WO2017126275A1 - 2原子結合基と2,3-ジフルオロフェニレンを有する4環液晶性化合物、液晶組成物および液晶表示素子 - Google Patents
2原子結合基と2,3-ジフルオロフェニレンを有する4環液晶性化合物、液晶組成物および液晶表示素子 Download PDFInfo
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- WO2017126275A1 WO2017126275A1 PCT/JP2016/087798 JP2016087798W WO2017126275A1 WO 2017126275 A1 WO2017126275 A1 WO 2017126275A1 JP 2016087798 W JP2016087798 W JP 2016087798W WO 2017126275 A1 WO2017126275 A1 WO 2017126275A1
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- carbons
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- diyl
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- liquid crystal
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- 0 NC1CC*CC1 Chemical compound NC1CC*CC1 0.000 description 8
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N CC(CC1)CCC1N Chemical compound CC(CC1)CCC1N KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- MVCSLRWYKQVLES-UHFFFAOYSA-N CC(CC1)CCC1c(cc1)ccc1-c(cc1)ccc1C#N Chemical compound CC(CC1)CCC1c(cc1)ccc1-c(cc1)ccc1C#N MVCSLRWYKQVLES-UHFFFAOYSA-N 0.000 description 1
- USJAJMMCQIBKSR-UHFFFAOYSA-N CC(CC1)CCC1c(cc1)ccc1C#N Chemical compound CC(CC1)CCC1c(cc1)ccc1C#N USJAJMMCQIBKSR-UHFFFAOYSA-N 0.000 description 1
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no 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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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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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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- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/3001—Cyclohexane rings
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- C09K19/3001—Cyclohexane rings
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
Definitions
- the present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal compound having 2,3-difluorophenylene and having a negative dielectric anisotropy, a liquid crystal composition containing the compound, and a liquid crystal display device including the composition.
- the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) mode.
- the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like.
- This device is filled with a liquid crystal composition.
- the physical properties of this composition are related to the characteristics of the device. Examples of physical properties in the composition are stability to heat and light, temperature range of the nematic phase, viscosity, optical anisotropy, dielectric anisotropy, specific resistance, elastic constant, and the like.
- the composition is prepared by mixing many liquid crystal compounds.
- the required physical properties of the compounds are high stability to environments such as water, air, heat, light, etc., wide temperature range of liquid crystal phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant And good compatibility with other liquid crystal compounds.
- a compound having a high maximum temperature of the nematic phase is preferred.
- a compound having a low minimum temperature in a liquid crystal phase such as a nematic phase or a smectic phase is preferred.
- a compound having a small viscosity contributes to a short response time of the device.
- the appropriate value of optical anisotropy varies depending on the element mode.
- a compound having a large positive or negative dielectric anisotropy is preferable for driving the device at a low voltage.
- To prepare the composition a compound having good compatibility with other liquid crystal compounds is preferable. Since the device may be used at a temperature below freezing point, a compound having good compatibility at a low temperature is preferable.
- WO 2010/082558 discloses compound (A) on page 300.
- WO 98/27036 discloses compound (B) on page 65.
- WO 2009/150966 pamphlet discloses compound (C) on page 213.
- WO 2009/031437 discloses compound (D) on page 233.
- JP 2014-114276 discloses compound (E) on page 63.
- JP 2002-193853 discloses compound (F) on page 103.
- CN10288226A1 discloses compound (G) on page 6.
- CN10192199A1 discloses compound (H) on page 10.
- WO 2010/095506 discloses compound (I) on page 64.
- Japanese Patent Application Laid-Open No. 2010-215609, page 54. 1-3-51 is the compound (J). Although the compounds (A) to (J) are disclosed, the liquid crystal performance is unknown.
- the first problem is high stability against heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant. It is to provide a liquid crystal compound satisfying at least one of physical properties such as isotropic property, appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having good physical properties as compared with a similar compound.
- the second problem is that it contains this compound and has high stability to heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric constant.
- the object is to provide a liquid crystal composition satisfying at least one of physical properties such as an isotropic property, a large specific resistance, and an appropriate elastic constant.
- An object of the present invention is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties.
- the third problem is a liquid crystal display comprising this composition and having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker ratio, and a long lifetime. It is to provide an element.
- the present invention relates to a compound represented by the formula (1), a liquid crystal composition containing the compound, and a liquid crystal display device including the composition.
- R 1 is alkyl having 1 to 15 carbons, in which at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — is —CH ⁇ CH—
- R 2 is alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyl having 2 to 15 carbons;
- Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2, 5-diyl or pyrimidine-2,5-diyl,
- ring A 3 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, tetra
- Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CH 2 CH 2 —, or —CH ⁇ CH—. is there.
- the first advantage is high stability against heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant. It is to provide a liquid crystal compound satisfying at least one of physical properties such as isotropic property, appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having a large dielectric anisotropy as compared with a similar compound. It is to provide a compound having better compatibility with other liquid crystal compounds, negatively large dielectric anisotropy, or small viscosity compared to similar compounds (see Comparative Examples 1 and 2). thing).
- the second advantage is that it contains this compound and has high stability against heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant.
- the object is to provide a liquid crystal composition satisfying at least one of physical properties such as an isotropic property, a large specific resistance, and an appropriate elastic constant.
- the advantage is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties.
- a third advantage is that this composition includes the composition, and a liquid crystal display having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker ratio, and a long lifetime. It is to provide an element.
- liquid crystal compound liquid crystal composition
- liquid crystal display element liquid crystal display element
- compound liquid crystal phase
- element physical properties of the composition
- This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
- Liquid crystal display element is a general term for liquid crystal display panels and liquid crystal display modules.
- the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
- the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives are added to this composition for the purpose of further adjusting the physical properties. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents are added as necessary.
- Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents are added as necessary.
- the Liquid crystal compounds and additives are mixed in such a procedure.
- the ratio (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when the additive is added.
- the ratio (addition amount) of the additive is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition not containing the additive. Weight parts per million (ppm) may be used.
- the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
- “Clearing point” is a transition temperature between a liquid crystal phase and an isotropic phase in a liquid crystal compound.
- “Lower limit temperature of liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (smectic phase, nematic phase, etc.) in a liquid crystal compound.
- the “maximum temperature of the nematic phase” is a transition temperature of a nematic phase to an isotropic phase in a mixture or liquid crystal composition of a liquid crystal compound and a mother liquid crystal, and may be abbreviated as “maximum temperature”.
- “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”.
- increasing dielectric anisotropy means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.
- High voltage holding ratio means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. It means having a retention rate.
- characteristics may be examined before and after a aging test (including an accelerated deterioration test).
- the compound represented by Formula (1) may be abbreviated as Compound (1).
- At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as compound (1).
- “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. These rules also apply to compounds represented by other formulas.
- symbols such as A 1 , B 1 , and C 1 surrounded by hexagons correspond to rings such as ring A 1 , ring B 1 , and ring C 1 , respectively.
- the hexagon represents a six-membered ring such as cyclohexane or benzene.
- the hexagon may represent a condensed ring such as naphthalene or a bridged ring such as adamantane.
- the symbol of the terminal group R 11 is used for a plurality of compounds.
- two groups represented by any two R 11 may be the same or different.
- R 11 of compound (2) is ethyl and R 11 of compound (3) is ethyl.
- R 11 of compound (2) is ethyl and R 11 of compound (3) is propyl.
- This rule also applies to symbols such as R 12 , R 13 and Z 11 .
- compound (15) when i is 2, two rings E 1 exist. In this compound, two groups represented by two rings E 1 may be the same or different. When i is greater than 2, it also applies to any two rings E 1 . This rule also applies to other symbols.
- the expression “at least one 'A'” means that the number of 'A' is arbitrary.
- the expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, it means that their positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'”.
- alkyl in which at least one —CH 2 — may be replaced by —O— or —CH ⁇ CH— includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkenyloxyalkyl.
- R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH 2 — is replaced by —O—.
- the expression "at least one hydrogen may be replaced by fluorine” may be used.
- in these groups may be interpreted literally.
- “these groups” means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” represents all of the groups described before the term “in these groups”. This common sense interpretation also applies to the terms “in these monovalent groups” and “in these divalent groups”. For example, “these monovalent groups” represent all of the groups described before the term “in these monovalent groups”.
- the alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl.
- Linear alkyl is generally preferred over branched alkyl.
- terminal groups such as alkoxy and alkenyl.
- trans is preferable to cis for increasing the maximum temperature.
- 2-Fluoro-1,4-phenylene means the following two divalent groups.
- fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
- the present invention includes the following items.
- R 1 is alkyl having 1 to 15 carbons, in which at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — is —CH ⁇ CH—
- R 2 is alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyl having 2 to 15 carbons;
- Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2, 5-diyl or pyrimidine-2,5-diyl,
- ring A 3 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl,
- Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CH 2 CH 2 —, or —CH ⁇ CH—. is there.
- ring A 3 is 2-fluoro-1,4-phenylene
- at least one of ring A 1 and ring A 2 is 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3- Dioxane-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl
- Z 3 is a single bond.
- R 1 is CH 2 ⁇ CH— or alkenyloxy
- Z 1 and Z 3 are a single bond
- Z 2 is —CH ⁇ CH—
- At least one of 3 is 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl It is.
- ring A 2 and ring A 3 are 1,4-phenylene, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl.
- R 1 is alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — May be replaced by —CH ⁇ CH—, R 2 is alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyl having 2 to 15 carbons;
- ring A 1 is 1, 4-cyclohexylene, ring A 2 and ring A 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5 -Diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl;
- Z 1 , Z 2 , and Z 3 are independently a single bond, -CH 2 O-, -OCH 2- , -COO- -OCO-, or -CH 2
- R 1 is alkenyl having 2 to 10 carbons
- R 2 is alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyl having 2 to 15 carbons
- a 1 is 1,4-cyclohexylene
- ring A 2 and ring A 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyridine-2,5-diyl or pyrimidine-2,5-diyl
- Z 1 , Z 2 and Z 3 are independently a single bond, -CH 2 O- , —OCH 2 —, —COO—, —OCO—, or —CH 2 CH 2 —, wherein at least one of Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, — COO-, -
- R 1 is alkyl having 1 to 10 carbons, in which at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — is —CH ⁇ CH
- R 2 is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyl having 2 to 10 carbons
- Ring A 2 and Ring A 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2, 5-diyl or pyrimidine-2,5-diyl
- Z 1 , Z 2 , and Z 3 are independently —CH 2 O—, —OCH 2 —, —COO—, —OCO— or —CH 2
- Item 6. The compound according to item 1, represented by any one of formulas (1-4) to (1-7):
- R 1 and R 2 are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyl having 2 to 10 carbons. Yes;
- Z 1 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, or —CH 2 CH 2 —.
- Item 6. The compound according to item 1, represented by any one of formulas (1-8) to (1-10):
- R 1 and R 2 are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyl having 2 to 10 carbons. Yes;
- Z 2 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, or —CH 2 CH 2 —.
- Item 7. The compound according to item 1, represented by any one of formula (1-11) and formula (1-12):
- R 1 and R 2 are alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyl having 2 to 10 carbons;
- Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, or —CH 2 CH 2 —.
- Item 8. Item 2. The compound according to item 1, represented by any one of formulas (1-13) to (1-24): In formulas (1-13) to (1-24), R 1 is alkenyl having 2 to 5 carbons, R 2 is alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or carbon number 2 to 5 alkenyl.
- Item 9. The compound according to item 1, represented by any one of formulas (1-25) to (1-31): In formulas (1-25) to (1-31), R 1 is alkenyl having 2 to 5 carbons, and R 2 is alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or carbon number 2 to 5 alkenyl.
- Item 10. The compound according to item 1, represented by any one of formulas (1-32) to (1-36): In formulas (1-32) to (1-36), R 1 is alkenyl having 2 to 5 carbons, R 2 is alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or carbon number 2 to 5 alkenyl.
- R 1 is alkenyl having 2 to 5 carbons
- R 2 is alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons 9. The compound according to 8.
- R 1 is alkenyl having 2 to 5 carbons
- R 2 is alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons 9. The compound according to 9.
- R 1 is alkenyl having 2 to 5 carbons
- R 2 is alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons 10. The compound according to 10.
- Item 14 A liquid crystal composition containing at least one of the compounds according to any one of items 1 to 13.
- Item 15. The liquid crystal composition according to item 14, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).
- R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
- Ring B 1 , Ring B 2 , Ring B 3 , and Ring B 4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
- Z 11 , Z 12 , and Z 13 are each independently a single bond, —COO—, —CH 2 CH 2 —, —CH ⁇ CH—, or —C ⁇ C—.
- Item 16 The liquid crystal composition according to item 15, further containing at least one compound selected from the group of compounds represented by formulas (5) to (11).
- R 13 , R 14 , and R 15 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is —O—.
- Ring C 1 , Ring C 2 , Ring C 3 , and Ring C 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen replaced with fluorine 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
- Ring C 5 and Ring C 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6 -Is diyl;
- Z 14, Z 15, Z 16 , and Z 17 are independently a single bond, -COO -, - CH 2 O -, - OCF 2 -, - CH 2 CH 2 -, or
- Item 17. The liquid crystal composition according to item 15 or 16, further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14).
- R 16 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — may be replaced by —O—, At least one hydrogen may be replaced by fluorine;
- X 11 is fluorine, chlorine, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 , —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
- Ring D 1 , Ring D 2 , and Ring D 3 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diy
- Item 18. The liquid crystal composition according to any one of items 15 to 17, further containing at least one compound selected from the group of compounds represented by formula (15).
- R 17 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — may be replaced by —O—, At least one hydrogen may be replaced by fluorine;
- X 12 is —C ⁇ N or —C ⁇ C—C ⁇ N;
- Ring E 1 is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, or pyrimidine-2,5-diyl;
- Z 21 is a single bond, —COO—, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, or
- Item 19 A liquid crystal display device comprising the liquid crystal composition according to any one of items 14 to 15.
- the present invention includes the following items.
- the present invention includes the following items.
- the above composition further comprising two, or at least three additives.
- (D) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C. ) Is ⁇ 2 or less.
- the present invention includes the following items.
- Compound (1) has a single bond, but at least one of Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO It is characterized by being a diatomic linking group such as —, —CH 2 CH 2 —, or —CH ⁇ CH—.
- Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CH 2 CH 2 —, or —CH ⁇ CH—, the rest It may be a single bond.
- the compound (1) has characteristics such as good compatibility, large dielectric anisotropy, and low viscosity compared to similar compounds (see Comparative Examples 1 and 2).
- 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. When this composition is stored at a low temperature, the compound is less likely to precipitate as crystals (or smectic phases).
- This compound has general physical properties necessary for the components of the composition, appropriate optical anisotropy, and appropriate dielectric anisotropy.
- terminal group R, ring A, and bonding group Z of the compound (1) are as follows. This example also applies to the sub-formula of compound (1).
- the compound (1) physical properties can be arbitrarily adjusted by appropriately combining these groups. Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance.
- the definition of the symbol of the compound (1) is as described in item 1.
- R 1 is alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — May be replaced by —CH ⁇ CH—, wherein R 2 is alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyl having 2 to 15 carbons.
- R 1 examples are alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkenyl, alkenyloxy, alkenyloxyalkyl or alkoxyalkenyl. In these groups, a straight chain is preferable to a branched chain. Even when R 1 is branched, it is preferable when it is optically active.
- Preferred R 1 is alkyl, alkoxy, alkoxyalkyl, alkenyl, or alkenyloxy. More desirable R 1 is fluorine, alkyl, alkoxy, or alkenyl. Particularly preferred R 1 is alkenyl.
- alkenyl The preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond.
- alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl
- the trans configuration is preferred.
- alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl
- the cis configuration is preferred.
- R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl, methoxyethyl, methoxypropyl, ethoxy Methyl, ethoxyethyl, ethoxypropyl, propoxymethyl, butoxymethyl, pentoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4- Pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 1-propynyl, or 1-pentenyl.
- Preferred R 1 is methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2 -Butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, or 2-pentenyloxy.
- R 1 is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, or 4-pentenyl.
- Particularly preferred R 1 is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, or 3-butenyl.
- R 2 is alkyl or alkoxy. More preferred R 2 is alkoxy. Particularly preferred R 2 is methyl or ethoxy. Most preferred R 2 is ethoxy.
- ring A 1 and ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5- Diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl
- ring A 3 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, tetrahydro Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl.
- Preferred ring A 1 or ring A 2 is 1,4-cyclohexylene, 1,4-phenylene, or tetrahydropyran-2,5-diyl. More preferred ring A 1 is 1,4-cyclohexylene. More preferred ring A 2 is 1,4-cyclohexylene or 1,4-phenylene. Preferred ring A 3 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or tetrahydropyran-2,5-diyl. More preferred ring A 3 is 1,4-cyclohexylene, 1,4-phenylene, or tetrahydropyran-2,5-diyl. Particularly preferred ring A 3 is 1,4-cyclohexylene or 1,4-phenylene.
- at least one of Z 1 , Z 2 , and Z 3 is —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CH 2 CH 2 —, or —CH ⁇ CH—. is there.
- two of Z 1 , Z 2 and Z 3 are a single bond, and the rest are —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CH 2 CH 2 —, Or —CH ⁇ CH—.
- Preferred Z 1 , Z 2 , or Z 3 is a single bond, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, or —CH 2 CH 2 —. Further preferred Z 1 , Z 2 or Z 3 is a single bond, —CH 2 O—, —COO—, or —CH 2 CH 2 —. Particularly preferred Z 1 , Z 2 , or Z 3 is a single bond, but at least one of Z 1 , Z 2 , and Z 3 is not a single bond. In the most preferred embodiment, two of Z 1 , Z 2 , and Z 3 are single bonds.
- Ring A 1 , Ring A 2 , or Ring A 3 is 1,4-phenylene, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, wherein at least one hydrogen may be replaced by fluorine When the optical anisotropy is large.
- ring A 1 , ring A 2 , or ring A 3 is 1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.
- the maximum temperature is high, the optical anisotropy is small, and the viscosity is small.
- the optical anisotropy is relatively large and the orientational parameter is large.
- the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the maximum temperature is high.
- the bonding group Z 1 , Z 2 , or Z 3 is a single bond, —CH 2 O—, —CH 2 CH 2 —, or —CH ⁇ CH—
- the viscosity is small.
- the bonding group is a single bond, —CH 2 CH 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 optical anisotropy is large.
- MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
- the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) used in the scheme may be the same or different.
- Compounds (1A) to (1J) correspond to compound (1).
- Liquid crystal composition 3-1 Component Compound
- This composition contains at least one compound (1) as component (a).
- This composition may contain two or more compounds (1).
- the component of the composition may be only compound (1).
- the composition preferably contains at least one compound (1) in the range of 1% by weight to 99% by weight in order to develop good physical properties.
- the preferred content of the compound (1) is in the range of 5 to 60% by weight.
- the preferred content of compound (1) is 30% by weight or less.
- This composition contains compound (1) as component (a).
- This composition preferably further contains a liquid crystalline compound selected from components (b) to (e) shown in Table 1.
- a liquid crystalline compound selected from components (b) to (e) shown in Table 1.
- This composition may contain a liquid crystal compound different from the compounds (1) to (15). This composition does not need to contain such a liquid crystalline compound.
- Component (b) is a compound in which two terminal groups are alkyl or the like.
- Preferred examples of component (b) include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). be able to.
- R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is —O—. And in these groups at least one hydrogen may be replaced by fluorine.
- Component (b) has a small dielectric anisotropy.
- Component (b) is close to neutrality.
- Compound (2) has an effect of decreasing the viscosity or adjusting the optical anisotropy.
- Compounds (3) and (4) have the effect of increasing the temperature range of the nematic phase by increasing the maximum temperature or adjusting the optical anisotropy.
- the content of component (b) As the content of component (b) is increased, the viscosity of the composition decreases, but the dielectric anisotropy decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably large.
- the content of component (b) is preferably 30% by weight or more, more preferably 40% by weight or more based on the weight of the liquid crystal composition. is there.
- Component (c) is compounds (5) to (11). These compounds have phenylene in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene.
- Preferred examples of component (c) include compounds (5-1) to (5-8), compounds (6-1) to (6-17), compound (7-1), and compounds (8-1) to ( 8-3), compounds (9-1) to (9-11), compounds (10-1) to (10-3), and compounds (11-1) to (11-3).
- R 13 , R 14 , and R 15 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — May be replaced with —O—, in which at least one hydrogen may be replaced with fluorine, and R 15 may be hydrogen or fluorine.
- Component (c) has a large negative dielectric anisotropy.
- Component (c) is used in preparing a composition for a mode such as IPS, VA, PSA.
- the content of component (c) is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the threshold voltage requirement of the element is satisfied, the content is preferably small.
- the dielectric anisotropy is about ⁇ 5
- the content is preferably 40% by weight or more for sufficient voltage driving.
- the compound (5) is a bicyclic compound, it has an effect of decreasing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (5) and (6) are tricyclic compounds, they have the effect of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (8) to (11) have the effect of increasing the dielectric anisotropy.
- the content of the component (c) is preferably 40% by weight or more, more preferably 50%, based on the weight of the liquid crystal composition. The range is from wt% to 95 wt%.
- the content of component (c) is preferably 30% by weight or less.
- Component (d) is a compound having a halogen- or fluorine-containing group at the right end.
- Preferred examples of component (d) include compounds (12-1) to (12-16), compounds (13-1) to (13-113), and compounds (14-1) to (14-57). Can do.
- R 16 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, In these groups, at least one hydrogen may be replaced by fluorine.
- X 11 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 .
- Component (d) has a positive dielectric anisotropy and has very good stability to heat and light, so it is used when preparing a composition for a mode such as IPS, FFS, OCB.
- the content of component (d) is suitably in the range of 1% to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% to 97% by weight, more preferably from 40% by weight. It is in the range of 95% by weight.
- the content of component (d) is preferably 30% by weight or less.
- Component (e) is a compound (15) in which the right terminal group is —C ⁇ N or —C ⁇ C—C ⁇ N.
- Preferable examples of component (e) include compounds (15-1) to (15-64).
- R 17 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, In these groups, at least one hydrogen may be replaced by fluorine.
- X 12 is —C ⁇ N or —C ⁇ C—C ⁇ N.
- Component (e) has a positive dielectric anisotropy and has a large value, so it is used when preparing a composition for a mode such as TN. By adding this component (e), the dielectric anisotropy of the composition can be increased.
- Component (e) has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy.
- Component (e) is also useful for adjusting the voltage-transmittance curve of the device.
- the content of the component (e) is suitably in the range of 1% by weight to 99% by weight based on the weight of the liquid crystal composition, preferably 10% by weight. % To 97% by weight, more preferably 40% to 95% by weight.
- the content of component (e) is preferably 30% by weight or less.
- a liquid crystal composition satisfying at least one of the physical properties can be prepared.
- a device including such a composition has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifetime.
- the flicker rate (%) can be expressed by (
- An element having a flicker rate in the range of 0% to 1% is less likely to cause flicker on the display screen even when the element is used for a long time.
- This flicker is related to image burn-in, and is presumed to be caused by a potential difference between a positive frame and a negative frame when driven with an alternating current.
- the composition containing the compound (1) is also useful for reducing the occurrence of flicker.
- the liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating.
- additives may be added to the composition.
- the additive include a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent.
- Such additives are well known to those skilled in the art and are described in the literature.
- the composition contains a polymer.
- the polymerizable compound is added for the purpose of forming a polymer in the composition.
- a polymer is produced in the composition by polymerizing the polymerizable compound by irradiating ultraviolet rays with a voltage applied between the electrodes.
- Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy.
- R 25 to R 31 are independently hydrogen or methyl;
- R 32 , R 33 , and R 34 are independently hydrogen or alkyl of 1 to 5 carbons, R 32 , At least one of R 33 and R 34 is alkyl having 1 to 5 carbons;
- v, w, and x are independently 0 or 1;
- u and y are independently 1 to 10 It is an integer.
- L 21 to L 26 are independently hydrogen or fluorine;
- L 27 and L 28 are independently hydrogen, fluorine, or methyl.
- the polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction conditions, the amount of the remaining polymerizable compound can be reduced.
- photo radical polymerization initiators are BASF's Darocur series to TPO, 1173, and 4265, and Irgacure series to 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850. , And 2959.
- photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture It is.
- Polymerization can be performed by adding a photoradical polymerization initiator to the liquid crystal composition and then irradiating it with ultraviolet rays in an applied electric field.
- the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display defects such as image burn-in on the device.
- photopolymerization may be performed without adding a polymerization initiator.
- a preferable wavelength of light to be irradiated is in a range of 150 nm to 500 nm.
- a more preferred wavelength is in the range of 250 nm to 450 nm, and a most preferred wavelength is in the range of 300 nm to 400 nm.
- a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
- the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
- the optically active compound has an effect of preventing reverse twisting by inducing a helical structure in liquid crystal molecules to give a necessary twist angle.
- the helical pitch can be adjusted by adding an optically active compound.
- Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the helical pitch.
- Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18).
- ring J is 1,4-cyclohexylene or 1,4-phenylene
- R 28 is alkyl having 1 to 10 carbons. * Represents an asymmetric carbon.
- An antioxidant is effective for maintaining a large voltage holding ratio.
- Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; BASF).
- the ultraviolet absorber is effective for preventing a decrease in the maximum temperature.
- Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
- AO-3 and AO-4 Specific examples include the following compounds (AO-3) and (AO-4); Tinuvin329, TinuvinP, Tinuvin326, Tinuvin234, Tinuvin213, Tinuvin400, Tinuvin 328 and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO).
- a light stabilizer such as an amine having steric hindrance is preferable in order to maintain a large voltage holding ratio.
- Preferred examples of the light stabilizer include the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770DF (trade name; BASF); LA-77Y and LA- 77G (trade name; ADEKA).
- a thermal stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is Irgafos 168 (trade name: BASF).
- a dichroic dye such as an azo dye or an anthraquinone dye, is added to the composition in order to adapt to a GH (guest host) mode device.
- Antifoaming agents are effective for preventing foaming.
- Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.
- R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR 41 , or —CH 2 CH 2 COOR 41 , where R 41 is 1 carbon atom To 20 alkyls.
- R 42 is alkyl having 1 to 20 carbons.
- R 43 is hydrogen, methyl or O ⁇ be (oxygen radicals); in the compound (AO-7); ring G 1 is 1,4-cyclohexylene or 1,4-phenylene Ring G 2 is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; in compounds (AO-5) and (AO-7) , Z is 1, 2 or 3.
- Liquid crystal display element A liquid crystal composition has operation modes, such as PC, TN, STN, OCB, and PSA, and can be used for the liquid crystal display element driven by an active matrix system.
- This composition has operation modes such as PC, TN, STN, OCB, VA, and IPS, and can also be used for a liquid crystal display element driven by a passive matrix method.
- These elements can be applied to any of a reflective type, a transmissive type, and a transflective type.
- This composition is also suitable for an NCAP (nematic-curvilinear-aligned-phase) element, in which the composition is microencapsulated.
- This composition can also be used for polymer dispersed liquid crystal display elements (PDLCD) and polymer network liquid crystal display elements (PNLCD).
- PDLCD polymer dispersed liquid crystal display elements
- PLCD polymer network liquid crystal display elements
- a PSA mode liquid crystal display element is produced.
- a desirable ratio is in the range of 0.1% by weight to 2% by weight.
- a more desirable ratio is in the range of 0.2% to 1.0% by weight.
- a PSA mode element can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of a reflection type, a transmission type, and a transflective type.
- NMR analysis DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement.
- the sample was dissolved in a deuterated solvent such as CDCl 3 and measured at room temperature, 500 MHz, and 16 integrations. Tetramethylsilane was used as an internal standard.
- CFCl 3 was used as an internal standard and the number of integrations was 24.
- s is a singlet
- d is a doublet
- t is a triplet
- q is a quartet
- quint is a quintet
- sex is a sextet
- m is a multiplet
- br is broad.
- a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
- capillary column DB-1 length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m
- Helium (1 mL / min) was used as the carrier gas.
- the temperature of the sample vaporization chamber was set to 300 ° C.
- the temperature of the detector (FID) was set to 300 ° C.
- the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the obtained solution was injected into the sample vaporization chamber.
- a GC Solution system manufactured by Shimadzu Corporation was used.
- HPLC analysis Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for measurement.
- YMC-Pack ODS-A length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m
- acetonitrile and water were appropriately mixed and used.
- a detector a UV detector, an RI detector, a CORONA detector, or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm.
- a sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 ⁇ L of this solution was introduced into the sample chamber.
- a recorder a C-R7Aplus manufactured by Shimadzu Corporation was used.
- Ultraviolet-visible spectroscopic analysis For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. 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.
- Measurement sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization start temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, dielectric anisotropy of the nematic phase, a mixture of a compound and a mother liquid crystal was used as a sample.
- the ratio of the compound to the base liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight.
- the physical properties of the samples were measured at a rate at which crystals (or smectic phases) did not precipitate at 25 ° C. Unless otherwise specified, the ratio of the compound to the mother liquid crystal is 15% by weight: 85% by weight.
- the dielectric anisotropy of the compound was zero or positive
- the following mother liquid crystal (A) was used.
- the ratio of each component was expressed in wt%.
- the dielectric anisotropy of the compound was zero or negative
- the following mother liquid crystal (B) was used.
- the ratio of each component was expressed in wt%.
- Mother liquid crystal (C) A mother liquid crystal (C) containing the following fluorine-based compound as a component may be used.
- Measurement method Physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberated by the Japan Electronics and Information Technology Industries Association (JEITA; Japan Electronics and Information Technology Industries Association). A modified version of this was also used. No thin film transistor (TFT) was attached to the TN device used for the measurement.
- JEITA Japan Electronics and Information Technology Industries Association
- TFT thin film transistor
- Phase structure A sample was placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measurement apparatus equipped with a polarizing microscope. While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.
- Transition temperature (° C.): For the measurement, a scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, Inc., X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, the end point of the endothermic peak or exothermic peak accompanying the phase change of the sample was obtained by extrapolation, and the transition temperature was determined. The melting point and polymerization initiation temperature of the compound were also measured using this apparatus.
- the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as “lower limit temperature of liquid crystal phase”.
- the temperature at which the compound transitions from the liquid crystal phase to the liquid may be abbreviated as “clearing point”.
- the crystal was represented as C. When two types of crystals could be distinguished, each was represented as C 1 or C 2 .
- the smectic phase is represented as S and the nematic phase is represented as N.
- S A , S B , S C , and S F When a distinction such as a smectic A phase, a smectic B phase, a smectic C phase, and a smectic F phase can be made, they are represented as S A , S B , S C , and S F , respectively.
- the liquid (isotropic) was designated as I.
- the transition temperature is expressed as “C 50.0 N 100.0 I”, for example. This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid is 100.0 ° C.
- T NI or NI; ° C. Maximum temperature of nematic phase
- T C Minimum Temperature of a Nematic Phase
- Viscosity (bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
- VHR-1 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed. The 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. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.
- VHR-2 Voltage holding ratio (10) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured by the above method except that it was measured at 80 ° C. instead of 25 ° C. The obtained results are indicated by the symbol VHR-2.
- Flicker rate (measured at 25 ° C .;%): A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for measurement. The light source was an LED. A sample was put into a normally black mode FFS element in which the distance between two glass substrates (cell gap) was 3.5 ⁇ m and the rubbing direction was anti-parallel. The device was sealed using an adhesive that was cured with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While applying this voltage to the element, the sensor portion was brought close to the element, and the displayed flicker rate was read.
- Viscosity (Rotational Viscosity; ⁇ 1; Measured at 25 ° C .; mPa ⁇ s): The measurement is performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 I followed. A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 ⁇ m. A voltage of 39 V to 50 V was applied to this device step by step. 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 (peak current) and peak time (peak time) of the transient current (transient current) generated by this application were measured.
- 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.
- Elastic constant (K 11 and K 33 ; measured at 25 ° C .; pN): An EC-1 elastic constant measuring instrument manufactured by Toyo Corporation was used for the measurement. A sample was put in a vertical alignment element in which the distance between two glass substrates (cell gap) was 20 ⁇ m. An electric charge of 20 V to 0 V was applied to the device, and electrostatic capacity (C) and applied voltage (V) were measured. These values are fitted using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), equation (2.98), equation (2.101) on page 75, and from equation (2.100) The value of the elastic constant was obtained.
- Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
- the light source was 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 was expressed as a voltage when the transmittance reached 10%.
- 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. It was considered that the transmittance was 100% when the light amount was the maximum, and the transmittance was 0% when the light amount was the minimum.
- the response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).
- Second step A 6N hydrochloric acid (180 mL, 1.08 mol) was added to an acetone solution of the compound (T-4) (293.17 g, 1.10 mol) and 2,2-dimethyl-1,3-propanediol (125.71 g, 1.21 mol). ) was added dropwise and stirred at room temperature for several days. The product was subjected to ordinary post-treatment, and purified by silica gel chromatography and recrystallization to obtain compound (T-5) (140.51 g, 0.48 mol; 43%).
- Step 6 A toluene (200 mL) solution of compound (T-8) (30.54 g, 0.098 mol), imidazole (8.82 g, 0.13 mol) and triphenylphosphine (34.06 g, 0.13 mol) was ice-cooled, A solution of iodine (32.9 g, 0.13 mol) in toluene (300 mL) was added dropwise, and the mixture was stirred at room temperature for several days. The product was subjected to ordinary post-treatment and purified by silica gel chromatography and recrystallization to obtain compound (T-9) (31.59 g, 0.075 mol; 77%).
- Step 7 Compound (T-9) (31.59 g, 0.075 mol) was added to triethylamine (0.8 g, 7.91 mmol), triphenylphosphine (20.89 g, 0.080 mol) and 1,3-dimethyl-3,4, 5,6-Tetrahydro-2 (1H) -pyrimidinone (11 mL) was added, and the mixture was stirred with heating for 7 days. The usual treatment was performed to obtain compound (T-10) (47.56 g, 0.07 mol; 93%).
- Step 8 A solution of compound (T-10) (15.61 g, 0.023 mol) in THF (100 mL) was cooled to ⁇ 60 ° C., potassium t-butoxide (2.80 g, 0.025 mol) was added dropwise, and the mixture was stirred for 1 hour. . Thereto was added dropwise a THF (40 mL) solution of the compound (T-11) (5.37 g, 0.02 mol) synthesized by a known method, and the mixture was returned to room temperature while stirring. The reaction mixture was poured into water, subjected to ordinary post-treatment, and purified by silica gel chromatography to obtain compound (T-12) (10.10 g, 0.019 mol; 93%).
- Step 11 Toluene (75 mL), methanol (150 mL) and p-toluenesulfonic acid (PTSA; 0.71 g, 3.73 mmol) were added to compound (T-14) (5.23 g, 0.011 mol), and the mixture was heated and stirred for 3 hours. . Ordinary post-treatment was performed to obtain compound (T-15) (5.40 g, 0.011 mol; quantitative).
- PTSA p-toluenesulfonic acid
- Step 12 To a solution of compound (T-15) (5.40 g, 0.011 mol) and tetrabutylammonium bromide (TBAB; 0.76 g, 2.36 mmol) in toluene (100 mL) was added 87% formic acid (20 mL) at room temperature. Stir for several hours. The usual post-treatment was performed to obtain the compound (T-16) (3.72 g, 8.08 mmol; 77%).
- TBAB tetrabutylammonium bromide
- Step 6 A solution of methyltriphenylphosphonium bromide (6.01 g, 16.82 mmol) in THF (100 mL) was cooled to ⁇ 70 ° C., potassium t-butoxide (1.82 g, 16.22 mmol) was added dropwise, and the mixture was stirred for 1 hour. A solution of compound (T-23) (6.10 g, 13.42 mmol) in THF (50 mL) was added dropwise thereto, and the mixture was returned to room temperature while stirring. The reaction mixture was poured into water, subjected to ordinary post-treatment, and purified by silica gel chromatography and recrystallization to obtain compound (No. 159) (4.72 g, 10.42 mmol; 78%).
- Phase transition temperature C 104.2 S B 112.6 S A 135.1 N 262.1 I.
- Step 6 To a solution of compound (T-30) (7.97 g, 16.11 mmol) and tetrabutylammonium bromide (TBAB; 1.56 g, 4.83 mmol) in toluene (70 mL) was added 87% formic acid (12.36 mL). Stir at room temperature for several hours. Normal post-treatment was performed. Meanwhile, a solution of methyltriphenylphosphonium bromide (3.47 g, 10.47 mol) in THF (50 mL) was cooled to ⁇ 70 ° C., potassium t-butoxide (1.21 g, 10.78 mmol) was added dropwise, and the mixture was stirred for 1 hour. did.
- TBAB tetrabutylammonium bromide
- Phase transition temperature C 4.8 S C 119.1 S A 187.1 N 277.9 I.
- Phase transition temperature C 21.8 S B 283.81 N 292.4 I.
- Second step A solution of compound (T-37) (3 g, 18.96 mmol), imidazole (1.68 g, 24.65 mmol) and triphenylphosphine (6.46 g, 24.65 mmol) in toluene (30 mL) was ice-cooled, and iodine ( A solution of 6.26 g (24.65 mmol) in toluene (30 mL) was added dropwise, and the mixture was stirred at room temperature for several days. The product was subjected to ordinary post-treatment and purified by silica gel chromatography and recrystallization to obtain compound (T-38) (3.85 g, 14.36 mmol; 70%).
- Phase transition temperature C 82 S B 134.6 S A 138.2 N 276.8 I.
- Phase transition temperature C 85.8 S C 135 S A 156.2 N 245 I.
- Phase transition temperature C 75.6 S C 112.6 S A 181.9 N 250.7 I.
- the present invention includes a mixture of the composition of Use Example 1 and the composition of Use Example 2 in addition to the composition of Use Example.
- the invention also includes a mixture prepared by mixing at least two of the example compositions.
- the compounds in the use examples were represented by symbols based on the definitions in Table 2 below. In Table 2, the configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol ( ⁇ ) means a liquid crystal compound different from the compounds (1) to (15).
- the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive.
- liquid crystal compound of the present invention has good physical properties. Liquid crystal compositions containing this compound can be widely used in liquid crystal display elements such as personal computers and televisions.
Abstract
Description
式(1)において、
R1は炭素数1から15のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は炭素数1から15のアルキル、炭素数1から15のアルコキシ、または炭素数2から15のアルケニルであり;
環A1および環A2は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり、環A3は、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z1、Z2、およびZ3は独立して、単結合、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-であり、Z1、Z2、およびZ3の少なくとも1つは、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-である。
式(1)において、
R1は炭素数1から15のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は炭素数1から15のアルキル、炭素数1から15のアルコキシ、または炭素数2から15のアルケニルであり;
環A1および環A2は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり、環A3は、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z1、Z2、およびZ3は独立して、単結合、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-であり、Z1、Z2、およびZ3の少なくとも1つは、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-である。
ここで、環A3が2-フルオロ-1,4-フェニレンであるとき、環A1および環A2の少なくとも一方は1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり、Z3は単結合である。
ここで、R1がCH2=CH-またはアルケニルオキシであり、Z1およびZ3が単結合であり、Z2が-CH=CH-であるとき、環A1、環A2および環A3の少なくとも1つは、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルである。
ここで、Z1およびZ2が単結合であり、Z3が-CH2O-であるとき、環A2および環A3の少なくとも一方は1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルである。
式(1-1)から式(1-3)において、
R1は、炭素数1から10のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は、炭素数1から10のアルキル、炭素数1から10のアルコキシ、または炭素数2から10のアルケニルであり;
環A2および環A3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z1、Z2、およびZ3は独立して、-CH2O-、-OCH2-、-COO-、-OCO-または-CH2CH2-である。
式(1-4)から式(1-7)において、R1およびR2は独立して、炭素数1から10のアルキル、炭素数1から10のアルコキシ、または炭素数2から10のアルケニルであり;Z1は、-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-である。
式(1-8)から式(1-10)において、R1およびR2は独立して、炭素数1から10のアルキル、炭素数1から10のアルコキシ、または炭素数2から10のアルケニルであり;Z2は、-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-である。
式(1-11)または式(1-12)において、R1およびR2は、炭素数1から10のアルキル、炭素数1から10のアルコキシ、または炭素数2から10のアルケニルであり;Z3は、-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-である。
式(1-13)から式(1-24)において、R1は炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキル、炭素数1から5のアルコキシ、または炭素数2から5のアルケニルである。
式(1-25)から式(1-31)において、R1は炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキル、炭素数1から5のアルコキシ、または炭素数2から5のアルケニルである。
式(1-32)から式(1-36)において、R1は炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキル、炭素数1から5のアルコキシ、または炭素数2から5のアルケニルである。
式(2)から(4)において、
R11およびR12は独立して、炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
環B1、環B2、環B3、および環B4は独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、2,5-ジフルオロ-1,4-フェニレン、またはピリミジン-2,5-ジイルであり;
Z11、Z12、およびZ13は独立して、単結合、-COO-、-CH2CH2-、-CH=CH-、または-C≡C-である。
式(5)から(11)において、
R13、R14、およびR15は独立して、炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく、そしてR15は、水素またはフッ素であってもよく;
環C1、環C2、環C3、および環C4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、少なくとも1つ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;
環C5および環C6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、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;
Z14、Z15、Z16、およびZ17は独立して、単結合、-COO-、-CH2O-、-OCF2-、-CH2CH2-、または-OCF2CH2CH2-であり;
L11およびL12は独立して、フッ素または塩素であり;
S11は、水素またはメチルであり;
Xは、-CHF-または-CF2-であり;
j、k、m、n、p、q、r、およびsは独立して、0または1であり、k、m、n、およびpの和は、1または2であり、q、r、およびsの和は、0、1、2、または3であり、tは、1、2、または3である。
式(12)から(14)において、
R16は炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
X11は、フッ素、塩素、-CF3、-CHF2、-CH2F、-OCF3、-OCHF2、-OCF2CHF2、または-OCF2CHFCF3であり;
環D1、環D2、および環D3は独立して、1,4-シクロヘキシレン、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、1,3-ジオキサン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z18、Z19、およびZ20は独立して、単結合、-COO-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CH=CH-、-C≡C-、または-(CH2)4-であり;
L13およびL14は独立して、水素またはフッ素である。
式(15)において、
R17は炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
X12は-C≡Nまたは-C≡C-C≡Nであり;
環E1は、1,4-シクロヘキシレン、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、1,3-ジオキサン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z21は、単結合、-COO-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、または-C≡C-であり;
L15およびL16は独立して、水素またはフッ素であり;
iは、1、2、3、または4である。
化合物(1)は、単結合を有するが、Z1、Z2、およびZ3の少なくとも1つは、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-のような、2原子の結合基であることを特徴とする。Z1、Z2、およびZ3の1つが、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-であり、残りが単結合であることもある。化合物(1)は、類似の化合物と比較して、相溶性が良好である、誘電率異方性が大きい、粘度が小さい、というような特徴がある(比較例1、2を参照)。
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、そして他の液晶性化合物との相溶性が良好である。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。この組成物を低い温度で保管したとき、この化合物が結晶(または、スメクチック相)として析出する傾向が小さい。この化合物は、組成物の成分に必要な一般的物性、適切な光学異方性、そして適切な誘電率異方性を有する。
化合物(1)の合成法を説明する。化合物(1)は、有機合成化学の方法を適切に組み合わせることによって合成できる。必要とする末端基、環および結合基を出発物に導入する方法は、「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)などの成書に記載されている。
結合基Z1からZ3を生成する方法に関して、最初にスキームを示す。次に、方法(1)から(11)でスキームに記載した反応を説明する。このスキームにおいて、MSG1(またはMSG2)は少なくとも1つの環を有する一価の有機基である。スキームで用いた複数のMSG1(またはMSG2)が表わす一価の有機基は、同一であってもよいし、または異なってもよい。化合物(1A)から(1J)は化合物(1)に相当する。
公知の方法で合成されるアリールホウ酸(21)とハロゲン化物(22)とを、炭酸塩およびテトラキス(トリフェニルホスフィン)パラジウムのような触媒の存在下で反応させて化合物(1A)を合成する。この化合物(1A)は、公知の方法で合成されるハロゲン化物(23)にn-ブチルリチウムを、次いで塩化亜鉛を反応させ、ジクロロビス(トリフェニルホスフィン)パラジウムのような触媒の存在下でハロゲン化物(22)を反応させることによっても合成される。
ハロゲン化物(23)にn-ブチルリチウムを、続いて二酸化炭素を反応させてカルボン酸(24)を得る。公知の方法で合成される化合物(25)とカルボン酸(24)とをDDC(1,3-ジシクロヘキシルカルボジイミド)とDMAP(4-ジメチルアミノピリジン)の存在下で脱水させて化合物(1B)を合成する。
化合物(1B)をローソン試薬のような硫黄化剤で処理してチオノエステル(26)を得る。チオノエステル(26)をフッ化水素ピリジン錯体とNBS(N-ブロモスクシンイミド)でフッ素化し、化合物(1C)を合成する。M. Kuroboshi et al., Chem. Lett., 1992,827.を参照。化合物(1C)はチオノエステル(26)をDAST((ジエチルアミノ)サルファートリフルオリド)でフッ素化しても合成される。W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768.を参照。Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480. に記載の方法によってこの結合基を生成させることも可能である。
ハロゲン化物(22)をn-ブチルリチウムで処理した後、DMF(N,N-ジメチルホルムアミド)と反応させてアルデヒド(28)を得る。公知の方法で合成されるホスホニウム塩(27)をカリウムt-ブトキシドのような塩基で処理してリンイリドを発生させる。このリンイリドをアルデヒド(28)に反応させて化合物(1D)を合成する。反応条件によってはシス体が生成するので、必要に応じて公知の方法によりシス体をトランス体に異性化する。
化合物(1D)をパラジウム炭素のような触媒の存在下で水素化することにより、化合物(1E)を合成する。
ホスホニウム塩(27)の代わりにホスホニウム塩(29)を用い、方法(4)の方法に従って-(CH2)2-CH=CH-を有する化合物を得る。これを接触水素化して化合物(1F)を合成する。
ホスホニウム塩(27)の代わりにホスホニウム塩(30)を、アルデヒド(28)の代わりにアルデヒド(31)を用い、方法(4)の方法に従って化合物(1G)を合成する。反応条件によってはトランス体が生成するので、必要に応じて公知の方法によりトランス体をシス体に異性化する。
ジクロロパラジウムとハロゲン化銅との触媒存在下で、ハロゲン化物(23)に2-メチル-3-ブチン-2-オールを反応させたのち、塩基性条件下で脱保護して化合物(32)を得る。ジクロロパラジウムとハロゲン化銅との触媒存在下、化合物(32)をハロゲン化物(22)と反応させて、化合物(1H)を合成する。
ハロゲン化物(23)をn-ブチルリチウムで処理したあと、テトラフルオロエチレンを反応させて化合物(33)を得る。ハロゲン化物(22)をn-ブチルリチウムで処理したあと化合物(33)と反応させて化合物(1I)を合成する。
アルデヒド(28)を水素化ホウ素ナトリウムなどの還元剤で還元して化合物(34)を得る。化合物(34)を臭化水素酸などで臭素化して臭化物(35)を得る。炭酸カリウムなどの塩基存在下で、臭化物(35)を化合物(36)と反応させて化合物(1J)を合成する。
J. Am. Chem. Soc., 2001, 123, 5414. に記載された方法に従い、ジケトン(-COCO-)をフッ化水素触媒の存在下、四フッ化硫黄でフッ素化して-(CF2)2-を有する化合物を得る。
3-1.成分化合物
本発明の液晶組成物について説明をする。この組成物は、少なくとも1つの化合物(1)を成分(a)として含有する。この組成物は、2つまたは3つ以上の化合物(1)を含有してもよい。組成物の成分が化合物(1)のみであってもよい。組成物は、化合物(1)の少なくとも1つを1重量%から99重量%の範囲で含有することが、良好な物性を発現させるために好ましい。誘電率異方性が負である組成物において、化合物(1)の好ましい含有量は5重量%から60重量%の範囲である。誘電率異方性が正である組成物において、化合物(1)の好ましい含有量は30重量%以下である。
液晶組成物は公知の方法によって調製される。例えば、成分化合物を混合し、そして加熱によって互いに溶解させる。用途に応じて、この組成物に添加物を添加してよい。添加物の例は、重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、消泡剤などである。このような添加物は当業者によく知られており、文献に記載されている。
液晶組成物は、PC、TN、STN、OCB、PSAなどの動作モードを有し、アクティブマトリックス方式で駆動する液晶表示素子に使用できる。この組成物は、PC、TN、STN、OCB、VA、IPSなどの動作モードを有し、パッシブマトリクス方式で駆動する液晶表示素子にも使用することができる。これらの素子は、反射型、透過型、半透過型のいずれのタイプにも適用ができる。
実施例により本発明をさらに詳しく説明する。実施例は典型的な例であるので、本発明は実施例によって制限されない。化合物(1)は、下記の手順により合成した。合成した化合物は、NMR分析などの方法により同定した。化合物や組成物の物性、および素子の特性は、下記の方法により測定した。
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。
公知の方法で合成した化合物(T-2)(15.5g、27.5mmol)のTHF(100mL)溶液を-60℃に冷却し、カリウムt-ブトキシド(3.08g、27.5mmol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-1)(6.7g、25mmol)のTHF(100mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製した。精製物(8.3g、17.6mmol;70%)にソルミックスA-11(100mL)、トルエン(50mL)と6Nの塩酸(20mL)を加え、加熱還流を4日間行った。通常の後処理を行い、カラムクロマトグラフィー、再結晶にて精製を行い、化合物(No.121)(4.6g、9.75mmol;55%)を得た。
(メトキシメチル)トリフェニルホスホニウムクロリド(482.08g、1.41mol)のTHF(2L)溶液を-60℃に冷却し、カリウムt-ブトキシド(215.66g、1.92mol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-3)(300.67g、1.26mol)のTHF(900mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-4)(293.17g、1.10mol;87%)を得た。
化合物(T-4)(293.17g、1.10mol)と2,2-ジメチル-1,3-プロパンジオール(125.71g、1.21mol)のアセトン溶液に6Nの塩酸(180mL、1.08mol)を滴下し、室温で数日間攪拌した。通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-5)(140.51g、0.48mol;43%)を得た。
(メトキシメチル)トリフェニルホスホニウムクロリド(197.39g、0.58mol)のTHF(700mL)溶液を-60℃に冷却し、カリウムt-ブトキシド(59.29g、0.53mol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-5)(140g、0.48mol)のTHF(700mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-6)(153.51g、0.48mol;定量的)を得た。
化合物(T-6)(153g、0.47mol)とテトラブチルアンモニウムブロミド(TBAB;9.28g、0.029mol)の塩化メチレン(600mL)溶液に6Nの塩酸(380mL、1.14mol)を滴下し、22時間攪拌した。通常の後処理を行った後、後処理を行った溶液にNaOH(1.13g、0.028mol)とソルミックスA-11(1.1L)を加え、室温で18時間攪拌した。通常の後処理を行い、化合物(T-7)(150.28g、0.49mol、cis/trans=9/91;定量的)を得た。ソルミックス(登録商標)A-11は、エタノール(85.5%)、メタノール(13.4%)とイソプロパノール(1.1%)の混合物であり、日本アルコール販売(株)から入手した。
水素化ホウ素ナトリウム(11.21g、0.30mol)のエタノール(500mL)溶液を氷冷し、化合物(T-7)(146.21g、0.47mol)のエタノール(600mL)溶液を滴下し、室温で18時間攪拌した。通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-8)(81.97g、0.26mol;56%)を得た。
化合物(T-8)(30.54g、0.098mol)、イミダゾール(8.82g、0.13mol)とトリフェニルホスフィン(34.06g、0.13mol)のトルエン(200mL)溶液を氷冷し、ヨウ素(32.9g、0.13mol)のトルエン(300mL)溶液を滴下した後、室温で数日間攪拌した。通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-9)(31.59g、0.075mol;77%)を得た。
化合物(T-9)(31.59g、0.075mol)にトリエチルアミン(0.8g、7.91mmol)、トリフェニルホスフィン(20.89g、0.080mol)と1,3-ジメチル-3,4,5,6-テトラヒドロ-2(1H)-ピリミジノン(11mL)を加え、加熱攪拌を7日間行った。通常の処理を行い、化合物(T-10)(47.56g、0.07mol;93%)を得た。
化合物(T-10)(15.61g、0.023mol)のTHF(100mL)溶液を-60℃に冷却し、カリウムt-ブトキシド(2.80g、0.025mol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-11)(5.37g、0.02mol)のTHF(40mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-12)(10.10g、0.019mol;93%)を得た。
化合物(T-12)(10.10g、0.019mol)をトルエン(100mL)と2-プロパノール(IPA;100mL)に溶解させ、さらにPd/C(0.24g)を加え水素雰囲気下、水素を吸収しなくなるまで、室温で攪拌した。Pd/Cを除去した後、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-13)(6.21g、0.011mol;61%)を得た。
化合物(T-13)(6.21g、0.011mol)とテトラブチルアンモニウムブロミド(TBAB;0.84g、2.61mmol)のトルエン(300mL)溶液に87%のギ酸(40mL)を加え、11時間加熱攪拌した。通常の後処理を行い、化合物(T-14)(6.47g、0.014mol、cis/trans=24/76;定量的)を得た。
化合物(T-14)(5.23g、0.011mol)にトルエン(75mL)、メタノール(150mL)とp-トルエンスルホン酸(PTSA;0.71g、3.73mmol)を加え、3時間加熱攪拌した。通常の後処理を行い、化合物(T-15)(5.40g、0.011mol;定量的)を得た。
化合物(T-15)(5.40g、0.011mol)とテトラブチルアンモニウムブロミド(TBAB;0.76g、2.36mmol)のトルエン(100mL)溶液に87%のギ酸(20mL)を加え、室温で数時間攪拌した。通常の後処理を行い、化合物(T-16)(3.72g、8.08mmol;77%)を得た。
メチルトリフェニルホスホニウムブロミド(3.47g、10.47mol)のTHF(50mL)溶液を-70℃に冷却し、カリウムt-ブトキシド(1.21g、10.78mmol)を滴下し、1時間攪拌した。そこへ化合物(T-16)(3.72g、8.08mmol)のTHF(50mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(No.122)(2.86g、6.24mmol;77%)を得た。
化合物(T-17)(15.86g、0.023mol)のTHF(200mL)溶液を-40℃に冷却し、カリウムt-ブトキシド(2.72g、0.024mol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-18)(5.30g、0.02mol)のTHF(40mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-19)(10.01g、0.018mol;92%)を得た。
化合物(T-19)(10.01g、0.019mol)をトルエン(500mL)と2-プロパノール(IPA;100mL)に溶解させ、さらにPd/C(0.98g)を加え、水素雰囲気下、水素を吸収しなくなるまで、室温で攪拌した。Pd/Cを除去した後、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-20)(8.55g、0.016mol;85%)を得た。
化合物(T-20)(8.55g、0.016mol)とテトラブチルアンモニウムブロミド(TBAB;1.10g、3.41mmol)のトルエン(400mL)溶液に87%のギ酸(40mL)を加え、17時間加熱攪拌した。通常の後処理を行い、化合物(T-21)(7.02g、0.015mol、cis/trans=28/72;定量的)を得た。
化合物(T-21)(7.02g、0.015mol)にトルエン(200mL)、メタノール(500mL)とp-トルエンスルホン酸(PTSA;0.93g、4.89mmol)を加え、7時間加熱攪拌した。通常の後処理を行い、再結晶により精製し、化合物(T-22)(7.04g、0.014mol;91%)を得た。
化合物(T-22)(7.04g、0.014mol)とテトラブチルアンモニウムブロミド(TBAB;0.91g、2.82mmol)のトルエン(150mL)溶液に87%のギ酸(15mL)を加え、室温で数時間攪拌した。通常の後処理を行い、化合物(T-23)(6.10g、13mmol;95%)を得た。
メチルトリフェニルホスホニウムブロミド(6.01g、16.82mmol)のTHF(100mL)溶液を-70℃に冷却し、カリウムt-ブトキシド(1.82g、16.22mmol)を滴下し、1時間攪拌した。そこへ化合物(T-23)(6.10g、13.42mmol)のTHF(50mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(No.159)(4.72g、10.42mmol;78%)を得た。
物性の比較
比較化合物として、特開2002-193853の段落0103に記載された、下記の化合物(S-1)を選んだ。この化合物の結合基が全て単結合であり、この点で本発明の化合物とは異なるからである。この化合物は公知の方法で合成した。
公知の方法で合成した化合物(T-25)(23.27g、42.56mmol)のTHF(150mL)溶液を-60℃に冷却し、カリウムt-ブトキシド(4.78g、42.56mmol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-24)(12g、35.47mmol)のTHF(50mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-26)(16.84g、35.34mmol;100%)を得た。
化合物(T-26)(16.9g、35.46mmol)をトルエン(150mL)と2-プロパノール(IPA;150mL)に溶解させ、さらにPd/C(0.507g)を加え水素雰囲気下、水素を吸収しなくなるまで、室温で攪拌した。Pd/Cを除去した後、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-27)(16.84g、35.19mmol;99%)を得た。
化合物(T-27)(16.84g、35.19mmol)のトルエン(160mL)溶液に87%のギ酸(13.5mL)を加え、8時間加熱攪拌した。通常の後処理を行い、化合物(T-28)(15.5g、35.67mmol;定量的)を得た。
(メトキシメチル)トリフェニルホスホニウムクロリド(13.49g、39.49mmol)のTHF(150mL)溶液を-60℃に冷却し、カリウムt-ブトキシド(4.42g、39.36mol)を滴下し、1時間攪拌した。化合物(T-28)(15.55g、35.79mmol)のTHF(150mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーにより精製し、化合物(T-29)(12g、25.94mmol;72%)を得た。
化合物(T-29)(11.45g、24.75mmol)にトルエン(300mL)、メタノール(200mL)とp-トルエンスルホン酸(PTSA;1.41g、7.43mmol)を加え、3時間加熱攪拌した。通常の後処理を行い、化合物(T-30)(7.97g、16.11mmol;65%)を得た。
化合物(T-30)(7.97g、16.11mmol)とテトラブチルアンモニウムブロミド(TBAB;1.56g、4.83mmol)のトルエン(70mL)溶液に87%のギ酸(12.36mL)を加え、室温で数時間攪拌した。通常の後処理を行った。一方、メチルトリフェニルホスホニウムブロミド(3.47g、10.47mol)のTHF(50mL)溶液を-70℃に冷却し、カリウムt-ブトキシド(1.21g、10.78mmol)を滴下し、1時間攪拌した。そこへ先ほど後処理を行った溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(No.76)(2.8g、6.27mmol;39%)を得た。
物性の比較
比較化合物として、下記の化合物(S-2)を選んだ。この化合物の結合基が全て単結合であり、この点で本発明の化合物とは異なるからである。この化合物は、特開2002-193853の式Iの化合物に包含される。この化合物は公知の方法で合成した。
公知の方法で合成した化合物(T-31)(5g、12.61mmol)のトルエン(50mL)溶液に87%のギ酸(9.7mL)を加え、数時間室温攪拌した。通常の後処理を行った。一方、公知の方法で合成した化合物(T-32)(6.7g、12.61mmol)のTHF(50mL)溶液を-30℃に冷却し、カリウムt-ブトキシド(1.56g、13.87mmol)を滴下し、1時間攪拌した。そこへ先ほど後処理を行った溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-33)(5g、10.58mmol;84%)を得た。
化合物(T-33)(5g、10.58mmol)をトルエン(50mL)と2-プロパノール(IPA;50mL)に溶解させ、さらにPd/C(0.15g)を加え水素雰囲気下、水素を吸収しなくなるまで、室温で攪拌した。Pd/Cを除去した後、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(No.1)(2.78g、5.86mmol;55%)を得た。
化合物(T-37)(3g、18.96mmol)、イミダゾール(1.68g、24.65mmol)とトリフェニルホスフィン(6.46g、24.65mmol)のトルエン(30mL)溶液を氷冷し、ヨウ素(6.26g、24.65mmol)のトルエン(30mL)溶液を滴下した後、室温で数日間攪拌した。通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(T-38)(3.85g、14.36mmol;70%)を得た。
化合物(T-38)(3.85g、14.36mmol)にトリエチルアミン(0.15g、1.44mmol)、トリフェニルホスフィン(3.95g、15.08mol)と1,3-ジメチル-3,4,5,6-テトラヒドロ-2(1H)-ピリミジノン(1.93mL)を加え、加熱攪拌を7日間行った。通常の処理を行い、化合物(T-39)(3.15g、5.94mmol;41%)を得た。
化合物(T-39)(3.15g、5.94mmol)のTHF(20mL)溶液を-30℃に冷却し、カリウムt-ブトキシド(0.67g、5.94mmol)を滴下し、1時間攪拌した。そこへ公知の方法で合成した化合物(T-40)(1.67g、4.95mmol)のTHF(10mL)溶液を滴下し、攪拌しながら室温に戻した。反応混合物を水へ注ぎ、通常の後処理を行い、シリカゲルクロマトグラフィーと再結晶により精製した。そこへトルエン(7mL)とTHF(15mL)を加え、さらにPd/C(0.13g)を加え水素雰囲気下、水素を吸収しなくなるまで、室温で攪拌した。Pd/Cを除去した後、シリカゲルクロマトグラフィーと再結晶により精製し、化合物(No.452)(0.95g、2.04mmol;72%)を得た。
V-HH2HB(2F,3F)-O2 (No.122) 2%
V-HH2BB(2F,3F)-O2 (No.159) 3%
2-HB-C (15-1) 5%
3-HB-C (15-1) 10%
3-HB-O2 (2-5) 15%
2-BTB-1 (2-10) 3%
3-HHB-F (13-1) 4%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 12%
3-HHEB-F (13-10) 4%
5-HHEB-F (13-10) 4%
2-HHB(F)-F (13-2) 7%
3-HHB(F)-F (13-2) 7%
5-HHB(F)-F (13-2) 7%
3-HHB(F,F)-F (13-3) 5%
NI=106.9℃;η=19.6mPa・s;Δn=0.103;Δε=4.1.
V-HH2BB(2F,3F)-O4 (No.160) 3%
V2-HH2BB(2F,3F)-O2 (No.163) 3%
3-HB-CL (12-2) 10%
3-HH-4 (2-1) 12%
3-HB-O2 (2-5) 8%
3-HHB(F,F)-F (13-3) 3%
3-HBB(F,F)-F (13-24) 28%
5-HBB(F,F)-F (13-24) 24%
5-HBB(F)B-2 (4-5) 4%
5-HBB(F)B-3 (4-5) 5%
V-H2BBB(2F,3F)-O2 (No.76) 2%
V-H2HBB(2F,3F)-O2 (No.45) 3%
7-HB(F,F)-F (12-4) 3%
3-HB-O2 (2-5) 7%
2-HHB(F)-F (13-2) 8%
3-HHB(F)-F (13-2) 9%
5-HHB(F)-F (13-2) 10%
2-HBB(F)-F (13-23) 9%
3-HBB(F)-F (13-23) 9%
5-HBB(F)-F (13-23) 14%
2-HBB-F (13-22) 4%
3-HBB-F (13-22) 4%
5-HBB-F (13-22) 3%
3-HBB(F,F)-F (13-24) 5%
5-HBB(F,F)-F (13-24) 10%
4-HH2BB(2F,3F)-O2 (No.158) 3%
V-HH1OBB(2F,3F)-O2 (No.161) 5%
5-HB-CL (15-2) 14%
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 4%
3-HHB-F (13-1) 3%
3-HHB-CL (13-1) 3%
4-HHB-CL (13-1) 3%
3-HHB(F)-F (13-2) 10%
4-HHB(F)-F (13-2) 9%
5-HHB(F)-F (13-2) 8%
7-HHB(F)-F (13-2) 8%
5-HBB(F)-F (13-23) 3%
1O1-HBBH-5 (4-1) 3%
3-HHBB(F,F)-F (14-6) 2%
4-HHBB(F,F)-F (14-6) 3%
5-HHBB(F,F)-F (14-6) 3%
3-HH2BB(F,F)-F (14-15) 3%
4-HH2BB(F,F)-F (14-15) 3%
V-HH1OBB(2F,3F)-3 (No.161) 3%
3-HHVHB(2F,3F)-O2 (No.121) 3%
3-HHB(F,F)-F (13-3) 8%
3-H2HB(F,F)-F (13-15) 8%
4-H2HB(F,F)-F (13-15) 8%
5-H2HB(F,F)-F (13-15) 7%
3-HBB(F,F)-F (13-24) 20%
5-HBB(F,F)-F (13-24) 18%
3-H2BB(F,F)-F (13-27) 10%
5-HHBB(F,F)-F (14-6) 3%
5-HHEBB-F (14-17) 2%
3-HH2BB(F,F)-F (14-15) 3%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 3%
3-BB2HB(2F,3F)-O2 (No.202) 3%
V-HVHBB(2F,3F)-3 (No.67) 3%
5-HB-F (12-2) 10%
6-HB-F (12-2) 9%
7-HB-F (12-2) 6%
2-HHB-OCF3 (13-1) 6%
3-HHB-OCF3 (13-1) 7%
4-HHB-OCF3 (13-1) 6%
5-HHB-OCF3 (13-1) 5%
3-HH2B-OCF3 (13-4) 4%
5-HH2B-OCF3 (13-4) 4%
3-HHB(F,F)-OCF2H (13-3) 4%
3-HHB(F,F)-OCF3 (13-3) 5%
3-HH2B(F)-F (13-5) 3%
3-HBB(F)-F (13-23) 9%
5-HBB(F)-F (13-23) 10%
5-HBBH-3 (4-1) 3%
3-HB(F)BH-3 (4-2) 3%
3-HBH1OB(2F,3F)-3 (No.422) 3%
V-HHH2B(2F,3F)-O2 (No.302) 5%
5-HB-CL (12-2) 9%
3-HH-4 (2-1) 8%
3-HHB-1 (3-1) 5%
3-HHB(F,F)-F (13-3) 7%
3-HBB(F,F)-F (13-24) 17%
5-HBB(F,F)-F (13-24) 15%
3-HHEB(F,F)-F (13-12) 9%
4-HHEB(F,F)-F (13-12) 3%
5-HHEB(F,F)-F (13-12) 3%
2-HBEB(F,F)-F (13-39) 3%
3-HBEB(F,F)-F (13-39) 5%
5-HBEB(F,F)-F (13-39) 3%
3-HHBB(F,F)-F (14-6) 5%
3-BH1OB(2F)B(2F,3F)-O2
(No.237) 3%
3-B2HB(F)B(2F,3F)-3 (No.108) 4%
3-HB-CL (12-2) 6%
5-HB-CL (12-2) 4%
3-HHB-OCF3 (13-1) 5%
3-H2HB-OCF3 (13-13) 4%
5-H4HB-OCF3 (13-19) 14%
V-HHB(F)-F (13-2) 4%
3-HHB(F)-F (13-2) 5%
5-HHB(F)-F (13-2) 5%
3-H4HB(F,F)-CF3 (13-21) 7%
5-H4HB(F,F)-CF3 (13-21) 9%
5-H2HB(F,F)-F (13-15) 5%
5-H4HB(F,F)-F (13-21) 6%
2-H2BB(F)-F (13-26) 4%
3-H2BB(F)-F (13-26) 10%
3-HBEB(F,F)-F (13-39) 5%
V-HHDh1OB(2F,3F)-O2 (No.446) 5%
5-HB-CL (12-2) 17%
7-HB(F,F)-F (12-4) 3%
3-HH-4 (2-1) 8%
3-HH-5 (2-1) 5%
3-HB-O2 (2-5) 15%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 5%
2-HHB(F)-F (13-2) 6%
3-HHB(F)-F (13-2) 6%
5-HHB(F)-F (13-2) 7%
3-HHB(F,F)-F (13-3) 6%
3-H2HB(F,F)-F (13-15) 5%
4-H2HB(F,F)-F (13-15) 5%
V-HH2HB(2F,3F)-O2 (No.122) 3%
5-HB-CL (12-2) 3%
7-HB(F)-F (12-3) 7%
3-HH-4 (2-1) 9%
3-HH-5 (2-1) 10%
3-HB-O2 (2-5) 13%
3-HHEB-F (13-10) 7%
5-HHEB-F (13-10) 7%
3-HHEB(F,F)-F (13-12) 10%
4-HHEB(F,F)-F (13-12) 5%
3-GHB(F,F)-F (13-109) 5%
4-GHB(F,F)-F (13-109) 5%
5-GHB(F,F)-F (13-109) 7%
2-HHB(F,F)-F (13-3) 4%
3-HHB(F,F)-F (13-3) 5%
NI=74.5℃;η=19.1mPa・s;Δn=0.069;Δε=5.4.
V-HH2BB(2F,3F)-O2 (No.159) 3%
1V2-BEB(F,F)-C (15-13) 6%
3-HB-C (15-1) 18%
2-BTB-1 (2-10) 10%
5-HH-VFF (2-1) 27%
3-HHB-1 (3-1) 4%
VFF-HHB-1 (3-1) 7%
VFF2-HHB-1 (3-1) 11%
3-H2BTB-2 (3-17) 6%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%
NI=87.3℃;η=13.6mPa・s;Δn=0.136;Δε=6.3.
V-HH2BB(2F,3F)-O4 (No.160) 5%
5-HB(F)B(F,F)XB(F,F)-F
(14-41) 5%
3-BB(F)B(F,F)XB(F,F)-F
(14-47) 3%
4-BB(F)B(F,F)XB(F,F)-F
(14-47) 5%
5-BB(F)B(F,F)XB(F,F)-F
(14-47) 3%
3-HH-V (2-1) 41%
3-HH-V1 (2-1) 6%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB(F)B-1 (3-6) 4%
1V2-BB-F (12-1) 3%
3-BB(F,F)XB(F,F)-F (13-97) 10%
3-HHBB(F,F)-F (14-6) 3%
V2-HH2BB(2F,3F)-O2 (No.163) 3%
V-H2BBB(2F,3F)-O2 (No.76) 3%
3-GB(F)B(F,F)XB(F,F)-F
(14-57) 5%
3-BB(F)B(F,F)XB(F,F)-F
(14-47) 3%
4-BB(F)B(F,F)XB(F,F)-F
(14-47) 7%
5-BB(F)B(F,F)XB(F,F)-F
(14-47) 3%
3-HH-V (2-1) 38%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 3%
V-HHB-1 (3-1) 3%
V2-BB(F)B-1 (3-6) 5%
1V2-BB-F (12-1) 3%
3-BB(F,F)XB(F,F)-F
(13-97) 6%
3-GB(F,F)XB(F,F)-F
(13-113) 5%
3-HHBB(F,F)-F (14-6) 3%
Claims (19)
- 式(1)で表される化合物。
式(1)において、
R1は炭素数1から15のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は炭素数1から15のアルキル、炭素数1から15のアルコキシ、または炭素数2から15のアルケニルであり;
環A1および環A2は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり、環A3は、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z1、Z2、およびZ3は独立して、単結合、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-であり、Z1、Z2、およびZ3の少なくとも1つは、-CH2O-、-OCH2-、-COO-、-OCO-、-CH2CH2-、または-CH=CH-である。
ここで、環A3が2-フルオロ-1,4-フェニレンであるとき、環A1および環A2の少なくとも一方は1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり、Z3は単結合である。
ここで、R1がCH2=CH-またはアルケニルオキシであり、Z1およびZ3が単結合であり、Z2が-CH=CH-であるとき、環A1、環A2および環A3の少なくとも1つは、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルである。
ここで、Z1およびZ2が単結合であり、Z3が-CH2O-であるとき、環A2および環A3の少なくとも一方は1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルである。 - 式(1)において、R1は炭素数1から15のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は炭素数1から15のアルキル、炭素数1から15のアルコキシ、または炭素数2から15のアルケニルであり;環A1は、1,4-シクロヘキシレンであり、環A2および環A3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z1、Z2、およびZ3は独立して、単結合、-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-であり、Z1、Z2、およびZ3の少なくとも1つは-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-である、請求項1に記載の化合物。
- 式(1)において、R1は炭素数2から10のアルケニルであり、R2は炭素数1から15のアルキル、炭素数1から15のアルコキシ、または炭素数2から15のアルケニルであり;環A1は、1,4-シクロヘキシレンであり、環A2および環A3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;Z1、Z2、およびZ3は独立して、単結合、-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-であり、Z1、Z2、およびZ3の少なくとも1つは-CH2O-、-OCH2-、-COO-、-OCO-、または-CH2CH2-である、請求項1に記載の化合物。
- 式(1-1)、式(1-2)、または式(1-3)で表される、請求項1に記載の化合物。
式(1-1)から式(1-3)において、
R1は、炭素数1から10のアルキルであり、このアルキルにおいて、少なくとも1つの-CH2-は-O-で置き換えられてもよく、少なくとも1つの-CH2CH2-は-CH=CH-で置き換えられてもよく、R2は、炭素数1から10のアルキル、炭素数1から10のアルコキシ、または炭素数2から10のアルケニルであり;
環A2および環A3は独立して、1,4-シクロヘキシレン、1,4-フェニレン、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリジン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z1、Z2、およびZ3は独立して、-CH2O-、-OCH2-、-COO-、-OCO-または-CH2CH2-である。 - 式(1-13)から式(1-18)において、R1が炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキルまたは炭素数1から5のアルコキシである、請求項8に記載の化合物。
- 式(1-25)から式(1-28)において、R1が炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキルまたは炭素数1から5のアルコキシである、請求項9に記載の化合物。
- 式(1-32)または式(1-33)において、R1が炭素数2から5のアルケニルであり、R2は炭素数1から5のアルキルまたは炭素数1から5のアルコキシである、請求項10に記載の化合物。
- 請求項1から13のいずれか1項に記載の化合物の少なくとも1つを含有する液晶組成物。
- 式(2)から(4)で表される化合物の群から選択された少なくとも1つの化合物をさらに含有する、請求項14に記載の液晶組成物。
式(2)から(4)において、
R11およびR12は独立して、炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
環B1、環B2、環B3、および環B4は独立して、1,4-シクロヘキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、2,5-ジフルオロ-1,4-フェニレン、またはピリミジン-2,5-ジイルであり;
Z11、Z12、およびZ13は独立して、単結合、-COO-、-CH2CH2-、-CH=CH-、または-C≡C-である。 - 式(5)から(11)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15に記載の液晶組成物。
式(5)から(11)において、
R13、R14、およびR15は独立して、炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく、そしてR15は、水素またはフッ素であってもよく;
環C1、環C2、環C3、および環C4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、少なくとも1つ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;
環C5および環C6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、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;
Z14、Z15、Z16、およびZ17は独立して、単結合、-COO-、-CH2O-、-OCF2-、-CH2CH2-、または-OCF2CH2CH2-であり;
L11およびL12は独立して、フッ素または塩素であり;
S11は、水素またはメチルであり;
Xは、-CHF-または-CF2-であり;
j、k、m、n、p、q、r、およびsは独立して、0または1であり、k、m、n、およびpの和は、1または2であり、q、r、およびsの和は、0、1、2、または3であり、tは、1、2、または3である。 - 式(12)から(14)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15または16に記載の液晶組成物。
式(12)から(14)において、
R16は炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
X11は、フッ素、塩素、-CF3、-CHF2、-CH2F、-OCF3、-OCHF2、-OCF2CHF2、または-OCF2CHFCF3であり;
環D1、環D2、および環D3は独立して、1,4-シクロヘキシレン、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、1,3-ジオキサン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z18、Z19、およびZ20は独立して、単結合、-COO-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CH=CH-、-C≡C-、または-(CH2)4-であり;
L13およびL14は独立して、水素またはフッ素である。 - 式(15)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15から17のいずれか1項に記載の液晶組成物。
式(15)において、
R17は炭素数1から10のアルキルまたは炭素数2から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、少なくとも1つの-CH2-は-O-で置き換えられてもよく、これらの基において、少なくとも1つの水素はフッ素で置き換えられてもよく;
X12は-C≡Nまたは-C≡C-C≡Nであり;
環E1は、1,4-シクロヘキシレン、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、1,3-ジオキサン-2,5-ジイル、またはピリミジン-2,5-ジイルであり;
Z21は、単結合、-COO-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、または-C≡C-であり;
L15およびL16は独立して、水素またはフッ素であり;
iは、1、2、3、または4である。 - 請求項14から18のいずれか1項に記載の液晶組成物を含む液晶表示素子。
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Publication number | Publication date |
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TWI693275B (zh) | 2020-05-11 |
JPWO2017126275A1 (ja) | 2018-11-08 |
EP3406585A4 (en) | 2019-07-31 |
EP3406585A1 (en) | 2018-11-28 |
US20200239775A1 (en) | 2020-07-30 |
JP6930429B2 (ja) | 2021-09-01 |
KR20180101346A (ko) | 2018-09-12 |
CN108473404A (zh) | 2018-08-31 |
TW201805408A (zh) | 2018-02-16 |
EP3406585B1 (en) | 2020-07-29 |
CN108473404B (zh) | 2022-02-11 |
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