WO2010106910A1 - 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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- WO2010106910A1 WO2010106910A1 PCT/JP2010/053339 JP2010053339W WO2010106910A1 WO 2010106910 A1 WO2010106910 A1 WO 2010106910A1 JP 2010053339 W JP2010053339 W JP 2010053339W WO 2010106910 A1 WO2010106910 A1 WO 2010106910A1
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- 0 CCCCCCC(*)Oc(ccc(-c1ccc(C2CCC(*)CC2)cc1)c1)c1F Chemical compound CCCCCCC(*)Oc(ccc(-c1ccc(C2CCC(*)CC2)cc1)c1)c1F 0.000 description 6
- UQOXYXPJPCYEAF-UHFFFAOYSA-N CC(C(C(CC=C)CC(C(C(CC=C)C1)=CC=C1O)=C1)=C1N)=C Chemical compound CC(C(C(CC=C)CC(C(C(CC=C)C1)=CC=C1O)=C1)=C1N)=C UQOXYXPJPCYEAF-UHFFFAOYSA-N 0.000 description 1
- RRUNAQULPNURIR-UHFFFAOYSA-N CCCCCCC(C)Oc(ccc(-c(cc1)ccc1-c1ccc(C)cc1)c1)c1F Chemical compound CCCCCCC(C)Oc(ccc(-c(cc1)ccc1-c1ccc(C)cc1)c1)c1F RRUNAQULPNURIR-UHFFFAOYSA-N 0.000 description 1
- FAFPYGVAQCJDCL-FOUAAFFMSA-N C[C@H](CC=C(C1)Br)C1F Chemical compound C[C@H](CC=C(C1)Br)C1F FAFPYGVAQCJDCL-FOUAAFFMSA-N 0.000 description 1
- ZWDVUDISDBCTFU-UHFFFAOYSA-N OC(CC=C(C1)Br)C1F Chemical compound OC(CC=C(C1)Br)C1F ZWDVUDISDBCTFU-UHFFFAOYSA-N 0.000 description 1
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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.
- a liquid crystal composition having a positive dielectric anisotropy, a TN (twisted nematic) mode, an OCB (optically compensated bend) mode, an IPS (in-plane switching) mode, or a PSA (polymer sustainable) containing the composition. alignment) mode element.
- the classification based on the operation mode of the liquid crystal 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), 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. For a device with a mode such as TN, a suitable value is about 0.45 ⁇ m.
- a composition having a large optical anisotropy is preferable for a device having a small cell gap.
- a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy 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 temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after being used for a long time is preferable.
- the stability of the composition against ultraviolet rays and heat relates to the lifetime of the liquid crystal display element. 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.
- an optically active compound is mixed with a composition for the purpose of inducing a helical structure of a liquid crystal to give a twist angle.
- a composition having positive dielectric anisotropy is used.
- 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.
- Examples of liquid crystal compositions having positive dielectric anisotropy are disclosed in the following patent documents.
- 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 large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a heat High stability against.
- 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 large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, and a high resistance to heat. It is a liquid crystal composition satisfying at least one characteristic in characteristics such as high stability. Another object is a liquid crystal composition having an appropriate balance regarding at least two properties. Another object is a liquid crystal display device containing such a composition.
- Another object is a composition having a large optical anisotropy, a large dielectric anisotropy, a high stability to ultraviolet light, etc., and has a short response time, a large voltage holding ratio, a large contrast ratio, a long lifetime, etc. It is an AM element.
- R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine;
- R 2 and R 3 are different from each other and are alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
- ring A is 1,4-cyclohexylene or 1,4-phenylene.
- the same pitch is used to shorten the helical pitch of the composition and to reduce the amount of the compound represented by the formula (1). It is preferable to use a compound having a twist direction. However, in order to adjust the temperature dependence of the length of the helical pitch of the composition, it is possible to combine twist compounds having the same twist direction and opposite directions.
- Advantages of the present invention include a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, and a high stability to heat. It is a liquid crystal composition that satisfies at least one characteristic such as property.
- 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.
- the other aspect is a composition having a large optical anisotropy, a large dielectric anisotropy, a high stability to ultraviolet light, etc., and has a short response time, a large voltage holding ratio, a large contrast ratio, a long lifetime, etc. It is an AM element.
- 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 in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large specific resistance even at a close temperature.
- “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to.
- the first component is one compound or two or more compounds.
- the “ratio of the first component” means the weight ratio (parts by weight) of the first component when the weight of the liquid crystal composition excluding the first component is 100.
- the ratio of the second component means the weight percentage (% by weight) of the second component based on the weight of the liquid crystal composition excluding the first component.
- the “ratio of the third component” is the same as that 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 the compound (1-1) is ethyl and R 1 of the compound (1-2) is ethyl.
- R 1 of compound (1-1) is ethyl and R 1 of compound (1-2) is propyl.
- R 4 , R 5 and the like represents chlorine.
- R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine;
- R 2 and R 3 are different from each other and are alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
- ring A is 1,4-cyclohexylene or 1,4-phenylene.
- Item 3 The liquid crystal composition according to item 2, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2).
- R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced with fluorine.
- Item 4 The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the first component is in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal composition excluding the first component.
- Item 5 The liquid crystal composition according to any one of items 1 to 4, further comprising at least one compound selected from the group of compounds represented by formula (2) as the second component.
- R 4 and R 5 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having any hydrogen substituted with fluorine.
- Ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene. , Or 2,5-difluoro-1,4-phenylene;
- Z 1 is independently a single bond, ethylene, or carbonyloxy;
- p is 1 or 2.
- Item 6 The liquid crystal composition according to item 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 4 and R 5 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having any hydrogen substituted with fluorine. To 12 alkenyl.
- At least one compound selected from the group of compounds represented by formula (2-1) and at least one compound selected from the group of compounds represented by formula (2-5) Item 7.
- At least one compound selected from the group of compounds represented by formula (2-1) and at least one compound selected from the group of compounds represented by formula (2-7) Item 7.
- Item 11 The liquid crystal composition according to any one of items 5 to 10, wherein the ratio of the second component is in the range of 35% by weight to 95% by weight based on the weight of the liquid crystal composition excluding the first component.
- R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine;
- Ring D is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4 -Phenylene, 3,5-difluoro-1,4-phenylene, or 2,5-pyrimidine;
- Z 2 is independently a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy;
- X 1 and X 2 is independently hydrogen or fluorine;
- Y 1 is fluorine, chlorine, or trifluoromethoxy;
- k is 1, 2, 3, or 4.
- Item 13 The liquid crystal composition according to item 12, wherein the third component is at least one compound selected from the group of compounds represented by formulas (3-1) to (3-23).
- R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine.
- X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , and X 9 are independently hydrogen or fluorine;
- Y 1 is fluorine, chlorine, or trifluoro; Methoxy.
- Item 14 The liquid crystal composition according to item 13, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-11).
- Item 21 The liquid crystal composition according to any one of items 12 to 20, wherein the ratio of the third component is in the range of 5% by weight to 60% by weight based on the weight of the liquid crystal composition excluding the first component.
- Item 23 A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 22.
- Item 24 The liquid crystal display device according to item 23, wherein an operation mode of the liquid crystal display device is a TN mode, an OCB mode, an IPS mode, or a PSA mode, and a driving method of the liquid crystal display device is an active matrix method.
- R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced with fluorine.
- 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, a polymerization initiator, 3) AM device containing the above composition 4) Device containing the above composition and having a TN, ECB, OCB, IPS, or PSA mode 5) Transmission type containing the above composition 6) Use of the above composition as a composition having a nematic phase, 7) Use of the above composition as an optically active composition.
- additives such as an antioxidant, an ultraviolet absorber, an antifoaming agent, a polymerizable compound, a polymerization initiator, 3) AM device containing the above composition 4) Device containing the above composition and having a TN, ECB, OCB, IPS, or PSA mode 5) Transmission type containing the above composition 6) Use of the above composition as a composition having a nematic phase, 7)
- 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), and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
- a smaller amount of cyano compound is preferable from the viewpoint of stability to heat or ultraviolet light.
- a more desirable ratio of the cyano compound is 0% by weight.
- Additives include optically active compounds other than the first component, 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), and compound (3). “Substantially” means that the composition may contain additives and impurities, but the composition 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.
- L, M, and S are classifications based on a qualitative comparison among the component compounds, and 0 (zero) means that the value is close to zero.
- the main effects of the component compound on the properties of the composition are as follows.
- Compound (2) increases the maximum temperature or decreases the viscosity.
- Compound (3) decreases the minimum temperature and increases the dielectric anisotropy.
- the combination of the components in the composition is only the first component, the first component + second component, the first component + third component, and the first component + second component + third component.
- the combination of components in a preferred composition is first component + second component + third component.
- a desirable ratio of the first component is 0.01 parts by weight or more and 5 parts by weight or less.
- a more desirable ratio is in the range of 0.05 to 3 parts by weight.
- a particularly desirable ratio is in the range of 0.1 to 2 parts by weight.
- a desirable ratio of the second component is 35% by weight or more for increasing the maximum temperature or decreasing the viscosity, and is 95% by weight or less for increasing the dielectric anisotropy.
- a more desirable ratio is in the range of 40% to 90% by weight.
- a particularly desirable ratio is in the range of 45% to 85% by weight.
- a desirable ratio of the third component is 5% by weight or more for increasing the dielectric anisotropy, and 60% by weight or less for decreasing the viscosity.
- a more desirable ratio is in the range of 10% to 55% by weight.
- a particularly desirable ratio is in the range of 15% to 50% by weight.
- R 1 , R 4 , R 5 and R 6 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or any hydrogen replaced with fluorine Alkenyl having 2 to 12 carbons.
- Desirable R 1 , R 5 or R 6 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.
- Desirable R 4 is alkenyl having 2 to 12 carbons for decreasing the minimum temperature or decreasing the viscosity.
- R 2 and R 3 are independently alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons. Desirable R 2 or R 3 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.
- 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 1,4-cyclohexylene or 1,4-phenylene. Desirable ring A is 1,4-cyclohexylene for decreasing the minimum temperature. Ring B and Ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-difluoro- When it is 1,4-phenylene and p is 2, any two rings B may be the same or different. Desirable ring B or ring C is 1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene for increasing the optical anisotropy.
- Ring D is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, Any two rings D when 3,5-difluoro-1,4-phenylene or 2,5-pyrimidine and k is 2 or 3 may be the same or different. Desirable ring D is 1,4-phenylene for increasing the optical anisotropy.
- Z 1 is a single bond, ethylene, or carbonyloxy, and any two Z 1 when p is 2 may be the same or different. Desirable Z 1 is a single bond for decreasing the viscosity.
- Z 2 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy, and any two Z 2 when k is 2 or 3 may be the same or different. Desirable Z 2 is difluoromethyleneoxy for increasing the dielectric anisotropy.
- X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , and X 9 are independently hydrogen or fluorine. Desirable X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , or X 9 is fluorine for increasing the dielectric anisotropy.
- Y 1 is fluorine, chlorine, or trifluoromethoxy. Desirable Y 1 is fluorine for decreasing the minimum temperature.
- p is independently 1 or 2. Preferred p is 1 for decreasing the viscosity. k is independently 1, 2, 3, or 4. Preferred k is 2 for decreasing the minimum temperature.
- R 7 and R 11 are independently straight-chain alkyl having 1 to 12 carbons.
- R 8 is straight-chain alkyl having 1 to 12 carbons or straight-chain alkoxy having 1 to 12 carbons.
- R 9 and R 10 are independently straight-chain alkyl having 1 to 12 carbons or straight-chain alkenyl having 2 to 12 carbons.
- trans is preferable to cis for the configuration of 1,4-cyclohexylene for increasing the maximum temperature.
- Desirable compounds (1) are the compound (1-1-1) and the compound (1-2-1). More desirable compound (1) is the compound (1-1-1). Desirable compounds (2) are from the compound (2-1-1) to the compound (2-7-1). More desirable compounds (2) are the compound (2-1-1), the compound (2-5-1), and the compound (2-7-1). Desirable compounds (3) are the compound (3-1-1) to the compound (3-18-1), the compound (3-19-1) to the compound (3-19-2), and the compound (3-20-1). ) To compound (3-20-3), compound (32-1-1) to compound (3-21-2), compound (3-22-1), compound (323-1) to compound (3 -23-2), and compound (3-24) to compound (3-32).
- More desirable compounds (3) are the compound (3-6-1), the compound (3-9-1), the compound (3-11-1), the compound (3-15-1), and the compound (3-18). -1). Particularly preferred compounds (3) are the compound (3-9-1), the compound (3-11-1), the compound (3-15-1), and the compound (3-18-1).
- additives that may be mixed with the composition will be described.
- Such additives are optically active compounds other than the first component, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, and the like.
- Examples of the optically active compound are the compound (4-1) to the compound (4-4).
- 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 optically active compound other than the first component When an optically active compound other than the first component is added, it is preferable to use an optically active compound having the same twist direction as that of the first component, that is, the compound (1), in order to shorten the helical pitch of the composition. .
- twist compounds having the same twist direction and in the opposite direction can be combined.
- oxidation prevention An agent is mixed into the composition.
- a preferred example of the antioxidant is a compound (5) wherein 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 (5) 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 (5) 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 temperature close to the upper limit temperature of the nematic phase after using the device 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 compound, vinyloxy compound, propenyl ether, epoxy compound (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 in the range of 0.1% 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 a photopolymerization initiator in the range of 0.1% to 5% by weight.
- the photopolymerization initiator is contained in the range of 1% by weight to 3% by weight.
- a phenol derivative (1-1b) is prepared by adding a catalyst such as Pd to a mixture of the corresponding boronic acid derivative (1-1a) and 2-fluoro-4-bromo-phenol and performing a Suzuki coupling reaction. .
- a catalyst such as Pd
- 2-fluoro-4-bromo-phenol performing a Suzuki coupling reaction.
- the compound (1-1b) and optically active 2-octanol By subjecting the obtained compound (1-1b) and optically active 2-octanol to Mitsunobu reaction using diethyl azocarboxylate (DEAD), the compound (1-1) can be derived.
- DEAD diethyl azocarboxylate
- tosyl chloride is added to optically active 2-octanol to add tosyl chloride, followed by etherification by adding a base to the obtained compound (1-1c) and 2-fluoro-4-bromophenol.
- the target compound (1-1) can be obtained by adding a catalyst such as Pd to the mixture of the compound (1-1d) and the boronic acid derivative (1-1a) and performing a Suzuki coupling reaction.
- the composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.
- the composition of the present invention mainly has 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, or 0.10 to 0.30 by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. You may prepare the composition which has the optical anisotropy of the range of these.
- This composition can be used as an optically active composition by adding an optically active compound.
- This composition can be used for an AM device. Further, it can be used for PM elements.
- This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, VA, and PSA.
- Use for an AM device having a TN, OCB or IPS 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 obtained compound was analyzed by nuclear magnetic resonance spectrum obtained by 1 H-NMR analysis and 19 F-NMR analysis, gas chromatogram obtained by gas chromatography (GC) analysis, specific optical rotation obtained by polarimeter analysis, etc. First, the analysis method will be described.
- 1 H-NMR analysis DRX-500 (Bruker Biospin Co., Ltd.) was used as the measuring apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl 3 was soluble, at room temperature, 500 MHz, and 32 times of integration.
- s means a singlet
- d is a doublet
- t is a triplet
- q is a quartet
- m is a multiplet
- br is broad.
- Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift ⁇ value.
- 19 F-NMR analysis DRX-500 (manufactured by Bruker BioSpin Corporation) was used as a measuring apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl 3 was soluble, at room temperature, 500 MHz, and 32 times of integration.
- s means a singlet
- d is a doublet
- t is a triplet
- q is a quartet
- m is a multiplet
- br is broad.
- trichlorofluoromethane was used as a reference material for the zero point of the chemical shift ⁇ value.
- GC analysis A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used as a measuring apparatus.
- a capillary column CBP1-M25-025 (length: 25 m, inner diameter: 0.22 mm, film thickness: 0.25 ⁇ m) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) as the stationary liquid phase was used.
- Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min.
- the temperature of the sample vaporizing chamber was set to 280 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.
- the sample was dissolved in toluene to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
- a recorder a C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used.
- the obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.
- capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc.
- HP-1 length 30 m, inner diameter 0
- Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m)
- BP-1 from SGE International Corporation Pty. Ltd (length 30 m, inner diameter) 0.32 mm, film thickness of 0.25 ⁇ m) or the like
- SGE International Corporation Pty. Ltd length 30 m, inner diameter 0.32 mm, film thickness of 0.25 ⁇ m
- the peak area ratio in the gas chromatogram corresponds to the ratio of the component compounds.
- the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample.
- the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds.
- an internal standard method by gas chromatogram is used.
- the measuring apparatus used was a JASCO DIP-360 digital polarimeter.
- the sample produced in Examples and the like was dissolved in CHCl 3 in which the sample is soluble, and placed in a CG1-100 cylindrical glass cell (diameter: 10 mm, length: 100 mm) manufactured by JASCO Corporation. The number of times was 10 times.
- a light source a sodium lamp (589 nm) standard was used.
- samples for measuring physical properties of liquid crystal compounds There are two types of samples for measuring the physical property values of the liquid crystal compound: when the compound itself is used as a sample, and when the compound is mixed with a mother liquid crystal as a sample.
- the components of the mother liquid crystals are as follows. The ratio of each component 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.
- the values obtained using the liquid crystal compound itself as a sample and the values obtained using the liquid crystal composition itself as a sample are described as experimental data.
- the value obtained by extrapolation was used as the value.
- Phase structure and transition temperature (°C) Measurement was carried out by the methods (1) and (2) below.
- a compound is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope, and a phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of phase.
- (2) Using a scanning calorimeter DSC-7 system or Diamond DSC system manufactured by PerkinElmer, Inc., the temperature is raised and lowered at a rate of 3 ° C / min, and the start point of the endothermic peak or exothermic peak accompanying the phase change of the sample is excluded.
- the transition temperature was determined by onset.
- the crystal was expressed as Cr.
- the smectic phase is represented as S and the nematic phase is represented as N.
- the liquid (isotropic) was expressed as Iso.
- the smectic phase if can be distinguished in the smectic F phase, or a smectic C phase, expressed as S F or S C, respectively.
- Cr 50.0 N 100.0 Iso means that the transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid ( NI) is 100.0 ° C. The same applies to other notations.
- 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. ⁇ Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a device in which the twist angle was 0 ° and the distance between two glass substrates (cell gap) was 5 ⁇ m. The voltage was applied stepwise to the device every 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 the calculation formula (8) described on page 40 in the paper by M. Imai et al.
- the value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity 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 was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was about 0.45 mm / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
- the voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V 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 90%.
- 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 that was cured with ultraviolet rays after the sample was placed.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- the area B is an area when it is not attenuated.
- the voltage holding ratio is a percentage of the area A with respect to the area B.
- Voltage holding ratio (VHR-2; 80 ° C .;%):
- the TN device used for the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 5 ⁇ m. This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
- the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- the area B is an area when it is not attenuated.
- the voltage holding ratio is a percentage of the area A with respect to the area B.
- VHR-3 Voltage holding ratio
- the TN device used for measurement has a polyimide alignment film, and the cell gap is 5 ⁇ m.
- a sample was injected into this 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.
- the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
- the fall time ( ⁇ f: fall time; millisecond) is the time required to change the transmittance from 10% to 90%.
- the response time is the sum of the rise time and the fall time thus obtained.
- Twist direction of helix A helical pitch (P 1 ) of a composition prepared by adding 1 part by weight of a sample to 100 parts by weight of a base liquid crystal was measured. Another composition was prepared by adding a standard sample of optically active compound that was right-twisted to the mother liquid crystals. The amount of the standard sample was determined in advance so that the helical pitch (P 2 ) of this composition was the same as that of P 1 . Next, these compositions were mixed in equal amounts, and the helical pitch (P mix ) was measured. The sample was determined to be right twist if P mix was between P 1 and P 2 , and was determined to be left twist when P mix was clearly greater than P 1 and P 2 .
- Standard optically active compounds are as follows. :
- 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 number of the preferred compound.
- the symbol ( ⁇ ) means other liquid crystal compounds.
- the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition excluding the first component, and the liquid crystal composition contains impurities in addition to this.
- Example 2 Synthesis of (S) -3-fluoro-4- (octane-2-yloxy) -4 ′-(4-propylcyclohexyl) biphenyl (compound (1-1-1) in which R 1 is propyl) [Example 1] (S) -3-fluoro-4- (octane) in the same manner except that (R) -2-octanol was used instead of (S) -2-octanol -2-yloxy) -4 ′-(4-propylcyclohexyl) biphenyl (1.5 g) was obtained.
- V-HH-3 (2-1-1) 28% V-HH-5 (2-1-1) 6% 1V-HH-3 (2-1-1) 5% 3-HH-O1 (2-1-1) 5% 1V2-BB-1 (2-3-1) 4% 3-HHEH-5 (2-4-1) 3% VFF-HHB-1 (2-5) 3% 3-HHB-O1 (2-5-1) 3% 3-HB-CL (3-1-1) 9% 3-HHXB (F, F) -F (3-6-1) 16% 3-HBB (F, F) -F (3-8-1) 8% 3-BB (F) B (F, F) -F (3-9-1) 7% 5-HBBB (F, F) XB (F, F) -F (3-20-1) 3% 0.8 parts by weight of the following compound (1-2-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 34% V-HH-5 (2-1-1) 3% 7-HB-1 (2-2-1) 4% V2-BB-1 (2-3-1) 6% V-HHB-1 (2-5-1) 14% 3-HBB-2 (2-6-1) 3% 1V2-BB-F (3-2) 5% 1V2-BB-CL (3-3) 3% 3-HHB (F, F) -F (3-5-1) 10% 3-BB (F) B (F, F) -F (3-9-1) 9% 3-HHB (F) B (F, F) -F (3-14-1) 6% 5-BB (F) B (F) B (F, F) XB (F, F) -F (3-21-2) 3% 0.5 parts by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- Example 8 V-HH-3 (2-1-1) 45% 1V-HH-3 (2-1-1) 9% V2-BB-1 (2-3-1) 3% V2-BB (F) B-1 (2-7-1) 12% 3-BB (F, F) XB (F, F) -F (3-11-1) 9% 3-BB (F, F) XB (F) -OCF3 (3-12-1) 8% 5-HBB (F, F) XB (F, F) -F (3-16-1) 3% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 5% 5-HB (F) B (F, F) XB (F) B (F, F) -F (3-22-1) 3% 1O1-HBBH-5 (-) 3% 2 parts by weight of the following compound (1) was added to 100 parts by weight of the composition.
- V-HH-3 (2-1-1) 42% 1V-HH-3 (2-1-1) 8% V-HHB-1 (2-5-1) 10% 3-HB-CL (3-1-1) 8% 3-HHB-CL (3-4-1) 6% 3-PyBB-F (3-10-1) 3% 4-PyBB-F (3-10-1) 3% 5-PyBB-F (3-10-1) 3% 3-HHBB (F, F) -F (3-13-1) 6% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 8% 5-PyB (F) B (F, F) XB (F) B (F, F) -F (3-32) 3% 1 part by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 44% 1V-HH-3 (2-1-1) 10% V2-BB-1 (2-3-1) 6% 3-HHB-1 (2-5-1) 3% V-HHB-1 (2-5-1) 6% 1-BB (F) B-2V (2-7-1) 3% 2-BB (F) B-2V (2-7-1) 3% 3-HBBBXB (F, F) -F (3-15-1) 7% 5-HGB (F, F) -F (3-28) 6% 3-GHB (F, F) -F (3-29) 6% 5-dhB (F) B (F, F) XB (F) B (F, F) -F (3-30) 3% 5-dhB (F) B (F, F) XB (F) B (F, F) -F (3-30) 3% 5 parts by weight of the following compound (1) was added to 100 parts by weight of the composition.
- VFF-HH-3 (2-1) 9% V-HH-3 (2-1-1) 39% 1V-HH-3 (2-1-1) 10% V-HHB-1 (2-5-1) 3% V2-HHB-1 (2-5-1) 8% 3-HHB (F, F) -F (3-5-1) 6% 3-HBB-F (3-7-1) 6% 3-BB (F, F) XB (F, F) -F (3-11-1) 13% 5-HB (F) B (F) B (F, F) XB (F, F) -F (3-20-3) 3% 5-BB (F) B (F, F) XB (F) B (F) -OCF3 (3-23-1) 3% 0.5 parts by weight of the following compound (1-1-2) was added to 100 parts by weight of the above composition.
- Example 13 V-HH-3 (2-1-1) 36% 1V-HH-3 (2-1-1) 7% V2-BB-1 (2-3-1) 4% 3-HHEH-5 (2-4-1) 4% 2-BB (F) B-3 (2-7-1) 9% 1-BB (F) B-2V (2-7-1) 7% 3-BB (F, F) XB (F, F) -F (3-11-1) 10% 5-BB (F) B (F, F) XB (F) B (F, F) -F (3-23-2) 3% 3-BB (F, F) XB (F) -F (3-25) 10% 3-HHEB (F, F) -F (3-26) 10% 1 part by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 34% 1V-HH-3 (2-1-1) 10% V-HHB-1 (2-5-1) 12% 2-BB (F) B-3 (2-7-1) 10% 2-BB (F) B-5 (2-7-1) 9% 3-BB (F, F) XB (F, F) -F (3-11-1) 20% 3-HHBB (F, F) -F (3-13-1) 5% 0.8 parts by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- Example 15 V-HH-3 (2-1-1) 39% 1V-HH-3 (2-1-1) 7% V-HHB-1 (2-5-1) 10% 2-BB (F) B-3 (2-7-1) 12% 2-BB (F) B-5 (2-7-1) 8% 3-BB (F, F) XB (F, F) -F (3-11-1) 13% 3-HHBB (F, F) -F (3-13-1) 5% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 6% 0.5 parts by weight of the following compound (1-2-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 45% V-HHB-1 (2-5-1) 11% 1-BB (F) B-2V (2-7-1) 6% 2-BB (F) B-2V (2-7-1) 8% 3-BB (F, F) XB (F, F) -F (3-11-1) 14% 3-BB (F) B (F, F) XB (F, F) -F (3-18-1) 3% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 9% 5-BB (F) B (F, F) XB (F, F) -F (3-18-1) 4% 0.4 parts by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 48% V2-BB-1 (2-3-1) 5% 1-BB (F) B-2V (2-7-1) 8% 2-BB (F) B-2V (2-7-1) 8% 3-BB (F) B-2V (2-7-1) 13% 3-BB (F, F) XB (F, F) -F (3-11-1) 9% 3-BB (F) B (F, F) XB (F, F) -F (3-18-1) 3% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 6% 0.5 parts by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- Example 18 V-HH-3 (2-1-1) 46% 1V-HH-3 (2-1-1) 10% V-HHB-1 (2-5-1) 11% V2-HHB-1 (2-5-1) 4% 2-BB (F) B-3 (2-7-1) 9% 2-BB (F) B-5 (2-7-1) 3% 3-HBB (F, F) -F (3-8-1) 5% 3-BB (F, F) XB (F, F) -F (3-11-1) 7% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 5% 0.5 parts by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- V-HH-3 (2-1-1) 42% 1V-HH-3 (2-1-1) 10% V-HHB-1 (2-5-1) 3% V2-HHB-1 (2-5-1) 4% 1-BB (F) B-2V (2-7-1) 3% 2-BB (F) B-2V (2-7-1) 8% 3-BB (F) B-2V (2-7-1) 9% 3-BB (F) B (F, F) -F (3-9-1) 5% 3-BB (F, F) XB (F, F) -F (3-11-1) 4% 3-BB (F) B (F, F) XB (F, F) -F (3-18-1) 3% 4-BB (F) B (F, F) XB (F, F) -F (3-18-1) 5% 5-BB (F) B (F, F) XB (F, F) -F (3-18-1) 4% 1 part by weight of the following compound (1-1-1) was added to 100 parts by weight of the above composition.
- the compositions of Examples 3 to 19 have a shorter helical pitch and a shorter response time than that of Comparative Example 1. Therefore, the liquid crystal composition according to the present invention has more excellent characteristics than the liquid crystal composition shown in Comparative Example 1.
- the present invention has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet rays, a high stability to heat, etc. Therefore, the liquid crystal display device using this composition has a short response time, a large voltage holding ratio, a liquid crystal composition satisfying at least one characteristic or having an appropriate balance with respect to at least two characteristics. Since it has a large contrast ratio and a long lifetime, it is suitable for an AM device or the like.
Abstract
Description
ここで、R1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;R2およびR3は互いに異なって、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;環Aは、1,4-シクロへキシレンまたは1,4-フェニレンである。
式(1)で表される化合物を2つ以上組み合わせて使用する場合、組成物のらせんピッチを短くするため、および式(1)で表される化合物の添加量を少なくするために、同一のねじれ方向を持つ化合物を使用することが好ましい。ただ、組成物のらせんピッチの長さの温度依存性を調整するために、同一のねじれ方向を持つ、及び逆向きのねじれ化合物を組み合わせることができる。
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つの光学活性化合物を含有し、ネマチック相を有する液晶組成物。
ここで、R1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;R2およびR3は互いに異なって、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;環Aは、1,4-シクロへキシレンまたは1,4-フェニレンである。
ここで、R1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、R4およびR5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;環Bおよび環Cは独立して、1,4-シクロへキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;Z1は独立して、単結合、エチレン、またはカルボニルオキシであり;pは1または2である。
ここで、R4およびR5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、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Dは独立して、1,4-シクロへキシレン、1,3-ジオキサン-2,5-ジイル、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレン、3,5-ジフルオロ-1,4-フェニレン、または2,5-ピリミジンであり;Z2は独立して、単結合、エチレン、カルボニルオキシ、またはジフルオロメチレンオキシであり;X1およびX2は独立して、水素またはフッ素であり;Y1は、フッ素、塩素、またはトリフルオロメトキシであり;kは、1、2、3、または4である。
ここで、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;X1、X2、X3、X4、X5、X6、X7、X8、およびX9は独立して、水素またはフッ素であり;Y1は、フッ素、塩素、またはトリフルオロメトキシである。
ここで、R1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。
環Bおよび環Cは独立して、1,4-シクロへキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレンまたは2,5-ジフルオロ-1,4-フェニレンであり、pが2である時の任意の2つの環Bは同じであっても、異なっていてもよい。好ましい環Bまたは環Cは、粘度を下げるために1,4-シクロへキシレンであり、光学異方性を上げるために1,4-フェニレンである。環Dは、1,4-シクロへキシレン、1,3-ジオキサン-2,5-ジイル、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレン、3,5-ジフルオロ-1,4-フェニレン、または2,5-ピリミジンであり、kが2または3である時の任意の2つの環Dは同じであっても、異なっていてもよい。好ましい環Dは、光学異方性を上げるために1,4-フェニレンである。
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれら実施例によっては制限されない。なお特に断りのない限り、「%」は「重量%」を意味する。
測定装置は、DRX-500(ブルカーバイオスピン(株)社製)を用いた。測定は、実施例等で製造したサンプルを、CDCl3等のサンプルが可溶な重水素化溶媒に溶解し、室温で、500MHz、積算回数32回の条件で行った。なお、得られた核磁気共鳴スペクトルの説明において、sはシングレット、dはダブレット、tはトリプレット、qはカルテット、mはマルチプレット、brはブロードであることを意味する。また、化学シフトδ値のゼロ点の基準物質としてはテトラメチルシラン(TMS)を用いた。
測定装置は、DRX-500(ブルカーバイオスピン(株)社製)を用いた。測定は、実施例等で製造したサンプルを、CDCl3等のサンプルが可溶な重水素化溶媒に溶解し、室温で、500MHz、積算回数32回の条件で行った。なお、得られた核磁気共鳴スペクトルの説明において、sはシングレット、dはダブレット、tはトリプレット、qはカルテット、mはマルチプレット、brはブロードであることを意味する。また、化学シフトδ値のゼロ点の基準物質としてはトリクロロフルオロメタンを用いた。
測定装置は、島津製作所製のGC-14B型ガスクロマトグラフを用いた。カラムは、島津製作所製のキャピラリーカラムCBP1-M25-025(長さ25m、内径0.22mm、膜厚0.25μm);固定液相はジメチルポリシロキサン;無極性)を用いた。キャリアーガスとしてはヘリウムを用い、流量は1ml/分に調整した。試料気化室の温度を280℃、検出器(FID)部分の温度を300℃に設定した。
記録計としては島津製作所製のC-R6A型Chromatopac、またはその同等品を用いた。得られたガスクロマトグラムには、成分化合物に対応するピークの保持時間およびピークの面積値が示されている。
測定装置は、日本分光DIP-360型ディジタル旋光計を用いた。測定は、実施例等で製造したサンプルを、サンプルが可溶なCHCl3に溶解し、日本分光社製CG1-100円筒形ガラスセル(直径10mm、長さ100mm)に入れ、28℃で、積算回数10回の条件で行った。また、光源としては、ナトリウムランプ(589nm)標準を用いた。
液晶性化合物の物性値を測定する試料としては、化合物そのものを試料とする場合、化合物を母液晶と混合して試料とする場合の2種類がある。
以下(1)、および(2)の方法で測定を行った。
(1)偏光顕微鏡を備えた融点測定装置のホットプレート(メトラー社FP-52型ホットステージ)に化合物を置き、3℃/分の速度で加熱しながら相状態とその変化を偏光顕微鏡で観察し、相の種類を特定した。
(2)パーキンエルマー社製走査熱量計DSC-7システム、またはDiamond DSCシステムを用いて、3℃/分速度で昇降温し、試料の相変化に伴う吸熱ピーク、または発熱ピークの開始点を外挿により求め(on set)、転移温度を決定した。
P=2×(d2-d1)×tanθ
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好ましい化合物の番号に対応する。(-)の記号はその他の液晶性化合物を意味する。液晶性化合物の割合(百分率)は、第一成分を除く液晶組成物の重量に基づいた重量百分率(重量%)であり、液晶組成物にはこの他に不純物が含れている。最後に、組成物の特性値をまとめた。
窒素気流下で、4-(4-プロピルシクロヘキシル)フェニルボロン酸(10.0g)、2-フルオロ-4-ブロモフェノール(7.76g)、炭酸カリウム(11.2g)、イソプロピルアルコール(90ml)の混合物に、ジクロロビストリフェニルホスフィンパラジウム(0.143g)を加えて70℃で4時間加熱還流した。反応混合物を水に空けてジエチルエーテルにて抽出し、水で3度洗浄して溶媒を留去した後、シリカゲルカラムクロマトグラフィー(溶媒(体積比):トルエン/酢酸エチル=10/1)、さらに再結晶ろ過(溶媒(体積比):トルエン/ヘプタン=0.5/2)によって精製し、無色結晶である3-フルオロ-4’-(4-プロピルシクロヘキシル)ビフェニル-4-オール(7.0g、GC純度:95%)を得た。
窒素気流下で、前段で得た3-フルオロ-4’-(4-プロピルシクロヘキシル)ビフェニル-4-オール(3.00g)、(S)-2-オクタノール(2.84g)、トリフェニルホスフィン(2.83g)のTHF溶液に、アゾカルボン酸ジエチル(DEAD)のトルエン溶液(2.2mol/l)(4.8ml)を30℃でゆっくりと滴下し、40℃で2時間攪拌した。反応混合物を水にあけてトルエンにて抽出し、水で3度洗浄して溶媒を留去した後、シリカゲルカラムクロマトグラフィー(溶媒(体積比):トルエン/ヘプタン=1/5)、さらに再結晶ろ過(溶媒(体積比):ヘプタン/エタノール=1/3)によって精製し、目的物である無色の(R)-3-フルオロ-4-(オクタン-2-イルオキシ)-4’-(4-プロピルシクロヘキシル)ビフェニル(2.8g)を得た。
1H-NMR(CDCl3)δ(ppm):7.44(d,2H)、7.30(dd,1H)、7.25(d,2H)、7.25~7.24(dd,1H)、7.00(dd,1H)、4.37(m,1H)、2.50(tt,1H)、1.90(m,4H)、1.84~1.76(m,1H)、1.64~1.20(m,18H)、1.12~1.02(m,2H)、0.92~0.86(m,6H)
19F-NMR(CDCl3)δ(ppm):133.66(dd,1F)
相転移 Cr 39.5 SF 58.1 SC 69.1 Iso
比旋光度 αD=+2.3(c=1.0、CHCl3、28℃)
ねじれの方向 左ねじれ
(S)-3-フルオロ-4-(オクタン-2-イルオキシ)-4’-(4-プロピルシクロヘキシル)ビフェニル(R1がプロピルである化合物(1-1-1))の合成
[実施例1]の(第2段)において、(S)-2-オクタノールの代わりに(R)-2-オクタノールを用いた以外は、全く同様の方法にて(S)-3-フルオロ-4-(オクタン-2-イルオキシ)-4’-(4-プロピルシクロヘキシル)ビフェニル(1.5g)を得た。
1H-NMR(CDCl3)δ(ppm):7.44(d,2H)、7.30(dd,1H)、7.25(d,2H)、7.25~7.24(dd,1H)、7.00(dd,1H)、4.37(m,1H)、2.50(tt,1H)、1.90(m,4H)、1.84~1.76(m,1H)、1.64~1.20(m,18H)、1.12~1.02(m,2H)、0.92~0.86(m,6H)
19F-NMR(CDCl3)δ(ppm):133.66(dd,1F)
相転移 Cr 39.5 SF 58.1 SC 69.1 Iso
比旋光度 αD=-2.3(c=1.0、CHCl3、28℃)
ねじれの方向 右ねじれ
V-HH-3 (2-1-1) 44%
V2-BB-1 (2-3-1) 7%
V-HHB-1 (2-5-1) 3%
1-BB(F)B-2V (2-7-1) 3%
3-BB(F,F)XB(F,F)-F (3-11-1) 6%
3-HBBXB(F,F)-F (3-15-1) 6%
4-HBBXB(F,F)-F (3-15-1) 6%
5-HBBXB(F,F)-F (3-15-1) 6%
3-BB(F)B(F,F)XB(F,F)-F (3-18-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 9%
5-BB(F)B(F,F)XB(F,F)-F (3-18-1) 7%
上記組成物100重量部に本発明の第一成分とは異なる下記化合物を1重量部添加した。
NI=77.2℃;Tc≦-20℃;Δn=0.118;Δε=5.7;Vth=1.38V;η=13.1mPa・s;γ1=54.8mPa・s;τ=12.6ms;VHR-1=99.1%;VHR-2=98.0%;P=149.2μm.
V-HH-3 (2-1-1) 44%
V2-BB-1 (2-3-1) 7%
V-HHB-1 (2-5-1) 3%
1-BB(F)B-2V (2-7-1) 3%
3-BB(F,F)XB(F,F)-F (3-11-1) 6%
3-HBBXB(F,F)-F (3-15-1) 6%
4-HBBXB(F,F)-F (3-15-1) 6%
5-HBBXB(F,F)-F (3-15-1) 6%
3-BB(F)B(F,F)XB(F,F)-F (3-18-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 9%
5-BB(F)B(F,F)XB(F,F)-F (3-18-1) 7%
上記組成物100重量部に下記化合物(1-1-1)を1重量部添加した。
NI=77.1℃;Tc≦-20℃;Δn=0.118;Δε=5.8;Vth=1.53V;η=13.2mPa・s;γ1=55.0mPa・s;τ=10.8ms;VHR-1=99.1%;VHR-2=97.9%;P=24.5μm.
V-HH-3 (2-1-1) 47%
1V-HH-3 (2-1-1) 8%
1-BB(F)B-2V (2-7-1) 6%
2-BB(F)B-2V (2-7-1) 7%
3-BB(F)B-2V (2-7-1) 11%
3-BB(F,F)XB(F,F)-F (3-11-1) 13%
4-BB(F)B(F,F)XB(F,F)-F(3-18-1) 5%
5-HHBB(F,F)XB(F,F)-F (3-19-1) 3%
上記組成物100重量部に下記化合物(1-2-1)を0.3重量部添加した。
NI=72.6℃;Tc≦-20℃;Δn=0.121;Δε=3.8;Vth=2.43V;η=10.8mPa・s;γ1=47.5mPa・s;τ=7.8ms;VHR-1=98.8%;VHR-2=98.3%;P=58.4μm.
2-HH-3 (2-1-1) 20%
V-HH-3 (2-1-1) 28%
3-HB-O2 (2-2-1) 4%
V2-BB-1 (2-3-1) 5%
V-HHB-1 (2-5-1) 5%
1V-HBB-2 (2-6-1) 5%
2-BB(F)B-3 (2-7-1) 7%
3-HHB-CL (3-4-1) 6%
3-BB(F,F)XB(F)-OCF3 (3-12-1) 9%
5-HB(F)B(F,F)XB(F,F)-F
(3-17-1) 8%
5-HHB(F)B(F,F)XB(F,F)-F
(3-19-2) 3%
上記組成物100重量部に下記化合物(1-1-1)を0.6重量部添加した。
NI=79.6℃;Tc≦-20℃;Δn=0.100;Δε=2.7;Vth=2.78V;η=13.1mPa・s;γ1=54.4mPa・s;τ=8.7ms;VHR-1=99.0%;VHR-2=98.6%;P=38.6μm.
V-HH-3 (2-1-1) 28%
V-HH-5 (2-1-1) 6%
1V-HH-3 (2-1-1) 5%
3-HH-O1 (2-1-1) 5%
1V2-BB-1 (2-3-1) 4%
3-HHEH-5 (2-4-1) 3%
VFF-HHB-1 (2-5) 3%
3-HHB-O1 (2-5-1) 3%
3-HB-CL (3-1-1) 9%
3-HHXB(F,F)-F (3-6-1) 16%
3-HBB(F,F)-F (3-8-1) 8%
3-BB(F)B(F,F)-F (3-9-1) 7%
5-HBBB(F,F)XB(F,F)-F (3-20-1) 3%
上記組成物100重量部に下記化合物(1-2-1)を0.8重量部添加した。
NI=74.3℃;Tc≦-20℃;Δn=0.094;Δε=3.7;Vth=2.56V;η=12.5mPa・s;γ1=51.9mPa・s;τ=8.0ms;VHR-1=99.2%;VHR-2=98.7%;P=28.1μm.
V-HH-3 (2-1-1) 34%
V-HH-5 (2-1-1) 3%
7-HB-1 (2-2-1) 4%
V2-BB-1 (2-3-1) 6%
V-HHB-1 (2-5-1) 14%
3-HBB-2 (2-6-1) 3%
1V2-BB-F (3-2) 5%
1V2-BB-CL (3-3) 3%
3-HHB(F,F)-F (3-5-1) 10%
3-BB(F)B(F,F)-F (3-9-1) 9%
3-HHB(F)B(F,F)-F (3-14-1) 6%
5-BB(F)B(F)B(F,F)XB(F,F)-F
(3-21-2) 3%
上記組成物100重量部に下記化合物(1-1-1)を0.5重量部添加した。
NI=71.4℃;Tc≦-20℃;Δn=0.106;Δε=3.3;Vth=2.64V;η=12.9mPa・s;γ1=52.7mPa・s;τ=8.7;VHR-1=99.1%;VHR-2=98.4%;P=41.6μm.
V-HH-3 (2-1-1) 45%
1V-HH-3 (2-1-1) 9%
V2-BB-1 (2-3-1) 3%
V2-BB(F)B-1 (2-7-1) 12%
3-BB(F,F)XB(F,F)-F (3-11-1) 9%
3-BB(F,F)XB(F)-OCF3 (3-12-1) 8%
5-HBB(F,F)XB(F,F)-F (3-16-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 5%
5-HB(F)B(F,F)XB(F)B(F,F)-F
(3-22-1) 3%
1O1-HBBH-5 (―) 3%
上記組成物100重量部に下記化合物(1)を2重量部添加した。
NI=79.3℃;Tc≦-20℃;Δn=0.106;Δε=4.9;Vth=1.86V;η=14.1mPa・s;γ1=60.4mPa・s;τ=10.1ms;VHR-1=99.0%;VHR-2=98.2%;P=48.1μm.
V-HH-3 (2-1-1) 42%
1V-HH-3 (2-1-1) 8%
V-HHB-1 (2-5-1) 10%
3-HB-CL (3-1-1) 8%
3-HHB-CL (3-4-1) 6%
3-PyBB-F (3-10-1) 3%
4-PyBB-F (3-10-1) 3%
5-PyBB-F (3-10-1) 3%
3-HHBB(F,F)-F (3-13-1) 6%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 8%
5-PyB(F)B(F,F)XB(F)B(F,F)-F
(3-32) 3%
上記組成物100重量部に下記化合物(1-1-1)を1重量部添加した。
NI=88.1℃;Tc≦-20℃;Δn=0.105;Δε=3.8;Vth=2.58V;η=13.5mPa・s;γ1=55.1mPa・s;τ=9.2ms;VHR-1=98.1%;VHR-2=97.4%;P=21.6μm.
V-HH-3 (2-1-1) 44%
1V-HH-3 (2-1-1) 10%
V2-BB-1 (2-3-1) 6%
3-HHB-1 (2-5-1) 3%
V-HHB-1 (2-5-1) 6%
1-BB(F)B-2V (2-7-1) 3%
2-BB(F)B-2V (2-7-1) 3%
3-HBBXB(F,F)-F (3-15-1) 7%
5-HGB(F,F)-F (3-28) 6%
3-GHB(F,F)-F (3-29) 6%
5-dhB(F)B(F,F)XB(F)B(F,F)-F
(3-30) 3%
5-dhB(F)B(F,F)XB(F)B(F,F)-F
(3-30) 3%
上記組成物100重量部に下記化合物(1)を5重量部添加した。
NI=79.8;Tc≦-20℃;Δn=0.093;Δε=3.4;Vth=2.64V;η=13.5mPa・s;γ1=54.5mPa・s;τ=9.0ms;VHR-1=99.1%;VHR-2=98.0%;P=85.3μm.
VFF-HH-3 (2-1) 9%
V-HH-3 (2-1-1) 39%
1V-HH-3 (2-1-1) 10%
V-HHB-1 (2-5-1) 3%
V2-HHB-1 (2-5-1) 8%
3-HHB(F,F)-F (3-5-1) 6%
3-HBB-F (3-7-1) 6%
3-BB(F,F)XB(F,F)-F (3-11-1)13%
5-HB(F)B(F)B(F,F)XB(F,F)-F
(3-20-3) 3%
5-BB(F)B(F,F)XB(F)B(F)-OCF3
(3-23-1) 3%
上記組成物100重量部に下記化合物(1-1-2)を0.5重量部添加した。
NI=75.5℃;Tc≦-20℃;Δn=0.098;Δε=4.2;Vth=2.13V;η=12.9mPa・s;γ1=53.1mPa・s;τ=8.9ms;VHR-1=99.2%;VHR-2=98.6%;P=44.1μm.
V-HH-3 (2-1-1) 36%
1V-HH-3 (2-1-1) 9%
V2-BB-1 (2-3-1) 4%
1-BB(F)B-2V (2-7-1) 5%
2-BB(F)B-2V (2-7-1) 8%
3-BB(F)B-2V (2-7-1) 5%
3-HBB(F,F)-F (3-8-1) 6%
3-BB(F,F)XB(F,F)-F (3-11-1)10%
5-HBB(F)B(F,F)XB(F,F)-F(3-20-2) 3%
5-BB(F)B(F)B(F,F)XB(F)-F
(3-21-1) 3%
3-HHXB(F)-OCF3 (3-24) 8%
3-HBEB(F,F)-F (3-27) 3%
上記組成物100重量部に下記化合物(1-1-1)を0.4重量部添加した。
NI=73.2℃;Tc≦-20℃;Δn=0.120;Δε=4.3;Vth=2.01V;η=13.7mPa・s;γ1=56.1mPa・s;τ=9.8ms;VHR-1=99.0%;VHR-2=98.6%;P=48.3μm.
V-HH-3 (2-1-1) 36%
1V-HH-3 (2-1-1) 7%
V2-BB-1 (2-3-1) 4%
3-HHEH-5 (2-4-1) 4%
2-BB(F)B-3 (2-7-1) 9%
1-BB(F)B-2V (2-7-1) 7%
3-BB(F,F)XB(F,F)-F (3-11-1)10%
5-BB(F)B(F,F)XB(F)B(F,F)-F
(3-23-2) 3%
3-BB(F,F)XB(F)-F (3-25) 10%
3-HHEB(F,F)-F (3-26) 10%
上記組成物100重量部に下記化合物(1-1-1)を1重量部添加した。
NI=73.3℃;Tc≦-20℃;Δn=0.119;Δε=4.4;Vth=1.90V;η=13.1mPa・s;γ1=55.2mPa・s;τ=9.5ms;VHR-1=98.9%;VHR-2=98.1%;P=21.6μm.
V-HH-3 (2-1-1) 34%
1V-HH-3 (2-1-1) 10%
V-HHB-1 (2-5-1) 12%
2-BB(F)B-3 (2-7-1) 10%
2-BB(F)B-5 (2-7-1) 9%
3-BB(F,F)XB(F,F)-F (3-11-1)20%
3-HHBB(F,F)-F (3-13-1) 5%
上記組成物100重量部に下記化合物(1-1-1)を0.8重量部添加した。
NI=73.9℃;Tc≦-20℃;Δn=0.114;Δε=3.9;Vth=2.30V;η=10.8mPa・s;γ1=46.9mPa・s;τ=7.8ms;VHR-1=99.0%;VHR-2=98.5%;P=27.6μm.
V-HH-3 (2-1-1) 39%
1V-HH-3 (2-1-1) 7%
V-HHB-1 (2-5-1) 10%
2-BB(F)B-3 (2-7-1) 12%
2-BB(F)B-5 (2-7-1) 8%
3-BB(F,F)XB(F,F)-F (3-11-1)13%
3-HHBB(F,F)-F (3-13-1) 5%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 6%
上記組成物100重量部に下記化合物(1-2-1)を0.5重量部添加した。
NI=77.8℃;Tc≦-20℃;Δn=0.118;Δε=3.9;Vth=2.15V;η=11.1mPa・s;γ1=47.9mPa・s;τ=8.0ms;VHR-1=99.3%;VHR-2=98.5%;P=42.1μm.
V-HH-3 (2-1-1) 45%
V-HHB-1 (2-5-1) 11%
1-BB(F)B-2V (2-7-1) 6%
2-BB(F)B-2V (2-7-1) 8%
3-BB(F,F)XB(F,F)-F (3-11-1)14%
3-BB(F)B(F,F)XB(F,F)-F (3-18-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 9%
5-BB(F)B(F,F)XB(F,F)-F (3-18-1) 4%
上記組成物100重量部に下記化合物(1-1-1)を0.4重量部添加した。
NI=72.5℃;Tc≦-20℃;Δn=0.120;Δε=5.5;Vth=1.62V;η=11.8mPa・s;γ1=49.6mPa・s;τ=8.5ms;VHR-1=99.2%;VHR-2=98.9%;P=47.1μm.
V-HH-3 (2-1-1) 48%
V2-BB-1 (2-3-1) 5%
1-BB(F)B-2V (2-7-1) 8%
2-BB(F)B-2V (2-7-1) 8%
3-BB(F)B-2V (2-7-1) 13%
3-BB(F,F)XB(F,F)-F (3-11-1) 9%
3-BB(F)B(F,F)XB(F,F)-F (3-18-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 6%
上記組成物100重量部に下記化合物(1-1-1)を0.5重量部添加した。
NI=71.2℃;Tc≦-20℃;Δn=0.137;Δε=4.0;Vth=2.30V;η=12.1mPa・s;γ1=52.1mPa・s;τ=8.8ms;VHR-1=99.4%;VHR-2=98.5%;P=40.1μm.
V-HH-3 (2-1-1) 46%
1V-HH-3 (2-1-1) 10%
V-HHB-1 (2-5-1) 11%
V2-HHB-1 (2-5-1) 4%
2-BB(F)B-3 (2-7-1) 9%
2-BB(F)B-5 (2-7-1) 3%
3-HBB(F,F)-F (3-8-1) 5%
3-BB(F,F)XB(F,F)-F (3-11-1) 7%
4-BB(F)B(F,F)XB(F,F)-F(3-18-1) 5%
上記組成物100重量部に下記化合物(1-1-1)を0.5重量部添加した。
NI=75.1℃;Tc≦-20℃;Δn=0.098;Δε=2.5;Vth=2.87V;η=9.37mPa・s.γ1=38.4mPa・s;τ=6.5ms;VHR-1=99.2%;VHR-2=98.8%;P=42.6μm.
V-HH-3 (2-1-1) 42%
1V-HH-3 (2-1-1) 10%
V-HHB-1 (2-5-1) 3%
V2-HHB-1 (2-5-1) 4%
1-BB(F)B-2V (2-7-1) 3%
2-BB(F)B-2V (2-7-1) 8%
3-BB(F)B-2V (2-7-1) 9%
3-BB(F)B(F,F)-F (3-9-1) 5%
3-BB(F,F)XB(F,F)-F (3-11-1) 4%
3-BB(F)B(F,F)XB(F,F)-F (3-18-1) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-18-1) 5%
5-BB(F)B(F,F)XB(F,F)-F (3-18-1) 4%
上記組成物100重量部に下記化合物(1-1-1)を1重量部添加した。
NI=79.9℃;Tc≦-20℃;Δn=0.126;Δε=4.0;Vth=2.38V;η=11.1mPa・s;γ1=48.9mPa・s;τ=8.2ms;VHR-1=98.9%;VHR-2=98.0%;P=21.6μm.
実施例3から実施例19の組成物は、比較例1のそれと比べて短いらせんピッチ、および短い応答時間を有する。よって、本発明による液晶組成物は、比較例1に示された液晶組成物よりも、さらに優れた特性を有する。
Claims (25)
- 式(1)において、R2およびR3の炭素数の和が3~10の範囲である、請求項1に記載の液晶組成物。
- 第一成分を除く液晶組成物100重量部に対して、第一成分の割合が0.01重量部から5重量部の範囲である請求項1から3のいずれか1項に記載の液晶組成物。
- 第二成分として式(2)で表される化合物の群から選択された少なくとも1つの化合物をさらに含有する、請求項1から4のいずれか1項に記載の液晶組成物。
ここで、R4およびR5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;環Bおよび環Cは独立して、1,4-シクロへキシレン、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレン、または2,5-ジフルオロ-1,4-フェニレンであり;Z1は独立して、単結合、エチレン、またはカルボニルオキシであり;pは1または2である。 - 第二成分が式(2-1)で表される化合物の群から選択された少なくとも1つの化合物である請求項6に記載の液晶組成物。
- 第二成分が、式(2-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(2-5)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項6に記載の液晶組成物。
- 第二成分が、式(2-1)で表される化合物の群から選択された少なくとも1つの化合物、および式(2-7)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項6に記載の液晶組成物。
- 第二成分が、式(2-1)で表される化合物の群から選択された少なくとも1つの化合物、式(2-5)で表される化合物の群から選択された少なくとも1つの化合物、および式(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つの化合物の混合物である請求項6に記載の液晶組成物。
- 第一成分を除く液晶組成物の重量に基づいて、第二成分の割合が35重量%から95重量%の範囲である請求項5から10のいずれか1項に記載の液晶組成物。
- 第三成分として式(3)で表される化合物の群から選択された少なくとも1つの化合物をさらに含有する、請求項1から11のいずれか1項に記載の液晶組成物。
ここで、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Dは独立して、1,4-シクロへキシレン、1,3-ジオキサン-2,5-ジイル、1,4-フェニレン、2-フルオロ-1,4-フェニレン、3-フルオロ-1,4-フェニレン、3,5-ジフルオロ-1,4-フェニレン、または2,5-ピリミジンであり;Z2は独立して、単結合、エチレン、カルボニルオキシ、またはジフルオロメチレンオキシであり;X1およびX2は独立して、水素またはフッ素であり;Y1は、フッ素、塩素、またはトリフルオロメトキシであり;kは、1、2、3、または4である。 - 第三成分が式(3-9)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13に記載の液晶組成物。
- 第三成分が式(3-11)で表される化合物の群から選択された少なくとも1つの化合物である請求項13に記載の液晶組成物。
- 第三成分が式(3-15)で表される化合物の群から選択された少なくとも1つの化合物である請求項13に記載の液晶組成物。
- 第三成分が式(3-18)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13に記載の液晶組成物。
- 第三成分が、式(3-6)で表される化合物の群から選択された少なくとも1つの化合物および式(3-11)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項13に記載の液晶組成物。
- 第三成分が、式(3-9)で表される化合物の群から選択された少なくとも1つの化合物および式(3-18)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項13に記載の液晶組成物。
- 第三成分が、式(3-15)で表される化合物の群から選択された少なくとも1つの化合物および式(3-18)で表される化合物の群から選択された少なくとも1つの化合物の混合物である請求項13に記載の液晶組成物。
- 第一成分を除く液晶組成物の重量に基づいて、第三成分の割合が5重量%から60重量%の範囲である請求項12から20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以上である請求項1から21のいずれか1項に記載の液晶組成物。
- 請求項1から22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、TNモード、OCB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23に記載の液晶表示素子。
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US13/255,509 US8609207B2 (en) | 2009-03-16 | 2010-03-02 | Liquid crystal composition and liquid crystal display device |
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JP5500322B1 (ja) * | 2013-03-25 | 2014-05-21 | Dic株式会社 | 液晶組成物及びこれを用いた液晶表示素子 |
WO2014155499A1 (ja) * | 2013-03-25 | 2014-10-02 | Dic株式会社 | 液晶組成物及びこれを用いた液晶表示素子 |
WO2014155480A1 (ja) * | 2013-03-25 | 2014-10-02 | Dic株式会社 | 液晶組成物及びこれを用いた液晶表示素子 |
US9695361B2 (en) | 2012-10-05 | 2017-07-04 | Dic Corporation | Liquid crystal composition and liquid crystal display element using the same |
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JP5534114B1 (ja) * | 2012-10-17 | 2014-06-25 | Dic株式会社 | ネマチック液晶組成物 |
CN103351874B (zh) * | 2013-06-25 | 2014-11-19 | 江苏和成显示科技股份有限公司 | 液晶组合物及其显示器件 |
US10544365B2 (en) | 2013-08-30 | 2020-01-28 | Dic Corporation | Nematic liquid crystal composition |
KR102116943B1 (ko) | 2013-09-12 | 2020-06-01 | 삼성디스플레이 주식회사 | 액정 표시 장치 |
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CN102348780A (zh) | 2012-02-08 |
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