WO2009154080A1 - 液晶組成物および液晶表示素子 - Google Patents
液晶組成物および液晶表示素子 Download PDFInfo
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- WO2009154080A1 WO2009154080A1 PCT/JP2009/060140 JP2009060140W WO2009154080A1 WO 2009154080 A1 WO2009154080 A1 WO 2009154080A1 JP 2009060140 W JP2009060140 W JP 2009060140W WO 2009154080 A1 WO2009154080 A1 WO 2009154080A1
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- 0 *C(CC1)CCC1c(ccc(*I)c1F)c1F Chemical compound *C(CC1)CCC1c(ccc(*I)c1F)c1F 0.000 description 7
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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
- C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
- C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
Definitions
- 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 relates to an IPS (in-plane switching) mode, VA (vertical alignment) mode, or PSA (polymer sustainable alignment) mode element containing the composition.
- the classification based on the operation mode of the liquid crystal includes 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), PSA (polymer sustained alignment) mode, and the like.
- the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film insulator), MIM (metal insulator metal), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process.
- the classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.
- the elements contain a liquid crystal composition having appropriate characteristics.
- This liquid crystal composition has a nematic phase.
- the general characteristics of the composition are improved.
- the relationships in the two general characteristics are summarized in Table 1 below.
- the general characteristics of the composition will be further described based on a commercially available AM device.
- the temperature range of the nematic phase is related to the temperature range in which the device can be used.
- the preferable upper limit temperature of the nematic phase is 70 ° C. or higher, and the preferable lower limit temperature of the nematic phase is ⁇ 10 ° C. or lower.
- the viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.
- 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 0.30 ⁇ m to 0.40 ⁇ m for the VA mode element, and the range is 0.20 ⁇ m to 0.30 ⁇ m for the IPS mode element.
- a composition having a large optical anisotropy is preferable for a device having a small cell gap.
- the dielectric anisotropy having a large absolute value in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device.
- a dielectric anisotropy having a large absolute value is preferable.
- a large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a high temperature in the initial stage is preferable.
- the stability of the composition against ultraviolet rays and heat is related to the lifetime of the liquid crystal display device. When their stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used in a liquid crystal projector, a liquid crystal television, and the like.
- a composition having a positive dielectric anisotropy is used for an AM device having a TN mode.
- a composition having negative dielectric anisotropy is used for an AM device having a VA mode.
- a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode.
- a composition having a positive or negative dielectric anisotropy is used in an AM device having a PSA mode.
- Patent Document 1 An example of a liquid crystal composition having negative dielectric anisotropy is disclosed in the following Patent Document 1. Although the liquid crystal composition containing the compound containing a 1st component is disclosed by patent document 2 and patent document 3, it is related with the liquid crystal composition which has positive dielectric constant anisotropy. An example of a liquid crystal composition containing the compound of the first component is disclosed in Patent Document 3, but a liquid crystal composition having negative dielectric anisotropy is not disclosed.
- Desirable AM elements have such characteristics as a wide usable temperature range, a short response time, a large contrast ratio, a low threshold voltage, a large voltage holding ratio, and a long life. A shorter response time is desirable even at 1 millisecond. Therefore, desirable properties of the composition include 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 positive or negative dielectric anisotropy, a large specific resistance, and a high resistance to ultraviolet light. High stability, high heat stability, etc.
- One object of the present invention is to provide 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.
- 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.
- Another purpose is a composition with suitable optical anisotropy, negatively large dielectric anisotropy, high stability to ultraviolet rays, etc., and short response time, large voltage holding ratio, large contrast ratio, long lifetime An AM device having the above.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number 2 in which any hydrogen is replaced with fluorine.
- R 3 is alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons
- one of X 1 and X 2 is hydrogen and the other is fluorine
- ring A is independently 1,4-cyclohexylene, the one CH 2 group that is present may be replaced by oxygen, or a 1,4-phenylene
- Z 1 is independently a single bond, ethylene, methyleneoxy or carbonyloxy,; m 1 or 2.
- the advantages of the present invention are that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, the small viscosity, the appropriate optical anisotropy, the negative dielectric constant anisotropy, the large specific resistance, the high stability to ultraviolet rays, the heat It is a liquid crystal composition satisfying at least one of the properties such as high stability against the liquid crystal.
- 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.
- Other aspects are compositions with suitable optical anisotropy, negatively large dielectric anisotropy, high stability to ultraviolet light, etc., and short response time, large voltage holding ratio, large contrast ratio, long lifetime An AM device having the above.
- 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.
- An optically active compound or polymerizable compound may be added to the composition.
- Compound (1) means one compound or two or more compounds represented by formula (1). The same applies to compounds represented by other formulas. “Arbitrary” indicates that not only the position but also the number is arbitrary, but the case where the number is 0 is not included.
- 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 but also at a high temperature in the initial stage, and has a large specific resistance not only at room temperature but also at a high temperature after a long period of use.
- “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature but also at a high temperature in the initial stage, and has a large voltage holding ratio not only at room temperature but also at a high temperature after long use. means.
- the first component is one compound or two or more compounds.
- the “ratio of the first component” means the percentage by weight (% by weight) of the first component based on the total weight of the liquid crystal composition. The same applies to the ratio of the second component.
- the ratio of the additive mixed with the composition means a percentage by weight (% by weight) or a percentage by weight (ppm) based on the total weight of the liquid crystal composition.
- R 1 is used for a plurality of compounds.
- the meanings of any two R 1 may be the same or different.
- R 1 of compound (1) is ethyl and R 1 of compound (1-1) is ethyl.
- R 1 of compound (1) is ethyl and R 1 of compound (1-1) is propyl.
- This rule also applies to R 2 , R 3 and the like.
- “CL” in the chemical formula represents chlorine.
- the present invention includes the following items. 1. Contains at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component And a liquid crystal composition having negative dielectric anisotropy.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number 2 in which any hydrogen is replaced with fluorine.
- R 3 is alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons
- one of X 1 and X 2 is hydrogen and the other is fluorine
- ring A is independently 1,4-cyclohexylene, or 1,4- phenylene, 1,4 to any one -CH 2 xylene cyclo - may be replaced by -O-
- Z 1 is independently a single bond, ethylene, methyleneoxy or carbonyloxy, It is alkoxy
- m is 1 or 2.
- the proportion of the first component is in the range of 5% to 30% by weight and the proportion of the second component is in the range of 30% to 95% by weight based on the total weight of the liquid crystal composition.
- Liquid crystal composition is in the range of 5% to 30% by weight and the proportion of the second component is in the range of 30% to 95% by weight based on the total weight of the liquid crystal composition.
- Item 3 The liquid crystal according to any one of items 1 and 2, which contains at least one compound selected from the group of compounds represented by formula (3) as a third component in addition to the first component and the second component.
- Composition where, R 5 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or from 2 carbons 12 alkenyl, or alkenyl having 2 to 12 carbon atoms in which any hydrogen is replaced by fluorine; ring B and ring C are each independently 1,4-cyclohexylene or 1,4-phenylene; ; Z 2 is a single bond, ethylene, methyleneoxy or carbonyloxy.
- Item 4 The liquid crystal composition according to item 3, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1).
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number 2 in which any hydrogen is replaced with fluorine. To 12 alkenyl.
- Item 6 The liquid crystal composition according to any one of items 3 to 5, wherein the second component is at least one compound selected from the group of compounds represented by formulas (2-1) to (2-7).
- R 3 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 carbons To 12 alkenyl.
- Item 7 The liquid crystal composition according to any one of items 3 to 6, wherein the third component is at least one compound selected from the group of compounds represented by formulas (3-1) to (3-3).
- R 5 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons
- R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or from 2 carbons 12 alkenyl, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine.
- the first component is at least one compound selected from the group of compounds represented by formula (1-1), and the second component is a compound represented by formulas (2-1) to (2-7) Item 3.
- the proportion of the first component is in the range of 5 wt% to 30 wt%
- the proportion of the second component is in the range of 30 wt% to 80 wt%
- the third component Item 10.
- Item 10 The component according to any one of Items 3 to 10, further comprising at least one compound selected from the group of compounds represented by formula (4) as a fourth component in addition to the first component, the second component, and the third component: 2.
- R 7 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons
- R 8 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 carbons
- Ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4.
- Z 3 is a single bond, ethylene, methyleneoxy or carbonyloxy.
- 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 15 The liquid crystal composition according to any one of items 1 to 14.
- Item 16 A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 15.
- Item 17 The liquid crystal display element according to item 16, wherein the operation mode of the liquid crystal display element is a VA mode, an IPS mode, or a PSA mode, and the driving method of the liquid crystal display element is an active matrix method.
- the present invention includes the following items. 1) The above composition further containing an optically active compound, 2) the above composition further containing additives such as an antioxidant, an ultraviolet absorber, an antifoaming agent, a polymerizable compound and a polymerization initiator. 3) an AM device containing the above composition, 4) a device containing the above composition and having a mode of TN, ECB, OCB, IPS, VA, or PSA, 5) containing the above composition Transmission type element, 6) Use of the above composition as a composition having a nematic phase, 7) Use of the above composition as an optically active composition by adding an optically active compound to the above composition.
- additives such as an antioxidant, an ultraviolet absorber, an antifoaming agent, a polymerizable compound and a polymerization initiator.
- additives such as an antioxidant, an ultraviolet absorber, an antifoaming agent, a polymerizable compound and a polymerization initiator.
- an AM device containing the above composition
- 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 component compounds, 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.
- the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), and the compound (4). 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.
- Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, and the like. Impurities are compounds mixed in a process such as synthesis of component compounds. Even if this compound is a liquid crystal compound, it is classified as an impurity here.
- Composition B consists essentially of a compound selected from compound (1), compound (2), compound (3), and compound (4). “Substantially” means that the composition may contain additives and impurities, but does not contain a liquid crystal compound different from these compounds. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the physical properties can be further adjusted by mixing other liquid crystal compounds.
- the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained.
- the main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention.
- L means large or high
- M means moderate
- S means small or low.
- the symbols L, M, and S are classifications based on a qualitative comparison among the component compounds.
- the symbol 0 (zero) in the dielectric anisotropy means that the characteristic of dielectric anisotropy is not large positively or negatively and is almost zero.
- Compound (1) increases the maximum temperature.
- Compound (2) increases the absolute value of dielectric anisotropy.
- Compound (3) decreases the viscosity.
- Compound (4) adjusts the appropriate optical anisotropy and lowers the minimum temperature.
- the combination of the components in the composition is first component + second component, first component + second component + third component, and first component + second component + third component + fourth component.
- a preferred combination of components in the composition is the first component + second component for further increasing the absolute value of the dielectric anisotropy, the first component + second component + third component for decreasing the viscosity, and First component + second component + third component + fourth component.
- a desirable ratio of the first component is 5% by weight or more for increasing the maximum temperature, and is 30% by weight or less for decreasing the minimum temperature.
- a more desirable ratio is in the range of 5% to 25% by weight.
- a particularly desirable ratio is in the range of 5% to 20% by weight.
- a desirable ratio of the second component is 30% by weight or more for increasing the absolute value of the dielectric anisotropy, and 95% by weight or less for decreasing the viscosity.
- a more desirable ratio is in the range of 30% to 80% by weight.
- a particularly desirable ratio is in the range of 40% by weight to 70% by weight.
- a desirable ratio of the third component is 5% by weight or more for decreasing the viscosity, and 50% by weight or less for increasing the absolute value of the dielectric anisotropy.
- a more desirable ratio is in the range of 5% to 40% by weight.
- a particularly desirable ratio is in the range of 10% to 30% by weight.
- a desirable ratio of the fourth component is 5% by weight or more for decreasing the minimum temperature, and 30% by weight or less for increasing the absolute value of the dielectric anisotropy.
- a more desirable ratio is in the range of 5% to 15% by weight.
- a particularly desirable ratio is in the range of 5% to 10% by weight.
- R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which any hydrogen is replaced by fluorine.
- R 3 , R 5 and R 7 are independently alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
- R 4 and R 8 are independently having 1 to 12 carbons.
- R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons Or an alkenyl having 2 to 12 carbon atoms in which any hydrogen is replaced by fluorine.
- Desirable R 1 and R 2 are each alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons for decreasing the minimum temperature. Further preferred R 1 and R 2 are at least one of alkenyl having 2 to 12 carbons. Desirable R 3 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat. Desirable R 4 is alkoxy having 1 to 12 carbons for increasing the absolute value of the dielectric anisotropy. Desirable R 5 , R 6 , R 7 and R 8 are each alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, or alkenyl having 2 to 12 carbons for decreasing the minimum temperature. It is.
- 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.
- Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
- Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
- the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
- Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
- Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
- linear alkenyl is preferable to branching.
- alkenyl in which any hydrogen is replaced by fluorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4- Pentenyl and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.
- Ring A is independently 1,4-cyclohexylene, one CH 2 group present in the ring may be replaced by oxygen, or 1,4-phenylene, ring B and ring C is independently 1,4-cyclohexylene or 1,4-phenylene, and when m is 2, the two rings A may be the same or different.
- Preferred ring A is 1,4-cyclohexylene for decreasing the viscosity.
- Ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. In the case of 3-fluoro-1,4-phenylene, either direction is acceptable. Desirable ring C, ring D and ring E are each 1,4-cyclohexylene for decreasing the viscosity, or 1,4-phenylene for increasing the optical anisotropy.
- One of X 1 and X 2 is hydrogen, and the other is fluorine.
- X 1 is hydrogen and X 2 is fluorine for decreasing the minimum temperature.
- Z 1 is independently a single bond, ethylene, methyleneoxy, or carbonyloxy. Z 1 when m is 2 may be the same or different. Preferred Z 1 is a single bond or ethylene for decreasing the viscosity, or methyleneoxy for increasing the absolute value of the dielectric anisotropy.
- Z 2 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z 2 is a single bond for decreasing the viscosity.
- Z 3 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z 3 is a single bond for decreasing the viscosity.
- M is 1 or 2.
- Preferred m is 1 for decreasing the minimum temperature, and 2 for increasing the maximum temperature.
- R 9 is alkenyl having 2 to 12 carbons.
- R 10 is straight-chain alkyl having 1 to 12 carbons or straight-chain alkoxy having 2 to 12 carbons.
- trans is preferable to cis for the configuration of 1,4-cyclohexylene for increasing the maximum temperature.
- Desirable compound (1) is compound (1-1), compound (1-2) and compound (1-1-1) to compound (1-1-3). More desirable compound (1) is compound (1-1). Particularly preferred compounds (1) are the compound (1-1-1) and the compound (1-1-2). Desirable compounds (2) are the compounds (2-1) to (2-7). More desirable compounds (2) are the compound (2-1), the compound (2-2), the compound (2-4) and the compound (2-7). Desirable compounds (3) are the compounds (3-1) to (3-3). More desirable compound (3) is the compound (3-1). Desirable compounds (4) are the compounds (4-1) to (4-3). More desirable compound (4) is the compound (4-1).
- additives that may be mixed with the composition will be described.
- Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators 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 compounds are compound (5-1) to compound (5-4).
- a desirable ratio of the optically active compound is 5% by weight or less.
- a more desirable ratio is in the range of 0.01% to 2% by weight.
- an antioxidant is mixed into the composition. Is done.
- Preferred examples of the antioxidant include a compound (6) where n is an integer of 1 to 9.
- n is 1, 3, 5, 7, or 9. Further preferred n is 1 or 7. Since the compound (6) in which n is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (6) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time.
- a desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 300 ppm.
- the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
- a desirable ratio in these absorbents and stabilizers is 50 ppm or more for obtaining the effect thereof, and 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 10,000 ppm.
- a dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition so as to be adapted to a GH (guest host) mode element.
- a preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight.
- an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition.
- a desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and 1000 ppm or less for preventing a poor display.
- a more desirable ratio is in the range of 1 ppm to 500 ppm.
- a polymerizable compound is mixed with the composition in order to adapt to a PSA (polymer-sustained alignment) mode element.
- Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl, vinyloxy, propenyl ether, or epoxy (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are acrylate or methacrylate derivatives.
- a desirable ratio of the polymerizable compound is 0.05% by weight or more for obtaining the effect thereof, and is 10% by weight or less for preventing a display defect. A more desirable ratio is from 0.1% by weight to 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
- Irgacure 184 registered trademark
- Darocure 1173 registered trademark
- the polymerizable compound preferably contains 0.1% to 5% of a photopolymerization initiator. Particularly preferably, it contains 1 to 3% by weight of a photopolymerization initiator.
- compositions have a minimum temperature of ⁇ 10 ° C. or lower, a maximum temperature of 70 ° C. or higher, and an optical anisotropy in the range of 0.07 to 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 0.08 to 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 an IPS or VA 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 sample When the sample was a composition, it was measured as it was and the obtained value was described.
- 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.
- the components of the mother liquid crystals are as follows. The proportion of the components is% by weight.
- Measured characteristic values according to the following method. Many of them are the methods described in the Standard of Electronics Industry Association of Japan EIAJ ED-2521A, or a modified method thereof.
- NI Maximum temperature of nematic phase
- a sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
- the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
- T C Minimum temperature of nematic phase
- Viscosity (bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s): An E-type viscometer was used for measurement.
- Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s): Measurement was performed according to the method described in M. ⁇ ImaiMet al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. This TN device was applied stepwise in increments of 0.5V in the range of 16V to 19.5V. 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 value of rotational viscosity was obtained from these measured values and M. Imai et al., The calculation formula (8) on page 40.
- the value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity was 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.
- 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 device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and this device is used with a UV curing adhesive. 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; 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 polymerized by ultraviolet rays after putting a sample.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- the area B is an area when it is not attenuated.
- the voltage holding ratio is a percentage of the area A with respect to the area B.
- Voltage holding ratio (VHR-2; 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 polymerized by ultraviolet rays after putting a sample.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- the area B is an area when it is not attenuated.
- the voltage holding ratio is a percentage of the area A with respect to the area B.
- 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 element and irradiated with light 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.
- the decreasing voltage was measured for 16.7 milliseconds.
- VHR-3 is preferably 90% or more, and more preferably 95% or more.
- VHR-4 Voltage holding ratio
- the TN device into which the sample was injected was heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured to evaluate the stability against heat.
- a composition having a large VHR-4 has a large stability to heat.
- the decreasing voltage was measured for 16.7 milliseconds.
- Response time ( ⁇ ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
- the light source is a halogen lamp.
- the low-pass filter was set to 5 kHz.
- a sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and this device is used with a UV curing adhesive. And sealed.
- a rectangular wave 60 Hz, 10 V, 0.5 seconds
- 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 the time (fall time; millisecond) required to change the transmittance from 90% to 10%.
- 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 ratio of the liquid crystal compound contained in the composition may be calculated by the following method. Liquid crystalline compounds can be detected by gas chromatography. The area ratio of peaks in the gas chromatogram corresponds to the ratio (number of moles) of liquid crystal compounds. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Accordingly, the ratio (% by weight) of the liquid crystal compound is calculated from the peak area ratio.
- the present invention will be described in detail by examples.
- the present invention is not limited by the following examples.
- 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 total weight of the liquid crystal composition, and the liquid crystal composition contains impurities in addition to this.
- Comparative Example 1 This composition is a liquid crystal composition having a negative dielectric anisotropy and not containing the first component of the present invention.
- the composition of Comparative Example 1 is a liquid crystal composition in which the first component of the composition of Inventive Example 1 is replaced with a 4-ring similar compound that is not replaced with fluorine. This composition was prepared and measured by the method described above. The components and properties of this composition are as follows.
- Example 1 The composition of Example 1 is a liquid crystal composition in which the tetracyclic compound contained in the composition of Comparative Example 1 is replaced with the first component compound (1-1-3).
- V-HB (F) HH-5 (1-1-1) 5% 3-HB (F) HH-5 (1-1-3) 5% V-HB (2F, 3F) -O2 (2-1) 15% 3-H1OB (2F, 3F) -O2 (2-3) 10% 3-HHB (2F, 3F) -O2 (2-4) 3% 2-HBB (2F, 3F) -O2 (2-7) 5% 3-HBB (2F, 3F) -O2 (2-7) 8% 5-HBB (2F, 3F) -O2 (2-7) 7% 2-HH-3 (3-1) 5% 3-HH-O1 (3-1) 16% 3-HHB-3 (4-1) 5% 3-HHB-O1 (4-1) 4% 5-HBB-2 (4-2) 3% 1-BB (F) B-2V (4-3) 2% 3-HHEH-3 (-) 3% 1O1-HBBH-5 (-) 2% 4-HHEBH-5 (-) 2% NI 91.2 ° C .; Tc ⁇ ⁇ 20 ° C
- the liquid crystal composition satisfies at least one characteristic or has an appropriate balance regarding at least two characteristics. Since it is a liquid crystal display element containing such a composition, it becomes an AM element having a short response time, a large voltage holding ratio, a large contrast ratio, a long lifetime, and the like, and can be used for a liquid crystal projector, a liquid crystal television, and the like.
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Abstract
Description
ここで、R1およびR2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、または任意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;R3は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R4は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルであり;X1、およびX2は一方が水素であり、他方がフッ素であり;環Aは独立して、1,4-シクロへキシレン、この環の中に存在する1個のCH2基は酸素で置き換えられてもよく、または1,4-フェニレンであり;Z1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;mは1または2である。
1. 第一成分として式(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つの化合物を含有し、そして負の誘電率異方性を有する液晶組成物。
ここで、R1およびR2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、または任意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;R3は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R4は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルであり;X1およびX2は、一方が水素であり、他方がフッ素であり;環Aは独立して、1,4-シクロへキシレン、または1,4-フェニレンであり、1,4-シクロへキシレンの任意の1つの-CH2-は-O-で置き換えられてもよく;Z1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;mは1または2である。
ここで、R5は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R6は、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、または任意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Cは独立して、1,4-シクロへキシレンまたは1,4-フェニレンであり、;Z2は、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る。
ここで、R1およびR2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、または任意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、R5は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R6は、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、または任意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、R7は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R8は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルであり;環Dおよび環Eは独立して、1,4-シクロへキシレン、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;Z3は、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る。
ここで、R7は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R8は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルである。
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、液晶組成物の全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誘電率異方性が負の液晶組成物である。この比較例1の組成物は、本発明実施例1の組成物の第一成分をフッ素で置き換えられていない4環の類似化合物に置き換えた液晶組成物である。本組成物を調製し、上述した方法により測定した。この組成物の成分および特性は下記のとおりである。
2-HBHH-3 (-) 8%
3-H2B(2F,3F)-O2 (2-2) 17%
5-H2B(2F,3F)-O2 (2-2) 17%
2-HBB(2F,3F)-O2 (2-7) 3%
3-HBB(2F,3F)-O2 (2-7) 10%
5-HBB(2F,3F)-O2 (2-7) 10%
2-HH-3 (3-1) 25%
V-HHB-1 (4-1) 4%
3-HHB(2F,3CL)-O2 (-) 3%
5-HHB(2F,3CL)-O2 (-) 3%
NI=79.9℃;Tc≦0℃;Δn=0.092;η=21.7mPa・s;Δε=-2.7;Vth=2.40V
実施例1の組成物は、比較例1の組成物に含有する4環の化合物を第一成分の化合物(1-1-3)に置き換えた液晶組成物である。
3-HB(F)HH-5 (1-1-3) 8%
3-H2B(2F,3F)-O2 (2-2) 17%
5-H2B(2F,3F)-O2 (2-2) 17%
2-HBB(2F,3F)-O2 (2-7) 3%
3-HBB(2F,3F)-O2 (2-7) 10%
5-HBB(2F,3F)-O2 (2-7) 10%
2-HH-3 (3-1) 25%
V-HHB-1 (4-1) 4%
3-HHB(2F,3CL)-O2 (-) 3%
5-HHB(2F,3CL)-O2 (-) 3%
NI=79.8℃;Tc≦-20℃;Δn=0.092;η=20.5mPa・s;Δε=-3.1;Vth=2.32V
実施例1の組成物は、比較例1のそれと比較して、低いネマチック相の下限温度、小さな粘度および負に大きな誘電率異方性を有する。
3-HB(F)HH-5 (1-1-3) 10%
3-H2B(2F,3F)-O2 (2-2) 20%
5-H2B(2F,3F)-O2 (2-2) 21%
3-HH-V (3-1) 19%
V-HHB-1 (4-1) 5%
3-HHB(2F,3CL)-O2 (-) 4%
5-HHB(2F,3CL)-O2 (-) 5%
3-HBB(2F,3CL)-O2 (-) 8%
5-HBB(2F,3CL)-O2 (-) 8%
NI=81.2℃;Tc≦-30℃;Δn=0.091;Δε=-3.3;Vth=2.32V
3-HB(F)HH-2 (1-1-3) 3%
3-HB(F)HH-5 (1-1-3) 6%
5-HB(F)HH-2 (1-1-3) 3%
5-HB(F)HH-5 (1-1-3) 4%
3-H2B(2F,3F)-O2 (2-2) 26%
5-H2B(2F,3F)-O2 (2-2) 27%
2-HBB(2F,3F)-O2 (2-7) 3%
3-HBB(2F,3F)-O2 (2-7) 9%
5-HBB(2F,3F)-O2 (2-7) 9%
3-HH1OCro(7F,8F)-5 (-) 2%
3-HHB(2F,3CL)-O2 (-) 3%
5-HHB(2F,3CL)-O2 (-) 3%
5-HBB(F)B-2 (-) 2%
NI=88.2℃;Tc≦-20℃;Δn=0.111;η=47.7mPa・s;Δε=-5.2;Vth=2.13V
3-HB(F)HH-V (1-1-2) 4%
5-HB(F)HH-V (1-1-2) 10%
5-HB(F)HH-V1 (1-1-2) 3%
3-H2B(2F,3F)-O2 (2-2) 24%
5-H2B(2F,3F)-O2 (2-2) 27%
V2-HHB(2F,3F)-O2 (2-4) 6%
3-HHB(2F,3F)-O2 (2-4) 4%
2-HBB(2F,3F)-O2 (2-7) 3%
3-HBB(2F,3F)-O2 (2-7) 10%
5-HBB(2F,3F)-O2 (2-7) 9%
NI=89.9℃;Tc≦-20℃;Δn=0.108;η=44.7mPa・s;Δε=-5.2;Vth=2.06V;VHR-1=99.2%;VHR-2=94.7%
3-HB(F)HH-5 (1-1-3) 15%
V-HB(2F,3F)-O1 (2-1) 10%
V-HB(2F,3F)-O2 (2-1) 20%
V-HB(2F,3F)-O4 (2-1) 15%
2-HBB(2F,3F)-O2 (2-7) 5%
3-HBB(2F,3F)-O2 (2-7) 9%
5-HBB(2F,3F)-O2 (2-7) 10%
2-HH-3 (3-1) 6%
3-HHB-1 (4-1) 5%
3-HHB-3 (4-1) 3%
2-HHB(2F,3CL)-O2 (-) 2%
NI=78.2℃;Tc≦-20℃;Δn=0.103;Δε=-4.4;Vth=1.79V
3-HB(F)HH-5 (1-1-3) 9%
V-HB(2F,3F)-O2 (2-1) 17%
V-HB(2F,3F)-O4 (2-1) 9%
2-HBB(2F,3F)-O2 (2-7) 3%
3-HBB(2F,3F)-O2 (2-7) 10%
5-HBB(2F,3F)-O2 (2-7) 10%
2-HH-3 (3-1) 29%
3-HHB-1 (4-1) 6%
2-HHB(2F,3CL)-O2 (-) 2%
3-HHB(2F,3CL)-O2 (-) 3%
5-HHB(2F,3CL)-O2 (-) 2%
NI=80.4℃;Tc≦-20℃;Δn=0.090;η=18.0mPa・s;Δε=-2.9;Vth=2.19V
3-HB(F)HH-5 (1-1-3) 10%
V-HB(2F,3F)-O2 (2-1) 25%
2-HBB(2F,3F)-O2 (2-7) 5%
3-HBB(2F,3F)-O2 (2-7) 11%
5-HBB(2F,3F)-O2 (2-7) 7%
3-HH-O1 (3-1) 28%
3-HHB-3 (4-1) 5%
3-HHB-O1 (4-1) 4%
3-HHEH-3 (-) 3%
3-HHEH-5 (-) 2%
NI=81.1℃;Tc≦-20℃;Δn=0.091;η=19.8mPa・s;Δε=-3.0;Vth=2.30V
3-HB(F)HH-5 (1-1-3) 9%
V-HB(2F,3F)-O2 (2-1) 14%
V-HB(2F,3F)-O4 (2-1) 14%
2-HBB(2F,3F)-O2 (2-7) 6%
3-HBB(2F,3F)-O2 (2-7) 11%
5-HBB(2F,3F)-O2 (2-7) 7%
2-HH-3 (3-1) 28%
3-HHB-3 (4-1) 3%
3-HHB-O1 (4-1) 3%
3-HHEH-3 (-) 3%
3-HHEH-5 (-) 2%
NI=79.7℃;Tc≦-20℃;Δn=0.091;η=17.2mPa・s;Δε=-2.8;Vth=2.27V
3-HB(F)HH-5 (1-1-3) 5%
3-HB(2F,3F)-O2 (2-1) 4%
5-HB(2F,3F)-O2 (2-1) 12%
1V2-HB(2F,3F)-O2 (2-1) 14%
2-HHB(2F,3F)-1 (2-4) 11%
3-HHB(2F,3F)-1 (2-4) 11%
3-HHB(2F,3F)-O2 (2-4) 11%
5-HHB(2F,3F)-O2 (2-4) 8%
3-HH-4 (3-1) 11%
3-HH-5 (3-1) 6%
3-HB-O2 (3-2) 7%
NI=82.5℃;Tc≦-30℃;Δn=0.083;η=21.7mPa・s;Δε=-3.2;Vth=2.24V
3-HB(F)HH-5 (1-1-3) 4%
5-HB(2F)HH-V (1-2) 4%
3-H2B(2F,3F)-O2 (2-2) 18%
5-H2B(2F,3F)-O2 (2-2) 16%
V-HHB(2F,3F)-O2 (2-4) 4%
V-HHB(2F,3F)-O4 (2-4) 4%
3-HH1OB(2F,3F)-O2 (2-6) 5%
4-HH1OB(2F,3F)-O2 (2-6) 4%
3-HBB(2F,3F)-O2 (2-7) 10%
5-HBB(2F,3F)-O2 (2-7) 3%
2-HH-3 (3-1) 20%
3-HHB-1 (4-1) 5%
3-HHB-O1 (4-1) 3%
NI=83.7℃;Tc≦-20℃;Δn=0.089;η=21.7mPa・s;Δε=-3.6;Vth=2.28V
3-HB(F)HH-5 (1-1-3) 4%
3-H2B(2F,3F)-O2 (2-2) 20%
5-H2B(2F,3F)-O2 (2-2) 20%
3-HH2B(2F,3F)-O2 (2-5) 10%
5-HH2B(2F,3F)-O2 (2-5) 10%
3-HBB(2F,3F)-O2 (2-7) 8%
5-HBB(2F,3F)-O2 (2-7) 8%
3-HH-V (3-1) 6%
V2-BB-1 (3-3) 4%
2-BB(F)B-3 (4-3) 10%
NI=82.6℃;Tc≦-30℃;Δn=0.120;η=23.6mPa・s;Δε=-4.2;Vth=2.01V
V-HB(F)HH-5 (1-1-1) 5%
3-HB(F)HH-5 (1-1-3) 5%
V-HB(2F,3F)-O2 (2-1) 15%
3-H1OB(2F,3F)-O2 (2-3) 10%
3-HHB(2F,3F)-O2 (2-4) 3%
2-HBB(2F,3F)-O2 (2-7) 5%
3-HBB(2F,3F)-O2 (2-7) 8%
5-HBB(2F,3F)-O2 (2-7) 7%
2-HH-3 (3-1) 5%
3-HH-O1 (3-1) 16%
3-HHB-3 (4-1) 5%
3-HHB-O1 (4-1) 4%
5-HBB-2 (4-2) 3%
1-BB(F)B-2V (4-3) 2%
3-HHEH-3 (-) 3%
1O1-HBBH-5 (-) 2%
4-HHEBH-5 (-) 2%
NI=91.2℃;Tc≦-20℃;Δn=0.102;η=22.9mPa・s;Δε=-3.5;Vth=2.29V
Claims (17)
- 第一成分として式(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つの化合物を含有し、そして負の誘電率異方性を有する液晶組成物。
ここで、R1およびR2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、または任意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;R3は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R4は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルであり;X1およびX2は、一方が水素であり、他方がフッ素であり;環Aは独立して、1,4-シクロへキシレン、または1,4-フェニレンであり、1,4-シクロへキシレンの任意の1つの-CH2-は-O-で置き換えられてもよく;Z1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;mは1または2である。 - 液晶組成物の全重量に基づいて、第一成分の割合が5重量%から30重量%の範囲であり、そして第二成分の割合が30重量%から95重量%の範囲である請求項1に記載の液晶組成物。
- 第一成分の上記式(1-1)において、R1およびR2の少なくとも一方が炭素数2から12のアルケニル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4に記載の液晶組成物。
- 第三成分が式(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7に記載の液晶組成物。
- 第一成分が式(1-1)で表される化合物の群から選択された少なくとも1つの化合物であり、第二成分が式(2-1)から式(2-7)で表される化合物の群から選択された少なくとも1つの化合物であり、そして第三成分が式(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項3から8のいずれか1項に記載の液晶組成物。
- 液晶組成物の全重量に基づいて、第一成分の割合が5重量%から30重量%の範囲であり、第二成分の割合が30重量%から80重量%の範囲であり、そして第三成分の割合が5重量%から50重量%の範囲である請求項3から9のいずれか1項に記載の液晶組成物。
- 第一成分、第二成分および第三成分に加えて、第四成分として式(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3から10のいずれか1項に記載の液晶組成物。
ここで、R7は、炭素数1から12のアルキル、または炭素数2から12のアルケニルであり;R8は、炭素数1から12のアルキル、炭素数1から12のアルコキシ、または炭素数2から12のアルケニルであり;環Dおよび環Eは独立して、1,4-シクロへキシレン、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;Z3は、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る。 - 第四成分が、式(4-1)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12に記載の液晶組成物。
- 液晶組成物の全重量に基づいて、第四成分の割合が5重量%から30重量%の範囲である請求項11から13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1から14のいずれか1項に記載の液晶組成物。
- 請求項1から15のいずれか1項に記載の液晶組成物を含有する液晶表示素子。
- 液晶表示素子の動作モードが、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16に記載の液晶表示素子。
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US12/999,047 US8491814B2 (en) | 2008-06-16 | 2009-06-03 | Liquid crystal composition and liquid crystal display device |
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JP2012077201A (ja) * | 2010-10-01 | 2012-04-19 | Dic Corp | ネマチック液晶組成物及びこれを用いた液晶表示素子 |
JP2014240486A (ja) * | 2008-12-22 | 2014-12-25 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 液晶媒体 |
JP2017048394A (ja) * | 2011-03-29 | 2017-03-09 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 液晶媒体 |
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CN102888226A (zh) * | 2012-10-13 | 2013-01-23 | 江苏和成显示科技股份有限公司 | 包含共轭分离型液晶化合物的向列相液晶组合物及其应用 |
CN110317613B (zh) * | 2018-03-28 | 2022-03-11 | 江苏和成显示科技有限公司 | 一种液晶组合物及液晶显示器件 |
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JP2002193853A (ja) * | 2000-12-19 | 2002-07-10 | Merck Patent Gmbh | 負のdc異方性の四環式化合物および液晶媒体 |
JP2002533526A (ja) * | 1998-12-22 | 2002-10-08 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | 液晶媒体 |
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ES2058433T3 (es) * | 1988-10-20 | 1994-11-01 | Merck Patent Gmbh | Indicador matriz de cristal liquido. |
US7595100B2 (en) * | 2006-06-29 | 2009-09-29 | Chisso Corporation | Liquid crystal composition and liquid crystal display device |
JP5098241B2 (ja) | 2006-07-20 | 2012-12-12 | Jnc株式会社 | 液晶組成物および液晶表示素子 |
CN102186946B (zh) * | 2008-10-15 | 2014-02-12 | Jnc株式会社 | 液晶组成物以及液晶显示元件 |
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JP2000328060A (ja) * | 1989-08-26 | 2000-11-28 | Merck Patent Gmbh | 液晶化合物 |
JP2002533526A (ja) * | 1998-12-22 | 2002-10-08 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | 液晶媒体 |
JP2002193853A (ja) * | 2000-12-19 | 2002-07-10 | Merck Patent Gmbh | 負のdc異方性の四環式化合物および液晶媒体 |
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JP2014240486A (ja) * | 2008-12-22 | 2014-12-25 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 液晶媒体 |
JP2012077201A (ja) * | 2010-10-01 | 2012-04-19 | Dic Corp | ネマチック液晶組成物及びこれを用いた液晶表示素子 |
JP2017048394A (ja) * | 2011-03-29 | 2017-03-09 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 液晶媒体 |
US20180119010A1 (en) * | 2011-03-29 | 2018-05-03 | Merck Patent Gmbh | Liquid-crystalline medium |
US20210277310A1 (en) * | 2011-03-29 | 2021-09-09 | Merck Patent Gmbh | Liquid-crystalline medium |
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CN102057016B (zh) | 2014-04-16 |
JPWO2009154080A1 (ja) | 2011-11-24 |
TW201009052A (en) | 2010-03-01 |
JP5333448B2 (ja) | 2013-11-06 |
TWI441904B (zh) | 2014-06-21 |
US20110163269A1 (en) | 2011-07-07 |
US8491814B2 (en) | 2013-07-23 |
CN102057016A (zh) | 2011-05-11 |
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