WO2014057780A1 - フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 - Google Patents
フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 Download PDFInfo
- Publication number
- WO2014057780A1 WO2014057780A1 PCT/JP2013/075266 JP2013075266W WO2014057780A1 WO 2014057780 A1 WO2014057780 A1 WO 2014057780A1 JP 2013075266 W JP2013075266 W JP 2013075266W WO 2014057780 A1 WO2014057780 A1 WO 2014057780A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- group
- compound
- general formula
- crystal composition
- Prior art date
Links
- YZKFCSOACWTUBF-UHFFFAOYSA-N CC(CC1)CCC1C(F)(F)F Chemical compound CC(CC1)CCC1C(F)(F)F YZKFCSOACWTUBF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—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
- C09K2019/0448—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 end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/301—Cy-Cy-Ph
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—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
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
Definitions
- the present invention relates to a compound having a fluorinated naphthalene structure, which is useful as an organic electronic material or medical pesticide, particularly as a material for a liquid crystal display element.
- Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, etc., including watches and calculators.
- Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type.
- Etc The liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage. Further, the liquid crystal composition must have optimum values of dielectric anisotropy ( ⁇ ), refractive index anisotropy ( ⁇ n) and the like in accordance with individual display elements.
- ⁇ dielectric anisotropy
- ⁇ n refractive index
- a liquid crystal composition having a positive ⁇ is used in a TN type, STN type, or IPS type horizontal alignment type display.
- a driving method has been reported in which a liquid crystal composition having a positive ⁇ is vertically aligned when no voltage is applied and a horizontal electric field is applied to display the liquid crystal composition, and the necessity of a liquid crystal composition having a positive ⁇ is further increased. Yes. Accordingly, the component constituting the liquid crystal composition is required to have as large ⁇ as possible.
- the liquid crystal composition is used as a display element or the like, it is required to exhibit a stable nematic phase in a wide temperature range. In order to maintain a nematic phase in a wide temperature range, it is required that individual components constituting the liquid crystal composition have high miscibility with other components and a high clearing point (T ni ).
- the problem to be solved by the present invention is to provide a compound having both large ⁇ , high T ni and excellent storage stability, and also to provide a liquid crystal composition and a liquid crystal display device comprising the compound as a constituent member. is there.
- the present invention is represented by the general formula (1)
- R represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, one —CH 2 — present in these groups or two or more not adjacent to each other
- Each of —CH 2 — may be independently replaced by —O—, —S—, —COO—, —OCO— or —CO—
- a 1 to A 4 are each independently (A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - each independently is O- or -S- in May be replaced.)
- B 1,4-phenylene group (one —CH ⁇ present in this group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ , present in this group)
- the hydrogen atom to be substituted may be substituted with a fluorine atom or a chlorine atom.
- a group selected from the group consisting of: Z 1 to Z 4 are
- the compound represented by the general formula (1) provided by the present invention has a large ⁇ , a high T ni and a high miscibility with other liquid crystal compounds.
- liquid crystal composition showing a liquid crystal phase in a large ⁇ and a wide temperature range can be obtained. For this reason, it is very useful as a component of the liquid crystal composition for liquid crystal display elements.
- R is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce the viscosity, and alkyl having 1 to 5 carbon atoms.
- a group or an alkenyl group having 2 to 5 carbon atoms is particularly preferred. Moreover, it is preferable that it is linear.
- Each of A 1 to A 4 present independently is preferably a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group when importance is placed on a decrease in viscosity.
- 4-cyclohexylene group is more preferable, and when emphasizing the increase in ⁇ ,
- Each of Z 1 to Z 3 present independently is preferably —CF 2 O—, —OCF 2 —, —CF ⁇ CF— or a single bond when importance is placed on the decrease in viscosity, —CF 2 More preferably, it is O—, —OCF 2 — or a single bond.
- Z 4 in the case of emphasizing an increase in the ⁇ is, -CF 2 O-or -OCF 2 - is preferably, it is more preferably -CF 2 O-.
- Z 1 and Z 2 present are —CH 2 CH 2 — or a single bond. It is preferable that Z 3 is —CF 2 O— and Z 4 is a single bond, or that Z 3 is a single bond and Z 4 is —CF 2 O—.
- X a to X d are each independently a fluorine atom when emphasizing the increase in ⁇ , and when emphasizing viscosity, X d is preferably a hydrogen atom, and the viscosity, ⁇ When importance is placed on the balance of storage stability, X a to X c are preferably fluorine atoms and X d is preferably a hydrogen atom.
- n is preferably 0 when emphasizing solubility, and is preferably 1 when emphasizing T ni .
- each R 1 independently represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms.
- the content of the compound represented by the general formula (1) is small in the liquid crystal composition of the present invention, the effect does not appear. The same shall apply hereinafter), preferably 2%, more preferably 5%. Further, since a large content causes problems such as precipitation, the upper limit is preferably 50%, more preferably 30%, still more preferably 20%, and particularly preferably 10%.
- the compound represented by General formula (1) can also be used by 1 type, you may use 2 or more types of compounds simultaneously.
- a compound other than the compound represented by the general formula (1) may be used.
- a compound having a liquid crystal phase a compound having no liquid crystal phase may be used as necessary. It can also be added.
- the general component (1) At least one compound represented by the formula (2), but it is preferable to contain at least one of the following second to sixth components as other components.
- the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (A1) to (A3).
- R b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms at the end.
- the compound may be optically active or racemic.
- Ring A, Ring B and Ring C may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms.
- An optional naphthalene-2,6-diyl group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms is preferred.
- ring A when ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring A may be a trans-1,4-cyclohexylene group.
- ring C when ring C is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1,4-cyclohexylene groups.
- ring A3 is preferably a trans-1,4-cyclohexylene group.
- L a , L b and L c are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, — CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— is preferable, and a single bond or an ethylene group is particularly preferable. Further, it is preferable that at least one of (A2) represents a single bond and at least two of (A3) represent
- Ring Z is an aromatic ring and represents any one of the following general formulas (La) to (Lc).
- Y a to Y j each independently represent a hydrogen atom or a fluorine atom.
- at least one of Y a and Y b is preferably a fluorine atom
- at least one of Y d to Y f is preferably a fluorine atom, more preferably Y d is more preferably a fluorine atom
- at least one of Y h and Y i is a fluorine atom
- Y h is more preferably a fluorine atom.
- Terminal group P a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group, two or more carbon atoms substituted by fluorine atoms 2 or 3 alkoxy groups, 2 An alkyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, an alkenyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, or a carbon substituted by 2 or more fluorine atoms Although an alkenyloxy group having 2 or 3 atoms is represented, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.
- the third component is a so-called cyano p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (B1) to (B3).
- R c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms at the end.
- the compound may be optically active or racemic.
- Ring D, Ring E and Ring F may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms.
- the good naphthalene-2,6-diyl group or 1 to 2 fluorine atoms also may be substituted 1,4-phenylene group is preferred.
- ring D when ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring D may be a trans-1,4-cyclohexylene group.
- Ring F is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group
- Ring D and Ring E are trans-1,4-cyclohexylene groups.
- ring D is preferably a trans-1,4-cyclohexylene group.
- L d , L e and L f are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and ) —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —OCH 2 —, —CH 2 O— or —CH ⁇ NN ⁇ CH— represents a single bond, an ethylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— are preferred, and a single bond, an ethylene group or —COO— is particularly preferred.
- at least one of them preferably represents a
- P b represents a cyano group
- Ring Y is an aromatic ring and represents any one of the following general formulas (Ld) to (Lf).
- Y k to Y q each independently represent a hydrogen atom or a fluorine atom.
- at least one of Y k and Y l is preferably a fluorine atom
- Y m to Y o are preferably fluorine atoms, particularly Y m is more preferably a fluorine atom
- at least one of Y p and Y q is a fluorine atom.
- Y p is a fluorine atom.
- the fourth component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formulas (C1) to (C3).
- R d and Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and may be a 3- to 6-membered ring
- Any —CH 2 — that may have a cyclic structure and is present in the group is —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or Any hydrogen atom present in the group may be substituted by —C ⁇ C— and may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl having 1 to 7 carbon atoms A straight-chain 1-alkenyl group having 2 to 7 carbon atoms, a straight-chain 3-alkenyl group having 4 to 7 carbon atoms, a straight-chain alkoxy group having 1 to 3 carbon atoms, or a terminal having the number of carbon atoms A linear alkyl group having 1 to 5 carbon atoms substituted with 1 to 3 alkoxy
- Ring G, Ring H, Ring I and Ring J are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or 1,4-phenylene group optionally substituted by a methyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, substituted by 1 or 2 fluorine atoms
- the other ring is a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group.
- the total number of fluorine atoms present in ring G, ring H, ring I and ring J is preferably 2 or less, and preferably 0 or 1.
- L g , L h and Li are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and ) —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH— are preferred, and in general formula (C2), at least one of them is represented by formula (C3 ), At least two of them preferably represent
- the compounds represented by the general formulas (C1) to (C3) exclude the compounds represented by the general formulas (A1) to (A3) and the compounds represented by the general formulas (B1) to (B3).
- the fifth component is an optically active compound used for inducing a helical structure in the liquid crystal composition.
- a compound having an asymmetric carbon atom is preferable, and a compound having a 1-methylheptyloxy group is more preferable.
- the sixth component is a compound having a polymerizable functional group that can be polymerized by ultraviolet irradiation or heating, which is added to improve the response speed or improve the orientation of the liquid crystal composition.
- the polymerizable group is preferably an acryloxy group or a methacryloxy group, and more preferably a methacryloxy group.
- R, A 1 to A 3 , Z 1 to Z 3 and n each independently represent the same meaning as R, A 1 to A 3 , Z 1 to Z 3 and n in formula (1);
- a 4 represents a 3-fluorophenyl group or a 3,5-difluorophenyl group.
- R, A 1 to A 3 , Z 1 to Z 3 and n each independently represent the same meaning as R, A 1 to A 3 , Z 1 to Z 3 and n in formula (1);
- a 4 represents a 3-fluorophenyl group or a 3,5-difluorophenyl group.
- ether solvents such as tetrahydrofuran and diethyl ether are preferred. These solvents may be used alone or in combination.
- the base may be any as long as it allows the reaction to proceed suitably, but is preferably an alkyllithium reagent such as n-butyllithium, sec-butyllithium or tert-butyllithium or a lithium amide such as lithium diisopropylamide.
- an alkyllithium reagent such as n-butyllithium, sec-butyllithium or tert-butyllithium or a lithium amide such as lithium diisopropylamide.
- a 4 is a 3-fluorophenyl group
- sec-butyllithium is more preferable
- a 4 is a 3,5-difluorophenyl group
- n-butyllithium or lithium diisopropylamide is preferable. More preferred.
- the reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably -76 ° to -40 ° C, more preferably -76 ° C to -60 ° C. After adding dibromodifluoromethane, it is preferable to react at room temperature.
- X a to X d each independently represents the same meaning as X a to X d in formula (1)
- a 4 is reacted in the presence of a base.
- a compound represented by the general formula (1) which is 3-fluoro-1,4-phenylene or 3,5-difluoro-1,4-phenylene can be obtained.
- the base may be any as long as it allows the reaction to proceed suitably, but is preferably a carbonate such as sodium carbonate, potassium carbonate or cesium carbonate, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. More preferred is potassium carbonate.
- Any solvent may be used as long as it allows the reaction to proceed smoothly, but amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, 1,4- Ether solvents such as dioxane and t-butyl methyl ether are preferable, and N, N-dimethylformamide or N-methylpyrrolidone is more preferable.
- amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, 1,4- Ether solvents such as dioxane and t-butyl methyl ether are preferable, and N, N-dimethylformamide or N-methylpyrrolidone is more preferable.
- the reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably from room temperature to the temperature at which the solvent is refluxed, more preferably from room temperature to 80 ° C., and preferably from 40 ° C. to 60 ° C. Is particularly preferred.
- Manufacturing method 2 General formula (5)
- any acid chloride may be used as long as it causes the reaction to proceed appropriately, but oxalic acid dichloride, thionyl chloride, and the like are preferable.
- Chlorine solvents such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane
- hydrocarbon solvents such as hexane and toluene
- diethyl Ether solvents such as ether and tetrahydrofuran are preferred, and dichloromethane and 1,2-dichloromethane are more preferred.
- the reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably 0 ° C. to the temperature at which the solvent is refluxed, more preferably 40 ° C. to the temperature at which the solvent is refluxed.
- the dithiols are preferably 1,3-propanedithiol or 1,4-butanedithiol.
- the reaction temperature may be any as long as it allows the reaction to proceed suitably, but at 0 ° C. when trifluoromethanesulfonic acid is added to a mixture of the compound represented by the general formula (6) and dithiols. It is preferable that the temperature is 100 ° C. to 130 ° C., and more preferably 110 ° C. to 120 ° C.
- the compound represented by the general formula (7) is reacted with the compound represented by the general formula (4) in the presence of a fluorinating reagent and an oxidizing agent to thereby obtain a compound represented by the general formula (1). Can be obtained.
- Any fluorinating reagent may be used as long as it allows the reaction to proceed suitably.
- Triethylamine trihydrofluoride, tetrabutylammonium dihydrogen trifluoride, pyridine / hydrogen fluoride complex, melamine / fluoride A hydrogen complex is preferred.
- the reaction temperature may be any temperature that allows the reaction to proceed suitably, but is preferably -76 ° C to -60 ° C.
- the phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).
- T n-i nematic phase - represents the transition temperature of the isotropic phase.
- THF Tetrahydrofuran
- DMF N, N-dimethylformamide
- Me Methyl group
- Pr n-propyl group
- Bu n-butyl group
- Tf trifluoromethanesulfonyl group (Example 1) [3,5-difluoro-trans-4 Preparation of — (4- (trans-4-propylcyclohexyl) cyclohexyl) phenyl]-(5,6,7-trifluoro-2-naphthyloxy) difluoromethane
- a liquid crystal composition (MA) comprising 20% of (trifluoro-2-naphthyloxy) difluoromethane was prepared.
- the physical properties of this composition are as follows.
- the prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Example 8 Preparation of Liquid Crystal Composition-2 Base liquid crystal (H) 80% and [3,5-difluoro-4- (2-fluoro-4- (trans-4-propylcyclohexyl) phenyl) phenyl]-(5,6,7) obtained in Example 2
- a liquid crystal composition (MB) comprising 20% of (trifluoro-2-naphthyloxy) difluoromethane was prepared.
- the physical properties of this composition are as follows.
- T ni 124.5 ° C.
- the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Example 9 Preparation of liquid crystal composition-3
- a liquid crystal composition (MC) comprising 10% of (5,6,7-trifluoro-2-naphthyl) phenyloxy] difluoromethane was prepared.
- the physical properties of this composition are as follows.
- T ni 128.8 ° C. ⁇ : 8.30 ⁇ n: 0.1106 ⁇ 20 : 31.8 mPa ⁇ s [3,5-difluoro-4- (2-fluoro-4- (trans-4-propylcyclohexyl) phenyl) phenyl]-[3-fluoro-4- (5,6,7-trifluoro-2-naphthyl)
- the prepared liquid crystal composition (MC) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Example 10 Preparation of Liquid Crystal Composition-4 80% of the base liquid crystal (H) and [4- (4- (5,6,7-trifluoro-2-naphthyl) -3-fluorophenyl) phenyloxy]-(2,6-
- a liquid crystal composition (MD) comprising 20% of (difluoro-4-propylphenyl) difluoromethane was prepared.
- the physical properties of this composition are as follows.
- the prepared liquid crystal composition (MD) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Example 11 Preparation of Liquid Crystal Composition-5
- the base liquid crystal (H) was 95% and [3,5-difluoro-4- (4- (2- (trans-4-propylcyclohexyl) -1-ethyl) phenyl) phenyl]-[4] obtained in Example 5 was used.
- a liquid crystal composition (ME) comprising 5% of-(5,6,7-trifluoro-2-naphthyl) phenyl] difluoromethane was prepared.
- the physical properties of this composition are as follows.
- T ni 126.1 ° C. ⁇ : 5.63 ⁇ n: 0.1017 ⁇ 20 : 30.8 mPa ⁇ s [3,5-difluoro-4- (4- (2- (trans-4-propylcyclohexyl) -1-ethyl) phenyl) phenyl]-[4- (5,6,7-trifluoro-2-naphthyl)
- the prepared liquid crystal composition (ME) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Example 12 Preparation of Liquid Crystal Composition-6 90% of the base liquid crystal (H) and [3,5-difluoro-4- (2-fluoro-4- (4-propylphenyl) phenyl) phenyl]-(5,6,7-trimethyl) obtained in Example 6
- a liquid crystal composition (MF) comprising 10% of (fluoro-2-naphthyloxy) difluoromethane was prepared.
- the physical properties of this composition are as follows.
- T ni 106.9 ° C. ⁇ : 9.79 ⁇ n: 0.1112 ⁇ 20 : 26.9 mPa ⁇ s
- the prepared liquid crystal composition (MG) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high storage stability.
- Liquid Crystal Composition-8 Liquid crystal composition comprising 90% of base liquid crystal (H) and 10% of 5,6,7-trifluoro-2- [3-fluoro-4- (4-propylphenyl) phenyl] naphthalene obtained in Reference Example 2. (MH) was prepared.
- the physical properties of this composition are as follows.
- Example 7 By comparing Example 7 and Comparative Example 1, it can be seen that the compound of the present invention is highly effective in increasing T ni and ⁇ while maintaining high storage stability as compared with the reference compound. Further, by comparing Example 7 with Comparative Example 2, it can be seen that the compound of the present invention has an extremely high effect of increasing storage stability and ⁇ while maintaining high Tni.
Abstract
Description
A1~A4はそれぞれ独立して、
(a)1,4-シクロへキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は各々独立してO-又は-S-に置き換えられても良い。)
(b)1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良く、この基中に存在する水素原子はフッ素原子又は塩素原子に置換されても良い。)
からなる群より選ばれる基であり、
Z1~Z4は各々独立して、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-、-CF=CF-、-C≡C-又は単結合を表すが、存在するZ1~Z4の内一つは必ず-CF2O-又は-OCF2-であり、
Xa~Xdは各々独立して、水素原子、フッ素原子又は塩素原子を表し、
nは0又は1を表す。)で表される化合物を提供し、併せて、当該化合物を含有する液晶組成物及び当該液晶組成物を用いた液晶表示素子を提供する。
Z3が-CF2O-であり、Z4が単結合であるか、又はZ3が単結合であり、Z4が-CF2O-であることが好ましい。
本発明の液晶組成物において一般式(1)で表される化合物の含有量が少ないとその効果が現れないため、液晶組成物中に下限値として、1%(組成物中の%は質量%を表す。以下同様。)が好ましく、2%が好ましく、5%が更に好ましい。又、含有量が多いと析出等の問題を引き起こすため、上限値としては、50%が好ましく、30%がより好ましく、20%が更に好ましく、10%が特に好ましい。一般式(1)で表される化合物は1種のみで使用することもできるが、2種以上の化合物を同時に使用してもよい。
(製法1)
一般式(2)
(製法2)
一般式(5)
DMF:N,N-ジメチルホルムアミド
Me:メチル基、Pr:n-プロピル基、Bu:n-ブチル基
Tf:トリフルオロメタンスルホニル基
(実施例1)[3,5-ジフルオロ-trans-4-(4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの製造
(1-2) (1-1)で得られた粗製3,5-ジフルオロ-4-(1-ヒドロキシ-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)ベンゼン(62.5g)及びp-トルエンスルホン酸1水和物(1.7g)をトルエン(300mL)に溶解させた溶液を還流させ、ディーンスターク装置を用いて発生する水を除去しながら5時間撹拌した。放冷し、水(150mL)を加えて分液し、有機層を飽和炭酸水素ナトリウム水溶液(150mL)、飽和食塩水(150mL)で洗浄し、無水硫酸ナトリウムを加えて乾燥した。有機溶媒を減圧留去し、得られた残渣をアルミナカラムクロマトグラフィーにより精製する事で、粗製3,5-ジフルオロ-4-(4-(trans-4-プロピルシクロヘキシル)-1-シクロヘキセニル)ベンゼン(64.1g)を得た。
(1-3) (1-2)で得られた粗製3,5-ジフルオロ-4-(4-(trans-4-プロピルシクロヘキシル)-1-シクロヘキセニル)ベンゼン(64.1g)及び5wt%パラジウム/カーボン(3.0g)をトルエン(200mL)、エタノール(100mL)に溶解させた溶液を、オートクレーブに入れ、水素雰囲気下(0.5MPa)40℃にて5時間撹拌した。パラジウム/カーボンを濾過により除去し、溶媒を減圧留去する事により、粗製3,5-ジフルオロ-4-(4-(trans-4-プロピルシクロヘキシル)-1-シクロヘキシル)ベンゼン(64.3g)を得た。
(1-4) 窒素雰囲気下、(1-3)にて得られた粗製3,5-ジフルオロ-4-(4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)ベンゼン(64.3g)及びt-ブチルオキシカリウム(2.0g)をDMF(300mL)に溶解させ、70℃にて3時間撹拌した。放冷後、トルエン(300mL)及び水(300mL)を加えて分液し、有機層を水(300mL)、飽和食塩水(300mL)にて洗浄し、無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去した。得られた残渣をシリカゲルカラムクロマトグラフィーによる精製、減圧蒸留(0.7mmHg、沸点171~174℃)、エタノールから再結晶する事により、3,5-ジフルオロ-4-(trans-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)ベンゼン(43.5g)を得た。
(1-5) 窒素雰囲気下、(1-4)で得られた3,5-ジフルオロ-4-(trans-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)ベンゼン(43.5g)をTHF(300mL)に溶解させた溶液を-76℃に冷却し、1.6mol/L n-ブチルリチウム/ヘキサン溶液(95mL)を加え、-76℃にて1時間撹拌した。続いて、ジブロモジフルオロメタン(19.0g)をTHF(90mL)に溶解させた溶液を加え、ゆっくりと室温まで昇温した。トルエン(300mL)及び水(200mL)を加えて分液し、有機層を10%亜硫酸ナトリウム水溶液(150mL)、飽和食塩水(159mL)にて洗浄し、無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去した。得られ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する事で、粗製(3,5-ジフルオロ-4-(trans-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル)ブロモジフルオロメタン(57.5g)を得た。
(1-6) 5,6,7-トリフルオロ-2-ナフトール(25.4g、特開2004-91361号に従って製造)、(1-5)で得られた(3,5-ジフルオロ-4-(trans-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル)ブロモジフルオロメタン(57.5g)及び無水炭酸カリウム(26.5g)をDMF(300mL)に懸濁させ、50℃にて18時間撹拌した。放冷後、水(200mL)及びトルエン(200mL)を加えて分液し、有機層を飽和食塩水(200mL)にて2回洗浄し、無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去した。得られ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、エタノール及びヘキサンから再結晶する事により、[3,5-ジフルオロ-4-(trans-4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン(47.4g)を得た。
MS m/z:566[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67(1H,s),7.48-7.46(1H,m),7.38-7.32(1H,m),7.19(2H,d,10.3Hz),2.35(1H,tt,J1=3.2Hz,J2=12.1Hz),1.90-1.71(8H,m),1.33-1.28(4H,m),1.56-0.94(9H,m),0.89-0.81(5H,m)
(実施例2)[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの製造
(2-2) 以下の工程は、実施例1に示した方法と同様に行い、[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン(20.5g)を得た。
MS m/z:578[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67(1H,s),7.49-7.45(1H,m),7.39-7.33(1H,m),7.27(1H,t,J=8.1Hz),7.18(2H,d,10.4Hz),7.06-6.97(2H,m),2.50-2.43(1H,m),1.93-1.86(4H,m),1.49-1.38(2H,m),1.36-1.26(3H,m),1.24-1.18(2H,m),1.11-1.00(2H,m),0.91(3H,t,J=7.1Hz)
(実施例3)[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-[3-フルオロ-4-(5,6,7-トリフルオロ-2-ナフチル)フェニルオキシ]ジフルオロメタンの製造
(3-2) 窒素雰囲気下、5,6,7-トリフルオロ-2-ナフトール(30g)及びピリジン(15.6g)をジクロロメタン(150mL)に溶解させ、5℃に冷却し、トリフルオロメタンスルホン酸無水物(47.0g)をジクロロメタン(150mL)に溶解させた溶液を加えた。室温にて1時間撹拌した後、水(200mL)を加えて分液し、有機層を10%塩酸(150mL)、飽和炭酸水素ナトリウム水溶液(150mL)、飽和食塩水(150mL)で洗浄した。無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去し、シリカゲルカラムクロマトグラフィーにより精製する事で、トリフルオロメタンスルホン酸5,6,7-トリフルオロ-2-ナフチル(49.4g)を得た。
(3-3) 窒素雰囲気下、(3-2)で得られたトリフルオロメタンスルホン酸5,6,7-トリフルオロ-2-ナフチル(40.0g)、テトラキストリフェニルホスフィンパラジウム(0)(1.4g)、2mol/L炭酸カリウム水溶液(120mL)及びTHF(200mL)を混合し、60℃に加熱し、(3-1)で得られた2-フルオロ-4-メトキシフェニルホウ酸(24.7g)をTHF(100mL)に溶解させた溶液を加え、60℃にて6時間撹拌した。室温まで冷却し、トルエン(150mL)を加えて分液し、有機層を水(100mL)、飽和食塩水(100mL)で洗浄し、無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去した。得られ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、粗製2-(2-フルオロ-4-メトキシフェニル)-5,6,7-トリフルオロナフタレン(35.1g)を得た。
(3-4) (3-3)で得られた粗製2-(2-フルオロ-4-メトキシフェニル)-5,6,7-トリフルオロナフタレン(35.1g)をジクロロメタン(350mL)に溶解させ、5℃に冷却し、三臭化ホウ素(14.4g)を加えた。室温にて3時間撹拌した後、5℃に冷却し、水(100mL)を加えて分液し、有機層を飽和食塩水(100mL)にて2回洗浄し、無水硫酸ナトリウムを加えて乾燥し、有機溶媒を減圧留去した。得られた残渣をアルミナカラムクロマトグラフィーにて精製し、ヘキサンから再結晶する事で、4-(5,6,7-トリフルオロ-2-ナフチル)-3-フルオロフェノール(25.3g)を得た。
(3-5) 以下の工程は実施例1と同様にして行う事で、[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-[3-フルオロ-4-(5,6,7-トリフルオロ-2-ナフチル)フェニルオキシ]ジフルオロメタン(49.9g)を得た。
MS m/z:672[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67-7.66(2H,m),7.49-7.46(1H,m),7.38-7.33(1H,m),7.27(1H,t,J=8.0Hz),7.19(2H,d,10.4Hz),7.06-6.97(2H,m),6.83-6.82(2H,m),2.52-2.45(1H,m),1.93-1.86(4H,m),1.49-1.38(2H,m),1.36-1.26(3H,m),1.24-1.18(2H,m),1.11-1.00(2H,m),0.91(3H,t,J=7.1Hz)
(実施例4)[4-(4-(5,6,7-トリフルオロ-2-ナフチル)-3-フルオロフェニル)フェニルオキシ]-(2,6-ジフルオロ-4-プロピルフェニル)ジフルオロメタンの製造
MS m/z:572[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67(1H,s),7.49-7.45(1H,m),7.39-7.33(1H,m),7.27(1H,t,J=8.1Hz),7.18(2H,d,10.4Hz),7.13(2H,d,J=8.8Hz),7.06-6.97(2H,m),6.85(2H,d,J=8.8Hz),2.64(2H,t,J=7.6),1.68(2H,quinted,J=8.0Hz),0.97(3H,t,J=7.2Hz)
(実施例5)[3,5-ジフルオロ-4-(4-(2-(trans-4-プロピルシクロヘキシル)-1-エチル)フェニル)フェニル]-[4-(5,6,7-トリフルオロ-2-ナフチル)フェニル]ジフルオロメタンの製造
MS m/z:664[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67(1H,s),7.49-7.45(3H,m),7.42(2H,d,J=7.9Hz),7.40-7.33(3H,m),7.27(2H,d,J=8.0Hz),7.19(2H,d,J=10.4Hz),2.38(2H,t,J=7.0Hz),1.60-1.58(2H,m),1.40-1.17(10H,m),1.07-0.97(4H,m),0.90(3H,t,J=7.2Hz)
(実施例6)[3,5-ジフルオロ-4-(2-フルオロ-4-(4-プロピルフェニル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの製造
MS m/z:572[M+]
相転移:Cr 99 N 217 Iso
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.06(1H,d,J=9.2Hz),7.71(1H,s),7.55-7.37(7H,m),7.27(2H,d,J=10.1Hz),2.65(2H,t,J=7.4Hz),1.69(2H,sixtet,J=7.6Hz),0.98(3H,t,J=7.3Hz)
(参考例1) [3,5-ジフルオロ-4-(4-プロピルフェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの製造
MS m/z:478[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.03(1H,d,J=9.2Hz),7.67(1H,s),7.49-7.45(3H,m),7.38-7.33(1H,m),7.27(2H,d,J=8.0Hz),7.19(2H,d,10.4Hz),2.63(2H,d,7.4Hz),1.67(2H,quinted,J=7.6Hz),0.96(3H,t,J=7.3Hz)
(参考例2)5,6,7-トリフルオロ-2-[3-フルオロ-4-(4-プロピルフェニル)フェニル]ナフタレンの製造
MS m/z:394[M+]
(実施例7) 液晶組成物の調製-1
以下の組成からなるホスト液晶組成物(H)
誘電率異方性(Δε):4.38
屈折率異方性(Δn):0.0899
粘度(η20):20.3mPa・s
この母体液晶(H)80%と、実施例1で得られた[3,5-ジフルオロ-trans-4-(4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン20%からなる液晶組成物(M-A)を調製した。この組成物の物性値は以下の通りである。
Δε:8.44
Δn:0.10232
η20:35.3mPa・s
[3,5-ジフルオロ-trans-4-(4-(trans-4-プロピルシクロヘキシル)シクロヘキシル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの添加による効果として、Tniを上昇させ(外挿Tni=168.2℃)、Δεが正に大きくなる(外挿Δε=24.7)ことが分かった。また、調製した液晶組成物(M-A)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(実施例8) 液晶組成物の調製-2
母体液晶(H)80%と実施例2で得られた[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン20%からなる液晶組成物(M-B)を調製した。この組成物の物性値は以下の通りである。
Δε:10.88
Δn:0.1135
η20:34.3mPa・s
[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの添加による効果として、Tniを上昇させ(外挿Tni=153.6℃)、Δεが正に大きくなる(外挿Δε=36.9)ことが分かった。また、調製した液晶組成物(M-B)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(実施例9) 液晶組成物の調製-3
母体液晶(H)90%と実施例3で得られた[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-[3-フルオロ-4-(5,6,7-トリフルオロ-2-ナフチル)フェニルオキシ]ジフルオロメタン10%からなる液晶組成物(M-C)を調製した。この組成物の物性値は以下の通りである。
Δε:8.30
Δn:0.1106
η20:31.8mPa・s
[3,5-ジフルオロ-4-(2-フルオロ-4-(trans-4-プロピルシクロヘキシル)フェニル)フェニル]-[3-フルオロ-4-(5,6,7-トリフルオロ-2-ナフチル)フェニルオキシ]ジフルオロメタンの添加による効果として、Tniを大きく上昇させ(外挿Tni=233.4℃)、Δεが正に大きくなる(外挿Δε=43.6)ことが分かった。また、調製した液晶組成物(M-C)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(実施例10)液晶組成物の調製-4
母体液晶(H)80%と実施例4で得られた[4-(4-(5,6,7-トリフルオロ-2-ナフチル)-3-フルオロフェニル)フェニルオキシ]-(2,6-ジフルオロ-4-プロピルフェニル)ジフルオロメタン20%からなる液晶組成物(M-D)を調製した。この組成物の物性値は以下の通りである。
Δε:9.77
Δn:0.1481
η20:28.3mPa・s
[4-(4-(5,6,7-トリフルオロ-2-ナフチル)-3-フルオロフェニル)フェニルオキシ]-(2,6-ジフルオロ-4-プロピルフェニル)ジフルオロメタンの添加による効果として、Tniを比較的大きく上昇させ(外挿Tni=119.7℃)、Δεが正に大きくなる(外挿Δε=31.2)ことが分かった。また、調製した液晶組成物(M-D)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(実施例11)液晶組成物の調製-5
母体液晶(H)95%と実施例5で得られた[3,5-ジフルオロ-4-(4-(2-(trans-4-プロピルシクロヘキシル)-1-エチル)フェニル)フェニル]-[4-(5,6,7-トリフルオロ-2-ナフチル)フェニル]ジフルオロメタン5%からなる液晶組成物(M-E)を調製した。この組成物の物性値は以下の通りである。
Δε:5.63
Δn:0.1017
η20:30.8mPa・s
[3,5-ジフルオロ-4-(4-(2-(trans-4-プロピルシクロヘキシル)-1-エチル)フェニル)フェニル]-[4-(5,6,7-トリフルオロ-2-ナフチル)フェニル]ジフルオロメタンの添加による効果として、Tniを極めて大きく上昇させ(外挿Tni=294.5℃)、Δεが正に大きくなる(外挿Δε=29.3)ことが分かった。また、調製した液晶組成物(M-E)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(実施例12) 液晶組成物の調製-6
母体液晶(H)90%と実施例6で得られた[3,5-ジフルオロ-4-(2-フルオロ-4-(4-プロピルフェニル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン10%からなる液晶組成物(M-F)を調製した。この組成物の物性値は以下の通りである。
Δε:7.51
Δn:0.1060
η20:26.2mPa・s
[3,5-ジフルオロ-4-(2-フルオロ-4-(4-プロピルフェニル)フェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの添加による効果として、Tniを大きく上昇させ(外挿Tni=178.2℃)、Δεが正に大きくなる(外挿Δε=32.3)ことが分かった。また、調製した液晶組成物(M-F)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(比較例1) 液晶組成物の調製-7
母体液晶(H)80%と参考例1にて得られた[3,5-ジフルオロ-4-(4-プロピルフェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタン20%からなる液晶組成物(M-G)を調製した。この組成物の物性値は以下の通りである。
Δε:9.79
Δn:0.1112
η20:26.9mPa・s
[3,5-ジフルオロ-4-(4-プロピルフェニル)フェニル]-(5,6,7-トリフルオロ-2-ナフチルオキシ)ジフルオロメタンの添加の効果として、Tniを低下させ(外挿Tni=65.8℃)、Δεを正に大きくできる(外挿Δε=31.4)事がわかる。調製した液晶組成物(M-G)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、高い保存安定性を示す事がわかった。
(比較例2)液晶組成物の調製-8
母体液晶(H)90%と参考例2にて得られた5,6,7-トリフルオロ-2-[3-フルオロ-4-(4-プロピルフェニル)フェニル]ナフタレン10%からなる液晶組成物(M-H)を調製した。この組成物の物性値は以下の通りである。
Δε:6.15
Δn:0.1137
η20:23.8mPa・s
5,6,7-トリフルオロ-2-[3-フルオロ-4-(4-プロピルフェニル)フェニル]ナフタレンの添加の効果として、Tn-iをやや上昇させ(外挿Tni=140.8℃)、Δεを正に大きくできる(外挿Δε=22.1)事がわかる。調製した液晶組成物(M-H)を、室温にて二週間保存したところ結晶が析出していた。
Claims (11)
- 一般式(1)
A1~A4はそれぞれ独立して、
(a)1,4-シクロへキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は各々独立してO-又は-S-に置き換えられても良い。)
(b)1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良く、この基中に存在する水素原子はフッ素原子又は塩素原子に置換されても良い。)
からなる群より選ばれる基であり、
Z1~Z4は各々独立して、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-、-CF=CF-、-C≡C-又は単結合を表すが、存在するZ1~Z4の内一つは必ず-CF2O-又は-OCF2-であり、
Xa~Xdは各々独立して、水素原子、フッ素原子又は塩素原子を表し、
nは0又は1を表す。)で表される化合物。 - 一般式(1)において、存在するZ1及びZ2が単結合を表す請求項1に記載の化合物。
- 一般式(1)において、Xdが水素原子を表す請求項1又は2に記載の化合物。
- 一般式(1)において、Xa~Xcがフッ素原子を表す請求項1から4のいずれか一項に記載の化合物。
- 一般式(1)において、nが0を表す請求項1から5のいずれか一項に記載の化合物。
- 一般式(1)において、nが1を表す請求項1から5のいずれか一項に記載の化合物。
- 一般式(1)において、Z3が-CF2O-でありZ4が単結合を表す請求項1から7のいずれか一項に記載の化合物。
- 一般式(1)において、Z3が単結合でありZ4が-CF2O-を表す請求項1から7のいずれか一項に記載の化合物。
- 請求項1から9のいずれか一項に記載の化合物を一種又は二種以上含有する液晶組成物。
- 請求項10記載の液晶組成物を使用した液晶表示素子。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/428,196 US9315727B2 (en) | 2012-10-09 | 2013-09-19 | Compound having fluorinated naphthalene structure and liquid crystal composition of the same |
KR1020157002045A KR101576962B1 (ko) | 2012-10-09 | 2013-09-19 | 불소화 나프탈렌 구조를 갖는 화합물 및 그 액정 조성물 |
JP2014521773A JP5622066B2 (ja) | 2012-10-09 | 2013-09-19 | フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 |
CN201380048974.0A CN104640832B (zh) | 2012-10-09 | 2013-09-19 | 具有氟化萘结构的化合物及其液晶组合物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012224114 | 2012-10-09 | ||
JP2012-224114 | 2012-10-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014057780A1 true WO2014057780A1 (ja) | 2014-04-17 |
Family
ID=50477251
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/075266 WO2014057780A1 (ja) | 2012-10-09 | 2013-09-19 | フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9315727B2 (ja) |
JP (1) | JP5622066B2 (ja) |
KR (1) | KR101576962B1 (ja) |
CN (1) | CN104640832B (ja) |
TW (1) | TWI588243B (ja) |
WO (1) | WO2014057780A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016030734A (ja) * | 2014-07-29 | 2016-03-07 | Dic株式会社 | フッ素化ナフタレン化合物及びその液晶組成物 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101613602B1 (ko) | 2013-07-25 | 2016-04-19 | 디아이씨 가부시끼가이샤 | 2,6-디플루오로페닐에테르 구조를 갖는 액정성 화합물 및 그 액정 조성물 |
JP5776864B1 (ja) | 2013-08-30 | 2015-09-09 | Dic株式会社 | ネマチック液晶組成物 |
US9573923B2 (en) * | 2013-10-03 | 2017-02-21 | Dic Corporation | Liquid crystal compound having 2, 6-difluorophenylether structure, and liquid crystal composition containing the same |
CN106459767B (zh) | 2014-07-31 | 2019-04-19 | Dic株式会社 | 向列型液晶组合物 |
CN106459765B (zh) | 2014-07-31 | 2018-03-09 | Dic株式会社 | 向列型液晶组合物 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001019649A (ja) * | 1999-07-06 | 2001-01-23 | Dainippon Ink & Chem Inc | 6−フルオロナフタレン誘導体である新規液晶性化合物とそれを含有する液晶組成物 |
JP2007070295A (ja) * | 2005-09-08 | 2007-03-22 | Chisso Corp | 末端が水素であるナフタレン誘導体、この誘導体を含有する液晶組成物およびこの液晶組成物を含有する液晶表示素子 |
WO2009034867A1 (ja) * | 2007-09-10 | 2009-03-19 | Chisso Corporation | 液晶性化合物、液晶組成物および液晶表示素子 |
JP2009067780A (ja) * | 2007-08-22 | 2009-04-02 | Chisso Corp | クロロナフタレン部位を有する液晶化合物、液晶組成物および光素子 |
WO2013018796A1 (ja) * | 2011-08-02 | 2013-02-07 | Dic株式会社 | ネマチック液晶組成物 |
JP2013170246A (ja) * | 2012-02-22 | 2013-09-02 | Dic Corp | ネマチック液晶組成物 |
WO2013141116A1 (ja) * | 2012-03-19 | 2013-09-26 | Dic株式会社 | ネマチック液晶組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5152947B2 (ja) | 1999-06-15 | 2013-02-27 | Dic株式会社 | 2−フルオロナフタレン誘導体である新規液晶性化合物とそれを含有する液晶組成物 |
EP1482019B1 (de) * | 2003-05-27 | 2006-09-27 | MERCK PATENT GmbH | Pyranderivate |
US8129002B2 (en) | 2003-08-25 | 2012-03-06 | Merck Patent Gmbh | Compounds for use in liquid crystal media |
-
2013
- 2013-09-19 WO PCT/JP2013/075266 patent/WO2014057780A1/ja active Application Filing
- 2013-09-19 CN CN201380048974.0A patent/CN104640832B/zh active Active
- 2013-09-19 JP JP2014521773A patent/JP5622066B2/ja not_active Expired - Fee Related
- 2013-09-19 US US14/428,196 patent/US9315727B2/en active Active
- 2013-09-19 KR KR1020157002045A patent/KR101576962B1/ko active IP Right Grant
- 2013-10-01 TW TW102135502A patent/TWI588243B/zh not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001019649A (ja) * | 1999-07-06 | 2001-01-23 | Dainippon Ink & Chem Inc | 6−フルオロナフタレン誘導体である新規液晶性化合物とそれを含有する液晶組成物 |
JP2007070295A (ja) * | 2005-09-08 | 2007-03-22 | Chisso Corp | 末端が水素であるナフタレン誘導体、この誘導体を含有する液晶組成物およびこの液晶組成物を含有する液晶表示素子 |
JP2009067780A (ja) * | 2007-08-22 | 2009-04-02 | Chisso Corp | クロロナフタレン部位を有する液晶化合物、液晶組成物および光素子 |
WO2009034867A1 (ja) * | 2007-09-10 | 2009-03-19 | Chisso Corporation | 液晶性化合物、液晶組成物および液晶表示素子 |
WO2013018796A1 (ja) * | 2011-08-02 | 2013-02-07 | Dic株式会社 | ネマチック液晶組成物 |
JP2013170246A (ja) * | 2012-02-22 | 2013-09-02 | Dic Corp | ネマチック液晶組成物 |
WO2013141116A1 (ja) * | 2012-03-19 | 2013-09-26 | Dic株式会社 | ネマチック液晶組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016030734A (ja) * | 2014-07-29 | 2016-03-07 | Dic株式会社 | フッ素化ナフタレン化合物及びその液晶組成物 |
Also Published As
Publication number | Publication date |
---|---|
CN104640832A (zh) | 2015-05-20 |
CN104640832B (zh) | 2016-03-02 |
KR20150020251A (ko) | 2015-02-25 |
TW201425546A (zh) | 2014-07-01 |
TWI588243B (zh) | 2017-06-21 |
KR101576962B1 (ko) | 2015-12-11 |
US20150259599A1 (en) | 2015-09-17 |
US9315727B2 (en) | 2016-04-19 |
JP5622066B2 (ja) | 2014-11-12 |
JPWO2014057780A1 (ja) | 2016-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5622066B2 (ja) | フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 | |
JP6137419B2 (ja) | ネマチック液晶組成物及びこれを用いた液晶表示素子 | |
TWI589679B (zh) | 液晶化合物、液晶組成物及液晶顯示元件 | |
JP5382268B1 (ja) | 2−フルオロフェニルオキシメタン構造を持つ化合物 | |
JP5435318B1 (ja) | 2−フルオロフェニルオキシメタン構造を持つ化合物 | |
JP6070110B2 (ja) | フッ素化ナフタレン構造を持つ化合物 | |
JP4887605B2 (ja) | クロマン誘導体及びこの化合物を含有する液晶組成物 | |
JP4691893B2 (ja) | トリフルオロナフタレン誘導体を含有する液晶組成物と表示素子及び化合物。 | |
JP5885017B2 (ja) | アゾベンゼン誘導体及びこれを含有する液晶組成物 | |
JP2019099515A (ja) | 液晶化合物及びその組成物 | |
JP6166313B2 (ja) | 液晶化合物、液晶組成物および液晶表示装置 | |
JP4835032B2 (ja) | トリフルオロナフタレン誘導体 | |
JP4193075B2 (ja) | アルケニルテルフェニル誘導体 | |
JP5680381B2 (ja) | 液晶化合物、その製造方法、液晶組成物および液晶電気光学素子 | |
JP2014031322A (ja) | 化合物、液晶組成物および液晶表示素子 | |
JP5962992B2 (ja) | フッ素化ナフタレン構造を持つ化合物 | |
JP6303895B2 (ja) | フッ素化ナフタレン化合物及びその液晶組成物 | |
JP4225064B2 (ja) | ビス(トリフルオロメチル)ビニル基を有する化合物、液晶組成物および液晶表示素子 | |
JP5680380B2 (ja) | 液晶化合物、その製造方法、液晶組成物および液晶電気光学素子 | |
KR20140034086A (ko) | 액정성 화합물, 액정 조성물 및 액정 표시 소자 | |
JP2001010997A (ja) | エチニルナフタレン誘導体 | |
JP2003261562A (ja) | 含フッ素結合基を有する化合物及びそれを含有する液晶組成物及び液晶素子 | |
JP2005097471A (ja) | ジフルオロテトラヒドロナフタレン誘導体を含有する液晶組成物及び液晶性化合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2014521773 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13845883 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157002045 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14428196 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13845883 Country of ref document: EP Kind code of ref document: A1 |