used as a liquid crystal composition prepared by mixing with many other liquid crystal compounds in order to develop characteristics that are difficult to be exhibited by a single compound.
- the liquid crystal compound used in the liquid crystal display element preferably has good compatibility with other liquid crystal compounds and the like as in (4).
- the liquid crystal display elements that have particularly higher display performance, such as contrast, display capacity, and response time characteristics.
- a liquid crystal composition having a low driving voltage is required for the liquid crystal material used.
- Patent Documents 1 to 3 and Non-Patent Documents 1 to 3 disclose optically isotropic liquid crystal compositions and polymer / liquid crystal composite materials in which the operating voltage is expected to be lowered as described above, the pyrimidine ring and coupler-CF 2 O of the present application are disclosed. There is no description pronounced of an optically isotropic liquid crystal composition and a polymer / liquid crystal composite material containing a compound having-.
- JP 2003-327966 A International Publication No. 2005/90520 Pamphlet JP 2005-336477 A JP 2006-89622 A JP 2006-299084 A JP 2006-506477 A JP 2006-506515 A International Publication No. 2006/063662 Pamphlet JP 2006-225655 A JP-A-2005-157109 International Publication No. 2005/80529 Pamphlet JP 2006-127707 A
- the first object of the present invention is to provide an optically isotropic liquid crystal phase having stability against heat, light, etc., a wide liquid crystal phase temperature range, a large refractive index anisotropy, and a large dielectric anisotropy. It is to provide a liquid crystal medium having the same.
- the second object is to provide various optical elements that contain this liquid crystal medium, can be used in a wide temperature range, have a short response time, a large contrast, and a low driving voltage.
- the present invention provides the following liquid crystal medium (liquid crystal composition or polymer / liquid crystal composite), an optical element containing the liquid crystal medium, and the like.
- R 1 is hydrogen or alkyl having 1 to 20 carbon atoms, and any —CH 2 — in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, or —C ⁇ C— may be substituted, and any —CH 2 — in the alkyl or alkyl may be replaced by —O—, —S—, —COO—.
- R 1 is alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 21 carbon atoms, alkynyl having 2 to 21 carbon atoms, alkoxy having 1 to 19 carbon atoms, or 2 to 20 carbon atoms.
- X 1 is hydrogen, halogen, —C ⁇ N, —N ⁇ C ⁇ S, —SF 5 , —CH 2 F, —CHF 2 , —CF 3 , — (CH 2 ) 2 —F, —CF 2 CH 2 F , —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , —CHFCF 2 CF 3 , — (CH 2) 4 -F, - (CF 2) 4 -F, - (C 2) 5 -F, - (CF 2) 5
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are independently a single bond, —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C -, - COO -, - CF 2 O -, - CH 2 O-, or -OCH 2 - is a section [1] or a liquid crystal composition according to [2].
- Ring A 1 , Ring A 2 , Ring A 3 , Ring A 4 , and Ring A 5 are each independently a group represented by one of formulas (RG-1) to (RG-15) , Y 1 , Y 2 , Y 3 and Y 4 are independently hydrogen or halogen, and fn1, fn2, fn3 and fn4 are independently 0, 1, 2 or 3, term [1] 4.
- the liquid crystal composition according to any one of [3].
- R1 are a group represented by any one of formulas (CHN-1) to (CHN-19), and R 1a is hydrogen or alkyl having 1 to 20 carbons.
- the liquid crystal composition according to any one of [4].
- R 1 is a group represented by any one of formulas (CHN-1) to (CHN-19), R 1a is hydrogen or alkyl having 1 to 20 carbons;
- a 1 , Ring A 2 , Ring A 3 , Ring A 4 , and Ring A 5 are independently selected from the formulas (RG-1), (RG-5), (RG-7), (RG-8-1) A group represented by (RG-8-5), (RG-9), (RG-10), (RG-11-1), (RG-13) or (RG-15);
- 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are each independently a single bond, —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C—, —COO—, —CF 2 O -, - CH 2 O- , or -OCH 2 - a and
- L 1 and L 2 are independently hydrogen,
- R 1 represents formulas (CHN-1), (CHN-2), (CHN-4) and (CHN-6) to (CHN-8) Item 6.
- R 1a is hydrogen or alkyl having 1 to 20 carbon atoms.
- R 2 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, arbitrary —CH 2 — may be replaced by —O—, In alkenyl, or in groups where any —CH 2 — in alkyl and alkenyl is replaced by —O—, any hydrogen may be replaced by fluorine;
- X 2 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
- Ring B 1 , Ring B 2 , and Ring B 3 are independently 1,4 -Cyclohexylene, 1,3-dioxane-2,5-diyl
- R 3 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, arbitrary —CH 2 — may be replaced by —O—, In alkenyl, or in groups where any —CH 2 — in alkyl and alkenyl is replaced by —O—, any hydrogen may be replaced by fluorine;
- X 3 is —C ⁇ N or —C ⁇ C— C ⁇ N;
- ring C 1 , ring C 2 and ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which any hydrogen is replaced by fluorine, Naphthalene-2,6-diyl, naphthalene-2,6-diyl, 1,3-dioxane-2,5-diy
- Any hydrogen may be replaced by fluorine in alkyl, alkenyl, or in groups in which any —CH 2 — in alkyl and alkenyl is replaced by —O—;
- ring D 1 , ring D 2 , Ring D 3 , and Ring D 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-substituted with any hydrogen replaced by fluorine.
- Z 10 , Z 11 , Z 12 , and Z 13 are independently -(CH 2 ) 2- , -COO-, -CH 2 O-, -OCF 2- , -OCF 2 (CH 2 ) 2- , or a single bond;
- L 9 and L 10 are independently , Fluorine, or chlorine;
- t, u, x, y, and z are independently 0 or 1, and u + x + y + z is 1 or 2.
- Any hydrogen may be replaced by fluorine in alkyl, alkenyl, or in groups in which any —CH 2 — in alkyl and alkenyl is replaced by —O—;
- ring E 1 , ring E 2 and ring E 3 are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4 - phenylene, or 2,5-difluoro-1,4-be-phenylene;
- R 8 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and in the alkyl, alkenyl and alkynyl, any —CH 2 — is —O—. Any hydrogen may be replaced by fluorine in alkyl, alkenyl, alkynyl or in groups in which any —CH 2 — is replaced by —O— in alkyl, alkenyl and alkynyl.
- X 4 is fluorine, chlorine, —SF 5 , —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
- 1, the ring F 2, ring F 3 and ring F 4 are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidin-2 5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, naphthalene-2,6-diyl, 1,4-phenylene with any hydrogen replaced with fluorine or chlorine, or any hydrogen with fluorine Or naphthalene-2,6-diyl substituted with chlorine;
- Z 16 , Z 17 and Z 18 are independently — (CH 2 ) 2 —, — (CH 2 ) 4 —, —COO—,
- liquid crystal composition according to any one of items [1] to [9], further containing at least one compound selected from the group of compounds represented by formula (19).
- R 9 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkynyl having 2 to 10 carbons, and in the alkyl, alkenyl and alkynyl, any —CH 2 — is —O—. Any hydrogen may be replaced by fluorine in alkyl, alkenyl, alkynyl or in groups in which any —CH 2 — is replaced by —O— in alkyl, alkenyl and alkynyl.
- X 5 is —C ⁇ N, —N ⁇ C ⁇ S, or —C ⁇ C—C ⁇ N;
- Ring G 1 , Ring G 2 and Ring G 3 are independently 1,4-cyclohexylene; 1,4-phenylene, 1,4-phenylene in which any hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, any hydrogen is placed in fluorine or chlorine
- Z 19 is - (CH 2 ) 2 —, —COO—, —CF 2 O—, —OCF 2 —, —C ⁇ C—, —CH 2 O—, or a single bond, provided that at least one of rings G 1 to G 3 is pyrimidine— When it is 2,5-diyl, Z 19 is not —CF 2
- liquid crystal composition according to any one of items [1] to [19], comprising at least one antioxidant and / or ultraviolet absorber.
- a liquid crystal composition is obtained by adding a chiral agent to a composition in which the difference between the upper limit temperature and the lower limit temperature at which the chiral nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C.
- the liquid crystal composition is obtained by adding a chiral agent to a composition having a difference between the upper limit temperature and the lower limit temperature at which the chiral nematic phase and the non-liquid crystal isotropic phase coexist at 5 to 150 ° C.
- the liquid crystal composition is obtained by adding a chiral agent to a composition having a difference between the upper limit temperature and the lower limit temperature at which the nematic phase and the non-liquid crystal isotropic phase coexist at 3 to 150 ° C., Item [21] or [22] liquid crystal composition.
- any —CH 2 — may be —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
- Any hydrogen in the group replaced with- may be replaced with halogen;
- A is independently an aromatic or non-aromatic 3- to 8-membered ring or a condensed ring having 9 or more carbon atoms; And any hydrogen in these rings is replaced by halogen, alkyl of 1 to 3 carbons or haloalkyl.
- Z is independently a single A bond, alkylene having 1 to 8 carbon atoms, but arbitrary —CH 2 — is —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —N ⁇ N—.
- X is independently a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 — or —CH 2 CH 2 —;
- mK is independently an integer of 1 to 4.
- the chiral agent includes at least one compound selected from the group of compounds represented by formulas (K2-1) to (K2-8) and (K5-1) to (K5-3), respectively.
- the liquid crystal composition according to any one of items [26] to [28].
- a mixture comprising the liquid crystal composition according to any one of items [1] to [30] and a polymerizable monomer.
- a polymer / liquid crystal composite material used for an element driven by an optically isotropic liquid crystal phase obtained by polymerizing the mixture according to item [31] or [32].
- An optical element comprising an electrode disposed on one or both surfaces, a liquid crystal medium disposed between the substrates, and an electric field applying means for applying an electric field to the liquid crystal medium via the electrode,
- An optical device comprising the liquid crystal composition according to any one of items [26] to [30] or the polymer / liquid crystal composite material according to any one of items [33] to [37].
- An electrode is disposed on one or both surfaces, and at least one of the substrates has a pair of transparent substrates, a liquid crystal medium disposed between the substrates, and a polarizing plate disposed on the outside of the substrate.
- An optical element comprising an electric field applying means for applying an electric field to the liquid crystal medium, wherein the liquid crystal medium is the liquid crystal composition or polymer / liquid crystal composite material according to any one of items [26] to [30]
- Electrodes are configured so that an electric field can be applied in at least two directions to one or both of a pair of substrates arranged in parallel to each other.
- the liquid crystal medium is a general term for a liquid crystal composition and a polymer / liquid crystal composite.
- the optical element refers to various elements that perform functions such as light modulation and optical switching by utilizing the electro-optic effect.
- display elements liquid crystal display elements
- optical communication systems optical information processing
- various types a light modulation element used in the sensor system.
- the Kerr effect is known for light modulation using a change in refractive index caused by voltage application to an optically isotropic liquid crystal medium.
- the electric birefringence value is a refractive index anisotropy value induced when an electric field is applied to the isotropic medium.
- a liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition.
- the chiral agent is an optically active compound and is added to give a desired twisted molecular arrangement to the liquid crystal composition.
- a liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module.
- a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be abbreviated as a compound, a composition, and an element, respectively.
- the upper limit temperature of the liquid crystal phase is the phase transition temperature of the liquid crystal phase-isotropic phase, and may simply be abbreviated as the clearing point or the upper limit temperature.
- the lower limit temperature of the liquid crystal phase may be simply abbreviated as the lower limit temperature.
- the compound represented by formula (1) may be abbreviated as compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like.
- symbols such as B, D, and E surrounded by hexagons correspond to Ring B, Ring D, and Ring E, respectively.
- the amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition.
- a plurality of the same symbols such as rings A 1 , Y 1 and B are described in the same formula or different formulas, but these may be the same or different.
- Alkyl in which any —CH 2 — may be replaced by —O— or —CH ⁇ CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, and the like.
- the liquid crystal composition of the present invention exhibits stability against heat, light, etc., a high upper limit temperature and a lower lower limit temperature of an optically isotropic liquid crystal phase, and is low in an element driven with an optically isotropic liquid crystal phase. It has a driving voltage.
- the polymer / liquid crystal composite material of the present invention having an optically isotropic liquid crystal phase exhibits a high maximum temperature and a low minimum temperature of the optically isotropic liquid crystal phase, and is optically isotropic.
- the element driven in the liquid crystal phase has a low driving voltage.
- the optical element driven by the optically isotropic liquid crystal phase of the present invention has a wide usable temperature range, a short response time, a large contrast ratio, and a low driving voltage.
- the comb-shaped electrode substrate used in the Example is shown.
- the optical system used in the Example is shown.
- the liquid crystal composition having an optically isotropic liquid crystal phase of the present invention contains the compound represented by the formula (1) as component A.
- the first aspect of the present invention is a composition containing only component A, or a composition containing component A and other components not specifically indicated in the present specification. First, the compound represented by Formula (1) is demonstrated.
- R 1 is hydrogen or alkyl having 1 to 20 carbon atoms, and any —CH 2 — in the alkyl is —O—, —S—, —COO—, —OCO—, — CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be substituted, and any —CH 2 — in the alkyl group and alkyl may be replaced by —O—, —S—, —COO—. , —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, or any hydrogen in the group replaced by —C ⁇ C— may be replaced by halogen or alkyl having 1 to 3 carbon atoms.
- examples of groups in which any —CH 2 — in CH 3 (CH 2 ) 3 — is replaced by —O—, —S—, or —CH ⁇ CH— are CH 3 (CH 2 ) 2 O—, CH 3 —O— (CH 2 ) 2 —, CH 3 —O—CH 2 —O—, CH 3 (CH 2 ) 2 S—, CH 3 —S— (CH 2 ) 2 —, CH 3 —S— CH 2 —S—, CH 2 ⁇ CH— (CH 2 ) 3 —, CH 3 —CH ⁇ CH— (CH 2 ) 2 —, CH 3 —CH ⁇ CH— (CH 2 ) 2 —, CH 3 —CH ⁇ CH—CH 2 O—, CH 3 CH 2 C ⁇ C- and the like.
- any —CH 2 — is replaced by —O—, —C ⁇ C— or —CH ⁇ CH—.
- Examples of the group in which hydrogen in the above is replaced by halogen include ClCH 2 (CH 2 ) 3 —, CF 2 ⁇ CH— (CH 2 ) 3 —, CH 2 F (CH 2 ) 2 O—, CH 2 FCH 2 C ⁇ C-.
- R 1 a straight chain is preferable to a branch. Even when R 1 is a branched group, it is preferable when it is optically active.
- the preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond. —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H 4 CH ⁇ CHC 2 In alkenyl having a double bond at odd positions such as H 5 , the trans configuration is preferable.
- -CH 2 CH CHCH 3
- An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
- Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
- the alkyl may be linear or branched, and specific examples of alkyl include —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9 , —C 5 H 11 , —C 6. H 13 , —C 7 H 15 , —C 8 H 17, —C 9 H 19 , —C 10 H 21 , —C 11 H 23 , —C 12 H 25 , —C 13 H 27 , —C 14 H 29 , And -C 15 H 31 .
- Alkoxy may be linear or branched, and specific examples of alkoxy include —OCH 3 , —OC 2 H 5 , —OC 3 H 7 , —OC 4 H 9 , —OC 5 H 11 , —OC 6. H 13 and -OC 7 H 15 , -OC 8 H 17, -OC 9 H 19 , -OC 10 H 21 , -OC 11 H 23 , -OC 12 H 25 , -OC 13 H 27 , and -OC 14 H 29 .
- the alkoxyalkyl may be linear or branched, and specific examples of alkoxyalkyl include —CH 2 OCH 3 , —CH 2 OC 2 H 5 , —CH 2 OC 3 H 7 , — (CH 2 ) 2. —OCH 3 , — (CH 2 ) 2 —OC 2 H 5 , — (CH 2 ) 2 —OC 3 H 7 , — (CH 2 ) 3 —OCH 3 , — (CH 2 ) 4 —OCH 3 , and — (CH 2 ) 5 —OCH 3 .
- the alkenyl may be linear or branched, and specific examples of alkenyl include —CH ⁇ CH 2 , —CH ⁇ CHCH 3 , —CH 2 CH ⁇ CH 2 , —CH ⁇ CHC 2 H 5 , —CH. 2 CH ⁇ CHCH 3 , — (CH 2 ) 2 —CH ⁇ CH 2 , —CH ⁇ CHC 3 H 7 , —CH 2 CH ⁇ CHC 2 H 5 , — (CH 2 ) 2 —CH ⁇ CHCH 3 , and — (CH 2 ) 3 —CH ⁇ CH 2 .
- Alkenyloxy may be linear or branched, and specific examples of alkenyloxy are —OCH 2 CH ⁇ CH 2 , —OCH 2 CH ⁇ CHCH 3 , and —OCH 2 CH ⁇ CHC 2 H 5 . .
- Alkynyl may be linear or branched. Specific examples of alkynyl include —C ⁇ CH, —C ⁇ CCH 3 , —CH 2 C ⁇ CH, —C ⁇ CC 2 H 5 , —CH 2 C ⁇ CCH. 3 , — (CH 2 ) 2 —C ⁇ CH, —C ⁇ CC 3 H 7 , —CH 2 C ⁇ CC 2 H 5 , — (CH 2 ) 2 —C ⁇ CCH 3 , and —C ⁇ C (CH 2 ) It is 5 .
- R 1 is preferably a structure represented by the formulas (CHN-1) to (CHN-19).
- R 1a is hydrogen or alkyl having 1 to 20 carbons. More preferred R 1 is a structure represented by the formulas (CHN-1) to (CHN-4) or (CHN-6) to (CHN-8). From the viewpoint of voltage holding ratio, (CHN-1), (CHN-4), (CHN-5) and (CHN-7) are more preferable.
- ring A 1 , ring A 2 , ring A 3 , ring A 4 , and ring A 5 are independently benzene ring, naphthalene ring, thiophene ring, cyclohexene ring, bicyclooctane ring, tetrahydronaphthalene ring or A cyclohexane ring, and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 3 carbon atoms, alkoxy or halogenated alkyl, and —CH 2 — in the ring is —O— or —S—.
- ring A 1 , ring A 2 , ring A 3 , ring A 4 , and ring A 5 are the formulas (RG-1) to (RG-15), and Y 1 , Y 2 , Y 3 and Y 4 is independently hydrogen or halogen, and fn1, fn2, fn3 and fn4 are independently 0, 1, 2, or 3.
- ring A 1 , ring A 2 , ring A 3 , ring A 4 , and ring A 5 include formulas (RG-1), (RG-5), (RG-7), (RG-8- 1) to (RG-8-5), (RG-9), (RG-10), (RG-11-1), (RG-13) or (RG-15).
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are each independently a single bond, alkylene having 1 to 4 carbon atoms, and any —CH 2 in the alkylene — May be replaced by —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Alkylene and any —CH 2 — in alkylene is —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —CH ⁇ CH—, —CF ⁇ CF—.
- any hydrogen in the group replaced with —C ⁇ C— may be replaced with halogen, but at least one is —CF 2 O—.
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 include a single bond, —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C—, —COO—, —CF. 2 O—, —CH 2 O— or —OCH 2 —.
- double bonds of linking groups such as —CH ⁇ CH—, —CF ⁇ CF—, —CH ⁇ CH— (CH 2 ) 2 —, and — (CH 2 ) 2 —CH ⁇ CH—
- the configuration of is preferably trans rather than cis.
- Most preferred Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are a single bond, —COO—, —CF 2 O—. Particularly preferred from the viewpoint of voltage holding ratio are single bond and —CF 2 O—.
- L 1 and L 2 are independently hydrogen or halogen. L 1 and L 2 are preferably independently hydrogen or fluorine.
- X 1 is hydrogen, halogen, —C ⁇ N, —N ⁇ C ⁇ S, —C ⁇ C—C ⁇ N, —SF 5 , or alkyl having 1 to 10 carbon atoms.
- Any —CH 2 — may be replaced by —O—, —S—, —CH ⁇ CH—, —C ⁇ C—, and any —CH 2 — in alkyl and alkyl may be Any hydrogen in the group replaced by —O—, —S—, —CH ⁇ CH—, — or —C ⁇ C— may be replaced by halogen.
- alkyl in which any hydrogen is replaced by halogen include —CH 2 F, —CHF 2 , —CF 3 , — (CH 2 ) 2 —F, —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , —CHFCF 2 CF 3 , — (CH 2 ) 4 -F,-(CF 2 ) 4 -F,-(CH 2 ) 5 -F, and-(CF 2 ) 5 -F.
- alkoxy in which any hydrogen is replaced by halogen include —OCH 2 F, —OCHF 2 , —OCF 3 , —O— (CH 2 ) 2 —F, —OCF 2 CH 2 F, —OCF 2 CHF 2 , —OCH 2 CF 3 , —O— (CH 2 ) 3 —F, —O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , —OCHFCF 2 CF 3 , —O (CH 2 ) 4- F, —O— (CF 2 ) 4 —F, —O— (CH 2 ) 5 —F, and —O— (CF 2 ) 5 —F.
- X 1 are hydrogen, fluorine, chlorine, —C ⁇ N, —N ⁇ C ⁇ S, —SF 5 , —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4. H 9 , —C 5 H 11 , —C 6 H 13 , —C 7 H 15 , —C 8 H 17, —C 9 H 19 , —C 10 H 21 , —CH 2 F, —CHF 2 , —CF 3 , — (CH 2 ) 2 —F, —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 -F, — (CF 2 ) 3 -F, -CF 2 CHFCF 3 , -CHFCF 2 CF 3 ,-(CH 2 ) 4 -F,-(CH 2 ) 5 -F,
- Preferred examples of X 1 are fluorine, chlorine, —C ⁇ N, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 and —OCH 2 F.
- the most preferred examples of X 1 are fluorine, chlorine, —CF 3 and —OCF 3 .
- l, m, n, o, and p are independently 0 or 1, and l + m + n + o + p ⁇ 4.
- l + m + n + o + p ⁇ 3 Preferably, l + m + n + o + p ⁇ 2.
- R 1 is a structure represented by any one of formulas (CHN-1) to (CHN-19), R 1a is hydrogen or alkyl having 1 to 20 carbons;
- a 1 , ring A 2 , ring A 3 , ring A 4 , and ring A 5 are each independently one of structures represented by formulas (RG-1) to (RG-15), and
- Y 1 , Y 2 , Y 3 and Y 4 are independently hydrogen or halogen, fn1, fn2, fn3 and fn4 are independently 0, 1, 2 or 3;
- Compound (1) is a liquid crystal compound having a pyrimidine ring and a linking group —CF 2 O—.
- This compound is extremely physically and chemically stable under the conditions under which the device is normally used, and has good compatibility with other liquid crystal compounds.
- a composition containing this compound is stable under conditions in which the device is normally used. Therefore, the temperature range of the optically isotropic liquid crystal phase in the composition can be expanded, and the composition can be used as a display element in a wide temperature range. Furthermore, since this compound has a large dielectric anisotropy and refractive index anisotropy, it is useful as a component for lowering the driving voltage of a composition driven with an optically isotropic liquid crystal phase.
- the structures represented by the formulas (RG-7), (RG-8-2) to (RG-8-5), (RG-9), (RG-10) and (RG-15) have a large dielectric constant. Has an effect on isotropic expression, and (RG-8-1) to (RG-8-5), (RG-9), (RG-10), (RG-11-1), (RG-13) and The structure represented by (RG-15) is effective in expressing a large refractive index anisotropy, and the structures represented by (RG-1) and (RG-5) contribute to good compatibility.
- R 1 When R 1 is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R 1 is branched, compatibility with other liquid crystal compounds is good. A compound in which R 1 is an optically active group is useful as a chiral dopant. A compound in which R 1 is not an optically active group is useful as a component of the composition.
- R 1 When R 1 is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
- the linking groups Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are single bonds, —CH 2 CH 2 —, —CH ⁇ CH—, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —CF ⁇ CF—, — (CH 2 ) 3 —O—, —O— (CH 2 ) 3 —, — (CH 2 ) 2 —CF 2 O—, —OCF 2 — When it is (CH 2 ) 2 — or — (CH 2 ) 4 —, the viscosity is small.
- the bonding group is a single bond, — (CH 2 ) 2 —, —CF 2 O—, —OCF 2 —, or —CH ⁇ CH—, the viscosity is smaller.
- the bonding group is —CH ⁇ CH—, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K 33 / K 11 (K 33 : bend elastic constant, K 11 : spray elastic constant) is large.
- the bonding group is —C ⁇ C—, the refractive index anisotropy is large.
- the bonding group is —COO— or —CF 2 O—, the dielectric anisotropy is large.
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are a single bond, — (CH 2 ) 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, — (CH 2 4 ) When it is-, it is chemically relatively stable and relatively difficult to deteriorate.
- the right terminal group X 1 is fluorine, chlorine, —C ⁇ N, —N ⁇ C ⁇ S, —SF 5 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 or —OCH 2
- F the dielectric anisotropy
- X 1 is —C ⁇ N, —N ⁇ C ⁇ S or alkenyl
- the refractive index anisotropy is large.
- X 1 is fluorine, chlorine, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 or —OCH 2 F, it is chemically stable.
- L 1 and L 2 are both fluorine
- X 1 is fluorine, chlorine, —C ⁇ N, —N ⁇ C ⁇ S, —SF 5 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 or —OCH 2 F, the dielectric anisotropy is large.
- a compound having desired physical properties can be obtained by appropriately selecting the kind of ring structure, terminal group, bonding group and the like.
- Preferred examples of the compound (1) are the formulas (1-1) to (1-8). More preferred examples include formulas (1-1A) to (1-1C), (1-2A) to (1-2B), (1-3A), (1-4A) to (1-4C), (1 -5A) to (1-5C), (1-6A) to (1-6C), and (1-7A).
- R 1 is one chain selected from the formulas (CHN-1), (CHN-2), (CHN-4) and (CHN-6) to (CHN-8)), Ring A 1 is selected from the above formulas (RG-7) (RG-8-1) to (RG-8-5), (RG-10), (RG-13) and (RG-15)
- X 1 is fluorine, chlorine, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 , or —C ⁇ C—CF 3 .
- a compound represented by the formula (103) is obtained by reacting the compound represented by the formula (101) with urea under acidic conditions, and reacting the obtained product with a chlorinating reagent such as phosphorus oxychloride. Can do.
- a chlorinating reagent such as phosphorus oxychloride.
- l and m are both 0 and R 1 is an alkyl group are commercially available depending on the alkyl chain length.
- compound (104) is reacted with 1,3-propanethiol and trifluoromethane sulfonic acid acid to give compound (107 ) Can be obtained.
- a compound (109) can be obtained by dropping a mixture of the compound (108) and triethylamine into the compound (107), reacting triethylamine hydrogen trifluoride at a low temperature, and further treating with bromine.
- Compound (111) can be obtained by reacting compound (109) with compound (110) in the presence of a catalyst such as tetrakistriphenylphosphine.
- Compound (112) can be obtained by reacting compound (103) with compound (111) in the presence of a catalyst such as tetrakistriphenylphosphine.
- a second aspect of the present invention is a liquid crystal composition obtained by adding a component selected from components B, C, D and E shown below to component A which is a compound represented by the formula (1).
- the driving voltage, the liquid crystal phase temperature range, the refractive index anisotropy value, the dielectric anisotropy value, the viscosity, and the like can be freely adjusted as compared with the composition containing only component A.
- the component added to component A was selected from the group consisting of at least one compound selected from the group consisting of the formulas (2), (3) and (4), or the group consisting of the formula (5).
- Mixing component C consisting of at least one compound or component D consisting of at least one compound selected from the group consisting of the formulas (6), (7), (8), (9) and (10) Is preferred.
- component E consisting of at least one compound selected from the group consisting of formulas (11), (12) and (13), threshold voltage, liquid crystal phase temperature range, refractive index anisotropy value
- the dielectric anisotropy value and viscosity can be adjusted.
- an analog composed of an isotope element of each element can be used because there is no great difference in physical properties.
- formulas (2-1) to (2-16) are preferred examples of the compound represented by formula (2), and formula (3-1) are preferred examples of the compound represented by formula (3).
- formulas (2-1) to (2-16) are preferred examples of the compound represented by formula (2), and formula (3-1) are preferred examples of the compound represented by formula (3).
- formulas (4-1) to (4-52) include formulas (4-1) to (4-52), respectively.
- These compounds represented by the formulas (2) to (4), that is, the component B have a positive dielectric anisotropy value and are very excellent in thermal stability and chemical stability. It is used when preparing a liquid crystal composition.
- the content of component B in the liquid crystal composition of the present invention is suitably in the range of 1 to 99% by weight with respect to the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40 to 95% by weight. It is.
- the viscosity can be adjusted by further containing a compound represented by formulas (11) to (13) (component E).
- Preferred examples of the compound represented by formula (5), that is, component C include formulas (5-1) to (5-62).
- the compound represented by the formula (5) that is, the component C has a positive dielectric anisotropy value and a very large value.
- the composition driving voltage can be reduced.
- the viscosity, the refractive index anisotropy value, and the liquid crystal phase temperature range can be expanded.
- the content of component C is preferably in the range of 0.1 to 99.9% by weight, more preferably in the range of 10 to 97% by weight, and still more preferably in the range of 40 to 95% by weight with respect to the total amount of the composition. .
- the threshold voltage, the liquid crystal phase temperature range, the refractive index anisotropy value, the dielectric anisotropy value, the viscosity, and the like can be adjusted by mixing the components described later.
- Component D consisting of at least one compound selected from the group consisting of formulas (6) to (10) is a preferred component when preparing the liquid crystal composition of the present invention having a negative dielectric anisotropy.
- Preferred examples of the compounds represented by formulas (6) to (10) (component D) include formulas (6-1) to (6-5), formulas (7-1) to (7-9), Examples include formulas (8-1) to (8-3) and formulas (10-1) to (10-11).
- These compounds of component D are mainly used for liquid crystal compositions having a negative dielectric anisotropy value. Since the compound represented by the formula (6) among the component D is a bicyclic compound, there is mainly an effect of adjusting the threshold voltage, adjusting the viscosity, or adjusting the refractive index anisotropy value. Further, since the compounds represented by the formulas (7) and (8) are tricyclic compounds, the clearing point is increased, the temperature range of the optically isotropic liquid crystal phase is increased, and the refractive index anisotropy is increased. Effects such as increasing the value can be obtained. Since the compounds represented by the formulas (9) and (10) have a negative dielectric anisotropy value, they are mainly effective in adjusting the driving voltage.
- the content of component D is preferably 40% by weight or more, more preferably 50 to 95% by weight, based on the total amount of the composition. Range. Further, by mixing the component D, it is possible to control the elastic constant and control the voltage transmittance curve of the composition.
- the content is preferably 30% by weight or less based on the total amount of the composition.
- Preferable examples of the compound (component E) represented by the formulas (11), (12) and (13) are the formulas (11-1) to (11-11) and the formulas (12-1) to (12-18), respectively. ) And formulas (13-1) to (13-6).
- the compounds represented by the formulas (11) to (13) are compounds having a small absolute value of dielectric anisotropy and close to neutrality.
- the compound represented by the formula (11) has an effect of mainly adjusting the viscosity or adjusting the refractive index anisotropy value
- the compounds represented by the formulas (12) and (13) are optical elements such as increasing the clearing point.
- the content of component E is preferably 60% by weight or less, more preferably 40% by weight or less based on the total amount of the composition.
- the liquid crystal composition of the present invention preferably contains at least one compound represented by the formula (1) of the present invention at a ratio of 0.1 to 99% by weight in order to develop excellent characteristics.
- the liquid crystal composition of the present invention is generally prepared by a known method, for example, a method of dissolving necessary components at a high temperature.
- the third aspect of the present invention is a liquid crystal composition obtained by adding a component selected from components F and G shown below to component A.
- component F consisting of at least one compound selected from the group consisting of the above formulas (15), (16), (17) and (18), or a group consisting of the above formula (19) What mixed the component G which consists of at least 1 sort (s) of compound chosen from these is preferable.
- each component of the liquid crystal composition used in the present invention is not greatly different in physical properties even if it is an analog composed of an isotope element of each element.
- Formulas (15-1) to (15-8) are preferable examples of the compound represented by Formula (15), and Formula (16-1) is a preferable example of the compound represented by Formula (16).
- Formula (17) to (16-26) and preferred examples of the compound represented by formula (17) include formulas (17-1) to (17-22), respectively.
- the compounds represented by the formulas (15) to (18), that is, the component F have a positive dielectric anisotropy value and are very large, and have excellent thermal stability and chemical stability. It is suitable for preparing a liquid crystal composition for active driving such as TFT driving.
- the content of Component F in the liquid crystal composition of the present invention is suitably in the range of 1 to 99% by weight, preferably 10 to 97% by weight, more preferably 40 to 95% by weight, based on the total weight of the liquid crystal composition. It is.
- the viscosity can be adjusted by further containing a compound represented by formulas (11) to (13) (component E).
- Preferred examples of the compound represented by formula (19), that is, component G, include formulas (19-1) to (19-37).
- the compound represented by the formula (19), that is, the component G has a positive dielectric anisotropy value and a very large value, it is an element driven in an optically isotropic liquid crystal phase, PDLCD, PNLCD It is mainly used for lowering the driving voltage of elements such as PSCLCD.
- the driving voltage of the composition can be reduced.
- the viscosity, the refractive index anisotropy value, and the liquid crystal phase temperature range can be expanded. It can also be used to improve steepness.
- the content of component G is preferably in the range of 0.1 to 99.9% by weight, more preferably in the range of 10 to 97% by weight, and still more preferably in the range of 40 to 95% by weight with respect to the total amount of the composition. .
- composition having optically isotropic liquid crystal phase 4-1 Composition of composition having optically isotropic liquid crystal phase
- the fourth aspect of the present invention is a compound represented by formula (1) And a chiral agent, which is a liquid crystal composition that can be used for an optical element driven in an optically isotropic liquid crystal phase.
- the liquid crystal composition is a composition that exhibits an optically isotropic liquid crystal phase.
- the chiral agent is preferably contained in an amount of 1 to 40% by weight, more preferably 3 to 25% by weight, and most preferably 5 to 15% by weight based on the total weight of the liquid crystal composition.
- a liquid crystal composition containing a chiral agent in these ranges is preferable because it tends to have an optically isotropic liquid crystal phase.
- the chiral agent contained in the liquid crystal composition may be one type or two or more types.
- a compound having a large twisting power is preferable.
- a compound having a large torsional force can reduce the amount of addition necessary to obtain a desired pitch, so that an increase in driving voltage can be suppressed and is practically advantageous.
- compounds represented by the above formulas (K1) to (K5) are preferable.
- R K is independently hydrogen, halogen, —C ⁇ N, —N ⁇ C ⁇ O, —N ⁇ C ⁇ S, or alkyl having 1 to 20 carbons; Any —CH 2 — in the alkyl may be replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—. Well, any —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Any hydrogen in the group replaced with may be replaced with halogen;
- A is independently an aromatic or non-aromatic 3- to 8-membered ring or a condensed ring having 9 or more carbon atoms. And any hydrogen in these rings is replaced by halogen, alkyl of 1 to 3 carbons or haloalkyl.
- Z is independently a single bond, alkylene having 1 to 8 carbons, and any —CH 2 — in the alkylene is —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —N ⁇ N—, —CH ⁇ N—, —N ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be substituted,
- any —CH 2 — in alkylene is —O—, —S—, —COO—, —OCO—, —CSO—, —OCS—, —N ⁇ N—, —CH ⁇ N—, Any hydrogen in the group replaced by —N ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF—
- X may be a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —; mK is 1 to 4.
- the formulas (K2-1) to (K2-8) included in the formula (K2) and the formula (K5-) included in the formula (K5) are included. 1) to formula (K5-3) are preferred.
- R K is independently alkyl having 3 to 10 carbon atoms, and —CH 2 — adjacent to the ring in this alkyl may be replaced by —O—, and Any non-adjacent —CH 2 — may be replaced with —CH ⁇ CH—).
- the liquid crystal composition is optically isotropic. Although the liquid crystal molecular arrangement is macroscopically isotropic, the liquid crystal composition is optically isotropic. Microscopically, it means that liquid crystal order exists. “Pitch based on microscopic order of liquid crystal composition (hereinafter, sometimes referred to as pitch)” is preferably 700 nm or less, more preferably 500 nm or less, and 350 nm or less. Is most preferred.
- non-liquid crystal isotropic phase is a generally defined isotropic phase, that is, a disordered phase, and even if a region where the local order parameter is not zero is generated, the cause is due to fluctuations.
- Isotropic phase For example, an isotropic phase appearing on the high temperature side of the nematic phase corresponds to a non-liquid crystal isotropic phase in this specification.
- the same definition shall apply to the chiral liquid crystal in this specification.
- the “optically isotropic liquid crystal phase” refers to a phase that expresses an optically isotropic liquid crystal phase instead of fluctuations, for example, a phase that expresses a platelet structure (in a narrow sense). Blue phase) is an example.
- optically isotropic liquid crystal composition of the present invention although it is an optically isotropic liquid crystal phase, a platelet structure typical of a blue phase may not be observed under a polarizing microscope. Therefore, in this specification, a phase that develops a platelet structure is referred to as a blue phase, and an optically isotropic liquid crystal phase including the blue phase is referred to as an optically isotropic liquid crystal phase. That is, the blue phase is included in the optically isotropic liquid crystal phase.
- blue phases are classified into three types (blue phase I, blue phase II, blue phase III), and these three types of blue phases are all optically active and isotropic.
- the blue phase I or blue phase II two or more types of diffracted light caused by Bragg reflection from different lattice planes are observed.
- the blue phase is generally observed between the non-liquid crystal isotropic phase and the chiral nematic phase.
- the state in which the optically isotropic liquid crystal phase does not show diffracted light of two or more colors means that the platelet structure observed in the blue phase I and the blue phase II is not observed and is generally monochromatic. To do.
- an optically isotropic liquid crystal phase that does not show diffracted light of two or more colors it is not necessary until the color brightness is uniform in the plane.
- An optically isotropic liquid crystal phase that does not show diffracted light of two or more colors has an advantage that the reflected light intensity due to Bragg reflection can be suppressed or shifted to the lower wavelength side.
- the liquid crystal material that reflects visible light may have a problem of color when used as a display element.
- the reflection wavelength is shifted by a low wavelength. Therefore, the reflection of visible light can be eliminated at a pitch longer than the narrowly defined blue phase (phase that expresses the platelet structure).
- the optically isotropic liquid crystal composition of the present invention can be obtained by adding a chiral agent to a composition having a nematic phase. At this time, the chiral agent is preferably added at a concentration such that the pitch is 700 nm or less. In addition, the composition which has a nematic phase contains the compound represented by Formula (1) and another component as needed.
- the optically isotropic liquid crystal composition of the present invention can also be obtained by adding a chiral agent to a composition having a chiral nematic phase and not having an optically isotropic liquid crystal phase. .
- the composition which has a chiral nematic phase and does not have an optically isotropic liquid crystal contains the compound represented by Formula (1), an optically active compound, and other components as needed.
- the optically active compound is preferably added at a concentration such that the pitch is 700 nm or more so as not to develop an optically isotropic liquid crystal phase.
- the optically active compound to be added is a compound (K-1) to (K-4), a formula (K2-1) to (K2-8) or a formula (K5- Compounds represented by 1) to (K5-4) can be used.
- the optically active compound to be added may be a compound that does not have a very large twisting force. Examples of such an optically active compound include a compound added to a liquid crystal composition for an element (TN mode, STN mode, etc.) driven in a nematic phase.
- the temperature range of the optically isotropic liquid crystal composition of the present invention is such that a chiral agent is added to a liquid crystal composition having a wide coexistence temperature range of a nematic phase or a chiral nematic phase and an isotropic phase, and the optical It can be widened by developing an isotropic liquid crystal phase.
- a liquid crystal compound having a high clearing point and a liquid crystal compound having a low clearing point are mixed to prepare a liquid crystal composition having a wide coexisting temperature range of a nematic phase and an isotropic phase over a wide temperature range, and a chiral agent is added thereto.
- a composition that exhibits an optically isotropic liquid crystal phase in a wide temperature range can be prepared.
- the difference between the maximum temperature and the minimum temperature at which the chiral nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C.
- a liquid crystal composition is preferable, and a liquid crystal composition having a difference of 5 to 150 ° C. is more preferable.
- a liquid crystal composition in which the difference between the upper limit temperature and the lower limit temperature at which the nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C. is preferable.
- the optically isotropic liquid crystal composition of the present invention may further contain other compounds such as a polymer substance as long as the properties of the composition are not affected.
- the liquid crystal composition of the present invention may contain, for example, a dichroic dye and a photochromic compound in addition to the polymer substance.
- dichroic dyes include merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine.
- a fifth aspect of the present invention is a composite material of a liquid crystal composition and a polymer containing a compound represented by formula (1) and a chiral agent, and optical Isotropic.
- This is an optically isotropic polymer / liquid crystal composite material that can be used in an optical element driven in an optically isotropic liquid crystal phase.
- Such a polymer / liquid crystal composite material is composed of, for example, the liquid crystal composition (liquid crystal composition CLC) described in the items [1] to [30] and a polymer.
- the “polymer / liquid crystal composite material” of the present invention is not particularly limited as long as it is a composite material containing both a liquid crystal material and a polymer compound, but part or all of the polymer is dissolved in the liquid crystal material.
- the polymer may be in a state of being phase-separated from the liquid crystal material.
- a nematic phase means a nematic phase in a narrow sense that does not include a chiral nematic phase.
- the optically isotropic polymer / liquid crystal composite material according to a preferred embodiment of the present invention can exhibit an optically isotropic liquid crystal phase in a wide temperature range. Further, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention has an extremely fast response speed. Moreover, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention can be suitably used for an optical element such as a display element based on these effects.
- the composite material of the present invention can be produced by mixing an optically isotropic liquid crystal composition and a polymer obtained by polymerization in advance. It is preferably produced by mixing a monomer having a molecular weight, a macromonomer, an oligomer or the like (hereinafter collectively referred to as “monomer or the like”) and the liquid crystal composition CLC, and then performing a polymerization reaction in the mixture.
- a monomer having a molecular weight, a macromonomer, an oligomer or the like hereinafter collectively referred to as “monomer or the like”
- the liquid crystal composition CLC a mixture containing a monomer or the like and a liquid crystal composition
- the “polymerizable monomer / liquid crystal mixture” includes a polymerization initiator, a curing agent, a catalyst, a stabilizer, a dichroic dye, or a photochromic compound, which will be described later, as necessary, as long as the effects of the present invention are not impaired. But you can.
- the polymerizable monomer / liquid crystal mixture of the present invention may contain a polymerization initiator in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer, if necessary.
- the polymerization temperature is preferably a temperature at which the polymer / liquid crystal composite material exhibits high transparency and isotropic properties. More preferably, the polymerization is terminated at a temperature at which the mixture of the monomer and the liquid crystal material develops an isotropic phase or a blue phase, and at the isotropic phase or the optically isotropic liquid crystal phase. That is, after polymerization, the polymer / liquid crystal composite material is preferably set to a temperature that does not substantially scatter light on the longer wavelength side than visible light and develops an optically isotropic state.
- the polymer raw material constituting the composite material of the present invention for example, a low molecular weight monomer, macromonomer, and oligomer can be used.
- the high molecular weight raw material monomer is a low molecular weight monomer, macromonomer. , Used to include oligomers and the like.
- the obtained polymer has a three-dimensional crosslinked structure. Therefore, it is preferable to use a polyfunctional monomer having two or more polymerizable functional groups as a raw material monomer for the polymer.
- the polymerizable functional group is not particularly limited, and an acrylic group, a methacryl group, a glycidyl group, an epoxy group, an oxetanyl group, a vinyl group, and the like can be raised, but an acrylic group and a methacryl group are preferable from the viewpoint of polymerization rate.
- a monomer having two or more polymerizable functional groups in the polymer raw material monomer is contained in an amount of 10% by weight or more, high transparency and isotropy are easily exhibited in the composite material of the present invention. This is preferable.
- the polymer preferably has a mesogen moiety, and a raw material monomer having a mesogen moiety can be used as a part or all of the polymer as a polymer raw material monomer.
- Monofunctional / bifunctional monomer having a mesogen moiety is not particularly limited in terms of structure.
- the following formula (M1) or (M2) The compound represented by these can be mentioned.
- each R a is independently hydrogen, halogen, —C ⁇ N, —N ⁇ C ⁇ O, —N ⁇ C ⁇ S, or alkyl having 1 to 20 carbons.
- alkyl any —CH 2 — is replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, or —C ⁇ C—.
- any —CH 2 — may be —O—, —S—, —CO—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, Or, in the group replaced with —C ⁇ C—, any hydrogen may be replaced with halogen or —C ⁇ N.
- R b is each independently a polymerizable group of formula (M3-1) to formula (M3-7).
- R a is hydrogen, halogen, —C ⁇ N, —CF 3 , —CF 2 H, —CFH 2 , —OCF 3 , —OCF 2 H, alkyl having 1 to 20 carbons, or alkyl having 1 to 19 carbons. Alkoxy, alkenyl having 2 to 21 carbons, and alkynyl having 2 to 21 carbons. Particularly preferred R a is —C ⁇ N, alkyl having 1 to 20 carbons and alkoxy having 1 to 19 carbons.
- each R b is independently a polymerizable group of the formulas (M3-1) to (M3-7).
- R d in the formulas (M3-1) to (M3-7) is each independently hydrogen, halogen or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen is replaced with halogen. May be.
- Preferred R d is hydrogen, halogen and methyl.
- Particularly preferred R d is hydrogen, fluorine and methyl.
- the formula (M3-2), the formula (M3-3), the formula (M3-4), and the formula (M3-7) are preferably polymerized by radical polymerization.
- the formula (M3-1), formula (M3-5), and formula (M3-6) are preferably polymerized by cationic polymerization.
- a polymerization initiator can be used for the purpose of accelerating the generation of active species. For example, light or heat can be used to generate the active species.
- a M is each independently an aromatic or non-aromatic 5-membered ring, 6-membered ring, or condensed ring having 9 or more carbon atoms.
- CH 2 — may be —O—, —S—, —NH—, or —NCH 3 —, and —CH ⁇ in the ring may be replaced by —N ⁇ , the hydrogen atom on the ring is halogen, and carbon number It may be replaced with 1 to 5 alkyls or alkyl halides.
- preferred A M are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene -2, 7-diyl, or bicyclo [2.2.2] octane-1,4-diyl, in which any —CH 2 — may be replaced by —O— —CH ⁇ may be replaced by —N ⁇ , and any hydrogen in these rings may be replaced by halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms.
- a M 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4 -Phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2 , 3-bis (trifluoromethyl) -1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7- Diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, and pyrimidine-2,5-diyl.
- the steric configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene is structurally identical to 3-fluoro-1,4-phenylene, the latter was not exemplified. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.
- each Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylenes, any —CH 2 — is —O—, —S—, — It may be replaced by CH ⁇ CH—, —C ⁇ C—, —COO—, or —OCO—.
- Preferred Y is a single bond, — (CH 2 ) m2 —, —O (CH 2 ) m2 —, and — (CH 2 ) m2 O— (wherein m2 is an integer of 1 to 20) .
- Y is a single bond, — (CH 2 ) m2 —, —O (CH 2 ) m2 —, and — (CH 2 ) m2 O— (wherein m2 is an integer of 1 to 10). is there.
- —Y—R a and —Y—R b are in their groups —O—O—, —O—S—, —S—O—, or —S—S. It is preferable not to have-.
- Z M independently represents a single bond, — (CH 2 ) m3 —, —O (CH 2 ) m3 —, — (CH 2 ) m3 O—, —O ( CH 2 ) m 3 O—, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, — (CF 2 ) 2 —, — (CH 2 ) 2 —COO—, —OCO— (CH 2 ) 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —CH ⁇ CH— (CH 2 ) 2 —, — (CH 2 ) 2 —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—CH ⁇ CH—, —CH ⁇ CH—C ⁇ C—, —OCF 2 — (CH 2 ) 2 —,
- Preferred Z M is a single bond, — (CH 2 ) m3 —, —O (CH 2 ) m3 —, — (CH 2 ) m3 O—, —CH ⁇ CH—, —C ⁇ C—, —COO—, — OCO—, — (CH 2 ) 2 —COO—, —OCO— (CH 2 ) 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —OCF 2 —, and —CF 2 O— It is.
- m1 is an integer of 1 to 6.
- Preferred m1 is an integer of 1 to 3.
- m1 is 1, it is a bicyclic compound having two rings such as a 6-membered ring.
- m1 is 2 or 3, they are tricyclic and tetracyclic compounds, respectively.
- two A M may be may be the same or different.
- three A M or two Z M ) may be the same or different.
- m1 is 3-6.
- the compound (M1) represented by the formula (M1) and the compound (M2) represented by the formula (M2) contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance. However, since it has the same characteristics, it can be preferably used.
- More preferred examples of the compound (M1) and the compound (M2) include compounds (M1-1) to (M1-1) to (M1-41) and (M2-1) to (M2-27) (M1-41) and compounds (M2-1) to (M2-27).
- the meanings of R a , R b , R d , Z M , A M , Y and p are the same as those in formula (M1) and formula (M2) described in the embodiments of the present invention.
- the partial structure (a1) represents 1,4-phenylene in which arbitrary hydrogen is replaced by fluorine.
- the partial structure (a2) represents 1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine.
- the partial structure (a3) represents 1,4-phenylene in which arbitrary hydrogen may be replaced by either fluorine or methyl.
- the partial structure (a4) represents fluorene in which the hydrogen at the 9-position may be replaced with methyl.
- a monomer having no mesogen moiety and a polymerizable compound other than the monomers (M1) and (M2) having a mesogen moiety can be used as necessary.
- a monomer having a mesogenic moiety and having three or more polymerizable functional groups may be used.
- known compounds can be preferably used. Examples thereof include (M4-1) to (M4-3).
- Examples thereof include compounds described in JP-A No. 2000-327632, JP-A No. 2004-182949, and JP-A No. 2004-59772.
- R b , Za, Y, and (F) have the same meaning as described above.
- Monomers having a polymerizable functional group not having a mesogen moiety for example, a linear or branched acrylate having 1 to 30 carbon atoms
- Monomers having 1 to 30 carbon atoms or straight chain or branched diacrylates, and monomers having three or more polymerizable functional groups include glycerol propoxylate (1PO / OH) triacrylate, pentaerythritol propoxylate triacrylate, penta Erythritol triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol Tetraacrylate, di (pentaerythritol) pentaacrylate, di (pentaerythritol) he
- the polymerization reaction in the production of the polymer constituting the composite material of the present invention is not particularly limited, and for example, photo radical polymerization, thermal radical polymerization, photo cation polymerization and the like are performed.
- photo radical polymerization initiator examples include DAROCUR (registered trademark) 1173 and 4265 (both trade names, Ciba Specialty Chemicals), Irgacure (IRGACURE, registered trademark). 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 (all trade names, Ciba Specialty Chemicals Co., Ltd.).
- thermal radical polymerization examples include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate , T-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbox Nitrile (ACN) and the like.
- MAIB dimethyl 2,2′-azobisisobutyrate
- DTBPO di-t-butyl peroxide
- AIBN azobisisobutyronitrile
- ACN azobiscyclohexanecarbox Nitrile
- photocationic polymerization initiator examples include diaryliodonium salts (hereinafter referred to as “DAS”), triarylsulfonium salts (hereinafter referred to as “TAS”), and the like.
- DAS diaryliodonium salts
- TAS triarylsulfonium salts
- DAS includes diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra (pentafluorophenyl) ) Borate, 4-methoxyphenyl phenyl iodonium tetrafluoroborate, 4-methoxyphenyl phenyl iodonium hexafluorophosphonate, 4-methoxyphenyl phenyl iodonium hexafluoroarsenate, 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate, 4-methoxyphen
- Sensitivity can be increased by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, rubrene to DAS.
- a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, rubrene to DAS.
- TAS includes triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane Sulfona
- Examples of specific trade names of the photocationic polymerization initiator include Cyracure (registered trademark) UVI-6990, Cyracure UVI-6974, Cyracure UVI-6922 (trade names, UCC Co., Ltd.) and Adekaoptomer SP, respectively.
- Cyracure registered trademark
- UVI-6990 Cyracure UVI-6974
- Cyracure UVI-6922 trade names, UCC Co., Ltd.
- Adekaoptomer SP Adekaoptomer SP, respectively.
- -150, SP-152, SP-170, SP-172 (trade names, ADEKA Corporation), Rhodorsil® Photoinitiator 2074 (trade name, Rhodia Japan Co., Ltd.), Irgacure (registered trademark) 250 (trade name) Ciba Specialty Chemicals Co., Ltd.), UV-9380C (trade name, GE Toshiba Silicone Co., Ltd.), and the like.
- 5-1-4 Curing Agent etc.
- one or more other suitable components for example, a curing agent Catalysts, stabilizers and the like may be added.
- the curing agent a conventionally known latent curing agent that is usually used as a curing agent for epoxy resins can be used.
- the latent epoxy resin curing agent include amine curing agents, novolak resin curing agents, imidazole curing agents, and acid anhydride curing agents.
- amine curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, and isophoronediamine.
- 1,3-bisaminomethylcyclohexane bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, alicyclic polyamines such as laromine, fragrances such as diaminodiphenylmethane, diaminodiphenylethane, metaphenylenediamine Group polyamines and the like.
- novolak resin-based curing agents examples include phenol novolac resins and bisphenol novolac resins.
- the imidazole curing agent include 2-methylimidazole, 2-ethylhexylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like.
- acid anhydride curing agents examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride and the like can be mentioned.
- a curing accelerator for accelerating the curing reaction between the polymerizable compound having a glycidyl group, an epoxy group, or an oxetanyl group and the curing agent may be further used.
- the curing accelerator include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methyl.
- Imidazoles such as imidazole, organophosphorus compounds such as triphenylphosphine, quaternary phosphonium salts such as tetraphenylphosphonium bromide, 1,8-diazabicyclo [5.4.0] undecene-7, and organic acid salts thereof
- examples thereof include quaternary ammonium salts such as diazabicycloalkenes, tetraethylammonium bromide and tetrabutylammonium bromide, and boron compounds such as boron trifluoride and triphenylborate.
- These curing accelerators can be used alone or in admixture of two or more.
- a stabilizer is preferably added in order to prevent undesired polymerization during storage.
- All compounds known to those skilled in the art can be used as stabilizers.
- Representative examples of stabilizers include 4-ethoxyphenol, hydroquinone, butylated hydroxytoluene (BHT) and the like.
- the content of the liquid crystal composition in the polymer / liquid crystal composite material of the present invention is possible as long as the composite material can express an optically isotropic liquid crystal phase. It is preferable that the content is as high as possible. This is because the electric birefringence value of the composite material of the present invention increases as the content of the liquid crystal composition is higher.
- the content of the liquid crystal composition is preferably from 60 to 99% by weight, more preferably from 60 to 95% by weight, particularly from 65 to 95% by weight, based on the composite material.
- the content of the polymer is preferably 1 to 40% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 35% by weight with respect to the composite material.
- the polymer / liquid crystal composite material of the present invention may contain, for example, a dichroic dye and a photochromic compound as long as the effects of the present invention are not impaired.
- EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict
- a sixth aspect of the present invention is a liquid crystal composition or a polymer / liquid crystal composite material (hereinafter, the liquid crystal composition of the present invention and the polymer / liquid crystal composite material may be collectively referred to as a liquid crystal medium). ) Including an optically isotropic liquid crystal phase. When no electric field is applied, the liquid crystal medium is optically isotropic, but when an electric field is applied, the liquid crystal medium exhibits optical anisotropy, and light modulation by the electric field becomes possible. As an example of the structure of the liquid crystal display element, as shown in FIG.
- GC analysis GC-14B gas chromatograph manufactured by Shimadzu Corporation was used as a measuring device.
- a capillary column CBP1-M25-025 (length: 25 m, inner diameter: 0.22 mm, film thickness: 0.25 ⁇ m) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) as the stationary liquid phase was used.
- Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min.
- the temperature of the sample vaporizing chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.
- the sample was dissolved in toluene to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
- a recorder a C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used.
- the obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.
- capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc.
- HP-1 length 30 m, inner diameter 0
- Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m)
- BP-1 from SGE International Corporation Pty. Ltd (length 30 m, inner diameter) 0.32 mm, film thickness of 0.25 ⁇ m) or the like
- SGE International Corporation Pty. Ltd length 30 m, inner diameter 0.32 mm, film thickness of 0.25 ⁇ m
- the peak area ratio in the gas chromatogram corresponds to the ratio of the component compounds.
- the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample.
- the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds.
- an internal standard method based on the gas chromatogram is used.
- the liquid crystal compound component (test component) weighed in a certain amount accurately and the reference liquid crystal compound (reference material) are simultaneously measured by gas chromatography, and the area ratio between the peak of the obtained test component and the peak of the reference material Is calculated in advance.
- the composition ratio of the liquid crystal compound in the liquid crystal composition can be determined more accurately from gas chromatography analysis.
- Samples for measuring physical property values of liquid crystal compounds etc. There are two types of samples for measuring the physical property values of liquid crystal compounds: when the compound itself is used as a sample, and when the compound is mixed with mother liquid crystals as a sample.
- the measurement is performed by the following method. First, 15% by weight of the obtained liquid crystal compound and 85% by weight of the mother liquid crystal are mixed to prepare a sample. Then, an extrapolated value is calculated from the measured value of the obtained sample according to the extrapolation method based on the following calculation formula. This extrapolated value is taken as the physical property value of this compound.
- ⁇ Extrapolated value> (100 ⁇ ⁇ Measured value of sample> ⁇ ⁇ Weight% of mother liquid crystal> ⁇ ⁇ Measured value of mother liquid crystal>) / ⁇ Weight% of liquid crystal compound>
- the ratio between the liquid crystal compound and the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio between the liquid crystal compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight. %: 95% by weight, 1% by weight: 99% by weight, and the physical properties of the sample were measured with a composition in which the smectic phase or crystals did not precipitate at 25 ° C., and extrapolated according to the above formula. This is taken as the physical property value of the liquid crystal compound.
- mother liquid crystals A there are various types of mother liquid crystals used for measurement.
- the composition (% by weight) of the mother liquid crystals A is as follows.
- Phase structure and phase transition temperature Measurement was performed by the following methods (1) and (2).
- a compound is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope, and the phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of liquid crystal phase.
- (2) Using a scanning calorimeter DSC-7 system or Diamond DSC system manufactured by PerkinElmer, Inc., the temperature is raised and lowered at a rate of 3 ° C / min, and the start point of the endothermic peak or exothermic peak accompanying the phase change of the sample The phase transition temperature was determined by onset.
- the crystal is expressed as K, and when the crystal can be distinguished, it is expressed as K 1 or K 2 , respectively.
- the smectic phase is represented as Sm
- the nematic phase is represented as N.
- the liquid (isotropic) was designated as I.
- SmB or SmA When the smectic phase can be distinguished from the smectic B phase or the smectic A phase, it is expressed as SmB or SmA, respectively.
- BP represents a blue phase or an optically isotropic liquid crystal phase.
- the coexistence state of two phases may be expressed in the form of (N * + I) and (N * + BP).
- (N * + I) represents a phase in which a non-liquid crystal isotropic phase and a chiral nematic phase coexist
- (N * + BP) represents a BP phase or an optically isotropic liquid crystal phase.
- Un represents an unidentified phase that is not optically isotropic.
- K 50.0 N 100.0 I means that the phase transition temperature (KN) from the crystal to the nematic phase is 50.0 ° C., and the phase from the nematic phase to the liquid
- the transition temperature (NI) is 100.0 ° C. The same applies to other notations.
- T NI Maximum temperature of nematic phase
- a sample (mixture of liquid crystal compound and mother liquid crystal) is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. The polarizing microscope was observed while heating at a rate of ° C / min.
- the temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase.
- the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.
- Low temperature compatibility A sample in which a mother liquid crystal and a liquid crystal compound were mixed so that the liquid crystal compound was in an amount of 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Make and place sample in glass bottle. The glass bottle was stored in a freezer at ⁇ 10 ° C. or ⁇ 20 ° C. for a certain period, and then it was observed whether crystals or smectic phases were precipitated.
- Viscosity ( ⁇ ; measured at 20 ° C .; mPa ⁇ s): A mixture of a liquid crystal compound and a mother liquid crystal was measured using an E-type rotational viscometer.
- Pitch P; measured at 25 ° C .; nm
- the pitch length was measured using selective reflection (Liquid Crystal Manual 196 pages 2000, Maruzen).
- ⁇ n> represents an average refractive index and is given by the following equation.
- ⁇ n> ⁇ (n ⁇ 2 + n ⁇ 2) / 2 ⁇ 1/2.
- the selective reflection wavelength was measured with a microspectrophotometer (JEOL Ltd., trade name MSV-350). The pitch was obtained by dividing the obtained reflection wavelength by the average refractive index.
- the pitch of cholesteric liquid crystals having a reflection wavelength in the longer wavelength region than visible light is proportional to the reciprocal of the concentration of the optically active compound in regions where the optically active compound concentration is low, so the pitch of liquid crystals having a selective reflection wavelength in the visible light region
- the length was measured at several points and determined by a linear extrapolation method.
- the “optically active compound” corresponds to the chiral agent in the present invention.
- phase transition temperature of the obtained compound (S1-10) was as follows. Phase transition temperature (° C.): K 77.1 SmA 116.7 N 140.2 I
- a liquid crystal composition B comprising 85% by weight of the base liquid crystal A and 15% by weight of (S1-10) obtained in Example 1 was prepared.
- the physical property value of the obtained liquid crystal composition B was measured, and the extrapolated value of the physical property of the liquid crystal compound (S1-10) was calculated by extrapolating the measured value.
- the liquid crystal compound (S1-10) has a high clearing point and excellent compatibility with other liquid crystal compounds, and has a dielectric anisotropy ( ⁇ ) and a refractive index anisotropy ( ⁇ n). It was found to be a large compound.
- phase transition temperature of the obtained compound (S2) was as follows. Phase transition temperature (° C.): K 56.6 I
- phase transition temperature of the obtained compound (S3) was as follows. Phase transition temperature (° C.): K 53.6 I
- a liquid crystal composition D comprising 85% by weight of mother liquid crystals A and 15% by weight of (S3) was prepared.
- the physical property value of the obtained liquid crystal composition D was measured, and the extrapolated value of the physical property of the liquid crystal compound (S3) was calculated by extrapolating the measured value.
- composition of the present invention the characteristic value of the liquid crystal composition can be measured according to the following method. Many of them are the methods described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof. No TFT was attached to the TN device used for measurement.
- NI Maximum temperature of nematic phase
- a sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
- the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
- T C Minimum temperature of nematic phase
- Optically isotropic liquid crystal phase transition temperature Place the sample on the hot plate of a melting point measurement device equipped with a polarizing microscope, and in the crossed Nicols state, the sample was first heated to a temperature at which the sample becomes an isotropic liquid crystal phase Thereafter, the temperature was lowered at a rate of 1 ° C./min, and a completely chiral nematic phase or an optically isotropic liquid crystal phase appeared. The temperature at which the phase transition in the temperature lowering process was measured, then the temperature was increased at a rate of 1 ° C./min, and the temperature at which the phase transition in the temperature rising process was measured.
- the phase transition temperature in the temperature raising process is defined as the phase transition temperature.
- the phase transition temperature In the optically isotropic liquid crystal phase, when it was difficult to determine the phase transition temperature in the dark field under crossed Nicols, the phase transition temperature was measured by shifting the polarizing plate by 1 to 10 ° from the crossed Nicols state.
- Viscosity ( ⁇ ; measured at 20 ° C .; mPa ⁇ s): An E-type rotational viscometer was used for measurement.
- Rotational viscosity ( ⁇ 1; measured at 25 ° C .; mPa ⁇ s): 1) Sample having positive dielectric anisotropy: Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. The voltage was applied to the TN device stepwise in the range of 16 to 19.5 volts every 0.5 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
- the peak current and peak time of the transient current generated by this application were measured.
- the value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al.
- the value of dielectric anisotropy necessary for this calculation was obtained by the following dielectric anisotropy measurement method using the element used for the measurement of the rotational viscosity.
- the refractive index anisotropy was measured by this method.
- the refractive index anisotropy was measured after mixing the compound with an appropriate composition.
- the refractive index anisotropy of the compound is an extrapolated value.
- Dielectric Anisotropy ( ⁇ ; measured at 25 ° C.): When the sample was a compound, the compound was mixed with an appropriate composition, and then the dielectric anisotropy was measured. The dielectric anisotropy of the compound is an extrapolated value.
- Threshold voltage (Vth; measured at 25 ° C .; V): When the sample was a compound, the threshold voltage was measured after mixing the compound with an appropriate composition. The threshold voltage of the compound is an extrapolated value.
- a composition having a positive dielectric anisotropy a normally white mode (normally white mode) in which a distance (gap) between two glass substrates is (0.5 / ⁇ n) ⁇ m and a twist angle is 80 degrees.
- ⁇ n is a value of refractive index anisotropy measured by the above method.
- a rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.
- composition having a negative dielectric anisotropy For a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 ⁇ m and processed in homeotropic alignment A sample was placed. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.
- Voltage holding ratio (VHR; measured at 25 ° C .;%):
- the TN device used for the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 6 ⁇ m. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- the area B is an area when it is not attenuated.
- the voltage holding ratio is a percentage of the area A with respect to the area B.
- the pitch length was measured using selective reflection (Liquid Crystal Manual 196 (issued in 2000, Maruzen).
- the selective reflection wavelength is a microspectrophotometer (JEOL Ltd., product)
- the pitch was determined by dividing the obtained reflection wavelength by the average refractive index.
- the pitch of a cholesteric liquid crystal having a reflection wavelength in the longer wavelength region than visible light is proportional to the reciprocal of the concentration of the chiral agent in a region where the chiral agent concentration is low, so the pitch length of a liquid crystal having a selective reflection wavelength in the visible light region is increased.
- the ratio (percentage) of the component or liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound.
- the composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component.
- Example 1 A liquid crystal composition NLC-1 was prepared by mixing the liquid crystal compounds shown in the following figure at the following ratios.
- Liquid crystal composition K A liquid crystal composition NLC-2 was prepared by mixing the liquid crystal composition NLC-1 (80 wt%) and the liquid crystal compound (S1-10) (20 wt%) shown below.
- liquid crystal composition CLC-1 comprising a liquid crystal composition NLC-2 (95.5 wt%) and a chiral agent ISO-60BA2 (4.5 wt%) represented by the following formula was obtained.
- the BP-I point of this product was 75.1 ° C.
- ISO-60BA2 was obtained by esterifying isosorbide and 4-hexyloxybenzoic acid in the presence of dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine.
- DCC dicyclohexylcarbodiimide
- Example 2 Preparation of Mixture of Monomer and Liquid Crystal Composition
- the liquid crystal composition CLC-1 was 79.4% by weight
- n-dodecyl acrylate was 10.0% by weight
- a liquid crystal composition CLC-1M was prepared.
- the liquid crystal composition CLC-1M was sandwiched between a comb-shaped electrode substrate not subjected to alignment treatment and a counter glass substrate (non-electrode provided) (cell thickness 10 ⁇ m). The cell was heated to 63.0 ° C. to obtain an isotropic phase. In this state, ultraviolet light (ultraviolet light intensity 13 mWcm ⁇ 2 (365 nm)) was irradiated for 1 minute to carry out a polymerization reaction.
- ultraviolet light ultraviolet light
- the thus obtained polymer / liquid crystal composite material CLC-1P maintained an optically isotropic liquid crystal phase even when cooled to room temperature.
- the electrodes of the comb-shaped electrode substrate are alternately arranged with electrodes 1 extending from the left side and electrodes 2 extending from the right side. Therefore, when there is a potential difference between the electrode 1 and the electrode 2, it is possible to provide a state in which electric fields in two directions, ie, an upper direction and a lower direction, exist on the comb-shaped electrode substrate as shown in FIG.
- Example 3 The cell sandwiched between the polymer / liquid crystal composite material CLC-1P obtained in Example 2 was set in the optical system shown in FIG. 2, and the electro-optical characteristics were measured.
- the white light source of a polarizing microscope (Nikon Optiphot-POL) is used as the light source, the incident angle to the cell is perpendicular to the cell surface, and the line direction of the comb electrode is relative to the Polarizer and the Analyzer polarizer, respectively.
- the cell was set in the optical system so as to be 45 °.
- an optical element such as a display element using a liquid crystal medium can be mentioned.
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Abstract
Description
素子の駆動方式に基づいた分類は、PM(passive matrix)とAM(active matrix)である。PM(passive matrix)はスタティック(static)とマルチプレックス(multiplex)などに分類され、AMはTFT(thin film transistor)、MIM(metal insulator metal)などに分類される。
(1)化学的に安定であること、および物理的に安定であること、
(2)高い透明点(液晶相-等方相の相転移温度)を有すること、
(3)液晶相(ネマチック相、コレステリック相、スメクチック相、ブルー相などの光学的に等方性の液晶相等)の下限温度が低いこと、
(4)他の液晶化合物との相溶性に優れること、
(5)適切な大きさの誘電率異方性を有すること、
(6)適切な大きさの屈折率異方性を有すること、
である。
特に、光学的に等方性の液晶相においては、誘電率異方性と屈折率異方性が大きな液晶化合物が駆動電圧低減の観点から好ましい。
また、(2)および(3)のように、高い透明点、あるいは液晶相の低い下限温度を有する液晶化合物を含む液晶組成物ではネマチック相や光学的に等方性の液晶相の温度範囲を広げることが可能となり、幅広い温度範囲で表示素子として使用することができる。液晶化合物は、単一の化合物では発揮することが困難な特性を発現させるために、他の多くの液晶化合物と混合して調製した液晶組成物として用いることが一般的である。したがって、液晶表示素子に用いられる液晶化合物は、(4)のように、他の液晶化合物等との相溶性が良好であることが好ましい。近年は特に表示性能、例えばコントラスト、表示容量、応答時間特性等のより高い液晶表示素子が要求されている。さらに使用される液晶材料には駆動電圧の低い液晶組成物が要求されている。また光学的に等方性の液晶相で駆動させる光素子を低電圧で駆動させるためには、誘電率異方性および屈折率異方性が大きい液晶化合物を用いることが好ましい。
(式(1)において、R1は水素または炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-、または-C≡C-で置き換えられた基中の任意の水素はハロゲンまたは炭素数1~3のアルキルで置き換えられてもよく、;環A1、環A2、環A3、環A4、および環A5は独立して、ベンゼン環、ナフタレン環、チオフェン環、ピペリジン環、シクロヘキセン環、ビシクロオクタン環、テトラヒドロナフタレン環またはシクロヘキサン環であり、これらの環の任意の水素がハロゲン、炭素数1~3のアルキル、炭素数1~3のアルコキシまたは炭素数1~3のハロゲン化アルキルで置き換えられてもよく、これらの環の-CH2-は-O-または-S-で置き換えられてもよく、-CH=は-N=で置き換えられてもよく;Z1、Z2、Z3、Z4、Z5、およびZ6は独立して、単結合または炭素数1~4のアルキレンであり、このアルキレン中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、アルキレン中およびアルキレン中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-CH=CH-、-CF=CF-、または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよいが、Z1、Z2、Z3、Z4、Z5、およびZ6のうち少なくとも一つは-CF2O-であり、;L1およびL2は独立して、水素またはハロゲンであり;X1は水素、ハロゲン、-C≡N、-N=C=S、-C≡C-C≡N、-SF5、または炭素数1~10のアルキルであり、このアルキルにおいて任意の-CH2-は、-O-、-S-、-CH=CH-、または-C≡C-により置き換えられてもよく、そしてアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-CH=CH-、-または-C≡C-で置き換えられた基中の任意の水素はハロゲンにより置き換えられてもよく;l、m、n、o、およびpは独立して、0または1であり、l+m+n+o+p≦4である。)
これらの式において、R1は式(CHN-1)~(CHN-19)のいずれか1つで表される基であり、R1aは水素または炭素数1~20のアルキルであり、;環A1、環A2、環A3、環A4、および環A5は独立して、式(RG-1)、(RG-5)、(RG-7)、(RG-8-1)~(RG-8-5)、(RG-9)、(RG-10)、(RG-11-1)、(RG-13)または(RG-15)で表される基であり、;Z1、Z2、Z3、Z4、Z5、およびZ6は独立して、単結合、-CH2CH2-、-CH=CH-、-C≡C-、-COO-、-CF2O-、-CH2O-、または-OCH2-であり;L1およびL2は独立して、水素、フッ素または塩素であり;X1はフッ素、塩素、-C≡N、-CF3、-CHF2、-CH2F、-OCF3、-OCHF2、-OCH2Fまたは-C=C-CF3である。
これらの式において、R2は炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X2はフッ素、塩素、-OCF3、-OCHF2、-CF3、-CHF2、-CH2F、-OCF2CHF2、または-OCF2CHFCF3であり;環B1、環B2、および環B3は独立して、1,4-シクロヘキシレン、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、ナフタレン-2,6-ジイル、任意の水素がフッ素で置き換えられた1,4-フェニレン、または任意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-ジイルであり;Z7およびZ8は独立して、-(CH2)2-、-(CH2)4-、-COO-、-CF2O-、-OCF2-、-CH=CH-、-C≡C-、-CH2O-、または単結合であり、ただし環B1~B3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z7およびZ8はそれぞれ-CF2O-ではなく;L5およびL6は独立して、水素またはフッ素である。
これらの式において、R3は炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X3は-C≡Nまたは-C≡C-C≡Nであり;環C1、環C2および環C3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、任意の水素がフッ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、任意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、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z9は-(CH2)2-、-COO-、-CF2O-、-OCF2-、-C≡C-、-CH2O-、または単結合であり、ただし環C1~C3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z9は-CF2O-ではなく;L7およびL8は独立して、水素またはフッ素であり;rは1または2であり、sは0または1であり、r+s=0、1または2である。
これらの式において中、R4およびR5は独立して、炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;環D1、環D2、環D3、および環D4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、1,4-フェニレン、任意の水素がフッ素で置き換えられた1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、またはデカヒドロナフタレン-2,6-ジイルであり;Z10、Z11、Z12、およびZ13は独立して、-(CH2)2-、-COO-、-CH2O-、-OCF2-、-OCF2(CH2)2-、または単結合であり;L9およびL10は独立して、フッ素または塩素であり;t、u、x、y、およびzは独立して0または1であり、u+x+y+zは1または2である。
これらの式において、R6およびR7は独立して、炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、このアルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;環E1、環E2、および環E3は独立して、1,4-シクロヘキシレン、ピリミジン-2,5-ジイル、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-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;Z14およびZ15は独立して、-C≡C-、-COO-、-(CH2)2-、-CH=CH-、または単結合であり、ただし環E1~E3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z14およびZ15はそれぞれ-CF2O-ではない。
これらの式において、R8は炭素数1~10のアルキル、炭素数2~10のアルケニルまたは炭素数2~10のアルキニルであり、アルキル、アルケニルおよびアルキニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、アルキニル中またはアルキル、アルケニルおよびアルキニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X4はフッ素、塩素、-SF5、-OCF3、-OCHF2、-CF3、-CHF2、-CH2F、-OCF2CHF2、または-OCF2CHFCF3であり;環F1、環F2、環F3および環F4は独立して、1,4-シクロヘキシレン、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、ナフタレン-2,6-ジイル、任意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、または任意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-ジイルであり;Z16、Z17およびZ18は独立して、-(CH2)2-、-(CH2)4-、-COO-、-CF2O-、-OCF2-、-CH=CH-、-C≡C-、-CH2O-、または単結合であり、ただし環F1~F4の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z16、Z17およびZ18はそれぞれ-CF2O-ではなく;L9およびL10は独立して、水素またはフッ素である。
これらの式において、R9は炭素数1~10のアルキル、炭素数2~10のアルケニルまたは炭素数2~10のアルキニルであり、アルキル、アルケニルおよびアルキニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、アルキニル中またはアルキル、アルケニルおよびアルキニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X5は-C≡N、-N=C=S、または-C≡C-C≡Nであり;環G1、環G2および環G3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、任意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、任意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、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z19は-(CH2)2-、-COO-、-CF2O-、-OCF2-、-C≡C-、-CH2O-、または単結合であり、ただし環G1~G3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z19は-CF2O-ではなく;L11およびL12は独立して、水素またはフッ素であり;aaは0、1または2であり、abは0または1であり、aa+abは0、1または2である。
(式(K1)~(K5)中、RKは独立して、水素、ハロゲン、-C≡N、-N=C=O、-N=C=Sまたは炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよく;Aは独立して、芳香族性あるいは非芳香族性の3ないし8員環、または、炭素数9以上の縮合環であり、これらの環の任意の水素がハロゲン、炭素数1~3のアルキルまたはハロアルキルで置き換えられてもよく、環の-CH2-は-O-、-S-または-NH-で置き換えられてもよく、-CH=は-N=で置き換えられてもよく;Zは独立して、単結合、炭素数1~8のアルキレンであるが、任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-N=N-、-CH=N-、-N=CH-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく;
Xは独立して、単結合、-COO-、-OCO-、-CH2O-、-OCH2-、-CF2O-、-OCF2-または-CH2CH2-であり;
mKは独立して、1~4の整数である。)
(RKは独立して、炭素数3~10のアルキルであり、このアルキル中の環に隣接する-CH2-は-O-で置き換えられてもよく、任意の-CH2-は、-CH=CH-で置き換えられてもよい。)
本発明の光学的に等方性の液晶相で駆動される光素子は、使用できる広い温度範囲、短い応答時間、大きなコントラスト比、および低い駆動電圧を有する。
本発明の光学的に等方性の液晶相を有する液晶組成物は、前記式(1)で表される化合物を成分Aとして含む。本発明の第1の態様は、この成分Aのみの組成物、または成分Aと本明細書中で特に成分名を示していないその他の成分を含有する組成物である。まず、式(1)で表される化合物について説明する。
式(1)において、R1は水素または炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル基中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられた基中の任意の水素はハロゲンまたは炭素数1~3のアルキルで置き換えられてもよい。
例えば、CH3(CH2)3-において任意の-CH2-を-O-、-S-、または-CH=CH-で置き換えた基の例は、CH3(CH2)2O-、CH3-O-(CH2)2-、CH3-O-CH2-O-、CH3(CH2)2S-、CH3-S-(CH2)2-、CH3-S-CH2-S-、CH2=CH-(CH2)3-、CH3-CH=CH-(CH2)2-、CH3-CH=CH-CH2O-、CH3CH2C≡C-などである。例えば、CH3(CH2)3-または、CH3(CH2)3-において任意の-CH2-を-O-、-C≡C-または-CH=CH-で置き換えた基中の任意の水素がハロゲンに置き換えられた基の例として、ClCH2(CH2)3-、CF2=CH-(CH2)3-、CH2F(CH2)2O-、CH2FCH2C≡C-が挙げられる。
これらの式において、R1は式(CHN-1)~(CHN-19)のいずれか1つで表される構造であり、R1aは水素または炭素数1~20のアルキルであり、;環A1、環A2、環A3、環A4、および環A5は独立して、式(RG-1)~(RG-15)で表される構造の一つであり、Y1、Y2、Y3およびY4は独立して水素またはハロゲンであり、fn1、fn2、fn3およびfn4は独立して0、1、2または3であり;Z1、Z2、Z3、Z4、Z5、およびZ6は独立して、単結合、-CH2CH2-、-CH=CH-、-C≡C-、-COO-、-CF2O-、-CH2O-、または-OCH2-であるが少なくとも一つは-CF2O-であり;L1およびL2は独立して、水素、フッ素または塩素であり;X1はフッ素、塩素、-CF3、-CHF2、-CH2F、-OCF3、-OCHF2、-OCH2Fまたは-C=C-CF3である。
本発明に用いられる化合物(1)をさらに詳細に説明する。化合物(1)はピリミジン環および連結基-CF2O-を有する液晶化合物である。この化合物は、素子が通常使用される条件下において物理的および化学的に極めて安定であり、そして他の液晶化合物との相溶性がよい。この化合物を含有する組成物は素子が通常使用される条件下で安定である。したがって組成物において光学的に等方性の液晶相の温度範囲を広げることが可能となり、幅広い温度範囲で表示素子として使用することができる。さらにこの化合物は誘電率異方性と屈折率異方性が大きい為、光学的に等方性の液晶相で駆動される組成物の駆動電圧を下げるための成分として有用である。
化合物(1)の好ましい例は、式(1-1)~(1-8)である。より好ましい例として、式(1-1A)~(1-1C)、(1-2A)~(1-2B)、(1-3A)、(1-4A)~(1-4C)、(1-5A)~(1-5C)、(1-6A)~(1-6C)、(1-7A)を挙げることができる。
次に、化合物(1)の合成について説明する。化合物(1)は有機合成化学における手法を適切に組み合わせることにより合成できる。出発物に目的の末端基、環および結合基を導入する方法は、オーガニックシンセシス(Organic Syntheses, John Wiley & Sons, Inc)、オーガニック・リアクションズ(Organic Reactions, John Wiley & Sons, Inc)、コンプリヘンシブ・オーガニック・シンセシス(Comprehensive Organic Synthesis, Pergamon Press)、新実験化学講座(丸善)などに記載されている。
式(1)で表される化合物を合成する方法は複数あり、市販の試薬から適宜、本明細書実施例や文献、書籍を参考にして合成することが可能である。以下に代表的化合物(一般式(112))の好ましい合成手順を示す。
(上記式において、Aは下記式を表し、
A1、A2、Z1、Z2、l、mは前述と同様の意味を表し、R1、L1、L2、X1、(H or Halo)は前述と同様の意味を表す。)
式(101)で表される化合物を酸性条件下で尿素と反応させ、得られた生成物にオキシ塩化リン等の塩素化試薬を作用させて、式(103)で表される化合物を得ることができる。式(103)のAにおいて、l、mが共に0であり、R1がアルキル基のものは、アルキル鎖長によっては市販されている。Journal of Fluorine Chemistry 112 (2001) 73-81頁、特表2003-525286に記載の方法に準じて、化合物(104)に1,3-プロパンチオールおよびトリフルオロメタンスルフォニック アシドを反応させ、化合物(107)を得ることができる。化合物(107)に化合物(108)とトリエチルアミンの混合物を滴下し、低温でトリエチルアミン 三フッ化水素を反応させ、さらに臭素で処理することで化合物(109)を得ることができる。化合物(109)と化合物(110)をテトラキストリフェニルフォスフィン等の触媒の存在下、反応させて化合物(111)を得ることができる。化合物(103)と化合物(111)をテトラキストリフェニルフォスフィン等の触媒の存在下、反応させて化合物(112)を得ることができる。
本発明の第2の態様は、前記式(1)で表される化合物である成分Aに以下に示す成分B、C、DおよびEから選ばれた成分を加えることにより得られる液晶組成物であり、成分Aのみの組成物に比べて、駆動電圧、液晶相温度範囲、屈折率異方性値、誘電率異方性値および粘度等を自由に調整することができる。
さらに式(11)、(12)および(13)からなる群から選ばれた少なくとも1種の化合物からなる成分Eを混合することによりしきい値電圧、液晶相温度範囲、屈折率異方性値、誘電率異方性値および粘度等を調整することができる。
前記、式(5)で表される化合物すなわち成分Cのうちの好適例として、式(5-1)~(5-62)を挙げることができる。
本発明の液晶組成物は、本発明の式(1)で表される化合物の少なくとも1種類を0.1~99重量%の割合で含有することが、優良な特性を発現せしめるために好ましい。
本発明の第3の態様は、成分Aに以下に示す成分FおよびGから選ばれた成分を加えることにより得られる液晶組成物である。
4-1 光学的に等方性の液晶相を有する組成物の組成
本発明の第4の態様は、式(1)で表される化合物およびキラル剤を含む組成物であり、光学的に等方性の液晶相で駆動される光素子に用いることのできる液晶組成物である。液晶組成物は、光学的等方性の液晶相を発現する組成物である。
液晶組成物の全重量に対して、キラル剤を1~40重量%含むことが好ましく、3~25重量%含むことがさらに好ましく、5~15重量%含むことが最も好ましい。これらの範囲でキラル剤を含有する液晶組成物は、光学的に等方性の液晶相を有するようになりやすく、好ましい。
液晶組成物に含有されるキラル剤は1種でも2種以上でもよい。
光学的に等方性の液晶組成物が含有するキラル剤としては、ねじり力(Helical Twisting Power)が大きい化合物が好ましい。ねじり力が大きい化合物は所望のピッチを得るために必要な添加量が少なくできるので、駆動電圧の上昇を抑えられ、実用上有利である。具体的には、上記式(K1)~(K5)で表される化合物が好ましい。
式(K1)~(K5)中、RKは独立して、水素、ハロゲン、-C≡N、-N=C=O、-N=C=Sまたは炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよく;Aは独立して、芳香族性あるいは非芳香族性の3ないし8員環、または、炭素数9以上の縮合環であり、これらの環の任意の水素がハロゲン、炭素数1~3のアルキルまたはハロアルキルで置き換えられてもよく、これらの環の任意の-CH2-は-O-、-S-または-NH-で置き換えられてもよく、これらの環の任意の-CH=は-N=で置き換えられてもよく;Zは独立して、単結合、炭素数1~8のアルキレンであるが、このアルキレン中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-N=N-、-CH=N-、-N=CH-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、アルキレン中およびアルキレン中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-N=N-、-CH=N-、-N=CH-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよく;Xは単結合、-COO-、-OCO-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2-であり;mKは1~4である。
(式中、RKは独立して、炭素数3~10のアルキルであり、このアルキル中の環に隣接する-CH2-は-O-で置き換えられてもよく、このアルキル中の環に隣接していない任意の-CH2-は、-CH=CH-で置き換えられてもよい。)。
液晶組成物が光学的に等方性を有するとは、巨視的には液晶分子配列は等方的であるため光学的に等方性を示すが、微視的には液晶秩序が存在することをいう。「液晶組成物が微視的に有する液晶秩序に基づくピッチ(以下では、ピッチと呼ぶことがある)」は700nm以下であることが好ましく、500nm以下であることがさらに好ましく、350nm以下であることが最も好ましい。
光学的に等方性の液晶相が二色以上の回折光を示さない状態とは、ブルー相I、ブルー相IIに観測されるプレートレット組織が観測されず、概ね一面単色であることを意味する。二色以上の回折光を示さない光学的に等方性の液晶相では、色の明暗が面内で均一であることまでは不要である。
また、可視光の光を反射する液晶材料では、表示素子として利用する場合に色味が問題となることがあるが、二色以上の回折光を示さない液晶では、反射波長が低波長シフトするため、狭義のブルー相(プレートレット組織を発現する相)より長いピッチで可視光の反射を消失させることができる。
光学的に等方性の液晶相における電気複屈折はピッチが長くなるほど大きくなるので、その他の光学特性(透過率、回折波長など)の要求を満たす限り、キラル剤の種類と含有量を調整して、ピッチを長く設定することにより、電気複屈折を大きくすることができる。
本発明の光学的に等方性の液晶組成物は、その組成物の特性に影響を与えない範囲で、さらに高分子物質等の他の化合物が添加されてもよい。本発明の液晶組成物は、高分子物質の他にも、たとえば二色性色素、フォトクロミック化合物を含有していてもよい。二色性色素の例としては、メロシアニン系、スチリル系、アゾ系、アゾメチン系、アゾキシ系、キノフタロン系、アントラキノン系、テトラジン系などが挙げられる。
本発明の第5の態様は、式(1)で表される化合物およびキラル剤を含む液晶組成物と高分子の複合材料であり、光学的に等方性を示すものである。光学的に等方性の液晶相で駆動される光素子に用いることのできる光学的に等方性の高分子/液晶複合材料である。このような高分子/液晶複合材料は例えば、項[1]~[30]に記載の液晶組成物(液晶組成物CLC)と高分子で構成される。
本発明の、「高分子/液晶複合材料」とは、液晶材料と高分子の化合物の両者を含む複合材料であれば特に限定されないが、高分子の一部または全部が液晶材料に溶解していない状態で高分子が液晶材料と相分離している状態でもよい。なお、本明細書において、特に言及がなければ、ネマチック相はキラルネマチック相を含まない、狭義のネマチック相を意味する。
本発明の複合材料は、光学的に等方性の液晶組成物と、予め重合されて得られた高分子とを混合しても製造できるが、高分子の材料となる低分子量のモノマー、マクロモノマー、オリゴマー等(以下、まとめて「モノマー等」という)と液晶組成物CLCとを混合してから、当該混合物において重合反応を行うことによって、製造されることが好ましい。モノマー等と液晶組成物とを含む混合物を本件明細書では、「重合性モノマー/液晶混合物」と呼ぶ。「重合性モノマー/液晶混合物」には必要に応じて、後述する重合開始剤、硬化剤、触媒、安定剤、二色性色素、またはフォトクロミック化合物等を、本発明の効果を損なわない範囲で含んでもよい。たとえば、本件発明の重合性モノマー/液晶混合物には必要に応じて、重合開始剤を重合性モノマー100重量部に対して0.1~20重量部含有してもよい。
また、好適な複合材料を得るためには、高分子はメソゲン部位を有するものが好ましく、高分子の原料モノマーとしてメソゲン部位を有する原料モノマーをその一部に、あるいは全部に用いることができる。
メソゲン部位を有する単官能性、または二官能性モノマーは構造上特に限定されないが、例えば下記の式(M1)または式(M2)で表される化合物を挙げることができる。
また、式(M3-2)、式(M3-3)、式(M3-4)、式(M3-7)はラジカル重合で重合するのが好適である。式(M3-1)、式(M3-5)、式(M3-6)はカチオン重合で重合するのが好適である。いずれもリビング重合なので、少量のラジカルあるいはカチオン活性種が反応系内に発生すれば重合は開始する。活性種の発生を加速する目的で重合開始剤を使用できる。活性種の発生には例えば光または熱を使用できる。
化合物の安定性を考慮して、酸素と酸素とが隣接した-CH2-O-O-CH2-よりも、酸素と酸素とが隣接しない-CH2-O-CH2-O-の方が好ましい。硫黄においても同様である。
2-フルオロ-1,4-フェニレンは、3-フルオロ-1,4-フェニレンと構造的に同一であるので、後者は例示しなかった。この規則は、2,5-ジフルオロ-1,4-フェニレンと3,6-ジフルオロ-1,4-フェニレンの関係などにも適用される。
メソゲン部位を有さない重合性のある官能基を持つモノマーとして、例えば、炭素数1~30の直鎖あるいは分岐アクリレート、炭素数1~30の直鎖あるいは分岐ジアクリレート、三つ以上の重合性官能基を有するモノマーとしては、グリセロール・プロポキシレート(1PO/OH)トリアクリレート、ペンタエリスリトール・プロポキシレート・トリアクリレート、ペンタエリスリトール・トリアクリレート、トリメチロールプロパン・エトキシレート・トリアクリレート、トリメチロールプロパン・プロポキシレート・トリアクリレート、トリメチロールプロパン・トリアクリレート、ジ(トリメチロールプロパン)テトラアクリレート、ペンタエリスリトール・テトラアクリレート、ジ(ペンタエリスリトール)ペンタアクリレート、ジ(ペンタエリスリトール)ヘキサアクリレート、トリメチロールプロパン・トリアクリレートなどを挙げることができるが、これらに限定されるものではない。
本発明の複合材料を構成する高分子の製造における重合反応は特に限定されず、例えば、光ラジカル重合、熱ラジカル重合、光カチオン重合等が行われる。
本発明の複合材料を構成する高分子の製造において、前記モノマー等および重合開始剤の他にさらに1種または2種以上の他の好適な成分、例えば、硬化剤、触媒、安定剤等を加えてもよい。
本発明の高分子/液晶複合材料中における液晶組成物の含有率は、複合材料が光学的に等方性の液晶相を発現できる範囲であれば、可能な限り高含有率であることが好ましい。液晶組成物の含有率が高い方が、本発明の複合材料の電気複屈折値が大きくなるからである。
本発明の高分子/液晶複合材料は、たとえば二色性色素、フォトクロミック化合物を本発明の効果を損なわない範囲で含有していてもよい。
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれら実施例によっては制限されない。なお特に断りのない限り、「%」は「重量%」を意味する。
本発明の第6の態様は、液晶組成物または高分子/液晶複合材料(以下では、本発明の液晶組成物および高分子/液晶複合材料を総称して液晶媒体と呼ぶことがある)を含む光学的に等方性の液晶相で駆動される光素子である。
電界無印加時には液晶媒体は光学的に等方性であるが、電場を印加すると、液晶媒体は光学的異方性を生じ、電界による光変調が可能となる。
液晶表示素子の構造例としては、図1に示すように、櫛型電極基板の電極が、左側から伸びる電極1と右側から伸びる電極2が交互に配置された構造を挙げることができる。電極1と電極2との間に電位差がある場合、図1に示すような櫛型電極基板上では、上方向と下方向の2つの方向の電界が存在する状態を提供できる。
記録計としては島津製作所製のC-R6A型Chromatopac、またはその同等品を用いた。得られたガスクロマトグラムには、成分化合物に対応するピークの保持時間およびピークの面積値が示されている。
液晶化合物の物性値を測定する試料としては、化合物そのものを試料とする場合、化合物を母液晶と混合して試料とする場合の2種類がある。
物性値の測定は後述する方法で行った。これら測定方法の多くは、日本電子機械工業会規格(Standard of Electric Industries Association of Japan)EIAJ・ED-2521Aに記載された方法、またはこれを修飾した方法である。また、測定に用いたTN素子には、TFTを取り付けなかった。
(1)偏光顕微鏡を備えた融点測定装置のホットプレート(メトラー社FP-52型ホットステージ)に化合物を置き、3℃/分の速度で加熱しながら相状態とその変化を偏光顕微鏡で観察し、液晶相の種類を特定した。
(2)パーキンエルマー社製走査熱量計DSC-7システム、またはDiamond DSCシステムを用いて、3℃/分速度で昇降温し、試料の相変化に伴う吸熱ピーク、または発熱ピークの開始点を外挿により求め(on set)、相転移温度を決定した。
ピッチ長は選択反射を用いて測定した(液晶便覧196頁 2000年発行、丸善)。選択反射波長λには、関係式<n>p/λ=1が成立する。ここで<n>は平均屈折率を表し、次式で与えられる。<n>={(n∥ 2+n⊥ 2)/2}1/2。選択反射波長は顕微分光光度計(日本電子(株)、商品名MSV-350)で測定した。得られた反射波長を平均屈折率で除すことにより、ピッチを求めた。可視光より長波長領域に反射波長を有するコレステリック液晶のピッチは、光学活性化合物濃度が低い領域では光学活性化合物の濃度の逆数に比例することから、可視光領域に選択反射波長を有する液晶のピッチ長を数点測定し、直線外挿法により求めた。「光学活性化合物」は本発明におけるキラル剤に相当する。
反応器へ、(S1-1)4.0gとトルエン/イソオクタン=1/1の混合溶媒20mlを加え、これに1,3-プロパンジチオール(S1-2)を1.43g滴下し、30分間撹拌した。反応液を60℃まで加温し、トリフルオロメタンスルフォニック アシド(S1-3)3.99g滴下し、60℃で1時間、90℃で2時間撹拌した。室温まで冷却し、溶媒を減圧にて留去し、t-ブチルメチルエーテルを加え、ろ過した。得られた固形物を乾燥することにより、化合物(S1-4)4.30gを得た。
窒素雰囲気下の反応器へ、3,4,5-トリフルオロフェノール(S1-5)1.38g、トリエチルアミン1.02g、塩化メチレン20mlを加え、-70℃まで冷却した。(S1-4)4.30gと塩化メチレン20mlの混合物を滴下し、1時間撹拌した。トリエチルアミン 三フッ化水素2.78gを滴下し、30分間撹拌し、さらに臭素6.22gを滴下し1時間撹拌した。徐々に0℃まで加温し、反応液を100mlの水に徐々に加えた。混合物に重曹を少しずつ加え、水相を中性とし、有機相を水洗し、硫酸ナトリウムで乾燥した。減圧にて溶媒を留去し、残分をヘプタンを展開溶媒としてシリカゲルカラムクロマトグラフィーにより精製し、(S1-6)2.10gを得た。このものの(S1-1)からの収率は36.0%であった。
窒素雰囲気下の反応器へ、(S1-6)1.70g、(S1-7)1.07g、酢酸カリウム1.03g、テトラキストリフェニルホスフィンパラジウム0.061g、ジオキサン20mlを加え、80℃で2時間撹拌した。室温まで冷却後、反応液にトルエン50mlを加え、有機相を水洗し、硫酸ナトリウムで乾燥し、溶媒を減圧にて留去した。残分をトルエン/酢酸エチル=10/1を展開溶媒として、シリカゲルカラムクロマトグラフィーにより精製し、減圧にて乾燥して(S1-8)約2gを得た。
窒素雰囲気下の反応器へ、化合物(S1-8)約2g、化合物(S1-9)0.65g、リン酸三カリウム1.60g、テトラキストリフェニルホスフィンパラジウム0.04g、ソルミックス30mlを加え、70℃で2時間撹拌した。室温まで冷却後、反応液にトルエン50mlを加え、有機相を水洗し、硫酸ナトリウムで乾燥し、溶媒を減圧にて留去した。残分をヘプタン/トルエン=1/1を展開溶媒として、シリカゲルカラムクロマトグラフィーにより精製し、減圧にて乾燥し、残分をヘプタン/エタノール=1/1で再結晶して(S1-10)1.02gを得た。このものの(S1-6)からの収率は54.3%であった。
相転移温度(℃) :K 77.1 SmA 116.7 N 140.2 I
前述した母液晶Aとして記載された4つの化合物を混合し、ネマチック相を有する母液晶Aを調製した。この母液晶Aの物性は以下のとおりであった。
上限温度(TNI)=71.7℃;誘電率異方性(Δε)=11.0;屈折率異方性(Δn)=0.137。
上限温度(TNI)=102.4℃;誘電率異方性(Δε)=50.3;屈折率異方性(Δn)=0.197。
これらのことから液晶化合物(S1-10)は、透明点が高く、他の液晶化合物との優れた相溶性を有し、誘電率異方性(Δε)、屈折率異方性(Δn)の大きい化合物であることがわかった。
相転移温度(℃) :K 56.6 I
母液晶A 85重量%と、(S2)の15重量%とからなる液晶組成物Cを調製した。得られた液晶組成物Cの物性値を測定し、測定値を外挿することで液晶化合物(S2)の物性の外挿値を算出した。その値は以下のとおりであった。
上限温度(TNI)=34.4℃;誘電率異方性(Δε)=40.4;屈折率異方性(Δn)=0.137。
これらのことから液晶化合物(S2)は、他の液晶化合物との優れた相溶性を有し、誘電率異方性(Δε)、屈折率異方性(Δn)の大きい化合物であることがわかった。
相転移温度(℃) :K 53.6 I
母液晶A 85重量%と、(S3)の15重量%とからなる液晶組成物Dを調製した。得られた液晶組成物Dの物性値を測定し、測定値を外挿することで液晶化合物(S3)の物性の外挿値を算出した。その値は以下のとおりであった。
上限温度(TNI)=10.4℃;誘電率異方性(Δε)=43.7;屈折率異方性(Δn)=0.124。
これらのことから液晶化合物(S3)は、他の液晶化合物との優れた相溶性を有し、誘電率異方性(Δε)、屈折率異方性(Δn)の大きい化合物であることがわかった。
本発明において、液晶組成物の特性値の測定は下記の方法にしたがって行うことができる。それらの多くは、日本電子機械工業会規格(Standard of Electric Industries Association of Japan)EIAJ・ED-2521Aに記載された方法、またはこれを修飾した方法である。測定に用いたTN素子には、TFTを取り付けなかった。
1)誘電率異方性が正である試料:測定はM. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) に記載された方法に従った。ツイスト角が0°であり、そして2枚のガラス基板の間隔(セルギャップ)が5μmであるTN素子に試料を入れた。TN素子に16ボルトから19.5ボルトの範囲で0.5ボルト毎に段階的に印加した。0.2秒の無印加のあと、ただ1つの矩形波(矩形パルス;0.2秒)と無印加(2秒)の条件で印加を繰り返した。この印加によって発生した過渡電流(transient current)のピーク電流(peak current)とピーク時間(peak time)を測定した。これらの測定値とM. Imaiらの論文の40頁の計算式(8)とから回転粘度の値を得た。この計算で必要な誘電率異方性の値は、この回転粘度の測定で使用した素子にて、下記の誘電率異方性の測定方法で求めた。
1)誘電率異方性が正である組成物:2枚のガラス基板の間隔(ギャップ)が約9μm、ツイスト角が80度の液晶セルに試料を入れた。このセルに20ボルトを印加して、液晶分子の長軸方向における誘電率(ε∥)を測定した。0.5ボルトを印加して、液晶分子の短軸方向における誘電率(ε⊥)を測定した。誘電率異方性の値は、Δε=ε∥-ε⊥、の式から計算した。
可視光より長波長領域に反射波長を有するコレステリック液晶のピッチは、キラル剤濃度が低い領域ではキラル剤の濃度の逆数に比例することから、可視光領域に選択反射波長を有する液晶のピッチ長を数点測定し、直線外挿法により求めた。
下図に示す液晶化合物を、下記の割合で混合することにより液晶組成物NLC-1を調製した。
液晶組成物K
液晶組成物NLC-1(80wt%)と下図に示す液晶化合物(S1-10)(20wt%)を混合することで液晶組成物NLC-2を調製した。
液晶化合物(S1-10)
なお、ISO-60BA2は、イソソルバイドと4-ヘキシルオキシ安息香酸とをジシクロヘキシルカルボジイミド(DCC)、4-ジメチルアミノピリジン存在下でエステル化することによって得た。
ISO-6OBA2
モノマーと液晶組成物の混合物の調製
液晶組成物とモノマーとの混合物として液晶組成物CLC-1を79.4重量%、n-ドデシルアクリレートを10.0重量%、1,4-ジ(4-(6-(アクリロイルオキシ)ヘキシルオキシ)ベンゾイルオキシ)-2-メチルベンゼン(LCA-6)を10.0重量%、光重合開始剤として2,2’-ジメトキシフェニルアセトフェノンを0.6重量%混合した液晶組成物CLC-1Mを調製した。
LCA-6
液晶組成物CLC-1Mを配向処理の施されていない櫛型電極基板と対向ガラス基板(非電極付与)の間に狭持し(セル厚10μm)、得られたセルを63.0℃まで加熱し、等方相とした。この状態で、紫外光(紫外光強度13mWcm-2(365nm))を1分間照射して、重合反応を行った。
実施例2で得られた高分子/液晶複合材料CLC-1Pが狭持されたセルを、図2に示した光学系にセットし、電気光学特性を測定した。光源として偏光顕微鏡(ニコン製 Optiphot-POL)の白色光源を用い、セルへの入射角度がセル面に対して垂直となるようにし、櫛型電極の線方向がPolarizerとAnalyzer偏光板に対してそれぞれ45°となるように前記セルを光学系にセットした。測定温度を透明点(75℃)-40℃=35℃として印加電圧と透過率の関係を調べた。86Vの矩形波を印加すると、透過率が97%となり、透過光強度は飽和した。
Claims (42)
- 式(1)で表される化合物およびキラル剤を含有し、光学的に等方性の液晶相を発現することを特徴とする液晶組成物。
式(1)において、R1は水素または炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-、または-C≡C-で置き換えられた基中の任意の水素はハロゲンまたは炭素数1~3のアルキルで置き換えられてもよく、;環A1、環A2、環A3、環A4、および環A5は独立して、ベンゼン環、ナフタレン環、チオフェン環、ピペリジン環、シクロヘキセン環、ビシクロオクタン環、テトラヒドロナフタレン環またはシクロヘキサン環であり、これらの環の任意の水素がハロゲン、炭素数1~3のアルキル、炭素数1~3のアルコキシまたは炭素数1~3のハロゲン化アルキルで置き換えられてもよく、これらの環の-CH2-は-O-または-S-で置き換えられてもよく、-CH=は-N=で置き換えられてもよく;Z1、Z2、Z3、Z4、Z5、およびZ6は独立して、単結合または炭素数1~4のアルキレンであり、このアルキレン中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、アルキレン中およびアルキレン中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-CH=CH-、-CF=CF-、または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよいが、Z1、Z2、Z3、Z4、Z5、およびZ6のうち少なくとも一つは-CF2O-であり、;L1およびL2は独立して、水素またはハロゲンであり;X1は水素、ハロゲン、-C≡N、-N=C=S、-C≡C-C≡N、-SF5、または炭素数1~10のアルキルであり、このアルキルにおいて任意の-CH2-は、-O-、-S-、-CH=CH-、または-C≡C-により置き換えられてもよく、そしてアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-CH=CH-、-または-C≡C-で置き換えられた基中の任意の水素はハロゲンにより置き換えられてもよく;l、m、n、o、およびpは独立して、0または1であり、l+m+n+o+p≦4である。 - 式(1)において、R1が炭素数1~20のアルキル、炭素数2~21のアルケニル、炭素数2~21のアルキニル、炭素数1~19のアルコキシ、炭素数2~20のアルケニルオキシ、炭素数1~19のアルキルチオ、炭素数1~19のアルケニルチオ、または-(CH2)v-CH=CF2であり、ここでvは0または1~19の整数であり;X1が水素、ハロゲン、-C≡N、-N=C=S、-SF5、-CH2F、-CHF2、-CF3、-(CH2)2-F、-CF2CH2F、-CF2CHF2、-CH2CF3、-CF2CF3、-(CH2)3-F、-(CF2)3-F、-CF2CHFCF3、-CHFCF2CF3、-(CH2)4-F、-(CF2)4-F、-(CH2)5-F、-(CF2)5-F、-OCH2F、-OCHF2、-OCF3、-O-(CH2)2-F、-OCF2CH2F、-OCF2CHF2、-OCH2CF3、-O-(CH2)3-F、-O-(CF2)3-F、-OCF2CHFCF3、-OCHFCF2CF3、-O(CH2)4-F、-O-(CF2)4-F、-O-(CH2)5-F、-O-(CF2)5-F、-CH=CHF、-CH=CF2、-CF=CHF、-CH=CHCH2F、-CH=CHCF3、-(CH2)2-CH=CF2、-CH2CH=CHCF3、または-CH=CHCF2CF3である請求項1に記載の液晶組成物。
- 式(1)において、Z1、Z2、Z3、Z4、Z5、およびZ6が独立して、単結合、-CH2CH2-、-CH=CH-、-C≡C-、-COO-、-CF2O-、-CH2O-、または-OCH2-である請求項1または2に記載の液晶組成物。
- 式(1-1)~(1-8)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物を含有する請求項1に記載の液晶組成物。
これらの式において、R1は式(CHN-1)~(CHN-19)のいずれか1つで表される基であり、R1aは水素または炭素数1~20のアルキルであり、;環A1、環A2、環A3、環A4、および環A5は独立して、式(RG-1)、(RG-5)、(RG-7)、(RG-8-1)~(RG-8-5)、(RG-9)、(RG-10)、(RG-11-1)、(RG-13)または(RG-15)で表される基であり、;Z1、Z2、Z3、Z4、Z5、およびZ6は独立して、単結合、-CH2CH2-、-CH=CH-、-C≡C-、-COO-、-CF2O-、-CH2O-、または-OCH2-であり;L1およびL2は独立して、水素、フッ素または塩素であり;X1はフッ素、塩素、-C≡N、-CF3、-CHF2、-CH2F、-OCF3、-OCHF2、-OCH2Fまたは-C=C-CF3である。
- 式(1-1)~(1-8)において、Z3が単結合である請求項6に記載の液晶組成物。
- 式(1-1)~(1-8)において、Z1、Z2、Z3、Z4、Z5、およびZ6のうち少なくとも1個が-CF2O-であり、他は単結合である請求項7に記載の液晶組成物。
- 式(2)、(3)および(4)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において、R2は炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X2はフッ素、塩素、-OCF3、-OCHF2、-CF3、-CHF2、-CH2F、-OCF2CHF2、または-OCF2CHFCF3であり;環B1、環B2、および環B3は独立して、1,4-シクロヘキシレン、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、ナフタレン-2,6-ジイル、任意の水素がフッ素で置き換えられた1,4-フェニレン、または任意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-ジイルであり;Z7およびZ8は独立して、-(CH2)2-、-(CH2)4-、-COO-、-CF2O-、-OCF2-、-CH=CH-、-C≡C-、-CH2O-、または単結合であり、ただし環B1~B3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z7およびZ8はそれぞれ-CF2O-ではなく;L5およびL6は独立して、水素またはフッ素である。 - 式(5)で表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において、R3は炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X3は-C≡Nまたは-C≡C-C≡Nであり;環C1、環C2および環C3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、任意の水素がフッ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、任意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、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z9は-(CH2)2-、-COO-、-CF2O-、-OCF2-、-C≡C-、-CH2O-、または単結合であり、ただし環C1~C3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z9は-CF2O-ではなく;L7およびL8は独立して、水素またはフッ素であり;rは1または2であり、sは0または1であり、r+s=0、1または2である。 - 式(6)、(7)、(8)、(9)および(10)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において中、R4およびR5は独立して、炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、アルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;環D1、環D2、環D3、および環D4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、1,4-フェニレン、任意の水素がフッ素で置き換えられた1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、またはデカヒドロナフタレン-2,6-ジイルであり;Z10、Z11、Z12、およびZ13は独立して、-(CH2)2-、-COO-、-CH2O-、-OCF2-、-OCF2(CH2)2-、または単結合であり;L9およびL10は独立して、フッ素または塩素であり;t、u、x、y、およびzは独立して0または1であり、u+x+y+zは1または2である。 - 式(11)、(12)および(13)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において、R6およびR7は独立して、炭素数1~10のアルキルまたは炭素数2~10のアルケニルであり、このアルキルおよびアルケニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、またはアルキルおよびアルケニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;環E1、環E2、および環E3は独立して、1,4-シクロヘキシレン、ピリミジン-2,5-ジイル、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-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;Z14およびZ15は独立して、-C≡C-、-COO-、-(CH2)2-、-CH=CH-、または単結合であり、ただし環E1~E3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z14およびZ15はそれぞれ-CF2O-ではない。 - 請求項11に記載の式(5)で表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項10に記載の液晶組成物。
- 請求項13に記載の式(11)、(12)および(13)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項10に記載の液晶組成物。
- 請求項13に記載の式(11)、(12)および(13)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項11に記載の液晶組成物。
- 請求項13に記載の式(11)、(12)および(13)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項12に記載の液晶組成物。
- 式(15)、(16)、(17)および(18)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において、R8は炭素数1~10のアルキル、炭素数2~10のアルケニルまたは炭素数2~10のアルキニルであり、アルキル、アルケニルおよびアルキニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、アルキニル中またはアルキル、アルケニルおよびアルキニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X4はフッ素、塩素、-SF5、-OCF3、-OCHF2、-CF3、-CHF2、-CH2F、-OCF2CHF2、または-OCF2CHFCF3であり;環F1、環F2、環F3および環F4は独立して、1,4-シクロヘキシレン、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、1,4-フェニレン、ナフタレン-2,6-ジイル、任意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、または任意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-ジイルであり;Z16、Z17およびZ18は独立して、-(CH2)2-、-(CH2)4-、-COO-、-CF2O-、-OCF2-、-CH=CH-、-C≡C-、-CH2O-、または単結合であり、ただし環F1~F4の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z16、Z17およびZ18はそれぞれ-CF2O-ではなく;L9およびL10は独立して、水素またはフッ素である。 - 式(19)で表される化合物の群から選択される少なくとも1つの化合物をさらに含有する、請求項1~9のいずれか1項に記載の液晶組成物。
これらの式において、R9は炭素数1~10のアルキル、炭素数2~10のアルケニルまたは炭素数2~10のアルキニルであり、アルキル、アルケニルおよびアルキニルにおいて任意の-CH2-は-O-で置き換えられてもよく、アルキル中、アルケニル中、アルキニル中またはアルキル、アルケニルおよびアルキニルにおいて任意の-CH2-が-O-で置き換えられた基中において任意の水素はフッ素で置き換えられてもよく;X5は-C≡N、-N=C=S、または-C≡C-C≡Nであり;環G1、環G2および環G3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、任意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、任意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、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z19は-(CH2)2-、-COO-、-CF2O-、-OCF2-、-C≡C-、-CH2O-、または単結合であり、ただし環G1~G3の少なくとも一つがピリミジン-2,5-ジイルである場合は、Z19は-CF2O-ではなく;L11およびL12は独立して、水素またはフッ素であり;aaは0、1または2であり、abは0または1であり、aa+abは0、1または2である。 - 少なくとも1つの酸化防止剤および/または紫外線吸収剤を含む請求項1~19のいずれか1項に記載の液晶組成物。
- 光学的に等方性の液晶相が二色以上の回折光を示さない、請求項1~20のいずれか1項に記載の液晶組成物。
- 光学的に等方性の液晶相が二色以上の回折光を示す、請求項1~20のいずれか1項に記載の液晶組成物。
- 液晶組成物が、キラルネマチック相と非液晶等方相とが共存する上限温度と下限温度との差が3~150℃である組成物にキラル剤を添加して得られるものである、請求項21または22に記載の液晶組成物。
- 液晶組成物が、キラルネマチック相と非液晶等方相とが共存する上限温度と下限温度との差が5~150℃である組成物にキラル剤を添加して得られるものである、請求項21または22に記載の液晶組成物。
- 液晶組成物が、ネマチック相と非液晶等方相とが共存する上限温度と下限温度との差が3~150℃である組成物にキラル剤を添加して得られるものである、請求項21または22に記載の液晶組成物。
- 液晶組成物の全重量に対して、キラル剤の割合が1~40重量%である、請求項1~25のいずれか1項に記載の液晶組成物。
- 液晶組成物の全重量に対して、キラル剤の割合が5~15重量%である、請求項1~25のいずれか1項に記載の液晶組成物。
- 70~-20℃のいずれかの温度においてカイラルネマチック相を示し、この温度範囲の少なくとも一部において螺旋ピッチが700nm以下である、請求項26または27に記載の液晶組成物。
- キラル剤が、式(K1)~(K5)のそれぞれで表される化合物の群から選択される少なくとも1つの化合物を含む、請求項26~28のいずれか1項に記載の液晶組成物。
(式(K1)~(K5)中、RKは独立して、水素、ハロゲン、-C≡N、-N=C=O、-N=C=Sまたは炭素数1~20のアルキルであり、このアルキル中の任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、このアルキル中およびアルキル中の任意の-CH2-が、-O-、-S-、-COO-、-OCO-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられた基中の任意の水素はハロゲンで置き換えられてもよく;Aは独立して、芳香族性あるいは非芳香族性の3ないし8員環、または、炭素数9以上の縮合環であり、これらの環の任意の水素がハロゲン、炭素数1~3のアルキルまたはハロアルキルで置き換えられてもよく、環の-CH2-は-O-、-S-または-NH-で置き換えられてもよく、-CH=は-N=で置き換えられてもよく;Zは独立して、単結合、炭素数1~8のアルキレンであるが、任意の-CH2-は、-O-、-S-、-COO-、-OCO-、-CSO-、-OCS-、-N=N-、-CH=N-、-N=CH-、-CH=CH-、-CF=CF-または-C≡C-で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく;
Xは独立して、単結合、-COO-、-OCO-、-CH2O-、-OCH2-、-CF2O-、-OCF2-または-CH2CH2-であり;
mKは独立して、1~4の整数である。) - 請求項1~30のいずれかに記載の液晶組成物と、重合性モノマーとを含む混合物。
- 重合性モノマーが光重合性モノマーまたは熱重合性モノマーである、請求項31に記載の混合物。
- 請求項31または32に記載の混合物を重合して得られる、光学的に等方性の液晶相で駆動される素子に用いられる高分子/液晶複合材料。
- 請求項31または32に記載の混合物を非液晶等方相または光学的に等方性の液晶相で重合させて得られる、請求項33に記載の高分子/液晶複合材料。
- 高分子/液晶複合材料に含まれる高分子がメソゲン部位を有する、請求項33に記載の高分子/液晶複合材料。
- 高分子/液晶複合材料に含まれる高分子が架橋構造を有する、請求項33~35のいずれかに記載の高分子/液晶複合材料。
- 液晶組成物の割合が60~99重量%であり、高分子の割合が1~40重量%である、請求項33~36のいずれか1項に記載の高分子/液晶複合材料。
- 一方または両方の面に電極が配置され、基板間に配置された液晶媒体、および電極を介して液晶媒体に電界を印加する電界印加手段を備えた光素子であって、液晶媒体が、請求項26~30のいずれか1項に記載の液晶組成物または請求項33~37のいずれか1項に記載の高分子/液晶複合材料である光素子。
- 一方または両方の面に電極が配置され、少なくとも一方が透明な一組の基板、基板間に配置された液晶媒体、および基板の外側に配置された偏光板を有し、電極を介して液晶媒体に電界を印加する電界印加手段を備えた光素子であって、液晶媒体が、請求項26~30のいずれか1項に記載の液晶組成物または高分子/液晶複合材料が請求項33~37のいずれか1項に記載の高分子/液晶複合材料である光素子。
- 一組の基板の少なくとも一方の基板上において、少なくとも2方向に電界を印加できるように電極が構成されている請求項39に記載の光素子。
- 互いに平行に配置された一組の基板の一方または両方に、少なくとも2方向に電界を印加できるように電極が構成されている請求項39に記載の光素子。
- 電極がマトリックス状に配置されて、画素電極を構成し、各画素がアクティブ素子を備え、このアクティブ素子が薄膜トランジスター(TFT)である請求項38~41のいずれか1項に記載の光素子。
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Also Published As
Publication number | Publication date |
---|---|
EP2302015B1 (en) | 2016-10-05 |
CN102007197B (zh) | 2014-09-24 |
EP2302015A4 (en) | 2013-06-26 |
KR20110008039A (ko) | 2011-01-25 |
TWI470065B (zh) | 2015-01-21 |
KR101577685B1 (ko) | 2015-12-15 |
EP2302015A1 (en) | 2011-03-30 |
JPWO2009139330A1 (ja) | 2011-09-22 |
TW201000611A (en) | 2010-01-01 |
US8475887B2 (en) | 2013-07-02 |
CN102007197A (zh) | 2011-04-06 |
US20110069245A1 (en) | 2011-03-24 |
JP5408130B2 (ja) | 2014-02-05 |
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