WO2013054682A1 - 重合性化合物、液晶組成物および液晶表示素子 - Google Patents
重合性化合物、液晶組成物および液晶表示素子 Download PDFInfo
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- WO2013054682A1 WO2013054682A1 PCT/JP2012/075382 JP2012075382W WO2013054682A1 WO 2013054682 A1 WO2013054682 A1 WO 2013054682A1 JP 2012075382 W JP2012075382 W JP 2012075382W WO 2013054682 A1 WO2013054682 A1 WO 2013054682A1
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- FAMZBHRUORBZHJ-OSICMAOHSA-N C/C=C/C(O)Oc(cc(/C=C/C(c(cc1)ccc1OC(C(C)=C)=O)=O)cc1)c1OC(C=C)=O Chemical compound C/C=C/C(O)Oc(cc(/C=C/C(c(cc1)ccc1OC(C(C)=C)=O)=O)cc1)c1OC(C=C)=O FAMZBHRUORBZHJ-OSICMAOHSA-N 0.000 description 1
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- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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Definitions
- the present invention relates to a polymerizable compound that is polymerized by, for example, light or heat, and a liquid crystal composition containing the polymerizable compound. Further, the present invention relates to a liquid crystal display element in which the liquid crystal composition is sealed between substrates and a polymerizable compound contained in the liquid crystal composition is polymerized while adjusting a voltage applied to the liquid crystal layer to fix the alignment of the liquid crystal.
- the technical field of the present invention mainly relates to a liquid crystal composition suitable for an AM (active matrix) device and the like, and an AM device containing the composition.
- the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and to an element in an IPS (in-plane switching) mode, a VA (vertical alignment) mode, or a PSA (polymer sustained alignment) mode containing the composition.
- the VA mode includes an MVA (multi-domain vertical alignment) mode, a PVA (patterned vertical alignment) mode, and the like.
- the optical anisotropy of the composition is related to the contrast ratio of the device.
- the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
- the appropriate product value depends on the type of operation mode.
- the range is about 0.30 ⁇ m to about 0.40 ⁇ m for the VA mode or PSA mode device, and the range is about 0.20 ⁇ m to about 0.30 ⁇ m for the IPS mode device. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap.
- a small amount (about 0.3 wt% to about 1 wt%) of a polymerizable compound (RM) is added to the liquid crystal composition, and after being introduced into the liquid crystal display cell, a voltage is applied between the electrodes.
- a polymerizable compound is polymerized under UV irradiation to form a polymer structure in the device.
- RM it is known that a polymerizable mesogenic or liquid crystal compound is particularly suitable as a liquid crystal composition additive monomer.
- the above-described PSA mode has an advantage that the response time is shorter than the TN mode, the IPS mode, and the like.
- Another object of the present invention is to provide a novel RM with a short response time, a liquid crystal composition containing them, and a liquid crystal display device containing such a composition.
- bifunctional (meth) acrylic acid ester is used as RM because the polymer is excellent in stability to ultraviolet rays and heat.
- a liquid crystal composition to be further improved to an RM in which a polymer has excellent stability to ultraviolet rays and heat.
- Another object of the present invention is that, as a monomer for addition of a liquid crystal composition of a tri- or higher functional (meth) acrylic acid ester, which is generally known that the polymer is very excellent in stability to ultraviolet rays and heat. Is an application.
- Other objectives are: high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance It is a liquid crystal composition satisfying at least one characteristic in characteristics such as high stability.
- Another object is a liquid crystal composition having an appropriate balance regarding at least two properties.
- Another object is a liquid crystal display device containing such a composition.
- the advantage of the present invention is high stability against ultraviolet rays or heat for a polymer of a polymerizable mesogenic or liquid crystalline compound.
- Other advantages of the present invention are a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, and a high stability to ultraviolet rays.
- the liquid crystal composition satisfies at least one characteristic in characteristics such as high stability to heat.
- One aspect of the present invention is a liquid crystal composition having an appropriate balance regarding at least two properties. Another aspect is a liquid crystal display device containing such a composition.
- liquid crystal composition of the present invention or the liquid crystal display device of the present invention may be abbreviated as “composition” or “device”, respectively.
- a liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module.
- Liquid crystal compound means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase but useful as a component of a composition. This useful compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. Optically active compounds and polymerizable compounds may be added to the composition.
- the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
- the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.
- “High specific resistance” means that the composition has a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large specific resistance even at a close temperature.
- “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to.
- the first component is one compound or two or more compounds.
- the “ratio of the first component” is expressed as a weight ratio (parts by weight) of the first component when the weight of the liquid crystal composition excluding the first component is 100.
- the “ratio of the second component” is expressed as a weight percentage (% by weight) of the second component based on the weight of the liquid crystal composition excluding the first component.
- the “ratio of the third component” is the same as the “ratio of the second component”.
- the ratio of the additive mixed with the composition is expressed in terms of weight percentage (% by weight) or weight parts per million (ppm) based on the total weight of the liquid crystal composition.
- R 6 is used for a plurality of compounds. In any two of these compounds, those selected for R 6 may be the same or different.
- R 6 of the compound (2-1) is ethyl
- R 6 is ethyl compound (2-2).
- R 6 of compound (2-1) is ethyl
- R 6 of compound (2-2) is propyl. This rule also applies to R 8 , Y 1 and the like.
- the present invention includes the following items. 1.
- the compound represented by Formula (1) is independently an aromatic ring group in which at least one hydrogen may be replaced with L, or a heteroaromatic ring group in which at least one hydrogen may be replaced with L.
- a 2 is independently an aromatic ring group in which at least one hydrogen may be replaced with L, or a heteroaromatic ring group in which at least one hydrogen may be replaced with L, or a single bond;
- R 1 and R 2 are independently Hydrogen, halogen, alkyl having 1 to 10 carbons, or alkyl having 1 to 10 carbons in which at least one hydrogen is replaced by fluorine;
- R 3 is a group selected from the group of groups represented by formula
- Item 2 The compound according to Item 1, wherein in formula (1), P 1 and P 2 are groups selected from the group of groups represented by formula (P-1); and Sp 1 and Sp 2 are single bonds.
- R 4 and R 5 are independently hydrogen, halogen, or alkyl having 1 to 4 carbons;
- X 2 is independently halogen or alkyl having 1 to 3 carbons;
- L 1 and L 2 is independently halogen or alkyl having 1 to 3 carbons;
- Y 4 and Y 7 are independently hydrogen, —CH 3 , —C 2 H 5 , halogen, —CF 3 , or — C ⁇ N;
- Y 5 , Y 6 , Y 8 , and Y 9 are independently hydrogen, —CH 3 , —C 2 H 5 , or halogen;
- m 4 and m 5 are from 0 to 5 An integer, the sum of m 4 and m 5 is 3 to 10;
- m 6 and m 7 are integers from 0 to 5;
- n 2 is an integer from 1 to 4;
- r is from 0 to 3 It is an integer.
- a liquid crystal composition containing at least one compound selected from the group of compounds according to any one of items 1 to 4 as a first component.
- Item 7 The liquid crystal composition according to item 6, wherein the proportion of the first component is in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the liquid crystal composition excluding the first component.
- Item 8 The liquid crystal composition according to item 6 or 7, further comprising at least one compound selected from the group of compounds represented by formula (2) as the second component.
- R 6 and R 7 are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or a carbon number in which at least one hydrogen is replaced by fluorine.
- ring B and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, Or tetrahydropyran-2,5-diyl;
- ring C is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5- methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,;
- Z 3 Oyo Z 4 is independently a single bond, ethylene, methyleneoxy or carbonyloxy,; s is 1, 2 or 3,; t is 0 or 1, and, the sum of s and t 3 or less.
- the second component is at least one compound selected from the group of compounds represented by formula (2-1) according to Item 9, and at least selected from the group of compounds represented by formula (2-6) Item 9.
- the second component is at least one compound selected from the group of compounds represented by formula (2-1) according to Item 9, and at least selected from the group of compounds represented by formula (2-13) Item 9.
- the second component is at least one compound selected from the group of compounds represented by formula (2-4) according to Item 9, and at least selected from the group of compounds represented by formula (2-8) Item 9.
- Item 15 The liquid crystal composition according to any one of items 6 to 14, further containing at least one compound selected from the group of compounds represented by formula (3) as a third component.
- R 8 and R 9 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number in which at least one hydrogen is replaced by fluorine.
- Item 16 The liquid crystal composition according to item 15, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13).
- R 8 and R 9 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number in which at least one hydrogen is replaced by fluorine. 2 to 12 alkenyl.
- the third component is at least one compound selected from the group of compounds represented by formula (3-1) according to item 16, and at least selected from the group of compounds represented by formula (3-5) Item 16.
- the third component is at least one compound selected from the group of compounds represented by formula (3-1) according to item 16, and at least selected from the group of compounds represented by formula (3-7) Item 16.
- the third component is at least one compound selected from the group of compounds represented by formula (3-1) according to item 16, at least one selected from the group of compounds represented by formula (3-5) Item 16.
- Item 21 The liquid crystal composition according to any one of items 15 to 20, wherein the ratio of the third component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition excluding the first component.
- Item 22 The liquid crystal composition according to any one of items 6 to 21, further comprising a polymerization initiator.
- Item 23 The liquid crystal composition according to any one of items 6 to 22, further containing a polymerization inhibitor.
- the upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (25 ° C.) at a wavelength of 589 nm is 0.08 or higher, and the dielectric anisotropy (25 ° C.) at a frequency of 1 kHz is ⁇ 2 or lower.
- Item 24. The liquid crystal composition according to any one of items 6 to 23.
- a liquid crystal display element comprising two substrates each having an electrode layer on at least one substrate, wherein the liquid crystal composition according to any one of items 6 to 24 is disposed between the two substrates.
- Item 26 The liquid crystal display device according to item 25, wherein the operation mode of the liquid crystal display device is a TN mode, a VA mode, an IPS mode, or a PSA mode, and a driving method of the liquid crystal display device is an active matrix method.
- Item 25 Use of the liquid crystal composition according to any one of items 6 to 24 in a liquid crystal display device.
- composition of the present invention will be described in the following order. First, the constitution of component compounds in the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, specific examples of component compounds are shown. Sixth, additives that may be mixed into the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.
- the composition of the component compounds in the composition will be described.
- the composition of the present invention is classified into Composition A and Composition B.
- the composition A may further contain other liquid crystal compounds, additives, impurities and the like in addition to the liquid crystal compound selected from the compound (1), the compound (2), and the compound (3).
- the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
- a smaller amount of cyano compound is preferable from the viewpoint of stability to heat or ultraviolet light.
- a more desirable ratio of the cyano compound is 0% by weight.
- preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.
- Ring B and Ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5- It is a diyl. Any one ring B when s is 2 or 3 may be the same or different. Tetrahydropyran-2,5-diyl is Tetrahydropyran-2,5-diyl is asymmetric on the left and right. However, it is defined that these rings can be positioned not only in the defined direction, but also in the opposite direction as described above. This definition also applies to other rings in which only one of the left and right asymmetric rings is defined.
- Ring C is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, Any two rings B when 5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl, and s is 2 or 3, May be different.
- Preferred ring B or ring D is 1,4-cyclohexylene for decreasing the viscosity.
- Preferred ring C is 2,3-difluoro-1,4-phenylene for decreasing the viscosity and increasing the absolute value of the dielectric anisotropy.
- Desirable Z 1 or Z 2 is —CO—CR 1 ⁇ CR 2 —, —CR 1 ⁇ CR 2 —CO—, in order to increase the polymerization reactivity of the polymerizable compound and to obtain characteristics that shorten the response time of the device.
- Z 1 and Z 2 are a type of linking group that connects a conjugated system of conjugated rings.
- the configuration of the double bond in Z 1 and Z 2 of compound (1) is a cis isomer, a trans isomer, or a mixture of a cis isomer and a trans isomer. The same applies to the steric configuration of the double bond of the linking group in the compound (1-1), compound (1-2), compound (1-3), compound (1-4) and the like.
- Z 3 , Z 4 , and Z 5 are independently a single bond, ethylene, methyleneoxy, or carbonyloxy, and any two Z 3 when s is 2 or 3 are the same, Any two Z 5 when u is 2 or 3 may be the same or different.
- Desirable Z 3 or Z 4 is a single bond for decreasing the viscosity, and methyleneoxy for increasing the absolute value of the dielectric anisotropy.
- Desirable Z 5 is a single bond for decreasing the viscosity.
- L is independently halogen, —CF 3 , —C ⁇ N, or alkyl having 1 to 6 carbons.
- L 1 and L 2 are independently halogen or alkyl having 1 to 3 carbon atoms.
- Preferred L, L 1 or L 2 is fluorine or alkyl having 1 to 3 carbons.
- Specific examples of L alkyl include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, s-butyl, t-butyl, pentyl and hexyl, and alicyclic rings such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. And a hydrocarbon group.
- X 1 is independently halogen, alkyl having 1 to 6 carbons, or fluoroalkyl.
- X 2 is independently halogen or alkyl having 1 to 3 carbons. Desirable X 1 and X 2 are fluorine or alkyl having 1 to 3 carbon atoms.
- Y 1 , Y 4 , and Y 7 are independently hydrogen, —CH 3 , —C 2 H 5 , halogen, —CF 3 or —C ⁇ N, and Y 2 , Y 3 , Y 5 , Y 6 , Y 8 , and Y 9 are each independently hydrogen, —CH 3 , —C 2 H 5 , or halogen.
- Preferred Y 1 , Y 4 , or Y 7 is hydrogen or —CH 3
- preferred Y 2 , Y 3 , Y 5 , Y 6 , Y 8 , or Y 9 is hydrogen.
- P 1 and P 2 are polymerizable functional groups, and are independently groups selected from the group of groups represented by formula (P-1) to formula (P-11).
- Preferred P 1 or P 2 is acryloyl or methacryloyl for increasing photoreactivity. Any two P 1 when m 1 is 2 or more may be the same or different, and any two P 2 when m 3 is 2 or more are the same or different Good.
- the wavy line from formula (P-1) to formula (P-10) indicates a site to be bonded as a group.
- Sp 1 and Sp 2 are spacer groups, independently a single bond or alkylene having 1 to 6 carbons, provided that they may be replaced by halogen or —C ⁇ N and are not adjacent to each other —CH 2 — represents —O—, —S—, —NH—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CH ⁇ CH—, or — C ⁇ C— may be substituted. Any two Sp 1 when m 1 is 2 or more may be the same or different, and any two Sp 2 when m 3 is 2 or more are the same or different. Good.
- the spacer group is already well known to those skilled in the art and is described in documents such as Tschierske, C. et al, Angew. Chem, Vol. 116, 6340, 2004.
- Preferred Sp 1 or Sp 2 is a single bond for increasing the photoreactivity.
- n 1 and m 3 are integers from 0 to 5, and the sum of m 1 and m 3 is an integer from 1 to 10.
- m 4 and m 5 are integers from 0 to 5, and the sum of m 4 and m 5 is an integer from 3 to 10. Desirable m 1 , m 3 , m 4 or m 5 is an integer of 1 to 3 for increasing photoreactivity, and the preferred sum of m 1 and m 3 or m 4 and m 5 is 3 or 4 to increase reactivity.
- n 2 is an integer from 0 to 4. Desirable m 2 is 0 for increasing the photoreactivity. m 6 and m 7 are integers from 0 to 5. Desirable m 6 or m 7 is an integer of 0 to 2 for increasing photoreactivity. More desirable m 6 or m 7 is 0.
- n 1 is an integer from 1 to 8.
- n 2 is an integer of 1 to 4. Desirable n 1 or n 2 is 1 or 2 for increasing the photoreactivity.
- p is an integer of 0 to 4.
- r is an integer from 0 to 3.
- Preferred p or r is an integer of 0 to 2 for increasing the photoreactivity. Further preferred p or r is 0.
- s is 1, 2, or 3, t is 0 or 1, and the sum of s and t is 3 or less. Desirable s is 1 for decreasing the minimum temperature. Preferred t is 0 for decreasing the viscosity. u is 1, 2 or 3. Preferred u is 1 for decreasing the viscosity, and 3 for increasing the maximum temperature.
- Compound (1) can form a homopolymer or a copolymer by homopolymerization or copolymerization with other polymerizable compounds.
- Preferred compound (1) is compound (1-1-1-1), compound (1-1-2-1), compound (1-2-1-1), compound (1-2-2-1).
- More desirable compound (1) is the compound (1-1-1-1) and the compound (1-1-2-1).
- Desirable compounds (2) are from the compound (2-1-1) to the compound (2-19-1). More desirable compounds (2) are the compound (2-1-1), the compound (2-2-1), the compound (2-4-1), the compound (2-6-1), the compound (2-8- 1), compound (2-11-1), and compound (2-13-1).
- Particularly preferred compounds (2) are the compound (2-1-1), the compound (2-4-1), the compound (2-6-1), the compound (2-8-1), and the compound (2-13).
- Desirable compounds (3) are from the compound (3-1-1) to the compound (3-13-1). More desirable compounds (3) are the compound (3-1-1), the compound (3-3-1), the compound (3-5-1), the compound (3-7-1), and the compound (3-9). -1).
- Particularly preferred compounds (3) are the compound (3-1-1), the compound (3-5-1),
- additives that may be mixed with the composition will be described.
- Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.
- An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such a compound are the compound (4-1) to the compound (4-4).
- a desirable ratio of the optically active compound is approximately 5% by weight or less.
- a more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.
- oxidation prevention An agent is mixed into the composition.
- a more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
- the polymerizable compound is preferably polymerized by UV irradiation or the like in the presence of a suitable initiator such as a photopolymerization initiator.
- a suitable initiator such as a photopolymerization initiator.
- Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
- Irgacure 651 registered trademark; BASF
- Irgacure 184 registered trademark; BASF
- Darocur 1173 registered trademark; BASF
- a preferred proportion of the photopolymerization initiator is in the range of about 0.1% to about 5% by weight of the polymerizable compound, and more preferably in the range of about 1% to about 3% by weight.
- the compound (1-1) of the present invention can be synthesized by the following known organic synthesis method.
- R 4 , R 5 , L 1 , L 2 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , m 4 , m 5 , m 6 and m 7 are as defined above. This is the same definition as described in 3.
- Miyashita et al. Miyashita, M. et al, J. Org. Chem., Vol.
- the compound (e) After obtaining the compound (e) from the compound (b) and the compound (d) by the aldol condensation reaction, the compound (e) is removed by the method of Brenady et al. (Brenady, KF et al, J. Org. Chem., Vol. 44, 1438, 1979). Protect to give compound (f). Next, in the presence of 4-dimethylaminopyridine (DMAP) and 1,3-dicyclohexylcarbodiimide (DCC) according to the method of Olsen et al. (Olsen, RK et al, J. Org. Chem., Vol. 60, 6025, 1995). The compound (1-1) can be obtained by dehydration condensation of the compound (g) or / and the compound (h) with the compound (f).
- DMAP 4-dimethylaminopyridine
- DCC 1,3-dicyclohexylcarbodiimide
- the compound (1-2) can be synthesized by the following known organic synthesis method.
- L 1 , L 2 , X 2 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , r, m 4 , m 5 , m 6 , m 7 and n 2 are the above This is the same definition as described in item 3.
- Compound (k) is obtained by Friedel-Crafts reaction of compound (i) and compound (j) by the method of Leiserson et al. (Leiserson, JL et al, Org. Synth. III, 183, 1955).
- compound (1-3) can be synthesized by changing compound (l) in the synthesis method of compound (1-2) to compound (o).
- R 4 , R 5 , L 1 , L 2 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , m 4 , m 5 , m 6 and m 7 are the above-mentioned items 3 This is the same definition as described above.
- the compound (1-4) can be synthesized by the known organic synthesis method as follows.
- R 4 , R 5 , L 1 , L 2 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , m 4 , m 5 , m 6 and m 7 are the same as the item 3 above. This is the same definition as described above.
- compositions have a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
- a device containing this composition has a large voltage holding ratio.
- This composition is suitable for an AM device.
- This composition is particularly suitable for a transmissive AM device.
- a composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds.
- This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.
- This composition can be used for an AM device. Further, it can be used for PM elements.
- This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, VA, and PSA.
- Use for an AM device having a PSA mode is particularly preferable.
- These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device.
- NCAP non-curvilinear-aligned-phase
- PD polymer-dispersed
- the liquid crystal display element of the present invention comprises two substrates having an electrode layer on at least one substrate, and a liquid crystal containing the liquid crystal composition of the present invention or a compound obtained by polymerizing the compound of the present invention between the two substrates. It is characterized by arranging the composition.
- the glass substrate includes two glass substrates called an array substrate and a color filter substrate, and a thin film transistor (TFT), a pixel, a colored layer, and the like are formed on each glass substrate.
- TFT thin film transistor
- aluminosilicate glass or aluminoborosilicate glass is used for the glass substrate.
- As the electrode layer indium-tin oxide (Indium-Tin Oxide) or indium-zinc oxide (Indium-Zinc Oxide) is generally used.
- the compound obtained by the synthesis was identified by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR), high performance liquid chromatography (HPLC), ultraviolet / visible spectroscopy (UV / Vis) and the like.
- the melting point of the compound was determined by differential scanning calorimetry (DSC). First, each analysis method will be described.
- the sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 ⁇ L of the obtained solution was introduced into the sample chamber.
- a recorder a C-R7Aplus manufactured by Shimadzu Corporation was used.
- the obtained chromatogram shows the peak retention time and peak area values corresponding to the component compounds.
- UV / Vis analysis PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used as a measuring apparatus. The detection wavelength was 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and the sample was placed in a quartz cell (optical path length 1 cm) and measured.
- Step 5 Synthesis of Compound (1-1-1-1) Under a nitrogen atmosphere, (T-4) (2.85 g), methacrylic acid (3.39 g), 4-dimethylaminopyridine (DMAP) (0. 40 g) and dichloromethane (120 mL), a solution of 1,3-dicyclohexylcarbodiimide (DCC) (8.12 g) in dichloromethane (30 mL) was added dropwise under ice cooling, and the mixture was stirred for 15 hours. After filtering the precipitate in the reaction solution, the organic layer was washed with water and dried over anhydrous magnesium sulfate.
- DMAP 4-dimethylaminopyridine
- dichloromethane 120 mL
- DCC 1,3-dicyclohexylcarbodiimide
- Example 3 According to the methods of Example 1 and Example 2, compound (1-1-1-1) to compound (1-1-1-12), compound (1-1-2-1) to compound (1-1-1- 2-12), compound (1-1-3-1), compound (1-1-4-1), and compound (1-1-4-2) are produced. The compound (1-1-1-1) shown in Example 1 and the compound (1-1-2-1) shown in Example 2 are also shown again.
- the composition and this compound are used as the measurement object.
- the object to be measured was a composition
- the measurement object was a compound
- a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight).
- the ratio of the 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 in this order. changed.
- the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.
- Measured characteristic values according to the following method. Many of them are the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA ED-2521B) or a modified method thereof. is there.
- the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and the element was sealed with an adhesive that was cured with ultraviolet rays.
- Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of the liquid crystal molecules was measured.
- 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 ⁇ m and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of the liquid crystal molecules was measured.
- Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
- the light source is a halogen lamp.
- a sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed.
- the voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V.
- the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
- a voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum.
- the threshold voltage is a voltage when the transmittance reaches 10%.
- Voltage holding ratio (VHR-1; 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 5 ⁇ m. This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
- 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.
- Voltage holding ratio (VHR-2; measured at 80 ° C .;%):
- the TN device used for the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 5 ⁇ m. This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
- 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.
- VHR-3 Voltage holding ratio
- the TN device used for measurement has a polyimide alignment film, and the cell gap is 5 ⁇ m. A sample was injected into this device and irradiated with ultraviolet rays for 20 minutes.
- the light source is an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source is 20 cm. In the measurement of VHR-3, the decreasing voltage was measured for 16.7 milliseconds.
- a composition having a large VHR-3 has a large stability to ultraviolet light.
- VHR-3 is preferably 90% or more, and more preferably 95% or more.
- VHR-4 Voltage holding ratio
- This device was irradiated with 25 mW / cm 2 ultraviolet light (EXECURE 4000-D type lamp manufactured by HOYA CANDEO OPTRONICS Co., Ltd.) for 400 seconds while applying a voltage of 15V.
- a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to this element.
- the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
- the transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum.
- the response time is a rise time (millisecond) required to change the transmittance from 0% to 90%.
- GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
- the carrier gas is helium (2 mL / min).
- the sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C.
- capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used.
- the column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min.
- a sample was prepared in an acetone solution (0.1% by weight), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
- the recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation, or an equivalent product.
- the obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.
- capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
- the following capillary column may be used.
- HP-1 from Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by SGE International Pty.
- a capillary column CBP1-M50-025 length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m
- Shimadzu Corporation may be used.
- the compounds in Comparative Examples and Examples were represented by symbols based on the definitions in Table 3 below.
- Table 3 the configuration regarding 1,4-cyclohexylene is trans.
- the number in parentheses after the symbol corresponds to the compound number.
- the symbol ( ⁇ ) means other liquid crystal compounds.
- the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition excluding the first component, and the liquid crystal composition contains impurities in addition to this.
- This composition is a liquid crystal composition not containing the first component of the present invention.
- the components and properties of this composition are as follows. 3-BB (2F, 3F) -O2 (2-4-1) 10% 5-BB (2F, 3F) -O2 (2-4-1) 10% 2-HH1OB (2F, 3F) -O2 (2-8-1) 5% 3-HH1OB (2F, 3F) -O2 (2-8-1) 10% 3-DhHB (2F, 3F) -O2 (2-10-1) 5% 3-HDhB (2F, 3F) -O2 (2-11-1) 6% 5-DhH1OB (2F, 3F) -O2 (2-12-1) 3% 3-dhBB (2F, 3F) -O2 (2-14-1) 5% 3-HEB (2F, 3F) B (2F, 3F) -O4 (2-15-1) 4% 2-HH-3 (3-1-1) 15% 3-HH-4 (3-1-1) 5% 1-BB-3 (3-3-1) 5% 3-HHB-1 (3-5-1) 3% 3-
- compositions of Examples 8 to 18 have a shorter response time than that of Comparative Example 2. Furthermore, the compositions of Examples 8 to 18 have a shorter response time than that of Comparative Example 3. Therefore, the formula (1-1-1-1), formula (1-1-2-8), formula (1-1-4-1), formula (1-1-4-2), formula, (1-2-1-1), the formula (1-2-2-1), the formula (1-4-1-1), and the conjugate rings represented by the formula (1-4-2-1) It can be seen that a polymerizable compound having a connecting group for connecting a conjugated system and a liquid crystal composition using the polymerizable compound are effective in shortening the response time.
- the liquid crystal composition satisfies at least one characteristic or has an appropriate balance regarding at least two characteristics.
- a liquid crystal display device containing such a composition is an AM device having a short response time, an appropriate pretilt, a large voltage holding ratio, a large contrast ratio, a long lifetime, and the like, and therefore is used for a liquid crystal projector, a liquid crystal television, and the like. Can do.
Abstract
Description
本発明の技術分野は、主としてAM(active matrix)素子などに適する液晶組成物、およびこの組成物を含有するAM素子などに関する。特に、誘電率異方性が負の液晶組成物に関し、この組成物を含有するIPS(in-plane switching)モード、VA(vertical alignment)モード、またはPSA(polymer sustained alignment)モードの素子などに関する。VAモードには、MVA(multi-domain vertical alignment)モード、PVA(patterned vertical alignment)モードなどが含まれる。
PSAモードのディスプレイでは、少量(約0.3重量%~約1重量%)の重合性化合物(RM)が液晶組成物に添加され、液晶表示セルに導入後、電極間に電圧を印加した状態で通常UV照射下に重合性化合物のみを重合させ、素子内でポリマー構造を形成する。RMとしては重合性のメソゲン性または液晶性化合物が液晶組成物添加モノマーとして特に適していることが知られている。
驚くべきことに、2つ以上の共役環同士の共役系が結合基でつながった構造を有するRMを用いることにより、応答時間を短縮することが見出せた。
ここで、A1およびA3は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基であり;A2は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基、または単結合であり;Z1は、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または、-C(=R3)-であり;Z2は独立して、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または-C(=R3)-であり;R1およびR2は独立して、水素、ハロゲン、炭素数1から10のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から10のアルキルであり;
R3は式(R-1)で表される基の群から選択された基であり;
X1は独立して、ハロゲン、炭素数1から6のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から10のアルキルであり;Lは独立して、ハロゲン、-CF3、-C≡N、または炭素数1から6のアルキルであり;P1およびP2は独立して、式(P-1)から式(P-11)で表される基の群から選択された基であり;Y1およびY2は独立して、水素、-CH3、-C2H5、またはハロゲンであり;Y3は、水素、-CH3、-C2H5、ハロゲン、-CF3、または-C≡Nであり;
Sp1およびSp2は独立して、単結合または炭素数1から6のアルキレンであり、このアルキレンの少なくとも1つの水素はハロゲンまたは-C≡Nで置き換えられていてもよく、少なくとも1つの隣接していない-CH2-は、-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH=CH-、または-C≡C-で置き換えられていてもよく;m1およびm3は0から5の整数であり、m2は0から4の整数であり、m1とm3との和が1から10の整数であり;n1は1から8の整数であり;pは0から4の整数である。
1. 式(1)で表される化合物。
ここで、A1およびA3は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基であり;A2は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基、または単結合であり;Z1は、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または、-C(=R3)-であり;Z2は独立して、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または-C(=R3)-であり;R1およびR2は独立して、水素、ハロゲン、炭素数1から10のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から10のアルキルであり;
R3は式(R-1)で表される基の群から選択された基であり;
X1は独立して、ハロゲン、炭素数1から6のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から10のアルキルであり;Lは独立して、ハロゲン、-CF3、-C≡N、または炭素数1から6のアルキルであり;P1およびP2は独立して、式(P-1)から式(P-11)で表される基の群から選択された基であり;Y1およびY2は独立して、水素、-CH3、-C2H5、またはハロゲンであり;Y3は、水素、-CH3、-C2H5、ハロゲン、-CF3、または-C≡Nであり;
Sp1およびSp2は独立して、単結合または炭素数1から6のアルキレンであり、このアルキレンの少なくとも1つの水素はハロゲンまたは-C≡Nで置き換えられていてもよく、少なくとも1つの隣接していない-CH2-は、-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH=CH-、または-C≡C-で置き換えられていてもよく;m1およびm3は0から5の整数であり、m2は0から4の整数であり、m1とm3との和が1から10の整数であり;n1は1から8の整数であり;pは0から4の整数である。
ここで、R4およびR5は独立して、水素、ハロゲン、または炭素数1から4のアルキルであり;X2は独立して、ハロゲンまたは炭素数1から3のアルキルであり;L1およびL2は独立して、ハロゲンまたは炭素数1から3のアルキルであり、;Y4およびY7は独立して、水素、-CH3、-C2H5、ハロゲン、-CF3、または-C≡Nであり;Y5、Y6、Y8、およびY9は独立して、水素、-CH3、-C2H5、またはハロゲンであり;m4およびm5は0から5の整数であり、m4とm5との和が3から10であり;m6およびm7は0から5の整数であり;n2は1から4の整数であり;rは0から3の整数である。
ここで、R6およびR7は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Bおよび環Dは独立して、1,4-シクロへキシレン、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、またはテトラヒドロピラン-2,5-ジイルであり;環Cは、2,3-ジフルオロ-1,4-フェニレン、2-クロロ-3-フルオロ-1,4-フェニレン、2,3-ジフルオロ-5-メチル-1,4-フェニレン、3,4,5-トリフルオロナフタレン-2,6-ジイル、または7,8-ジフルオロクロマン-2,6-ジイルであり;Z3およびZ4は独立して、単結合、エチレン、メチレンオキシ、またはカルボニルオキシであり;sは、1、2、または3であり;tは0または1であり、そして、sとtとの和が3以下である。
ここで、R6およびR7は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルである。
ここで、R8およびR9は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Eおよび環Fは独立して、1,4-シクロへキシレン、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;Z5は独立して、単結合、エチレン、メチレンオキシ、またはカルボニルオキシであり;uは、1、2、または3である。
ここで、R8およびR9は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルである。
R3は式(R-1)で表される基の群から選択された基である。
式(R-1)の波線は、基として結合する部位を示す。
テトラヒドロピラン-2,5-ジイルは左右が非対称である。しかしながら、これらの環が定義された方向のみならず、前記のように左右逆である方向にも位置することができるものと定義する。この定義は左右が非対称な環において、その一方のみが定義されたその他の環にも適用する。
このZ1およびZ2は、共役環同士の共役系を繋げるタイプの結合基である。化合物(1)のZ1およびZ2における二重結合の立体配置は、シス体、トランス体、またはシス体とトランス体の混合物である。化合物(1-1)、化合物(1-2)、化合物(1-3)、化合物(1-4)などにおける結合基の二重結合の立体配置についても同様である。
式(P-1)から式(P-10)の波線は、基として結合する部位を示す。
m6およびm7は0から5の整数である。好ましいm6またはm7は、光反応性を上げるために0から2の整数である。さらに好ましいm6またはm7は、0である。
pは0から4の整数である。rは0から3の整数である。好ましいpまたはrは、光反応性を上げるために0から2の整数である。さらに好ましいpまたはrは、0である。
uは、1、2、または3である。好ましいuは、粘度を下げるために1であり、上限温度を上げるために3である。
試料はアセトニトリルに溶解して、0.1重量%の溶液となるように調製し、得られた溶液1μLを試料室に導入した。
記録計としては島津製作所製のC-R7Aplusを用いた。得られた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。
試料はアセトニトリルに溶解して、0.01mmol/Lの溶液となるように調製し、石英セル(光路長1cm)に入れて測定した。
窒素雰囲気下、p-アセトフェノール(10.0g)、ピリジニウムp-トルエンスルホナート(PPTS)(0.44g)、ジクロロメタン(300mL)の混合物に氷冷下、3,4-ジヒドロ-2H-ピラン(DHP)(18.5g)のジクロロメタン(20mL)溶液を滴下した。滴下終了後、室温で16時間撹拌した。反応溶液を水洗し、次いで無水硫酸マグネシウムで乾燥した後、溶媒を減圧下留去し、化合物(T-1)を無色結晶として定量的に得た。
窒素雰囲気下、3,4-ジヒドロキシベンズアルデヒド(10.0g)、PPTS(0.87g)、ジクロロメタン(300mL)の混合物に氷冷下、DHP(36.5g)のジクロロメタン(20mL)溶液を滴下した。滴下終了後、室温で16時間撹拌した。反応溶液を水洗し、次いで無水硫酸マグネシウムで乾燥した後、溶媒を減圧下留去し、化合物(T-2)を油状物として定量的に得た。
窒素雰囲気下、(T-1)(10.0g)、(T-2)(13.9g)、水酸化バリウム八水和物(14.3g)、メタノール(200mL)を40℃で6時間加熱撹拌した。反応溶液を減圧下溶媒留去し、残渣に水を加え1M塩酸で中和した。有機層を酢酸エチルで抽出し、水洗後、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、化合物(T-3)を油状物として定量的に得た。
窒素雰囲気下、(T-3)(24.0g)、p-トルエンスルホン酸一水和物(PTS)(0.22g)、メタノール(200mL)を室温で16時間撹拌した。反応溶液の溶媒を減圧下留去した後、残渣に水を加え、飽和炭酸水素ナトリウム水溶液で中和した。有機層を酢酸エチルで抽出、次いで水洗し、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去後、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=5:5(容量比))で精製し、化合物(T-4)を黄色結晶(5.2g)として得た。
窒素雰囲気下、(T-4)(2.85g)、メタクリル酸(3.39g)、4-ジメチルアミノピリジン(DMAP)(0.40g)、ジクロロメタン(120mL)の混合物に氷冷下、1,3-ジシクロヘキシルカルボジイミド(DCC)(8.12g)のジクロロメタン(30mL)溶液を滴下し、15時間撹拌した。反応溶液中の析出物をろ過後、有機層を水洗し、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=9:1(容量比))で精製後、トルエンとエタノールの混合溶媒より再結晶し、化合物(1-1-1-1)を淡黄色結晶(1.84g)として得た。
融点:116℃
1H-NMR(CDCl3;δ ppm):8.08(d,2H),7.79(d,1H),7.57(d,1H),7.55(dd,1H),7.48(d,1H),7.34(d,1H),7.28(d,2H),6.39(s,1H),6.33(s,1H),6.31(s,1H),5.81(t,1H),5.77(t,1H),5.76(t,1H),2.09(s,3H),2.03(s,3H),2.02(s,3H).
メタクリル酸をアクリル酸(4.05g)に変更した他は、実施例1の第5工程に記載の方法と同様に合成を行い、化合物(1-1-2-1)を淡黄色結晶(1.82g)として得た。
融点:160℃
1H-NMR(CDCl3;δ ppm):8.08(d,2H),7.78(d,1H),7.56-7.55(m,2H),7.47(d,1H),7.34(d,1H),7.30(d,2H),6.67-6.58(m,3H),6.38-6.25(m,3H),6.09-6.03(m,3H).
実施例1および実施例2の方法に従い、化合物(1-1-1-1)から化合物(1-1-1-12)、化合物(1-1-2-1)から化合物(1-1-2-12)、化合物(1-1-3-1)、化合物(1-1-4-1)、および化合物(1-1-4-2)を製造する。実施例1で示した化合物(1-1-1-1)および実施例2で示した化合物(1-1-2-1)も再掲する。
窒素雰囲気下、1,2-ジメトキシベンゼン(10.0g)、ジクロロメタン(150mL)の混合物に氷冷下、塩化アルミニウム(9.65g)を加え撹拌した。次に4-メトキシベンゾイルクロリド(12.4g)のジクロロメタン(100mL)を加えた後、氷浴をはずし、室温にて16時間撹拌した。反応溶液を氷水に注ぎ、有機層をジクロロメタンで抽出し、水洗した後、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=9:1(容量比))で精製し、化合物(T-5)を無色結晶(18.9g)として得た。
窒素雰囲気下、亜鉛(18.0g)とテトラヒドロフラン(THF)(600mL)の混合物中、-10℃で四塩化チタン(25.8g)を滴下した後、2.5時間加熱還流した。室温まで放冷し、(T-5)(10.0g)とシクロヘキサノン(3.60g)のTHF(100mL)溶液を加え、4時間加熱還流した。反応溶液を10%炭酸カリウム水溶液に注ぎ、有機層を酢酸エチルで抽出し、水洗後、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=9:1(容量比))で精製し、化合物(T-6)を無色結晶として定量的に得た。
窒素雰囲気下、(T-6)(10.1g)のジクロロメタン(100mL)溶液に-60℃で1Mの三臭化ホウ素ジクロロメタン溶液(100mL)を滴下し、室温にて16時間撹拌した。反応溶液を氷水に注ぎ、有機層を酢酸エチルで抽出した後、水洗し、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=5:5(容量比))で精製し、化合物(T-7)をオレンジ色固体(3.80g)として得た。
(T-4)を(T-7)(2.80g)に変更した他は、実施例1の第5工程に記載の方法と同様に合成を行い、化合物(1-2-1-1)を無色結晶(1.82g)として得た。
融点:119℃
1H-NMR(CDCl3;δ ppm):7.16(d,1H),7.13(d,2H),7.04(d,2H),7.02-7.00(m,2H),6.33(s,1H),6.27-6.26(m,2H),5.75-5.74(m,1H),5.71-5.70(m,2H),2.31-2.29(m,2H),2.25-2.23(m,2H),2.06(s,3H),2.00-1.99(m,6H),1.65-1.54(m,6H).
実施例4および実施例2の方法に従い、化合物(1-2-1-1)から化合物(1-2-1-8)、化合物(1-2-2-1)から化合物(1-2-2-8)、化合物(1-3-1-1)から化合物(1-3-1-6)、および化合物(1-3-2-1)から化合物(1-3-2-6)を製造する。実施例4で示した化合物(1-2-1-1)も再掲する。
窒素雰囲気下、亜鉛(36.5g)とTHF(600mL)の混合物中、-5℃で四塩化チタン(53.0g)を滴下後、室温まで昇温し0.5時間撹拌し、さらに2.5時間加熱還流した。反応溶液を-5℃に冷却し、ピリジン(11.1g)を添加し、10分間撹拌した。次に4’メトキシアセトフェノン(10.1g)と3',4’-ジメトキシアセトフェノン(10.1g)のTHF(300mL)溶液を加え、10時間加熱還流した。反応溶液を10%炭酸カリウム水溶液に注ぎ、有機層を酢酸エチルで抽出し、水洗後、無水硫酸マグネシウムで乾燥した。有機溶媒を減圧下留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 トルエン:酢酸エチル=9:1(容量比))で精製し、化合物(T-8)を無色油状物(7.98g)として得た。
(T-6)を(T-8)(6.00g)に変更した他は、実施例4の第3工程に記載の方法と同様に合成を行い、化合物(T-9)を茶色結晶(3.15g)として得た。
(T-7)を(T-9)(3.30g)に、メタクリル酸をアクリル酸に変更した他は、実施例1の第5工程に記載の方法と同様に合成を行い、化合物(1-4-2-1)を無色油状物(1.14g)として得た。
1H-NMR(CDCl3;δ ppm):7.27-7.24(m,3H),7.19-7.17(m,2H),7.14(d,2H),6.64-6.57(m,3H),6.37-6.24(m,3H),6.04-6.00(m,3H),1.93(d,3H),1.89(d,3H).
実施例6および実施例1の第5工程に記載の方法に従い、化合物(1-4-1-1)から化合物(1-4-1-9)、および化合物(1-4-2-1)から化合物(1-4-2-9)を製造する。実施例6で示した化合物(1-4-2-1)も再掲する。
1)誘電率(ε∥)の測定:よく洗浄したガラス基板にオクタデシルトリエトキシシラン(0.16mL)のエタノール(20mL)溶液を塗布した。ガラス基板をスピンナーで回転させたあと、150℃で1時間加熱した。2枚のガラス基板の間隔(セルギャップ)が4μmであるVA素子に試料を入れ、この素子を紫外線で硬化する接着剤で密閉した。この素子にサイン波(0.5V、1kHz)を印加し、2秒後に液晶分子の長軸方向における誘電率(ε∥)を測定した。
2)誘電率(ε⊥)の測定:よく洗浄したガラス基板にポリイミド溶液を塗布した。このガラス基板を焼成した後、得られた配向膜にラビング処理をした。2枚のガラス基板の間隔(セルギャップ)が9μmであり、ツイスト角が80度であるTN素子に試料を入れた。この素子にサイン波(0.5V、1kHz)を印加し、2秒後に液晶分子の短軸方向における誘電率(ε⊥)を測定した。
表3において、1,4-シクロヘキシレンに関する立体配置はトランスである。実施例において記号の後にあるかっこ内の番号は化合物の番号に対応する。(-)の記号はその他の液晶性化合物を意味する。液晶性化合物の割合(百分率)は、第一成分を除く液晶組成物の重量に基づいた重量百分率(重量%)であり、液晶組成物にはこの他に不純物が含まれている。最後に、組成物の特性値をまとめた。
この組成物は本発明の第一成分を含有していない液晶組成物である。この組成物の成分および特性は下記のとおりである。
3-BB(2F,3F)-O2 (2-4-1) 10%
5-BB(2F,3F)-O2 (2-4-1) 10%
2-HH1OB(2F,3F)-O2 (2-8-1) 5%
3-HH1OB(2F,3F)-O2 (2-8-1) 10%
3-DhHB(2F,3F)-O2 (2-10-1) 5%
3-HDhB(2F,3F)-O2 (2-11-1) 6%
5-DhH1OB(2F,3F)-O2 (2-12-1) 3%
3-dhBB(2F,3F)-O2 (2-14-1) 5%
3-HEB(2F,3F)B(2F,3F)-O4
(2-15-1) 4%
2-HH-3 (3-1-1) 15%
3-HH-4 (3-1-1) 5%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 3%
3-HHB-3 (3-5-1) 3%
V-HHB-1 (3-5-1) 3%
5-B(F)BB-2 (3-7-1) 4%
5-B(F)BB-2 (3-7-1) 4%
NI=83.8℃;Tc<-20℃;Δn=0.121;Δε=-4.0;Vth=2.07V;τ=8.0ms;VHR-1=99.3%;VHR-2=98.2%.
3-BB(2F,3F)-O2 (2-4-1) 10%
5-BB(2F,3F)-O2 (2-4-1) 10%
2-HH1OB(2F,3F)-O2 (2-8-1) 5%
3-HH1OB(2F,3F)-O2 (2-8-1) 10%
3-DhHB(2F,3F)-O2 (2-10-1) 5%
3-HDhB(2F,3F)-O2 (2-11-1) 6%
5-DhH1OB(2F,3F)-O2 (2-12-1) 3%
3-dhBB(2F,3F)-O2 (2-14-1) 5%
3-HEB(2F,3F)B(2F,3F)-O4
(2-15-1) 4%
2-HH-3 (3-1-1) 15%
3-HH-4 (3-1-1) 5%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 3%
3-HHB-3 (3-5-1) 3%
V-HHB-1 (3-5-1) 3%
5-B(F)BB-2 (3-7-1) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に、比較例1で合成した下記化合物(A-1)を0.3重量部添加した。
NI=83.6℃;Tc<-20℃;Δn=0.121;Δε=-4.0;Vth=2.05V;τ=7.3ms;VHR-1=99.2%;VHR-2=98.1%.
3-BB(2F,3F)-O2 (2-4-1) 10%
5-BB(2F,3F)-O2 (2-4-1) 10%
2-HH1OB(2F,3F)-O2 (2-8-1) 5%
3-HH1OB(2F,3F)-O2 (2-8-1) 10%
3-DhHB(2F,3F)-O2 (2-10-1) 5%
3-HDhB(2F,3F)-O2 (2-11-1) 6%
5-DhH1OB(2F,3F)-O2 (2-12-1) 3%
3-dhBB(2F,3F)-O2 (2-14-1) 5%
3-HEB(2F,3F)B(2F,3F)-O4
(2-15-1) 4%
2-HH-3 (3-1-1) 15%
3-HH-4 (3-1-1) 5%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 3%
3-HHB-3 (3-5-1) 3%
V-HHB-1 (3-5-1) 3%
5-B(F)BB-2 (3-7-1) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に下記化合物(1-1-1-1)を0.3重量部添加した。
NI=83.5℃;Tc<-20℃;Δn=0.121;Δε=-4.0;Vth=2.04V;τ=5.7ms;VHR-1=99.3%;VHR-2=98.2%.
3-H2B(2F,3F)-O2 (2-2-1) 19%
5-H2B(2F,3F)-O2 (2-2-1) 15%
5-HH2B(2F,3F)-O2 (2-7-1) 5%
3-HBB(2F,3F)-O2 (2-13-1) 10%
5-HBB(2F,3F)-O2 (2-13-1) 4%
3-HHB(2F,3CL)-O2 (2-16-1) 3%
3-HBB(2F,3CL)-O2 (2-17-1) 3%
2-HH-3 (3-1-1) 25%
3-HHEH-3 (3-4-1) 3%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6-1) 3%
3-HB(F)HH-5 (3-10-1) 3%
5-HBBH-3 (3-11-1) 3%
上記組成物100重量部に下記化合物(1-2-1-1)を0.3重量部添加した。
NI=81.3℃;Tc<-20℃;Δn=0.090;Δε=-2.8;Vth=2.38V;τ=5.4ms;VHR-1=99.2%;VHR-2=97.6%.
3-H2B(2F,3F)-O2 (2-2-1) 20%
5-H2B(2F,3F)-O2 (2-2-1) 15%
2-BB(2F,3F)B-3 (2-9-1) 7%
3-DhHB(2F,3F)-O2 (2-10-1) 3%
3-HBB(2F,3F)-O2 (2-13-1) 9%
4-HBB(2F,3F)-O2 (2-13-1) 5%
3-H1OCro(7F,8F)-5 (2-18-1) 3%
3-HH1OCro(7F,8F)-5 (2-19-1) 3%
V-HH-3 (3-1-1) 18%
1V-HH-3 (3-1-1) 5%
3-HHB-O1 (3-5) 3%
3-HHEBH-3 (3-9-1) 3%
3-HB(F)BH-3 (3-12-1) 3%
5-HBB(F)B-2 (3-13-1) 3%
上記組成物100重量部に下記化合物(1-2-2-1)を0.3重量部添加した。
NI=77.5℃;Tc<-20℃;Δn=0.106;Δε=-3.5;Vth=2.14V;τ=4.8ms;VHR-1=99.3%;VHR-2=97.9%.
3-H2B(2F,3F)-O2 (2-2-1) 20%
1V2-H2B(2F,3F)-O2 (2-2-1) 12%
3-HHB(2F,3F)-O2 (2-6-1) 8%
3-HHB(2F,3F)-1 (2-6-1) 5%
3-HDhB(2F,3F)-O2 (2-11-1) 5%
3-HBB(2F,3F)-O2 (2-13-1) 10%
4-HBB(2F,3F)-O2 (2-13-1) 6%
5-HBB(2F,3F)-O2 (2-13-1) 3%
2-HH-3 (3-1-1) 10%
3-HH-4 (3-1-1) 10%
1V-HH-3 (3-1-1) 8%
3-HHB-1 (3-5-1) 3%
上記組成物100重量部に下記化合物(1-4-2-1)を0.4重量部添加した。
NI=79.0℃;Tc<-20℃;Δn=0.095;Δε=-3.8;Vth=2.08V;τ=5.1ms;VHR-1=99.1%;VHR-2=98.2%.
3-BB(2F,3F)-O2 (2-4-1) 9%
5-BB(2F,3F)-O2 (2-4-1) 6%
2-HH1OB(2F,3F)-O2 (2-8-1) 13%
3-HH1OB(2F,3F)-O2 (2-8-1) 21%
V-HH-3 (3-1-1) 28%
3-HB-O2 (3-2) 5%
1-BB-3 (3-3-1) 7%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に下記化合物(1-1-1-1)を0.4重量部添加した。
NI=74.1℃;Tc<-20℃;Δn=0.100;Δε=-3.1;Vth=2.22V;τ=3.8ms;VHR-1=99.1%;VHR-2=97.9%.
3-HB(2F,3F)-O2 (2-1-1) 10%
V-HB(2F,3F)-O2 (2-1-1) 10%
V-HB(2F,3F)-O4 (2-1-1) 8%
1V2-HB(2F,3F)-O2 (2-1-1) 4%
3-HBB(2F,3F)-O2 (2-13-1) 10%
4-HBB(2F,3F)-O2 (2-13-1) 6%
5-HBB(2F,3F)-O2 (2-13-1) 10%
3-HH1OCro(7F,8F)-5 (2-19-1) 5%
3-HH1OB(2F,3F,6Me)-O2
(2) 3%
2-HH-3 (3-1-1) 15%
VFF-HH-3 (3-1) 6%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 3%
5-HBB(F)B-2 (3-13-1) 4%
1O1-HBBH-5 (-) 3%
上記組成物100重量部に下記化合物(1-4-1-1)を0.2重量部添加した。
NI=85.4℃;Tc<-20℃;Δn=0.106;Δε=-3.8;Vth=1.94V;τ=6.1ms;VHR-1=99.1%;VHR-2=97.8%.
3-BB(2F,3F)-O2 (2-4-1) 10%
5-BB(2F,3F)-O2 (2-4-1) 7%
3-B(2F,3F)B(2F,3F)-O2
(2-5-1) 3%
2-HH1OB(2F,3F)-O2 (2-8-1) 13%
3-HH1OB(2F,3F)-O2 (2-8-1) 12%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 9%
3-HH-O1 (3-1) 3%
3-HB-O2 (3-2) 3%
V2-BB-1 (3-3-1) 5%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 3%
1-BB(F)B-2V (3-8-1) 5%
3-HHEBH-4 (3-9-1) 4%
上記組成物100重量部に下記化合物(1-1-1-1)を0.15重量部、
および下記化合物(1-1-2-1)を0.15重量部添加した。
NI=76.0℃;Tc<-20℃;Δn=0.100;Δε=-2.9;Vth=2.24V;τ=4.0ms;VHR-1=99.1%;VHR-2=98.1%.
3-H1OB(2F,3F)-O2 (2-3-1) 6%
3-BB(2F,3F)-O2 (2-4-1) 6%
5-BB(2F,3F)-O2 (2-4-1) 5%
2O-B(2F,3F)B(2F,3F)-O6
(2-5) 3%
V-HHB(2F,3F)-O2 (2-6-1) 8%
2-HH1OB(2F,3F)-O2 (2-8-1) 7%
3-HH1OB(2F,3F)-O2 (2-8-1) 10%
2-HH-3 (3-1-1) 22%
3-HH-4 (3-1-1) 8%
3-HH-O1 (3-1) 5%
V2-BB-1 (3-3-1) 5%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 4%
2-BB(F)B-3 (3-8-1) 4%
3-HHEBH-4 (3-9-1) 4%
上記組成物100重量部に下記化合物(1-1-2-1)を0.3重量部添加した。
NI=77.2℃;Tc<-20℃;Δn=0.092;Δε=-3.0;Vth=2.28V;τ=3.9ms;VHR-1=99.2%;VHR-2=97.9%.
3-BB(2F,3F)-O2 (2-4-1) 9%
5-BB(2F,3F)-O2 (2-4-1) 6%
2-HH1OB(2F,3F)-O2 (2-8-1) 13%
3-HH1OB(2F,3F)-O2 (2-8-1) 21%
V-HH-3 (3-1-1) 26%
3-HB-O2 (3-2) 7%
1-BB-3 (3-3-1) 7%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に下記化合物(1-1-2-8)を0.3重量部添加した。
NI=74.1℃;Tc<-20℃;Δn=0.102;Δε=-3.1;Vth=2.21V;τ=3.9ms;VHR-1=99.0%;VHR-2=97.8%.
3-BB(2F,3F)-O2 (2-4-1) 9%
5-BB(2F,3F)-O2 (2-4-1) 6%
2-HH1OB(2F,3F)-O2 (2-8-1) 13%
3-HH1OB(2F,3F)-O2 (2-8-1) 21%
V-HH-3 (3-1-1) 26%
3-HB-O2 (3-2) 7%
1-BB-3 (3-3-1) 7%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に下記化合物(1-1-4-1)を0.3重量部添加した。
NI=74.0℃;Tc<-20℃;Δn=0.102;Δε=-3.1;Vth=2.20V;τ=4.1ms;VHR-1=99.1%;VHR-2=97.8%.
3-BB(2F,3F)-O2 (2-4-1) 9%
5-BB(2F,3F)-O2 (2-4-1) 6%
2-HH1OB(2F,3F)-O2 (2-8-1) 13%
3-HH1OB(2F,3F)-O2 (2-8-1) 21%
V-HH-3 (3-1-1) 28%
3-HB-O2 (3-2) 5%
1-BB-3 (3-3-1) 7%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5) 4%
5-B(F)BB-2 (3-7-1) 4%
上記組成物100重量部に下記化合物(1-1-4-2)を0.4重量部添加した。
NI=73.9℃;Tc<-20℃;Δn=0.100;Δε=-3.1;Vth=2.24V;τ=4.0ms;VHR-1=99.0%;VHR-2=98.0%.
Claims (27)
- 式(1)で表される化合物。
ここで、A1およびA3は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基であり;A2は独立して、少なくとも1つの水素がLに置き換えられていてもよい芳香環基、または少なくとも1つの水素がLに置き換えられていてもよい複素芳香環基、または単結合であり;Z1は、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または、-C(=R3)-であり;Z2は独立して、-CO-CR1=CR2-、-CR1=CR2-CO-、-CR1=CR2-、-C(=CR1R2)-、または-C(=R3)-であり;R1およびR2は独立して、水素、ハロゲン、炭素数1から10のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から10のアルキルであり;
R3は式(R-1)で表される基の群から選択された基であり;
X1は独立して、ハロゲン、炭素数1から6のアルキル、または少なくとも1つの水素がフッ素に置き換えられた炭素数1から6のアルキルであり;Lは独立して、ハロゲン、-CF3、-C≡N、または炭素数1から6のアルキルであり;P1およびP2は独立して、式(P-1)から式(P-11)で表される基の群から選択された基であり;Y1およびY2は独立して、水素、-CH3、-C2H5、またはハロゲンであり;Y3は、水素、-CH3、-C2H5、ハロゲン、-CF3、または-C≡Nであり;
Sp1およびSp2は独立して、単結合または炭素数1から6のアルキレンであり、このアルキレンの少なくとも1つの水素はハロゲンまたは-C≡Nで置き換えられていてもよく、少なくとも1つの隣接していない-CH2-は、-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CH=CH-、または-C≡C-で置き換えられていてもよく;m1およびm3は0から5の整数であり、m2は0から4の整数であり、m1とm3との和が1から10の整数であり;n1は1から8の整数であり;pは0から4の整数である。 - 式(1)において、P1およびP2が式(P-1)で表される基の群から選択された基であり;Sp1およびSp2が単結合である請求項1に記載の化合物。
- 式(1-1)から式(1-4)で表される請求項1または2に記載の化合物。
ここで、R4およびR5は独立して、水素、ハロゲン、または炭素数1から4のアルキルであり;X2は独立して、ハロゲンまたは炭素数1から3のアルキルであり;L1およびL2は独立して、ハロゲンまたは炭素数1から3のアルキルであり、;Y4およびY7は独立して、水素、-CH3、-C2H5、ハロゲン、-CF3、または-C≡Nであり;Y5、Y6、Y8、およびY9は独立して、水素、-CH3、-C2H5、またはハロゲンであり;m4およびm5は0から5の整数であり、m4とm5との和が3から10であり;m6およびm7は0から5の整数であり;n2は1から4の整数であり;rは0から3の整数である。 - 式(1-1)から式(1-4)において、Y4およびY7が独立して、水素または-CH3であり;Y5、Y6、Y8、およびY9が水素であり;m4およびm5が0から3の整数であり、m4とm5の和が3または4である請求項3に記載の化合物。
- 請求項1から4のいずれか1項に記載の化合物の単独重合または共重合によって得られるホモポリマーまたはコポリマー。
- 第一成分として、請求項1から4のいずれか1項に記載の化合物の群から選択された少なくとも1つの化合物を含有する液晶組成物。
- 第一成分を除く液晶組成物100重量部に対して、第一成分の割合が0.05重量部から10重量部の範囲である請求項6に記載の液晶組成物。
- 第二成分として式(2)で表される化合物の群から選択された少なくとも1つの化合物をさらに含有する請求項6または7に記載の液晶組成物。
ここで、R6およびR7は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Bおよび環Dは独立して、1,4-シクロへキシレン、1,4-フェニレン、少なくとも1つの水素がフッ素または塩素で置き換えられた1,4-フェニレン、またはテトラヒドロピラン-2,5-ジイルであり;環Cは、2,3-ジフルオロ-1,4-フェニレン、2-クロロ-3-フルオロ-1,4-フェニレン、2,3-ジフルオロ-5-メチル-1,4-フェニレン、3,4,5-トリフルオロナフタレン-2,6-ジイル、または7,8-ジフルオロクロマン-2,6-ジイルであり;Z3およびZ4は独立して、単結合、エチレン、メチレンオキシ、またはカルボニルオキシであり;sは、1、2、または3であり;tは0または1であり、そして、sとtとの和が3以下である。 - 第二成分が、請求項9記載の式(2-1)で表される化合物の群から選択された少なくとも1つの化合物である請求項8に記載の液晶組成物。
- 第二成分が、請求項9記載の式(2-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(2-6)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項8に記載の液晶組成物。
- 第二成分が、請求項9記載の式(2-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(2-13)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項8に記載の液晶組成物。
- 第二成分が、請求項9記載の式(2-4)で表される化合物の群から選択された少なくとも1つの化合物、および式(2-8)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項8に記載の液晶組成物。
- 第一成分を除く液晶組成物の重量に基づいて、第二成分の割合が10重量%から90重量%の範囲である請求項8から13のいずれか1項に記載の液晶組成物。
- 第三成分として式(3)で表される化合物の群から選択された少なくとも1つの化合物をさらに含有する、請求項6から14のいずれか1項に記載の液晶組成物。
ここで、R8およびR9は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Eおよび環Fは独立して、1,4-シクロへキシレン、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;Z5は独立して、単結合、エチレン、メチレンオキシ、またはカルボニルオキシであり;uは、1、2、または3である。 - 第三成分が請求項16記載の式(3-1)で表される化合物の群から選択された少なくとも1つの化合物である請求項15に記載の液晶組成物。
- 第三成分が、請求項16記載の式(3-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(3-5)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項15に記載の液晶組成物。
- 第三成分が、請求項16記載の式(3-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(3-7)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項15に記載の液晶組成物。
- 第三成分が、請求項16記載の式(3-1)で表される化合物の群から選択された少なくとも1つの化合物、式(3-5)で表される化合物の群から選択された少なくとも1つの化合物、および式(3-7)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項15に記載の液晶組成物。
- 第一成分を除く液晶組成物の重量に基づいて、第三成分の割合が10重量%から90重量%の範囲である請求項15から20のいずれか1項に記載の液晶組成物。
- 重合開始剤をさらに含有する請求項6から21のいずれか1項に記載の液晶組成物。
- 重合禁止剤をさらに含有する請求項6から22のいずれか1項に記載の液晶組成物。
- ネマチック相の上限温度が70℃以上であり、波長589nmにおける光学異方性(25℃)が0.08以上であり、そして周波数1kHzにおける誘電率異方性(25℃)が-2以下である請求項6から23のいずれか1項に記載の液晶組成物。
- 少なくとも一方の基板に電極層を有する2つの基板から構成され、この2つの基板の間に請求項6から24のいずれか1項に記載の液晶組成物を配置する事を特徴とする液晶表示素子。
- 液晶表示素子の動作モードが、TNモード、VAモード、IPSモード、またはPSAモードであり、液晶表示素子の駆動方式がアクティブマトリックス方式である請求項25に記載の液晶表示素子。
- 請求項6から24のいずれか1項に記載の液晶組成物の液晶表示素子における使用。
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US20140346399A1 (en) | 2014-11-27 |
US9139672B2 (en) | 2015-09-22 |
TWI586645B (zh) | 2017-06-11 |
JPWO2013054682A1 (ja) | 2015-03-30 |
TW201319035A (zh) | 2013-05-16 |
JP6061098B2 (ja) | 2017-01-18 |
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