WO2014136654A1 - ネマチック液晶組成物及びこれを用いた液晶表示素子 - Google Patents
ネマチック液晶組成物及びこれを用いた液晶表示素子 Download PDFInfo
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- WO2014136654A1 WO2014136654A1 PCT/JP2014/054921 JP2014054921W WO2014136654A1 WO 2014136654 A1 WO2014136654 A1 WO 2014136654A1 JP 2014054921 W JP2014054921 W JP 2014054921W WO 2014136654 A1 WO2014136654 A1 WO 2014136654A1
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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
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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
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- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
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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
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- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- C09K19/06—Non-steroidal liquid crystal compounds
- 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
- 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
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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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
- 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
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- 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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- C09K19/08—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)
- C09K2019/3016—Cy-Ph-Ph
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- C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
Definitions
- the present invention relates to a nematic liquid crystal composition having a negative dielectric anisotropy ( ⁇ ) useful as a liquid crystal display material, and a liquid crystal display device using the same.
- Liquid crystal display elements are used in clocks, calculators, various household electrical devices, measuring devices, automotive panels, word processors, electronic notebooks, printers, computers, televisions, and the like.
- Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching).
- Type OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal), etc.
- Examples of the driving method include static driving, multiplex driving, simple matrix method, active matrix (AM) method driven by TFT (thin film transistor), TFD (thin film diode), and the like.
- the IPS type, ECB type, VA type, CSH type, and the like have a feature that a liquid crystal material having a negative value of ⁇ is used.
- the VA type display method by AM driving is used for a display element that requires a high speed and a wide viewing angle, such as a television.
- a nematic liquid crystal composition used for a display method such as a VA type is required to have a low voltage drive, a high-speed response, and a wide operating temperature range. That is, ⁇ is negative, the absolute value is large, the viscosity is low, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required. Further, from the setting of ⁇ n ⁇ d, which is the product of refractive index anisotropy ( ⁇ n) and cell gap (d), it is necessary to adjust ⁇ n of the liquid crystal material to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal material having a low viscosity ( ⁇ ) is required.
- a liquid crystal composition using the following liquid crystal compounds (A) and (B) having a 2,3-difluorophenylene skeleton (see Patent Document 1) as a liquid crystal material having a negative ⁇ is disclosed.
- liquid crystal compounds (C) and (D) are used as compounds having ⁇ of approximately 0.
- this liquid crystal composition is used in a liquid crystal composition that requires a high-speed response such as a liquid crystal television. A sufficiently low viscosity has not been achieved.
- a liquid crystal composition using a compound represented by the formula (G) has already been disclosed (see Patent Document 4), but this liquid crystal composition also contains an alkenyl compound as in the above liquid crystal compound (F). Since it is a liquid crystal composition containing a compound, there is a problem that display defects such as image sticking and display unevenness are likely to occur.
- Patent Document 6 discloses that the response speed of a homeotropic liquid crystal cell is improved by using a liquid crystal material having a large index represented by (Equation 1), but this is not sufficient. .
- JP-A-8-104869 European Patent Application No. 0474402 JP 2006-37054 A JP 2001-354967 A JP 2008-144135 A JP 2006-301643 A
- the problem to be solved by the present invention is that the viscosity ( ⁇ ) is sufficiently small without reducing the refractive index anisotropy ( ⁇ n) and the nematic phase-isotropic liquid phase transition temperature (T ni ), and the rotational viscosity
- a liquid crystal composition having a negative dielectric anisotropy ( ⁇ ) having a sufficiently small ( ⁇ 1), a large elastic constant (K 33 ), and a large absolute value is provided. It is an object of the present invention to provide a liquid crystal display element which is excellent in display quality and has a high response speed, with no defects or suppressed.
- the present inventor has studied various compounds and found that the above problems can be solved by combining specific compounds, and has completed the present invention.
- the liquid crystal composition of the present invention has the formula (I-1) as the first component
- liquid crystal composition characterized by containing a compound having a negative dielectric anisotropy ( ⁇ ) and an absolute value larger than 3 as a third component, and A liquid crystal display device using the same is provided.
- the liquid crystal composition of the present invention has a sufficiently low viscosity ( ⁇ ) and a rotational viscosity ( ⁇ 1) without lowering the refractive index anisotropy ( ⁇ n) and the nematic phase-isotropic liquid phase transition temperature (T ni ). ) Is sufficiently small, the elastic constant (K 33 ) is large, and the absolute value has a large negative dielectric anisotropy ( ⁇ ). Therefore, a VA-type liquid crystal display element using this has no display defect or Suppressed, excellent display quality and fast response speed.
- the liquid crystal composition of the present invention contains 3 to 25% by mass of the compound represented by the general formula (I-1) as the first component, more preferably 5 to 20% by mass. It is particularly preferable that the content is mass%. More specifically, the content is preferably 10 to 25% by mass in order to obtain low viscosity or low rotational viscosity, but the content is preferably 3 to 15% by mass when emphasizing the suppression of precipitation at low temperatures. .
- the compound represented by the general formula (I-2) is contained in an amount of 3 to 20% by mass, more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass. . More specifically, the content is preferably 10 to 20% by mass in order to obtain low viscosity or low rotational viscosity, but the content is preferably 3 to 10% by mass when importance is attached to the suppression of precipitation at low temperatures. .
- a compound having a negative dielectric anisotropy ( ⁇ ) and an absolute value larger than 3 is contained.
- Specific examples include compounds represented by general formula (II-1) and general formula (II-2).
- R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. of represents alkenyloxy group, R 1 and R present in the 2 one -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O- and / or -S- In addition, one or two or more hydrogen atoms present in R 1 and R 2 may be independently substituted with a fluorine atom or a chlorine atom, but R 1 is a carbon atom.
- An alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms Or 2 carbon atoms More preferably an alkenyl group et 5, alkyl group or -C 3 alkenyl radicals having one to three carbon atoms (propenyl) more preferably, R 2 is an alkyl group having 1 to 5 carbon atoms, carbon atoms A 1 to 5 alkoxyl group or an alkenyloxy group is preferable, and an alkyl group having 1 to 2 carbon atoms or an alkoxy group having 1 to 2 carbon atoms is more preferable.
- ring A and ring B are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4. -Phenylene group, 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] ]
- Octylene group piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
- Z 1 and Z 2 are each independently —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 —. or represents a single bond, each independently, -CH 2 O -, - CF 2 O -, - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond are preferred, -CH 2 O -, - CH 2 CH 2 — or a single bond is more preferable, —CH 2 O— or a single bond is still more preferable.
- the compounds represented by the general formula (II-1) and the general formula (II-2) are contained in one kind or two or more kinds, but are preferably contained in two to ten kinds.
- the content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.
- the liquid crystal composition of the present invention preferably contains the compound represented by the general formula (II-1) and the compound represented by the general formula (II-2) at the same time.
- R 3 and R 4 each independently represents the same meaning as R 1 and R 2 ), but are compounds represented by the general formula (II-A1) Is preferable, and is preferably a compound represented by the general formula (II-A3), preferably a compound represented by the general formula (II-A4), and represented by the general formula (II-A1).
- a compound is more preferable, and a compound represented by the general formula (II-A4) is further preferable.
- Compounds represented by general formula (II-2) are represented by general formula (II-B1) to general formula (II-B6).
- R 3 and R 4 each independently represent the same meaning as R 1 and R 2
- R 3 and R 4 are the compounds selected from general formula (II-B1) and general formula (II-B3) More preferably, the compound is represented by the general formula (II-B4), the general formula (II-B5) or the general formula (II-B6), and particularly preferably the compound represented by the general formula (II-B1). preferable.
- the third component is preferably a combination of the general formula (II-A1) and the general formula (II-B1), and the general formula (II-A1), the general formula (II-B1) and the general formula A combination of (II-A3) is more preferable, and a combination of general formula (II-A1), general formula (II-B1) and general formula (II-A4) is more preferable.
- the third component is preferably a combination of the general formula (II-A3) and the general formula (II-B4), and the general formula (II-A3), the general formula (II-B4) and the general formula A combination of (II-B5) is more preferable, and a combination of general formula (II-A3), general formula (II-B4) and general formula (II-B1) is more preferable.
- the third component is preferably a combination of the general formula (II-A4) and the general formula (II-B4), and the combination of the general formula (II-A4) and the general formula (II-B1) More preferably, it is more preferably a combination of the general formula (II-A4) and the general formula (II-B1) and the general formula (II-B5), and the general formula (II-A4) and the general formula (II- More preferred is a combination of B1) and general formula (II-B3).
- the liquid crystal composition of the present invention includes, as a fourth component, general formula (III-A) to general formula (III-J)
- R 5 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- R 6 is an alkyl group having 1 to 5 carbon atoms, and an alkoxyl having 1 to 5 carbon atoms.
- a group, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferably contained.
- the compound represented by the general formula (III-A) does not include the same compounds as the compounds represented by the formula (I-1) and the formula (I-2).
- the fourth component is a compound selected from general formula (III-A), general formula (III-D), general formula (III-F), general formula (III-G), and general formula (III-H).
- the compound is selected from the general formula (III-A), the general formula (III-F), the general formula (III-G), and the general formula (III-H).
- -A) a compound selected from general formula (III-G) and general formula (III-H) is more preferable, and general formula (III-A), general formula (III-F) and general formula (III) A compound selected from -H) is also preferable, and a compound selected from general formula (III-A) and general formula (III-F) is particularly preferable.
- R 5 represents an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms.
- R 6 is preferably an alkoxy group having 1 to 5 alkyl groups or carbon atoms of 1 to 5 carbon atoms, that R 5 is an alkenyl group having 2 to 5 carbon atoms More preferably, it is more preferably an alkenyl group having 2 or 3 carbon atoms.
- R 5 and R 6 are each independently 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms.
- the liquid crystal composition of the present invention preferably contains a compound represented by the general formula (III-A) as the fourth component.
- the liquid crystal composition of the present invention preferably contains a compound represented by the general formula (III-F) as the fourth component.
- the liquid crystal composition of the present invention particularly preferably contains the compound represented by the general formula (III-A) and the compound represented by the general formula (III-F) as the fourth component at the same time.
- R 5 is particularly preferably an alkenyl group having 2 carbon atoms
- R 6 is particularly preferably an alkyl group having 3 carbon atoms.
- the content of the fourth component is preferably 1% by mass to 40% by mass, preferably 5% by mass to 40% by mass, preferably 10% by mass to 40% by mass, and 20% by mass. To 40% by weight is particularly preferred.
- R 5 is particularly preferably an alkyl group having 2 to 5 carbon atoms
- R 6 is an alkyl group having 1 to 3 carbon atoms. Is particularly preferred.
- the content of the fourth component is preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 40% by mass.
- one or more compounds represented by the general formula (V) may be contained.
- R 21 and R 22 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms.
- an alkenyloxyl group is represented, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable.
- one or more compounds represented by general formula (VIII-a), general formula (VIII-c) or general formula (VIII-d) may be contained.
- R 51 and R 52 each independently represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- each of R 51 and R 52 are independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 2 to 5
- X 51 and X 52 each independently represents a fluorine atom or a hydrogen atom, and at least one of X 51 and X 52 is a fluorine atom.
- each of R 51 and R 52 are independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 2 to 5
- X 51 and X 52 each independently represents a fluorine atom or a hydrogen atom, and at least one of X 51 and X 52 is a fluorine atom.
- one or more compounds represented by formulas (V-9.1) to (V-9.3) may be contained.
- the liquid crystal composition of the present invention preferably contains a compound of formula (I-1), formula (I-2), general formula (II-A1) and general formula (III-A) at the same time.
- -1), formula (I-2), general formula (II-A3) and general formula (III-A) are preferably contained at the same time, and the compounds of formula (I-1), formula (I-2), It is preferable to simultaneously contain the compounds of the general formula (II-A4) and the general formula (III-A), and the compounds of the formula (I-1), formula (I-2), general formula (II-B1) and general formula (II)
- the liquid crystal composition of the invention simultaneously contains compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B1) and general formula (III-A) More preferably, the compounds of formula (I-1), formula (I-2), general formula (II-A3), general formula (II-B5) and general formula (III-A) are contained simultaneously. Is more preferable, and it further contains a compound of the formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B4) and general formula (III-A) at the same time. It is more preferable that the compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B5) and general formula (III-A) are simultaneously contained.
- the liquid crystal composition of the invention simultaneously contains compounds of formula (I-1), formula (I-2), general formula (II-A4), general formula (II-B5) and general formula (III-H) More preferably, the compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B1) and general formula (III-H) are contained simultaneously.
- the total content of the first component, the second component, the third component and the fourth component is preferably 70 to 100% by mass, and preferably 80 to 100% by mass. More preferred is 85 to 100% by mass.
- the liquid crystal composition of the present invention has a dielectric anisotropy ( ⁇ ) at ⁇ 25 ° C. of ⁇ 2.0 to ⁇ 8.0, preferably ⁇ 2.0 to ⁇ 6.0, -5.0 is more preferable, and -2.5 to -4.0 is particularly preferable.
- the liquid crystal composition of the present invention has a refractive index anisotropy ( ⁇ n) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.12. Particularly preferred. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.
- the liquid crystal composition of the present invention has a viscosity ( ⁇ ) at 20 ° C. of 10 to 30 mPa ⁇ s, more preferably 10 to 25 mPa ⁇ s, and particularly preferably 10 to 22 mPa ⁇ s.
- the liquid crystal composition of the present invention has a rotational viscosity ( ⁇ 1 ) at 20 ° C. of 60 to 130 mPa ⁇ s, more preferably 60 to 110 mPa ⁇ s, and particularly preferably 60 to 100 mPa ⁇ s. .
- the liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T ni ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C.
- T ni nematic phase-isotropic liquid phase transition temperature
- the liquid crystal composition of the present invention contains ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers (HALS), infrared absorbers or polymerizable monomers. You may do it.
- the liquid crystal composition may contain 0.01 to 2% by mass of a polymerizable compound such as a biphenyl derivative or a terphenyl derivative as a polymerizable monomer. More specifically, the general formula (M)
- X 201 and X 202 each independently represent a hydrogen atom, a methyl group, or a —CF 3 group.
- X 201 and X 202 are each preferably a diacrylate derivative that is a hydrogen atom, and a dimethacrylate derivative that is both a methyl group, and a compound in which one is a hydrogen atom and the other is a methyl group.
- a preferred compound can be used depending on the application, but in the PSA display element, the polymerizable compound represented by the general formula (M) preferably has at least one methacrylate derivative, and preferably has two.
- Sp 201 and Sp 202 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH 2 ) s — (wherein s is 2 to 7 And an oxygen atom is bonded to the ring.
- at least one of Sp 201 and Sp 202 is preferably a single bond, either a single bond compound or one of which is a single bond and the other is an alkylene having 1 to 8 carbon atoms.
- ring M 201 , ring M 202 and ring M 203 are each independently a trans-1,4-cyclohexylene group (one or non-adjacent two or more —CH in the group). 2 — may be substituted by —O— or —S—), 1,4-phenylene group (one or two or more non-adjacent —CH ⁇ in the group is substituted by —N ⁇ .
- Z 201 and Z 202 each independently represent —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, — CH 2 CH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO —, —CH 2 —OCO—, —CY 1 ⁇ CY 2 — (wherein Y 1 and Y 2 each independently represents a fluorine atom or a hydrogen atom), —C ⁇ C— or a single bond
- n 201 represents 0, 1 or 2, with 0 or 1 being preferred. However, when there are a plurality of rings M 202 and Z 202 , they may be different or the same.
- It may contain at least one polymerizable compound represented by formula (M), preferably 1 to 5 types, more preferably 1 to 3 types.
- the content of the general formula (M) is preferably 0.01 to 2.00% by mass, more preferably 0.05 to 1.00% by mass, and 0.10 to 0.50% by mass. It is particularly preferred.
- the ring structure between Sp 201 and Sp 202 is preferably a formula (XXa-1) to a formula (XXa-5),
- the formula (XXa-1) to the formula (XXa-3) are more preferable, and the formula (XXa-1) or the formula (XXa-2) is particularly preferable.
- both ends of the equation shall be connected to Sp 201 or Sp 202 .
- the polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.
- the polymerizable monomer is preferably a compound represented by the formula (XX-1) to the general formula (XX-10), more preferably the formula (XX-1) to the formula (XX-4).
- Sp xx represents an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s — (wherein s represents an integer of 2 to 7) And an oxygen atom is bonded to the ring).
- the hydrogen atom in the 1,4-phenylene group is further —F, —Cl, —CF 3 , —CH 3 , formula (R-1) To any one of formulas (R-15).
- n 201 is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M48) is preferable.
- the hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formula (M31) to the formula (M48) are further represented by —F, —Cl, —CF 3 , —CH 3 , and the formula (R-1) to the formula It may be substituted by any of (R-15).
- the polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.
- n 201 is 1 and there are a plurality of formulas (R-1) or (R-2), for example, polymerizable compounds such as formulas (M301) to (M316) preferable.
- the hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formulas (M301) to (M316) may be further substituted with —F, —Cl, —CF 3 , or —CH 3 .
- polymerizable compounds represented by the general formula (M) for example, polymerizable compounds such as formula (Ia-1) to formula (Ia-31) are also preferable.
- the liquid crystal composition of the present invention further preferably contains any one or two or more polymerizable monomers described above as the polymerizable monomer, and is represented by the general formula (XX-1) or general formula (XX-2). More preferably, it contains one or more polymerizable monomers represented by general formula (XX-4), general formula (M-302) and general formula (M31). Further, the liquid crystal composition of the present invention can contain an antioxidant. A hindered phenol type compound represented by general formula (H-1) to general formula (H-4) is preferable.
- R H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH 2 present in the radical - or non-adjacent two or more -CH 2 - are each independently -O- or -S- In addition, one or two or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom.
- alkyl group having 2 to 7 carbon atoms an alkoxyl group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms.
- An alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.
- M H4 is -CH 2 1, two or more of the alkylene group (the alkylene group having from 1 to 15 carbon atoms - as the oxygen atoms are not directly adjacent, - O—, —CO—, —COO—, —OCO— may be substituted.), —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, — OCF 2 —, —CF 2 CF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, — C ⁇ C—, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or a trans-1,4-cyclohexylene group.
- an alkylene group having 1 to 14 carbon atoms In consideration of the viscosity, a large number of carbon atoms is preferable, but in consideration of the viscosity, the number of carbon atoms is preferably not too large. Therefore, the number of carbon atoms is more preferably 2 to 12, more preferably 3 to 10. 4 to 10 carbon atoms are more preferred, 5 to 10 carbon atoms are more preferred, and 6 to 10 carbon atoms are more preferred.
- one or more non-adjacent —CH ⁇ in the 1,4-phenylene group may be substituted by —N ⁇ .
- each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
- general formula (H-1) to general formula (H-4) one or more non-adjacent —CH 2 — in the 1,4-cyclohexylene group is replaced by —O— or —S—. May be.
- each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
- the liquid crystal composition of the present invention further preferably contains any one or more antioxidants represented by formulas (H-11) to (H-15) as an antioxidant.
- the liquid crystal composition of the present invention may contain 1 ppm by mass or more of an antioxidant, preferably 10 ppm by mass or more, preferably 20 ppm by mass or more, and more preferably 50 ppm by mass or more.
- the upper limit of content of antioxidant is 10000 mass ppm, 1000 mass ppm is preferable, 500 mass ppm is preferable, and 100 mass ppm is preferable.
- the liquid crystal display device using the liquid crystal composition of the present invention has no display defects or is suppressed and has excellent display quality and high response speed, and in particular, active matrix driving VA mode, PSVA mode, PSA mode , IPS mode, FFS mode or ECB mode.
- the measured characteristics are as follows.
- T ni Nematic phase-isotropic liquid phase transition temperature (° C.) ⁇ n: refractive index anisotropy at 20 ° C. ⁇ : dielectric anisotropy at 25 ° C. ⁇ : viscosity at 20 ° C. (mPa ⁇ s) ⁇ 1 : rotational viscosity at 20 ° C. (mPa ⁇ s) K 33 : Elastic constant at 20 ° C. K 33 (pN) (Comparative Example 1, Example 1, Example 2 and Example 3) LC-A (Comparative Example 1), LC-1 (Example 1), LC-2 (Example 2) and LC-3 (Example 3) liquid crystal compositions were prepared and their physical properties were measured. The composition of the liquid crystal composition and the results of its physical properties are shown in Table 1.
- the liquid crystal compositions LC-1, LC-2 and LC-3 of the present invention have a small viscosity ( ⁇ ), a small rotational viscosity ( ⁇ 1 ), a large elastic constant (K 33 ) and a ⁇ 1 / K 33 of The values were 7.9, 7.4, and 6.9, respectively, which were smaller than those of the comparative example LC-A.
- LC-1, LC-2 and LC-3 had sufficiently high-speed response, and 10% or more faster than LC-A.
- the cell thickness is 3.5 ⁇ m
- the alignment film is JALS2096
- the response speed measurement conditions are Von 5.5 V, Voff 1.0 V, measurement temperature 20 ° C.
- AUTRONIC-MELCHERS DMS301 is used. It was. Further, when a liquid crystal composition prepared by using 99.6% by mass of LC-1 and 0.4% by mass of formula (XX-2) as a polymerizable monomer was manufactured, a PSVA mode liquid crystal display device was manufactured. It was confirmed that there was no defect and the response was sufficiently fast.
- a liquid crystal display device of PSVA mode was prepared using a liquid crystal composition prepared with 99.6% by mass of LC-1 and 0.4% by mass of formula (XX-4) as a polymerizable monomer.
- a liquid crystal display device of PSVA mode was prepared using a liquid crystal composition prepared with 99.6% by mass of LC-1 and 0.3% by mass of the formula (M-302) as a polymerizable monomer. It was confirmed that there was no defect and the response was sufficiently fast. Further, a liquid crystal composition prepared by preparing 99.6% by mass of LC-1, 0.3% by mass of formula (XX-4) and 0.1% by mass of formula (Ia-31) as a polymerizable monomer was used. When a liquid crystal display element of PSVA mode was fabricated, it was confirmed that there was no display defect and the response was sufficiently fast.
- the liquid crystal compositions LC-4 and LC-5 of the present invention have a small viscosity ( ⁇ ), a small rotational viscosity ( ⁇ 1 ), a large elastic constant (K 33 ), and a ⁇ 1 / K 33 of 7. 6 and 7.4, which were smaller than those of the comparative example LC-B.
- LC-4 and LC-5 were sufficiently high-speed responses and 15% or more faster than LC-B.
- the cell thickness is 3.3 ⁇ m
- the alignment film is JALS2096
- the response speed measurement conditions are Von 5.5 V, Voff 1.0 V
- measurement temperature 20 ° C. and AUTRONIC-MELCHERS DMS301 is used. It was.
- a liquid crystal display device of PSVA mode was prepared using a liquid crystal composition prepared with 99.6% by mass of LC-4 and 0.4% by mass of formula (XX-1) as a polymerizable monomer. It was confirmed that there was no defect and the response was sufficiently fast.
- a liquid crystal display element of PSVA mode was prepared using a liquid crystal composition prepared with 99.6% by mass of LC-4 and 0.4% by mass of formula (XX-2) as a polymerizable monomer. It was confirmed that there was no defect and the response was sufficiently fast. Further, a liquid crystal display device of PSVA mode was prepared using a liquid crystal composition prepared with 99.5% by mass of LC-4 and 0.5% by mass of the formula (M-302) as a polymerizable monomer.
- liquid crystal display device of PSVA mode was prepared using a liquid crystal composition prepared with 99.65% by mass of LC-5 and 0.35% by mass of the formula (M33) as a polymerizable monomer, display defects were observed. It was confirmed that the response was sufficiently fast.
- the liquid crystal composition of the present invention has a sufficiently small viscosity ( ⁇ ) without lowering the refractive index anisotropy ( ⁇ n) and the nematic phase-isotropic liquid phase transition temperature (T ni ). , Having a sufficiently low rotational viscosity ( ⁇ 1 ), a large elastic constant (K 33 ), and a large absolute value and a negative dielectric anisotropy ( ⁇ ), VA type and PSVA type using this Alternatively, it was confirmed that the PSA type liquid crystal display element has excellent display quality and high response speed.
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Abstract
Description
更に詳述すると、第三成分は一般式(II-A3)及び一般式(II-B4)の組み合わせであることが好ましく、一般式(II-A3)及び一般式(II-B4)及び一般式(II-B5)の組み合わせであることが更に好ましく、一般式(II-A3)及び一般式(II-B4)及び一般式(II-B1)の組み合わせであることが更に好ましい。
更に詳述すると、第三成分は一般式(II-A4)及び一般式(II-B4)の組み合わせであることが好ましく、一般式(II-A4)及び一般式(II-B1)の組み合わせであることが好ましく、一般式(II-A4)及び一般式(II-B1)及び一般式(II-B5)の組み合わせであることが更に好ましく、一般式(II-A4)及び一般式(II-B1)及び一般式(II-B3)の組み合わせであることが更に好ましい。
第四成分は、一般式(III-A)、一般式(III-D)、一般式(III-F)、一般式(III-G)及び一般式(III-H)から選ばれる化合物であることが好ましく、一般式(III-A)、一般式(III-F)、一般式(III-G)及び一般式(III-H)から選ばれる化合物であることが更に好ましく、一般式(III-A)、一般式(III-G)及び一般式(III-H)から選ばれる化合物であることが更に好ましく、一般式(III-A)、一般式(III-F)及び一般式(III-H)から選ばれる化合物であることも好ましく、一般式(III-A)及び一般式(III-F)から選ばれる化合物であることが特に好ましい。
また、一般式(III-D)、一般式(III-G)及び一般式(III-H)で表される化合物においては、R5は炭素原子数1から5のアルキル基又は炭素原子数2から5のアルケニル基、R6は炭素原子数1から5のアルキル基又は炭素原子数1から5のアルコキシ基であることが好ましく、R5は炭素原子数2から5のアルケニル基であることが更に好ましく、炭素原子数2又は3のアルケニル基であることが更に好ましく、一般式(III-F)で表される化合物においては、R5及びR6はそれぞれ独立的に炭素原子数1から5のアルキル基又は炭素原子数2から5のアルケニル基であることが好ましい。
本発明の液晶組成物は、第四成分である一般式(III-A)で表される化合物を含有することが好ましい。
本発明の液晶組成物は、第四成分である一般式(III-F)で表される化合物を含有することが好ましい。
本発明の液晶組成物は、第四成分である一般式(III-A)で表される化合物及び一般式(III-F)で表される化合物を同時に含有することが特に好ましい。
また、一般式(III-A)で表される化合物は、R5は炭素原子数2のアルケニル基であることが特に好ましく、R6は炭素原子数3のアルキル基であることが特に好ましい。
第四成分の含有量は、1質量%から40質量%であることが好ましく、5質量%から40質量%であることが好ましく、10質量%から40質量%であることが好ましく、20質量%から40質量%であることが特に好ましい。
また、一般式(III-F)で表される化合物は、R5は炭素原子数2から5のアルキル基であることが特に好ましく、R6は炭素原子数1から3のアルキル基であることが特に好ましい。
第四成分の含有量は、1質量%から40質量%であることが好ましく、5質量%から40質量%であることが好ましい。
更なる成分として、一般式(V-9.1)から一般式(V-9.3)で表される化合物を1種又は2種以上含有しても良い。
一般式(M)の含有量は0.01~2.00質量%であることが好ましく、0.05~1.00質量%であることが更に好ましく、0.10~0.50質量%であることが特に好ましい。
また、本発明の液晶組成物は、酸化防止剤を含有することができる。一般式(H-1)から一般式(H-4)で表されるヒンダードフェノール型化合物が好ましい。
一般式(H-4)中、MH4は炭素原子数1から15のアルキレン基(該アルキレン基中の1つ又は2つ以上の-CH2-は、酸素原子が直接隣接しないように、-O-、-CO-、-COO-、-OCO-に置換されていても良い。)、-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-CH=CH-、-C≡C-、単結合、1,4-フェニレン基(1,4-フェニレン基中の任意の水素原子はフッ素原子により置換されていても良い。)又はトランス-1,4-シクロヘキシレン基を表すが、炭素原子数1から14のアルキレン基であることが好ましく、揮発性を考慮すると炭素原子数は大きい数値が好ましいが、粘度を考慮すると炭素原子数は大き過ぎない方が好ましいことから、炭素原子数2から12が更に好ましく、炭素原子数3から10が更に好ましく、炭素原子数4から10が更に好ましく、炭素原子数5から10が更に好ましく、炭素原子数6から10が更に好ましい。
一般式(H-1)から一般式(H-4)中、1,4-フェニレン基中の1個又は非隣接の2個以上の-CH=は-N=によって置換されていても良い。また、1,4-フェニレン基中の水素原子はそれぞれ独立的に、フッ素原子又は塩素原子で置換されていても良い。
一般式(H-1)から一般式(H-4)中、1,4-シクロヘキシレン基中の1個又は非隣接の2個以上の-CH2-は-O-又は-S-によって置換されていても良い。また、1,4-シクロヘキシレン基中の水素原子はそれぞれ独立的に、フッ素原子又は塩素原子で置換されていても良い。
本発明の液晶組成物は、酸化防止剤を1質量ppm以上含有しても良いが、10質量ppm以上が好ましく、20質量ppm以上が好ましく、50質量ppm以上が好ましい。酸化防止剤の含有量の上限は10000質量ppmであるが、1000質量ppmが好ましく、500質量ppmが好ましく、100質量ppmが好ましい。
実施例において化合物の記載について以下の略号を用いる。
(側鎖)
-n -CnH2n+1 炭素数nの直鎖状のアルキル基
n- CnH2n+1- 炭素数nの直鎖状のアルキル基
-On -OCnH2n+1 炭素数nの直鎖状のアルコキシル基
nO- CnH2n+1O- 炭素数nの直鎖状のアルコキシル基
-V -CH=CH2
V- CH2=CH-
-V1 -CH=CH-CH3
1V- CH3-CH=CH-
-2V -CH2-CH2-CH=CH3
V2- CH3=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH2
(連結基)
-CF2O- -CF2-O-
-OCF2- -O-CF2-
-1O- -CH2-O-
-O1- -O-CH2-
-COO- -COO-
(環構造)
Δn :20℃における屈折率異方性
Δε :25℃における誘電率異方性
η :20℃における粘度(mPa・s)
γ1 :20℃における回転粘性(mPa・s)
K33 :20℃における弾性定数K33(pN)
(比較例1、実施例1、実施例2及び実施例3)
LC-A(比較例1)、LC-1(実施例1)、LC-2(実施例2)及びLC-3(実施例3)の液晶組成物を調製し、その物性値を測定した。液晶組成物の構成とその物性値の結果は表1のとおりであった。
これらを使用した液晶表示素子の応答速度を測定したところ、LC-1、LC-2及びLC-3は、十分に高速応答であり、LC-Aよりも10%以上高速であった。なお、セル厚は3.5um、配向膜はJALS2096であり、応答速度の測定条件は、Vonは5.5V、Voffは1.0V、測定温度は20℃で、AUTRONIC-MELCHERS社のDMS301を用いた。
また、LC-1を99.6質量%、重合性モノマーとして式(XX-2)を0.4質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-1を99.6質量%、重合性モノマーとして式(XX-4)を0.4質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-1を99.6質量%、重合性モノマーとして式(M-302)を0.3質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-1を99.6質量%、重合性モノマーとして式(XX-4)を0.3質量%及び式(Ia-31)を0.1質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
更に、LC-2及びLC-3についても同様に重合性モノマーを添加して、PSVAモードの液晶表示素子を作製し、表示不良がなく、十分に高速応答であることを確認した。
(比較例2、実施例4及び実施例5)
LC-B(比較例2)、LC-4(実施例4)及びLC-5(実施例5)の液晶組成物を調製し、その物性値を測定した。液晶組成物の構成とその物性値の結果は表2のとおりであった。
これらを使用した液晶表示素子の応答速度を測定したところ、LC-4及びLC-5は、十分に高速応答であり、LC-Bよりも15%以上高速であった。なお、セル厚は3.3um、配向膜はJALS2096であり、応答速度の測定条件は、Vonは5.5V、Voffは1.0V、測定温度は20℃で、AUTRONIC-MELCHERS社のDMS301を用いた。
また、LC-4を99.6質量%、重合性モノマーとして式(XX-1)を0.4質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-4を99.6質量%、重合性モノマーとして式(XX-2)を0.4質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-4を99.5質量%、重合性モノマーとして式(M-302)を0.5質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-4を99.6質量%、重合性モノマーとして式(XX-1)を0.2質量%及び式(XX-2)を0.2質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-5を99.7質量%、重合性モノマーとして式(M31)を0.3質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
また、LC-5を99.65質量%、重合性モノマーとして式(M33)を0.35質量%で調製した液晶組成物を用いて、PSVAモードの液晶表示素子を作製したところ、表示不良がなく、十分に高速応答であることを確認した。
Claims (12)
- 25℃における誘電率異方性(Δε)が-2.0から-8.0の範囲であり、20℃における屈折率異方性(Δn)が0.08から0.14の範囲であり、20℃における粘度(η)が10から30mPa・sの範囲であり、20℃における回転粘性(γ1)が60から130mPa・sの範囲であり、ネマチック相-等方性液体相転移温度(Tni)が60℃から120℃の範囲である請求項1に記載の液晶組成物。
- 第三成分として、一般式(II-1)及び一般式(II-2)
- 一般式(II-1)で表される化合物と一般式(II-2)で表される化合物を同時に含有する請求項3又は4に記載の液晶組成物。
- 一般式(II-1)及び一般式(II-2)中のR1がプロペニル基である化合物の群から選ばれる化合物を1種又は2種以上含有する請求項3から6のいずれか1項に記載の液晶組成物。
- 重合性化合物を1種又は2種以上含有する請求項1から7のいずれか1項に記載の液晶組成物。
- 重合性化合物が、一般式(M)
- 請求項1から9のいずれか1項に記載の液晶組成物を用いた液晶表示素子。
- 請求項1から9のいずれか1項に記載の液晶組成物を用いたアクティブマトリックス駆動用液晶表示素子。
- 請求項1から9のいずれか1項に記載の液晶組成物を用いたVAモード、PSAモード、PSVAモード、IPSモード又はECBモード用液晶表示素子。
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EP2966150A4 (en) | 2016-12-28 |
KR20150116448A (ko) | 2015-10-15 |
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