WO2015015904A1 - 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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- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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- C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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- C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
Definitions
- the present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like.
- the present invention relates to a liquid crystal composition having a positive dielectric anisotropy, and an AM (active matrix) device containing this composition and having a TN, OCB, IPS, FFS, or FPA mode.
- the present invention also relates to a polymer-supported alignment type liquid crystal display element.
- the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (Fringe field Switching), FPA (field-induced photo-reactive alignment), etc.
- 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 liquid crystal display element contains a liquid crystal composition having a nematic phase.
- This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The 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.
- a preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or less.
- 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.
- the elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.
- the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate optical anisotropy is required.
- 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. In this case, 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 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 liquid crystal composition containing a polymer is used.
- a composition to which a small amount of a polymerizable compound is added is injected into the device.
- the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device.
- the polymerizable compound polymerizes to form a polymer network in the composition.
- the response time of the device is shortened, and image burn-in is improved.
- Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
- a composition having a positive dielectric anisotropy is used for an AM device having a TN mode.
- a composition having a negative dielectric anisotropy is used in an AM device having a VA mode.
- an AM device having an IPS mode or an FFS mode a composition having a positive or negative dielectric anisotropy is used.
- a composition having positive or negative dielectric anisotropy is used in a polymer-supported orientation type AM device.
- Examples of compositions related to the present invention are disclosed in Patent Document 1 and Patent Document 2.
- An example of a composition for a polymer-supported orientation type element is disclosed in Patent Document 3.
- German publication 102010025572A1 specification International Publication No. 2011-009524 International Publication No. 2011-029510
- 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 dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a high heat It is a liquid crystal composition satisfying at least one characteristic in the characteristics such as high stability with respect to and a large elastic constant. Another object is a liquid crystal composition having an appropriate balance between at least two properties. Another object is a liquid crystal display device containing such a composition. Another object is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
- the present invention includes, as a first component, a liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) and having a positive dielectric anisotropy, and this composition It is a liquid crystal display element to contain.
- R 1 , R 2 , and R 3 are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen.
- R 2 and R 3 may be hydrogen
- ring A is 1,4-phenylene, 1,4-cyclohexylene, 1 , 4-Cyclohexenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine or methyl by and
- X 1, X 2, and X 3 is independently fluorine, chlorine, or at least one hydrogen in the alkyl having carbon atoms 1 be replaced by fluorine 12 Ri
- Z 1, Z 2, Z 3, and Z 4 are each independently a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO-, or a -OCO- A, b, and c are independently 0, 1, 2, 3, or 4; d is 0, 1, or 2.
- 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 suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet light, and a high heat resistance.
- the liquid crystal composition satisfies at least one characteristic in characteristics such as stability and a large elastic constant.
- Another advantage is a liquid crystal composition having an appropriate balance between at least two properties.
- Another advantage is a liquid crystal display device containing such a composition.
- Another advantage is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
- liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
- “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
- “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a composition that does not have a liquid crystal phase, but has the purpose of adjusting properties such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products.
- This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
- the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
- At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”.
- “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
- the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds.
- the ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition.
- additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor are added to the composition.
- the ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used.
- the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
- the upper limit temperature of the nematic phase may be abbreviated as “the upper limit temperature”.
- “Lower limit temperature of 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 expression“ at least one ‘A’ may be replaced by ‘B’ ” means that the number of‘ A ’is arbitrary. When the number of ‘A’ is one, the position of ‘A’ is arbitrary, and when the number of ‘A’ is two or more, the positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'”.
- the symbol of the terminal group R 1 is used for a plurality of compounds.
- two groups represented by two arbitrary 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 symbols such as R 3 and X 1 .
- d when d is 2, two rings A exist.
- the two rings represented by the two rings A may be the same or different.
- This rule also applies to any two rings A when d is greater than 2.
- This rule also applies to Z 5 , ring C, and the like.
- 2-Fluoro-1,4-phenylene means the following two divalent groups.
- fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric ring divalent groups such as tetrahydropyran-2,5-diyl.
- the vertical line across the benzene ring indicates that any hydrogen on the benzene ring may be replaced by X 1 or the like.
- a subscript such as a indicates the number of X 1 replaced. This rule is also applied to the compound (1-1).
- a vertical line across the hexagon represents that any hydrogen on the six-membered ring may be replaced by P 1 -Sp 1 or the like.
- a subscript such as h indicates the number of P 1 -Sp 1 replaced.
- the wavy line indicates the position of the bond.
- the present invention includes the following items.
- Item 1 A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component and having a positive dielectric anisotropy.
- R 1 , R 2 , and R 3 are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen.
- R 2 and R 3 may be hydrogen
- ring A is 1,4-phenylene, 1,4-cyclohexylene, 1 , 4-Cyclohexenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine or methyl by and
- X 1, X 2, and X 3 is independently fluorine, chlorine, or at least one hydrogen in the alkyl having carbon atoms 1 be replaced by fluorine 12 Ri
- Z 1, Z 2, Z 3, and Z 4 are each independently a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO-, or a -OCO- A, b, and c are independently 0, 1, 2, 3, or 4; d is 0, 1, or 2.
- Item 2. The liquid crystal composition according to item 1, comprising at least one compound selected from the group of compounds represented by formulas (1-1) to (1-3) as a first component.
- R 1 and R 3 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine;
- rings A 1 and A 2 are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclo Hexenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine, or methyl;
- X 1, X 2, and X 3 are independently fluorine, chlorine or at least one hydrogen from a good 1 carbon atoms be replaced by fluorine 12 alkyl,; a
- the first component is selected from the group of compounds represented by formula (1-1-1) to formula (1-1-9), formula (1-2-1), and formula (1-2-2) Item 3.
- R 1 and R 3 are independently It is an alkyl having 1 to 12, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
- Item 4 The liquid crystal composition according to any one of claims 1 to 3, wherein the ratio of the first component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.
- Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising at least one compound selected from the group of compounds represented by formula (2) as the second component.
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons;
- ring B is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran- Z 5 is a single bond, —CH 2 CH 2 —, —COO—, or —CF 2 O—;
- X 4 and X 5 are independently hydrogen or fluorine ;
- Y 1 is fluorine, chlorine, carbon number of 1 was replaced with at least one hydrogen halide 12 alkyl, at least one hydrogen from a carbon number
- Item 6. The liquid crystal composition according to any one of items 1 to 5, comprising at least one compound selected from the group of compounds represented by formulas (2-1) to (2-27) as a second component: object.
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
- Item 7 The liquid crystal composition according to item 5 or 6, wherein the ratio of the second component is in the range of 10% by weight to 85% by weight based on the weight of the liquid crystal composition.
- Item 8. The liquid crystal composition according to any one of items 1 to 7, further containing at least one compound selected from the group of compounds represented by formula (3) as a third component.
- 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 at least one hydrogen is replaced by fluorine.
- Ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5- Difluoro-1,4-phenylene;
- Z 6 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—; 2, or 3.
- Item 9 The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a third component: object.
- 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 C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine.
- Item 10 The liquid crystal composition according to item 8 or 9, wherein the ratio of the third component is in the range of 5% by weight to 70% by weight based on the weight of the liquid crystal composition.
- Item 11 The liquid crystal composition according to any one of items 1 to 10, comprising at least one polymerizable compound selected from the group of compounds represented by formula (4) as an additive component.
- ring E and ring G are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen being halogen.
- ring F is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, Phthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in
- P 1 , P 2 and P 3 are each independently selected from the group of groups represented by formula (P-1) to formula (P-5) Item 12.
- M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen
- n 1 is 1 , 2, 3, or 4; both P 1 and P 3 are in formula (P-4)
- at least one of Sp 1 and Sp 3 is an alkylene in which at least one —CH 2 — is replaced by —O—, —COO—, —OCO—, or —OCOO—. is there.
- Item 13 The item according to any one of Items 1 to 12, comprising at least one polymerizable compound selected from the group of compounds represented by formula (4-1) to formula (4-27) as an additive component: Liquid crystal composition.
- P 4 , P 5 and P 6 are each independently a group represented by formula (P-1) to formula (P-3);
- M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen
- Sp 1 , Sp 2 , and Sp 3 are each independently a single bond or a carbon number of 1 to 10
- An alkylene, wherein at least one —CH 2 — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH 2 —CH 2 —. May be replaced with —CH ⁇ CH
- Item 14 The liquid crystal according to any one of items 11 to 13, wherein the addition ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition before the additive is added. Composition.
- R 1 , R 2 , and R 3 are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen.
- R 2 and R 3 may be hydrogen
- ring A is 1,4-phenylene, 1,4-cyclohexylene, 1 , 4-Cyclohexenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine or methyl by and
- X 1, X 2, and X 3 is independently fluorine, chlorine, or at least one hydrogen in the alkyl having carbon atoms 1 be replaced by fluorine 12 Ri
- Z 1, Z 2, Z 3, and Z 4 are each independently a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO-, or a -OCO- A, b, and c are independently 0, 1, 2, 3, or 4; d is 0, 1, or 2.
- R 1 and R 3 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine;
- rings A 1 and A 2 are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclo Hexenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine, or methyl;
- X 1 , X 2 , and X 3 are independently fluorine, chlorine, or methyl;
- a, b, and c are independently 0, 1, 2, 3, or 4.
- Item 17. The item 15 or 16 represented by any one of the formula (1-1-1) to the formula (1-1-9), the formula (1-2-1), and the formula (1-2-2) Compound.
- R 1 and R 3 are independently It is an alkyl having 1 to 12, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
- Item 18 A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 14.
- Item 19 The liquid crystal display element according to item 18, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.
- Item 20 A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized.
- Item 21 Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.
- Item 22 Use of the liquid crystal composition according to any one of items 11 to 14 in a polymer supported alignment type liquid crystal display element.
- the present invention includes the following items.
- A The above composition further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor.
- B An AM device containing the above composition.
- C The above-mentioned composition further containing a polymerizable compound, and a polymer-supported orientation (PSA) type AM device containing this composition.
- D A polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized.
- (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.
- (F) A transmissive device containing the above composition.
- (G) Use of the above composition as a composition having a nematic phase.
- (H) Use as an optically active composition by adding an optically active compound to 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 components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to 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.
- 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 crystalline compounds, additives and the like in addition to the compound selected from the compound (1), the compound (2), the compound (3), and the compound (4).
- the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3).
- Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.
- 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 an additive but no other liquid crystal compound. 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 characteristics 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 almost zero.
- Compound (1) maintains high stability to ultraviolet light.
- Compound (2) increases the dielectric anisotropy.
- Compound (3) increases the maximum temperature or decreases the viscosity.
- first component + second component first component + second component + third component
- first component + second component + additive component first component + second component + additive component
- first component + second component + Third component + additive component first component + second component + additive component.
- the combination of components in a preferred composition is first component + second component + third component.
- a desirable ratio of the first component is approximately 0.03% by weight or more for maintaining high stability to ultraviolet light based on the weight of the liquid crystal composition, and approximately 10% by weight or less for decreasing the minimum temperature. It is. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight. A particularly preferred ratio is in the range of approximately 0.3% by weight to approximately 1.5% by weight.
- a desirable ratio of the second component is approximately 10% by weight or more for increasing the dielectric anisotropy, and approximately 85% by weight or less for decreasing the minimum temperature.
- a more desirable ratio is in the range of approximately 20% by weight to approximately 80% by weight.
- a particularly preferred ratio is in the range of approximately 40% by weight to approximately 75% by weight.
- a desirable ratio of the third component is approximately 5% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 70% by weight or less for increasing the dielectric anisotropy.
- a more desirable ratio is in the range of approximately 15% by weight to approximately 60% by weight.
- a particularly desirable ratio is in the range of approximately 25% by weight to approximately 55% by weight.
- Compound (4) is added to the composition for the purpose of adapting to a polymer-supported orientation type device.
- a preferable addition ratio of this additive is about 0.03% by weight or more for aligning liquid crystal molecules based on the weight of the liquid crystal composition before the addition of the additive, and about 10% by weight or less.
- a more preferred addition ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
- a particularly preferred addition ratio is in the range of about 0.2% by weight to about 1% by weight.
- R 1 , R 2 , R 3 , R 5 , and R 6 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon 2 To alkenyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine, provided that one of R 2 and R 3 may be hydrogen. When one of R 2 and R 3 is hydrogen, it is preferred that R 2 is hydrogen. Desirable R 1 , R 2 or R 3 is alkyl having 1 to 12 carbons for increasing the stability, and alkenyl having 2 to 12 carbons for decreasing the minimum temperature.
- Desirable R 5 or R 6 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, etc., and alkenyl having 2 to 12 carbons for decreasing the minimum temperature or decreasing the viscosity. is there.
- R 4 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R 4 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 at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
- Alkyl is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to alkoxy, alkenyl, or alkenyl in which at least one hydrogen is replaced by fluorine. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.
- Ring A, Ring A 1 , and Ring A 2 are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, Tetrahydropyran-2,5-diyl or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine or methyl.
- Desirable ring A, ring A 1 or ring A 2 is 1,4-cyclohexylene for decreasing the minimum temperature.
- Ring B is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1, 3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl.
- Desirable ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy.
- trans is preferable to cis for increasing the maximum temperature.
- Tetrahydropyran-2,5-diyl is
- Ring C and Ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
- Z 6 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
- Preferred ring C or ring D is 1,4-cyclohexylene for decreasing the viscosity, or 1,4-phenylene for increasing the optical anisotropy.
- X 1 , X 2 , and X 3 are independently fluorine, chlorine, or alkyl having 1 to 12 carbons in which at least one hydrogen may be replaced with fluorine. Desirable X 1 , X 2 or X 3 is fluorine for decreasing the minimum temperature.
- X 4 and X 5 are independently hydrogen or fluorine. Desirable X 4 or X 5 is fluorine for increasing the dielectric anisotropy.
- Y 1 is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with halogen, or alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with halogen.
- Preferred halogen is fluorine or chlorine.
- a more preferred halogen is fluorine.
- Desirable Y 1 is fluorine for decreasing the minimum temperature.
- Z 1 , Z 2 , Z 3 , Z 4 , and Z 6 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. is there. Desirable Z 1 , Z 2 , Z 3 , or Z 4 is a single bond for increasing the stability. Preferred Z 6 is a single bond for decreasing the viscosity.
- Z 5 is a single bond, —CH 2 CH 2 —, —COO—, or —CF 2 O—. Desirable Z 5 is —CF 2 O— for increasing the dielectric anisotropy.
- A, b and c are independently 0, 1, 2, 3 or 4; Desirable a, b or c is 1 or 2 for decreasing the minimum temperature, and is 0 for increasing the maximum temperature.
- d is 0, 1, or 2.
- Preferred d is 0 for decreasing the minimum temperature.
- e is 1, 2, 3, or 4;
- Preferred e is 2 for decreasing the minimum temperature.
- f is 1, 2 or 3.
- Desirable f is 2 for increasing the maximum temperature.
- P 1 , P 2 and P 3 are independently a polymerizable group.
- Preferred P 1 , P 2 or P 3 is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5).
- Preferred P 1 , P 2 or P 3 are a group (P-1) and a group (P-2).
- Further preferred groups (P-1) are —OCO—CH ⁇ CH 2 and —OCO—C (CH 3 ) ⁇ CH 2 .
- the wavy line from the group (P-1) to the group (P-5) indicates the site to be bound.
- M 1 , M 2 and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Alkyl.
- Preferred M 1 , M 2 or M 3 is hydrogen or methyl for increasing the reactivity. More preferred M 1 is methyl, and more preferred M 2 or M 3 is hydrogen.
- n 1 is 1 , 2, 3, or 4. Desirable n 1 is 1 or 2 for increasing the reactivity. Further preferred n 1 is 1.
- both P 1 and P 3 are groups (P-2), at least one of Sp 1 and Sp 3 is at least one —CH 2 — is —O—, —COO—, —OCO—, Or alkylene substituted with —OCOO—. That is, both P 1 and P 3 are not alkenyl such as 1-propenyl.
- Sp 1 , Sp 2 , and Sp 3 are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, — OCO—, or —OCOO— may be replaced, and at least one —CH 2 —CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups, at least One hydrogen may be replaced with fluorine or chlorine. When hydrogen is replaced with —C ⁇ N, the total number of carbon atoms of alkylene substituted with cyano is preferably up to 10.
- Preferred Sp 1 , Sp 2 , or Sp 3 is a single bond.
- Ring E and Ring G are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridine -2-yl, and in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon in which at least one hydrogen is replaced by halogen. To 12 alkyls. Preferred ring E or ring G is phenyl.
- Ring F is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings , At least one hydrogen is halogen, al
- Z 7 and Z 8 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO— may be substituted, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH—, —C (CH 3 ) ⁇ CH—, —CH ⁇ C (CH 3 ) —, or —C (CH 3 ) ⁇ C (CH 3 ) — may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine.
- Preferred Z 7 or Z 8 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 7 or Z 8 is a single bond.
- G is 0, 1, or 2.
- Preferred g is 0 or 1.
- h, j, and k are independently 0, 1, 2, 3, or 4, and the sum of h, j, and k is 1 or greater.
- Preferred h, j, or k is 1 or 2.
- Desirable compounds (1) are the above compounds (1-1) to (1-3). In these compounds, it is preferable that at least one of the first components is the compound (1-1) or the compound (1-2). It is preferable that at least two of the first components are a combination of the compound (1-1) and the compound (1-2). More desirable compound (1) is the compound (1-1-1) to the compound (1-2-2). It is preferable that at least one of the first components is the compound (1-1-1), the compound (1-1-2), the compound (1-2-1), or the compound (1-2-2). It is preferable that at least two of the first components are a combination of the compound (1-1-1) and the compound (1-1-2).
- Desirable compound (2) is the above compound (2-1) to compound (2-27).
- at least one of the second components is compound (2-5), compound (2-11), compound (2-12), compound (2-13), compound (2-15), compound ( 2-16), compound (2-20), compound (2-23), or compound (2-25) is preferred.
- At least two of the second components are the compound (2-12) and the compound (2-23), the compound (2-13) and the compound (2-16), the compound (2-15) and the compound (2-16), The compound (2-16) and the compound (2-25), or a combination of the compound (2-23) and the compound (2-25) is preferable.
- Desirable compounds (3) are the above compounds (3-1) to (3-13).
- at least one of the third components is the compound (3-1), the compound (3-3), the compound (3-5), the compound (3-6), the compound (3-7), or the compound (3-8) is preferred.
- At least two of the third components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6). It is preferable that it is the combination of these.
- Desirable compounds (4) are the compounds (4-1) to (4-27) described above.
- at least one of the additive components is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or compound (4-27) is preferred.
- At least two of the additive components are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), Compound (4-2) and Compound (4-25), Compound (4-2) and Compound (4-26), Compound (4-25) and Compound (4-26), or Compound (4-18) and A combination of compounds (4-24) is preferred.
- preferred M 1 , M 2 , or M 3 is hydrogen or methyl.
- additives that may be added to the composition will be described.
- Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.
- An optically active compound is added to 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 (5-5).
- a desirable ratio of the optically active compound is approximately 5% by weight or less.
- a more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.
- an antioxidant is composed. Added to the product.
- a preferred example of the antioxidant is a compound (6) in which t is an integer of 1 to 9.
- preferred t is 1, 3, 5, 7, or 9. Further preferred t is 1 or 7. Since the compound (6) in which t 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 t 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 after using the device for a long time.
- a desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 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 approximately 100 ppm to approximately 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 of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 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 approximately 100 ppm to approximately 10,000 ppm.
- a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element.
- a preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight.
- an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition.
- a desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect.
- a more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
- a polymerizable compound is added to the composition in order to adapt it to a polymer support alignment (PSA) type device.
- 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. Further preferred examples are acrylate or methacrylate derivatives.
- a desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for achieving the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
- the polymerizable compound is polymerized by irradiation with ultraviolet rays.
- the polymerization may be performed in the presence of an initiator such as a photopolymerization initiator.
- an initiator such as a photopolymerization initiator.
- Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
- Irgacure 651 registered trademark; BASF
- Irgacure 184 registered trademark; BASF
- Darocur 1173 registered trademark; BASF
- a desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the weight of the polymerizable compound.
- a more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.
- a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
- the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
- the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
- the composition of the present invention mainly has a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
- a device containing this composition has a large voltage holding ratio.
- This composition is suitable for an AM device.
- This composition is particularly suitable for a transmissive AM device.
- a composition having an optical anisotropy in the range of about 0.08 to about 0.25 by controlling the proportion of the component compounds or by mixing other liquid crystal compounds, and further from about 0.10 Compositions having optical anisotropy in the range of about 0.30 may be prepared.
- 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, FFS, VA, and FPA.
- Use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferable.
- the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate.
- 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 present invention will be described in more detail with reference to examples. The invention is not limited by these examples.
- the present invention includes a mixture of the composition of Example M1 and the composition of Example M2.
- the invention also includes a mixture of at least two of the example compositions.
- the synthesized compound was identified by a method such as NMR analysis. The properties of the compounds and compositions were measured by the methods described below.
- NMR analysis DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement.
- the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration.
- Tetramethylsilane was used as an internal standard.
- CFCl 3 was used as an internal standard and the number of integrations was 24.
- s is a singlet
- d is a doublet
- t is a triplet
- q is a quartet
- quint is a quintet
- sex is a sextet
- m is a multiplet
- br is broad.
- 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.
- a mixture of liquid crystal compounds is detected by a gas chromatograph (FID).
- the area ratio of peaks in the gas chromatogram corresponds to the ratio (weight ratio) of liquid crystal compounds.
- the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.
- Measurement sample When measuring the properties of the composition, the composition was used as it was as a sample.
- a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation.
- (Extrapolated value) ⁇ (Measured value of sample) ⁇ 0.85 ⁇ (Measured value of mother liquid crystal) ⁇ / 0.15.
- 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 following mother liquid crystals were used.
- the ratio of the component compounds is shown by weight%.
- Measurement method The characteristics were measured by the following method. Many of these methods have been modified by the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). Was the way. No thin film transistor (TFT) was attached to the TN device used for the measurement.
- JEITA Japan Electronics and Information Technology Industries Association
- NI nematic phase
- T C Minimum temperature of nematic phase
- Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
- Viscosity (Rotational Viscosity; ⁇ 1; Measured at 25 ° C .; mPa ⁇ s): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. 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. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. 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 the measurement.
- the light source was 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 0.45 / ⁇ 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 was expressed as a voltage when the transmittance reached 90%.
- VHR-1 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
- the TN device was charged by applying a pulse voltage (60 microseconds at 1 V).
- the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
- Area B was the area when it was not attenuated.
- the voltage holding ratio was expressed as a percentage of area A with respect to area B.
- VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as above except that it was measured at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.
- VHR-3 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m.
- a sample was injected into this element and irradiated with light for 20 minutes.
- the light source was an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source was 20 cm.
- a decaying voltage was measured for 16.7 milliseconds.
- a composition having a large VHR-3 has a large stability to ultraviolet light.
- VHR-3 is preferably 90% or more, and more preferably 95% or more.
- VHR-4 Voltage holding ratio
- the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m.
- a sample was injected into this device and irradiated with light for 67 minutes.
- the light source was black light (peak wavelength: 369 nm), and the distance between the element and the light source was 5 mm.
- a decaying voltage was measured for 166.7 milliseconds.
- a composition having a large VHR-4 has a large stability to ultraviolet light.
- VHR-5 Voltage holding ratio
- the TN device injected with the sample is heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio is measured to determine the stability against heat. Evaluated. In the measurement of VHR-4, a voltage decaying for 16.7 milliseconds was measured. A composition having a large VHR-4 has a large stability to heat.
- 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 was expressed as the sum of the rise time and the fall time thus obtained.
- Helical pitch (P; measured at room temperature; ⁇ m): The helical pitch was measured by the wedge method. See “Liquid Crystal Handbook", page 196 (2000 published, Maruzen). The sample was poured into a wedge-shaped cell and allowed to stand at room temperature for 2 hours, and then the disclination line interval (d2-d1) was observed with a polarizing microscope (Nikon Corporation, trade name: MM40 / 60 series). The helical pitch (P) was calculated from the following equation in which the angle of the wedge cell was expressed as ⁇ . P 2 ⁇ (d2 ⁇ d1) ⁇ tan ⁇ .
- the compounds in Examples were represented by symbols based on the definitions in Table 3 below.
- Table 3 the configuration regarding 1,4-cyclohexylene is trans.
- the number in parentheses after the symbol corresponds to the compound number.
- the symbol ( ⁇ ) means other liquid crystal compounds.
- the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition.
- reaction mixture was extracted with toluene.
- the combined organic layers were washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off with an evaporator.
- the residue was purified by silica gel column chromatography to obtain 4′-bromo-3-ethyl-1,1′-biphenyl (E-7) (15.5 g, yield 83.5%).
- a liquid crystal composition was prepared from 10% by weight of the compound (1-1-1) and 90% by weight of the mother liquid crystal.
- the properties of the obtained liquid crystal composition were measured, and the properties of the compound (1-1-1) were calculated by extrapolating the measured values.
- the results were as follows.
- Maximum temperature (NI) 132.7 ° C .
- dielectric anisotropy ( ⁇ ) 5.1
- optical anisotropy ( ⁇ n) 0.287
- viscosity ( ⁇ ) 92.7 mPa ⁇ s.
- VHR-4 voltage holding ratio after ultraviolet irradiation of the composition of Example M1 was 51.3%, and that of the composition of Comparative Example M1 was 34.3%. From this result, it was found that the TN device of Example M1 had a larger voltage holding ratio than that of Comparative Example M1.
- the liquid crystal composition of the present invention has a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a large elastic constant, a high stability against ultraviolet rays, and a high heat resistance.
- properties such as stability, large elastic constants, at least one property is satisfied, or an appropriate balance is achieved with respect to at least two properties. Since the liquid crystal display element containing this composition has a short response time, a large voltage holding ratio, a large contrast ratio, a long lifetime, and the like, it can be used for a liquid crystal projector, a liquid crystal television, and the like.
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Abstract
Description
式(1)において、R1、R2、およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり、そしてR2およびR3の一方は水素であってもよく;環Aは、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;Z1、Z2、Z3、およびZ4は独立して、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;a、b、およびcは独立して、0、1、2、3、または4であり;dは、0、1、または2である。
式(1)において、R1、R2、およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり、そしてR2およびR3の一方は水素であってもよく;環Aは、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;Z1、Z2、Z3、およびZ4は独立して、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;a、b、およびcは独立して、0、1、2、3、または4であり;dは、0、1、または2である。
式(1-1)から式(1-3)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環A1およびA2は独立して、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;a、b、およびcは独立して、0、1、2、3、または4である。
式(1-1-1)から式(1-1-9)、式(1-2-1)、および式(1-2-2)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルである。
式(2)において、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;環Bは、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、2,6-ジフルオロ-1,4-フェニレン、ピリミジン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、またはテトラヒドロピラン-2,5-ジイルであり;Z5は、単結合、-CH2CH2-、-COO-、または-CF2O-であり;X4およびX5は独立して、水素またはフッ素であり;Y1は、フッ素、塩素、少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキル、少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルコキシ、または少なくとも1つの水素がハロゲンで置き換えられた炭素数2から12のアルケニルオキシであり;eは、1、2、3、または4である。
式(2-1)から式(2-27)において、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のアルケニルである。
式(3)において、R5およびR6は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Cおよび環Dは独立して、1,4-シクロへキシレン、1,4-フェニレン、2-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;Z6は、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;fは、1、2、または3である。
式(3-1)から式(3-13)において、R5およびR6は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルである。
式(4)において、環Eおよび環Gは独立して、シクロヘキシル、シクロヘキセニル、フェニル、1-ナフチル、2-ナフチル、テトラヒドロピラン-2-イル、1,3-ジオキサン-2-イル、ピリミジン-2-イル、またはピリジン-2-イルであり、これらの環において、少なくとも1つの水素は、ハロゲン、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、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキルで置き換えられてもよく;環Fは、1,4-シクロへキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-1,2-ジイル、ナフタレン-1,3-ジイル、ナフタレン-1,4-ジイル、ナフタレン-1,5-ジイル、ナフタレン-1,6-ジイル、ナフタレン-1,7-ジイル、ナフタレン-1,8-ジイル、ナフタレン-2,3-ジイル、ナフタレン-2,6-ジイル、ナフタレン-2,7-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、またはピリジン-2,5-ジイルであり、これらの環において、少なくとも1つの水素は、ハロゲン、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、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z7およびZ8は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、または-C(CH3)=C(CH3)-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;P1、P2、およびP3は重合性基であり;Sp1、Sp2、およびSp3は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;gは、0、1、または2であり;h、j、およびkは独立して、0、1、2、3、または4であり、そしてh、j、およびkの和は1以上である。
式(P-1)から式(P-3)において、M1、M2、およびM3は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から5のアルキルであり;式(P-5)において、n1は、1、2、3、または4であり;P1およびP3の両方が式(P-4)で表される基であるとき、Sp1およびSp3の少なくとも1つは、少なくとも1つの-CH2-が、-O-、-COO-、-OCO-、または-OCOO-で置き換えられたアルキレンである。
式(4-1)から式(4-27)において、P4、P5、およびP6は独立して、式(P-1)から式(P-3)で表される基であり;
式(P-1)から式(P-3)において、M1、M2、およびM3は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から5のアルキルであり;(4-1)から式(4-27)において、Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよい。
式(1)において、R1、R2、およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり、そしてR2およびR3の一方は水素であってもよく;環Aは、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;Z1、Z2、Z3、およびZ4は独立して、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;a、b、およびcは独立して、0、1、2、3、または4であり;dは、0、1、または2である。
式(1-1)から式(1-3)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環A1およびA2は独立して、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、またはメチルであり;a、b、およびcは独立して、0、1、2、3、または4である。
式(1-1-1)から式(1-1-9)、式(1-2-1)、および式(1-2-2)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルである。
窒素雰囲気下の反応器中、(4-ペンチルフェニル)ボロン酸(E-1)(26.8g,139.58mmol)、4-ブロモ-2-フルオロ-1-ヨードベンゼン(E-2)(40.0g,132.94mmol)、テトラキストリフェニルホスフィンパラジウム(1.54g,1.33mmol)、炭酸カリウム(27.6g,199.41mmol)およびテトラブチルアンモニウムブロミド(10.71g,33.23mmol)を、トルエン200ml-エタノール50ml-水200mlの混合溶媒中、8時間還流した。反応混合物をトルエンで抽出した。一緒にした有機層を、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させ、エバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィーおよび再結晶にて精製し、4-ブロモ-2-フルオロ-4’-ペンチル-1,1’-ビフェニル(E-3)を得た(35.1g,収率78.3%)。
窒素雰囲気下の反応器中、マグネシウム(2.92g,120.20mmol)のTHF(50ml)懸濁液へ、第一工程で得られた化合物(E-3)(35.1g,109.27mmol)のTHF(200ml)溶液を50℃以下で滴下した。反応混合物を室温で1時間攪拌したのち-60℃以下に冷却し、ホウ酸トリメチル(13.6g,131.12mmol)のTHF溶液(100ml)を滴下した。反応混合物を室温に戻し、3N-塩酸でクエンチしトルエンで抽出した。一緒にした有機層を、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させ、エバポレーターで溶媒を留去した。残渣をヘプタンで洗浄することにより、(2-フルオロ-4’-ペンチル-[1,1’-ビフェニル]-4-イル)ボロン酸(E-4)を得た(21.4g,収率68.4%)。
窒素雰囲気下の反応器中、1-ブロモ-4-ヨードベンゼン(E-5)(19.6g,69.10mmol)、3-エチルフェニルボロン酸(E-6)(11.4g,76.01mmol)、テトラキストリフェニルホスフィンパラジウム(2.4g,2.07mmol)、炭酸カリウム(14.3g,103.65mmol)およびテトラブチルアンモニウムブロミド(5.57g,17.27mmol)を、トルエン100ml-エタノール20ml-水100mlの混合溶媒中、8時間還流した。反応混合物をトルエンで抽出した。一緒にした有機層を、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させ、エバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィーにて精製し、4’-ブロモ-3-エチル-1,1’-ビフェニル(E-7)を得た(15.5g,収率83.5%)。
窒素雰囲気下の反応器中、第二工程で得られた化合物(E-4)(15.9g,55.52mmol)、第三工程で得られた化合物(E-7)(14.5g,55.52mmol)、テトラキストリフェニルホスフィンパラジウム(0.64g,0.55mmol)、炭酸カリウム(11.5g,83.28mmol)およびテトラブチルアンモニウムブロミド(4.47g,13.88mmol)を、トルエン100ml-エタノール20ml-水100mlの混合溶媒中、8時間還流した。反応混合物をトルエンで抽出した。一緒にした有機層を、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させ、エバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィーおよび再結晶にて精製し、化合物(1-1-1)を得た(17.4g,収率74.2%)。
上限温度(NI)=132.7℃;誘電率異方性(Δε)=5.1;光学的異方性(Δn)=0.287;粘度(η)=92.7mPa・s.
(液晶組成物への溶解性の比較)
母液晶に化合物(1-1-1)を10重量%の割合で添加し、100℃で10分間加熱した。得られた溶液を室温で2日間放置した。その後、結晶が析出したか否かを目視により観察した。一方、以下の化合物(R-1)についても同様な方法で観察した。表4に結果を示す。表4中の記号において“○”は結晶が析出しなかったことを、“×”は結晶が析出したことを示す。表4から、本発明の化合物は、母液晶への溶解性が良好であることが分かる。
5-BB(2F)BBm-2 (1-1-1) 0.5%
3-HHXB(F,F)-F (2-5) 9.0%
4-GHB(F,F)-F (2-7) 5.0%
2-HHBB(F,F)-F (2-17) 4.0%
3-HHBB(F,F)-F (2-17) 6.0%
4-HHBB(F,F)-F (2-17) 5.0%
4-GB(F)B(F,F)XB(F,F)-F
(2-23) 7.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 9.0%
5-BB(F)B(F,F)XB(F,F)-F
(2-25) 7.0%
3-HHB-CL (2) 3.0%
3-HH-V (3-1) 29.0%
3-HH-VFF (3-1) 4.0%
3-HB-O2 (3-2) 3.0%
3-HHB-3 (3-5) 3.0%
5-HBB-2 (3-6) 2.5%
3-HBBH-1O1 (-) 3.0%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=107.1℃;Tc<-20℃;Δn=0.114;Δε=11.0;Vth=1.48V;η=16.4mPa・s;VHR-4=51.3%.
化合物(1-1-1)を含有しない組成物を調製した。実施例M1の組成物において、化合物(1-1-1)を除いた15の化合物を同じ比率で混合した。この組成物の特性を測定した。
NI=107.2℃;Tc<-20℃;Δn=0.113;Δε=11.0;Vth=1.48V;η=16.0mPa・s;VHR-4=34.3%.
5-BB(2F)B(2F)Bm-2 (1-1-2) 0.3%
5-HBB(2F)B(2F)Bm-2 (1-2-2) 0.3%
3-HHXB(F,F)-F (2-5) 9.0%
4-GHB(F,F)-F (2-7) 5.0%
2-HHBB(F,F)-F (2-17) 4.0%
3-HHBB(F,F)-F (2-17) 6.0%
4-HHBB(F,F)-F (2-17) 5.0%
4-GB(F)B(F,F)XB(F,F)-F
(2-23) 7.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 9.0%
5-BB(F)B(F,F)XB(F,F)-F
(2-25) 7.0%
3-HHB-CL (2) 3.0%
3-HH-V (3-1) 29.0%
3-HH-VFF (3-1) 4.0%
3-HB-O2 (3-2) 3.0%
3-HHB-3 (3-5) 3.0%
5-HBB-2 (3-6) 2.4%
3-HBBH-1O1 (-) 3.0%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=109.3℃;Tc<-20℃;Δn=0.113;Δε=10.4;Vth=1.59V;η=15.9mPa・s;VHR-4=52.1%.
5-B(F)BB(2F)Bm-2 (1-1-3) 1.0%
3-HHXB(F,F)-F (2-5) 11.0%
3-HGB(F,F)-F (2-6) 3.0%
4-GHB(F,F)-F (2-7) 10.0%
3-BB(F,F)XB(F,F)-F (2-16) 9.0%
2-HHBB(F,F)-F (2-17) 4.0%
3-HHBB(F,F)-F (2-17) 5.0%
4-HHBB(F,F)-F (2-17) 5.0%
5-HHBB(F,F)-F (2-17) 5.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 9.0%
5-BB(F)B(F,F)XB(F,F)-F
(2-25) 3.0%
3-HH-V (3-1) 20.0%
3-HH-V1 (3-1) 5.0%
3-HHB-1 (3-5) 8.0%
3-HBB-2 (3-6) 2.0%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=106.6℃;Tc<-20℃;Δn=0.110;Δε=11.3;Vth=1.50V;η=20.8mPa・s;VHR-4=54.0%.
5-BB(2F,5F)BBm-2 (1-1-4) 0.5%
3-HHB(F,F)-F (2-3) 3.0%
3-HHXB(F,F)-F (2-5) 13.0%
3-HB(F)B(F,F)-F (2-9) 5.0%
3-BB(F,F)XB(F,F)-F (2-16) 16.0%
3-HHBB(F,F)-F (2-17) 3.0%
4-GBB(F)B(F,F)-F (2-19) 3.0%
3-HBBXB(F,F)-F (2-20) 8.0%
3-HBB(F,F)XB(F,F)-F (2-21) 6.0%
3-HH-V (3-1) 24.0%
3-HH-V1 (3-1) 7.0%
V2-BB-1 (3-3) 3.0%
3-HHEH-3 (3-4) 3.0%
1-BB(F)B-2V (3-8) 3.0%
5-HBB(F)B-2 (3-13) 2.5%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=84.5℃;Tc<-20℃;Δn=0.109;Δε=8.5;Vth=1.45V;η=17.2mPa・s;VHR-4=50.9%.
5-BB(2F,5F)B(2F)Bm-2(1-1-5) 0.5%
3-HB-CL (2-1) 6.0%
5-HXB(F,F)-F (2-2) 5.0%
3-HHB(F,F)-F (2-3) 10.0%
3-HHEB(F,F)-F (2-4) 9.0%
3-HHXB(F,F)-F (2-5) 19.0%
2-HBEB(F,F)-F (2-10) 3.0%
3-HBEB(F,F)-F (2-10) 3.0%
3-BBXB(F,F)-F (2-15) 3.0%
3-BB(F,F)XB(F,F)-F (2-16) 7.0%
3-dhBB(F,F)XB(F,F)-F(2-22) 4.0%
3-BB(F)B(F,F)XB(F)B(F,F)-F
(2-27) 3.0%
3-HH-V (3-1) 7.0%
3-HH-V1 (3-1) 10.0%
5-HH-V (3-1) 7.0%
3-HHEBH-3 (3-9) 3.5%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=78.0℃;Tc<-20℃;Δn=0.086;Δε=10.0;Vth=1.09V;η=17.0mPa・s;VHR-4=49.5%.
V2-B(F)B(2F)B(2F)Bm-2
(1-1-6) 0.5%
3-GB(F,F)XB(F,F)-F (2-12) 4.0%
3-BB(F)B(F,F)-CF3 (2-14) 3.0%
3-BB(F,F)XB(F,F)-F (2-16) 16.0%
3-HHB(F)B(F,F)-F (2-18) 4.0%
3-HBBXB(F,F)-F (2-20) 10.0%
4-GB(F)B(F,F)XB(F,F)-F
(2-23) 4.0%
5-GB(F)B(F,F)XB(F,F)-F
(2-23) 4.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 7.0%
3-HH-V (3-1) 25.0%
3-HH-O1 (3-1) 3.0%
1-BB-3 (3-3) 3.0%
V-HHB-1 (3-5) 11.0%
5-B(F)BB-2 (3-7) 2.5%
2-BB(F)B-3 (3-8) 3.0%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=74.0℃;Tc<-20℃;Δn=0.120;Δε=12.4;Vth=1.24V;η=17.8mPa・s;VHR-4=55.8%.
3-B(2F)B(2F)B(2F)Bm-2
(1-1-7) 1.2%
3-HBB(F,F)-F (2-8) 4.0%
3-GB(F)B(F,F)-F (2-11) 3.0%
3-BB(F)B(F,F)-F (2-13) 6.0%
3-BB(F,F)XB(F,F)-F (2-16) 18.0%
3-HBBXB(F,F)-F (2-20) 3.0%
3-BB(F)B(F,F)XB(F,F)-F
(2-25) 3.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 7.0%
4-BB(F,F)XB(F)B(F,F)-F
(2-26) 3.0%
3-HH-V (3-1) 29.0%
V-HHB-1 (3-5) 11.0%
2-BB(F)B-2V (3-8) 2.8%
3-HB(F)HH-5 (3-10) 3.0%
5-HBBH-3 (3-11) 3.0%
3-HB(F)BH-3 (3-12) 3.0%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=80.7℃;Tc<-30℃;Δn=0.124;Δε=9.9;Vth=1.54V;η=20.6mPa・s;VHR-4=56.2%.
5-HBB(2F)B(2F)Bm-2 (1-2-2) 0.5%
3-HHXB(F,F)-F (2-5) 10.0%
4-GHB(F,F)-F (2-7) 10.0%
3-BB(F,F)XB(F,F)-F (2-16) 6.0%
2-HHBB(F,F)-F (2-17) 4.0%
3-HHBB(F,F)-F (2-17) 6.0%
4-HHBB(F,F)-F (2-17) 5.0%
5-HHBB(F,F)-F (2-17) 5.0%
3-GBB(F)B(F,F)-F (2-19) 3.0%
4-BB(F)B(F,F)XB(F,F)-F
(2-25) 8.0%
5-BB(F)B(F,F)XB(F,F)-F
(2-25) 3.0%
3-HH-V (3-1) 19.0%
2-HH-3 (3-1) 4.0%
3-HH-4 (3-1) 3.0%
V2-BB-1 (3-3) 6.0%
3-HHB-1 (3-5) 5.0%
5-HBB(F)B-3 (3-13) 2.5%
誘電率異方性が正である上記の組成物を調製し、特性を測定した。
NI=106.6℃;Tc<-20℃;Δn=0.115;Δε=10.6;Vth=1.55V;η=19.4mPa・s;VHR-4=52.4%.
Claims (22)
- 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つの化合物を含有し、そして正の誘電率異方性を有する液晶組成物。
式(1)において、R1、R2、およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり、そしてR2およびR3の一方は水素であってもよく;環Aは、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;Z1、Z2、Z3、およびZ4は独立して、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;a、b、およびcは独立して、0、1、2、3、または4であり;dは、0、1、または2である。 - 第一成分として式(1-1)から式(1-3)で表される化合物の群から選択された少なくとも1つの化合物を含有する、請求項1に記載の液晶組成物。
式(1-1)から式(1-3)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環A1およびA2は独立して、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;a、b、およびcは独立して、0、1、2、3、または4である。 - 液晶組成物の重量に基づいて、第一成分の割合が0.03重量%から10重量%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。
式(2)において、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;環Bは、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、2,6-ジフルオロ-1,4-フェニレン、ピリミジン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、またはテトラヒドロピラン-2,5-ジイルであり;Z5は、単結合、-CH2CH2-、-COO-、または-CF2O-であり;X4およびX5は独立して、水素またはフッ素であり;Y1は、フッ素、塩素、少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキル、少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルコキシ、または少なくとも1つの水素がハロゲンで置き換えられた炭素数2から12のアルケニルオキシであり;eは、1、2、3、または4である。 - 液晶組成物の重量に基づいて、第二成分の割合が10重量%から85重量%の範囲である、請求項5または6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7のいずれか1項に記載の液晶組成物。
式(3)において、R5およびR6は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環Cおよび環Dは独立して、1,4-シクロへキシレン、1,4-フェニレン、2-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;Z6は、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;fは、1、2、または3である。 - 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70重量%の範囲である、請求項8または9に記載の液晶組成物。
- 添加物成分として式(4)で表される化合物の群から選択された少なくとも1つの重合性化合物を含有する、請求項1から10のいずれか1項に記載の液晶組成物。
式(4)において、環Eおよび環Gは独立して、シクロヘキシル、シクロヘキセニル、フェニル、1-ナフチル、2-ナフチル、テトラヒドロピラン-2-イル、1,3-ジオキサン-2-イル、ピリミジン-2-イル、またはピリジン-2-イルであり、これらの環において、少なくとも1つの水素は、ハロゲン、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、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキルで置き換えられてもよく;環Fは、1,4-シクロへキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-1,2-ジイル、ナフタレン-1,3-ジイル、ナフタレン-1,4-ジイル、ナフタレン-1,5-ジイル、ナフタレン-1,6-ジイル、ナフタレン-1,7-ジイル、ナフタレン-1,8-ジイル、ナフタレン-2,3-ジイル、ナフタレン-2,6-ジイル、ナフタレン-2,7-ジイル、テトラヒドロピラン-2,5-ジイル、1,3-ジオキサン-2,5-ジイル、ピリミジン-2,5-ジイル、またはピリジン-2,5-ジイルであり、これらの環において、少なくとも1つの水素は、ハロゲン、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、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から12のアルキルで置き換えられてもよく;Z7およびZ8は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、または-C(CH3)=C(CH3)-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;P1、P2、およびP3は重合性基であり;Sp1、Sp2、およびSp3は独立して、単結合または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよく;gは、0、1、または2であり;h、j、およびkは独立して、0、1、2、3、または4であり、そしてh、j、およびkの和は1以上である。 - 請求項11に記載の式(4)において、P1、P2、およびP3が独立して式(P-1)から式(P-5)で表される基の群から選択された重合性基である請求項11に記載の液晶組成物。
式(P-1)から式(P-3)において、M1、M2、およびM3は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から5のアルキルであり;式(P-5)において、n1は、1、2、3、または4であり;P1およびP3の両方が式(P-4)で表される基であるとき、Sp1およびSp3の少なくとも1つは、少なくとも1つの-CH2-が、-O-、-COO-、-OCO-、または-OCOO-で置き換えられたアルキレンである。 - 添加物成分として式(4-1)から式(4-27)で表される化合物の群から選択された少なくとも1つの重合性化合物を含有する、請求項1から12のいずれか1項に記載の液晶組成物。
式(4-1)から式(4-27)において、P4、P5、およびP6は独立して、式(P-1)から式(P-3)で表される基であり;
式(P-1)から式(P-3)において、M1、M2、およびM3は独立して、水素、フッ素、炭素数1から5のアルキル、または少なくとも1つの水素がハロゲンで置き換えられた炭素数1から5のアルキルであり;式(4-1)から式(4-27)において、Sp1、Sp2、およびSp3は独立して、単結合、または炭素数1から10のアルキレンであり、このアルキレンにおいて、少なくとも1つの-CH2-は、-O-、-COO-、-OCO-、または-OCOO-で置き換えられてもよく、少なくとも1つの-CH2-CH2-は、-CH=CH-または-C≡C-で置き換えられてもよく、これらの基において、少なくとも1つの水素は、フッ素または塩素で置き換えられてもよい。 - 添加物を添加する前の液晶組成物の重量に基づいて、添加物成分の添加割合が0.03重量%から10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。
- 式(1)で表される化合物。
式(1)において、R1、R2、およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり、そしてR2およびR3の一方は水素であってもよく;環Aは、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、または少なくとも1つの水素がフッ素で置き換えられてもよい炭素数1から12のアルキルであり;Z1、Z2、Z3、およびZ4は独立して、単結合、-CH2CH2-、-CH2O-、-OCH2-、-COO-、または-OCO-であり;a、b、およびcは独立して、0、1、2、3、または4であり;dは、0、1、または2である。 - 式(1-1)から式(1-3)のいずれかで表される請求項15に記載の化合物。
式(1-1)から式(1-3)において、R1およびR3は独立して、炭素数1から12のアルキル、炭素数1から12のアルコキシ、炭素数2から12のアルケニル、または少なくとも1つの水素がフッ素で置き換えられた炭素数2から12のアルケニルであり;環A1およびA2は独立して、1,4-フェニレン、1,4-シクロへキシレン、1,4-シクロへキセニレン、1,3-ジオキサン-2,5-ジイル、テトラヒドロピラン-2,5-ジイル、または少なくとも1つの水素が、フッ素、塩素、またはメチルで置き換えられた1,4-フェニレンであり;X1、X2、およびX3は独立して、フッ素、塩素、またはメチルであり;a、b、およびcは独立して、0、1、2、3、または4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を含有する液晶表示素子。
- 液晶表示素子の動作モードが、IPSモード、VAモード、FFSモード、またはFPA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18に記載の液晶表示素子。
- 請求項11から14のいずれか1項に記載の液晶組成物を含有し、この液晶組成物中の重合性化合物が重合されている、高分子支持配向型の液晶表示素子。
- 請求項1から14のいずれか1項に記載の液晶組成物の、液晶表示素子における使用。
- 請求項11から14のいずれか1項に記載の液晶組成物の、高分子支持配向型の液晶表示素子における使用。
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US3600445A (en) * | 1965-07-20 | 1971-08-17 | Merck Ag E | Organic scintillators |
US3988437A (en) * | 1974-03-25 | 1976-10-26 | Research Corporation | Suntan composition containing fluorescent compounds |
DE3225741A1 (de) * | 1982-07-09 | 1984-02-16 | Lambda Physik GmbH, 3400 Göttingen | Stimulierbares medium fuer farbstofflaser |
JPH0333183A (ja) * | 1989-03-15 | 1991-02-13 | Idemitsu Kosan Co Ltd | 有機薄膜エレクトロルミネッセンス素子 |
JPH03162484A (ja) * | 1989-11-20 | 1991-07-12 | Pioneer Electron Corp | 電界発光素子 |
DE102010025572A1 (de) * | 2010-06-30 | 2012-01-05 | Merck Patent Gmbh | Flüssigkristallines Medium und dieses enthaltende Hochfrequenzbauteile |
JP2012533662A (ja) * | 2009-07-21 | 2012-12-27 | 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 | 液晶媒体およびこれを含む高周波構成要素 |
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US5126214A (en) | 1989-03-15 | 1992-06-30 | Idemitsu Kosan Co., Ltd. | Electroluminescent element |
EP2292720A1 (en) | 2009-09-08 | 2011-03-09 | Merck Patent GmbH | Liquid-crystal display |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3600445A (en) * | 1965-07-20 | 1971-08-17 | Merck Ag E | Organic scintillators |
US3988437A (en) * | 1974-03-25 | 1976-10-26 | Research Corporation | Suntan composition containing fluorescent compounds |
DE3225741A1 (de) * | 1982-07-09 | 1984-02-16 | Lambda Physik GmbH, 3400 Göttingen | Stimulierbares medium fuer farbstofflaser |
JPH0333183A (ja) * | 1989-03-15 | 1991-02-13 | Idemitsu Kosan Co Ltd | 有機薄膜エレクトロルミネッセンス素子 |
JPH03162484A (ja) * | 1989-11-20 | 1991-07-12 | Pioneer Electron Corp | 電界発光素子 |
JP2012533662A (ja) * | 2009-07-21 | 2012-12-27 | 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 | 液晶媒体およびこれを含む高周波構成要素 |
DE102010025572A1 (de) * | 2010-06-30 | 2012-01-05 | Merck Patent Gmbh | Flüssigkristallines Medium und dieses enthaltende Hochfrequenzbauteile |
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