WO2018096932A1 - 液晶組成物及び液晶表示素子 - Google Patents
液晶組成物及び液晶表示素子 Download PDFInfo
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- WO2018096932A1 WO2018096932A1 PCT/JP2017/040370 JP2017040370W WO2018096932A1 WO 2018096932 A1 WO2018096932 A1 WO 2018096932A1 JP 2017040370 W JP2017040370 W JP 2017040370W WO 2018096932 A1 WO2018096932 A1 WO 2018096932A1
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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- C09K19/3001—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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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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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-)
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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
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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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- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
Definitions
- the present invention relates to a liquid crystal composition and a liquid crystal display device using the same.
- Liquid crystal display elements are used in various electric appliances for home use, measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., including watches and calculators.
- 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 composition having a negative ⁇ (dielectric anisotropy) is used.
- the VA type display method by AM driving is used for a display element that requires a high speed response and a wide viewing angle, such as a television or a monitor.
- liquid crystal compounds (C) and (D) are used as the liquid crystal compound having ⁇ of approximately 0.
- the liquid crystal composition has a sufficiently low viscosity. It has not been realized.
- liquid crystal composition using the liquid crystal compound (E) has already been disclosed, but a liquid crystal composition having a small refractive index anisotropy ⁇ n in combination with the liquid crystal compound (D) (see Patent Document 2) and response.
- a liquid crystal composition to which a liquid crystal compound (F) is added for improving the speed has been introduced.
- Patent Document 5 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 it cannot be said to be sufficiently satisfactory. Met.
- a PSA type liquid crystal display device is manufactured by injecting a liquid crystal composition containing a polymerizable compound between substrates, irradiating ultraviolet rays in a state where liquid crystal molecules are aligned by applying a voltage, and polymerizing the polymerizable compound. This is done by fixing the orientation of the liquid crystal molecules. At this time, the polymerization rate of the polymerizable compound is very important. When the polymerization rate is moderately high, the residual amount of the polymerizable compound is reduced in a short ultraviolet irradiation time, so that deterioration of peripheral members such as a liquid crystal composition due to ultraviolet rays hardly occurs.
- the liquid crystal composition used in the PSA type liquid crystal display element is required not to be deteriorated or hardly deteriorated by the irradiation of ultraviolet rays. It is required that it does not occur and the response speed is fast.
- JP-A-8-104869 European Patent Application No. 0474402 JP 2006-037054 A JP 2001-354967 A WO2012 / 137810 JP 2006-301643 A
- the problem to be solved by the present invention is that K 33 is large, ⁇ 1 / K 33 is small, VHR after ultraviolet irradiation is high, the polymerization rate of the polymerizable compound is high, and there is no display defect due to a change in pretilt angle.
- a liquid crystal composition for producing a PSA type or PSVA type liquid crystal display device having an extremely small and sufficient pretilt angle and excellent response performance, or a liquid crystal composition containing a polymerizable compound and
- An object of the present invention is to provide a liquid crystal display device using the same.
- liquid crystal composition comprising a combination of a compound having a specific chemical structure and a polymerizable compound, and the present invention has been completed.
- the liquid crystal composition of the present invention has a small rotational viscosity ( ⁇ 1 ) and a large elastic constant ( ⁇ n) and a nematic phase-isotropic liquid phase transition temperature (T ni ) with almost no decrease.
- K 33 a liquid crystal composition having a small value of ⁇ 1 / K 33 and a high polymerization rate of the polymerizable compound during ultraviolet irradiation.
- a liquid crystal display element using the liquid crystal composition of the present invention has a sufficient pretilt angle, exhibits a high voltage holding ratio (VHR), a high-speed response, and has no or suppressed display defects such as alignment failure and image sticking.
- VHR voltage holding ratio
- the residual amount of the polymerizable compound is small, and the liquid crystal display element is hardly adversely affected and excellent display quality is exhibited.
- the liquid crystal composition of the present invention comprises a compound of formula (B31) and a compound of formula (CB31)
- the content of the compound of formula (B31) in the liquid crystal composition of the present invention is preferably 3% by mass, more preferably 5% by mass, and further 7% by mass as a lower limit.
- the upper limit is preferably 25% by mass, more preferably 20% by mass, more preferably 18% by mass, more preferably 15% by mass, and 13% by mass.
- the content is 11% by mass, and the content range is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and more preferably 5 to 15% by mass. More preferably it is.
- the content of the compound of formula (CB31) in the liquid crystal composition of the present invention is preferably 2% by mass, more preferably 3% by mass, and further preferably 5% by mass as a lower limit.
- the content is more preferably 8% by mass, and the upper limit is preferably 15% by mass, more preferably 13% by mass, still more preferably 11% by mass, and the content range. It is preferably 2 to 15% by mass, more preferably 2 to 13% by mass, and still more preferably 2 to 11% by mass.
- the liquid crystal composition of the invention has the general formulas (N-01), (N-02), (N-03) and (N-04) It is preferable to contain 1 type or 2 types or more of compounds chosen from the compound group represented by these. These compounds correspond to compounds having dielectrically negative anisotropy. These compounds have a negative sign of ⁇ and an absolute value greater than 2.
- the ⁇ of the compound is a value extrapolated from the measured value of dielectric anisotropy of a composition obtained by adding the compound to a dielectrically neutral composition at 25 ° C.
- R 21 and R 22 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 carbon atoms. 8 alkenyloxy groups in which one or two or more non-adjacent —CH 2 — groups are each independently —CH ⁇ CH—, —C ⁇ C—, —O—, —CO.
- R 21 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
- R 21 is preferably an alkyl group having 1 to 3 carbon atoms.
- R 22 is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. An alkoxy group having 1 to 4 carbon atoms is more preferable.
- R 21 and R 22 can also be an alkenyl group, from a group represented by any one of formulas (R1) to (R5) (the black dots in each formula represent carbon atoms in the ring structure). It is preferably selected, and the formula (R1) or the formula (R2) is preferable, but the content of the compound in which R 21 and R 22 are alkenyl groups is preferably as small as possible, and it is often preferable not to include them.
- Z 1 is each independently a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, — Represents CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, preferably a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, a single bond or —CH 2 O— -Is more preferable.
- a single bond is more preferable.
- m is preferably 1.
- the fluorine atom of the compounds represented by the general formulas (N-01), (N-02), (N-03) and (N-04) may be substituted with a chlorine atom which is the same halogen group.
- the content of the compound substituted with a chlorine atom should be as small as possible, and preferably not contained.
- the hydrogen atom of the ring of the compound represented by the general formula (N-01), (N-02), (N-03) or (N-04) may be further substituted with a fluorine atom or a chlorine atom.
- the content of the compound substituted with a chlorine atom should be as small as possible, and preferably not contained.
- the compounds represented by the general formulas (N-01), (N-02), (N-03) and (N-04) are preferably compounds having a negative ⁇ and an absolute value larger than 3. .
- Examples of the compound represented by the general formula (N-01) include the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3), and the general formula (N-01). It is preferable to contain one or more compounds selected from the compound group represented by -4). Among these compounds, compounds represented by general formula (N-01-1) or general formula (N-01-4) are more preferable. When higher VHR or higher reliability is required, it is preferable not to include the compound represented by the general formula (N-01-3).
- R 21 represents the same meaning as described above, and R 23 each independently represents an alkoxy group having 1 to 4 carbon atoms.
- compounds represented by general formula (N-02), compounds represented by general formula (N-02-1), general formula (N-02-2), and general formula (N-02-3) It is preferable to contain one or more compounds selected from: Among these compounds, compounds represented by general formula (N-02-1) or general formula (N-02-3) are more preferable, and compounds represented by general formula (N-02-1) are preferred. Particularly preferred. It is particularly preferable to combine the compound represented by the general formula (N-01-4) with the compound represented by the general formula (N-02-1).
- R 21 represents the same meaning as described above, and R 23 each independently represents an alkoxy group having 1 to 4 carbon atoms.
- the compound represented by the general formula (N-03) preferably contains one or more compounds represented by the general formula (N-03-1).
- R 21 represents the same meaning as described above, and R 23 represents an alkoxy group having 1 to 4 carbon atoms.
- the compound represented by the general formula (N-04) preferably contains one or more compounds represented by the general formula (N-04-1).
- the liquid crystal composition of the present invention comprises a compound selected from the group of compounds represented by formula (N-01), formula (N-02), formula (N-03), and formula (N-04).
- the total content is preferably 10% by weight to 80% by weight, preferably 20% by weight to 75% by weight, preferably 30% by weight to 73% by weight, and 35% by weight to 70% by weight.
- % Is preferred. Hereinafter, although content is described in%, this means mass%.
- the lower limit of the preferable content of the compound represented by the general formula (N-01) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 1%, 5%, 10% 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% It is.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% 15% and 10%.
- the lower limit of the preferable content of the compound represented by the general formula (N-02) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 1%, 5%, 10% 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% It is.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% 15% and 10%.
- the lower limit of the preferable content of the compound represented by the general formula (N-03) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 1%, 5%, 10% 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% It is.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% 15% and 10%.
- the lower limit of the preferable content of the compound represented by the general formula (N-04) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 1%, 5%, 10% 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% It is.
- the upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% 15% and 10%.
- the liquid crystal composition of the present invention is represented by general formula (N-01-1), general formula (N-01-4), general formula (N-02-1), and general formula (N-03-1). It is preferable to contain a total of 10% to 80% of compounds selected from the group of compounds.
- the lower limit is preferably low and the upper limit is preferably low.
- the dielectric anisotropy ( ⁇ ) in order to keep the driving voltage low, it is preferable to increase the lower limit and increase the upper limit.
- the liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-05).
- R 21 and R 22 represent the same meaning as described above, but when they represent an alkenyl group, the formula (R4) or the formula (R5) is preferred.
- the compound represented by the general formula (N-05) is effective for adjusting various physical properties, but can be used to obtain a particularly large refractive index anisotropy ( ⁇ n).
- the lower limit of the preferable content of the compound represented by the formula (N-05) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 2%, 5%, 8% Yes, 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferable content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, and 13%.
- the compound represented by the general formula (N-05) is preferably a compound selected from the group of compounds represented by the formula (N-05-1) to the formula (N-05-3).
- the liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06).
- R 21 and R 22 represent the same meaning as described above.
- the compound represented by the general formula (N-06) is effective for adjusting various physical properties, but is particularly used to obtain a large refractive index anisotropy ( ⁇ n), a high T, and a large ⁇ . Can do.
- the lower limit of the preferable content of the compound represented by the formula (N-06) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 2%, 5%, 8% Yes, 10%, 13%, 15%, 17%, 20%.
- the upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% And 5%.
- the liquid crystal composition of the present invention preferably contains one or more compounds selected from the compound group represented by formulas (NU-01) to (NU-06).
- R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU41 , R NU42 , R NU51 , R NU61 and R NU62 are each independently an alkyl group having 1 to 8 carbon atoms, carbon Represents an alkoxy group having 1 to 8 atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or non-adjacent two or more —CH 2 — in the group Each independently may be substituted by —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—, wherein R NU32 and R NU52 are each independently An alkyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkenyloxy group having 2 to 8 carbon atoms, And one
- R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU41 , R NU42 , R NU51 , R NU61 and R NU62 are each an alkyl group or carbon atom having 1 to 5 carbon atoms It is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and R NU32 and R NU52 are alkyl groups having 2 to 5 carbon atoms or carbon atoms having 1 to 5 carbon atoms. An alkoxy group is preferred, and an alkyl group having 2 to 5 carbon atoms is more preferred.
- R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61, and R NU62 have as little content as possible In many cases, it is preferable not to contain them.
- the liquid crystal composition of the present invention is represented by the general formula (NU-01) or the general formula (NU-02) among the compound groups represented by the general formulas (NU-01) to (NU-06). It is preferable to contain a compound represented by the general formula (NU-01).
- the content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass. preferable.
- the content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 20% by mass. preferable.
- the content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 10% by mass. preferable.
- the content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.
- the content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 10% by mass. preferable.
- the content of the compound represented by the general formula (NU-06) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.
- the liquid crystal composition of the present invention may contain one or more polymerizable compounds.
- the liquid crystal composition of the present invention may contain one or more polymerizable compounds represented by the general formula (RM) as the polymerizable compound.
- R 101, R 102, R 103, R 104, R 105, R 106, R 107 and R 108 are each independently, P 13 -S 13 -, carbon atoms which may be substituted by fluorine atoms Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, and P 11 , P 12 and P 13 are each independently Formula (Re-1) to Formula (Re-9)
- R 11 , R 12 , R 13 , R 14, and R 15 each independently represent an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom, and m r5 , m r7 , N r5 and n r7 each independently represents 0, 1, or 2.
- S 11 , S 12 and S 13 each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one — CH 2 — or two or more non-adjacent —CH 2 — may be substituted with —O—, —OCO— or —COO— so that the oxygen atom is not directly adjacent, and P 13 and S 13 In the case where a plurality of are present, they may be the same or different.
- a liquid crystal composition containing a polymerizable compound represented by the general formula (RM) is suitable for producing a PSA type or PSVA type liquid crystal display element.
- a liquid crystal composition containing a polymerizable compound represented by the general formula (RM) has a moderately high polymerization rate, a desired pretilt angle can be imparted in a short ultraviolet irradiation time. Furthermore, the residual amount of the polymerizable compound can be reduced. Thereby, it is possible to improve the production efficiency of manufacturing the PSA type or PSVA type liquid crystal display element. In addition, there is an effect that display defects (for example, defects such as burn-in) due to changes in the pretilt angle do not occur or are extremely small.
- the display failure in this specification means a display failure due to a change in pretilt angle with time, a display failure due to a residual amount of an unreacted polymerizable compound, and a display failure due to a decrease in voltage holding ratio. Yes.
- R 101, R 102, R 103, R 104, R 105, R 106, R 107 and R 108 are each independently, P 13 -S 13 - is replaced by a fluorine atom
- the number of carbon atoms is preferably 1 to 16, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 6, even more preferably 1 to 3. is there.
- the alkyl group and alkoxy group may be linear or branched, but linear is particularly preferable.
- R 101, R 102, R 103, R 104, R 105, R 106, R 107 and R 108 are, P 13 -S 13 -, carbon atoms which may be substituted by fluorine atoms preferably represents one of several 1 3 alkoxy group, a fluorine atom or a hydrogen atom, P 13 -S 13 -, alkoxy group having one to three carbon atoms, may represent either a fluorine atom or a hydrogen atom Is more preferable.
- the alkoxy group preferably has 1 or more and 3 or less carbon atoms, more preferably 1 or more and 2 or less, and particularly preferably 1.
- P 11 , P 12 and P 13 may all be the same polymerizable group (formula (Re-1) to (Re-9)) or different polymerizable groups.
- P 11 , P 12 and P 13 are each independently represented by the formula (Re-1), the formula (Re-2), the formula (Re-3), and the formula (Re-4).
- the formula (Re-1) is more preferable, and an acryl group or a methacryl group is still more preferable.
- At least one of P 11 and P 12 is preferably the formula (Re-1), more preferably an acrylic group or a methacryl group, still more preferably a methacryl group, and P 11 and P 12 are methacryl groups. Particularly preferred is a group.
- S 11 , S 12 and S 13 are each independently preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond.
- S 11 , S 12 and S 13 are single bonds, the residual amount of the polymerizable compound after ultraviolet irradiation is sufficiently small, and display defects due to changes in the pretilt angle are less likely to occur.
- the lower limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 0.01% by mass, preferably 0.02% by mass, and preferably 0.03% by mass, 0.04 mass% is preferable, 0.05 mass% is preferable, 0.06 mass% is preferable, 0.07 mass% is preferable, 0.08 mass% is preferable, 0.09 mass% is preferable, 1% by mass is preferable, 0.12% by mass is preferable, 0.15% by mass is preferable, 0.17% by mass is preferable, 0.2% by mass is preferable, 0.22% by mass is preferable, and 0.25% by mass.
- % Is preferable 0.27% by mass is preferable, 0.3% by mass is preferable, 0.32% by mass is preferable, 0.35% by mass is preferable, 0.37% by mass is preferable, and 0.4% by mass is preferable.
- 0.42% by mass is preferred Ku, preferably 0.45 mass%, preferably 0.5 wt%, preferably 0.55% by mass.
- the upper limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 5% by mass, preferably 4.5% by mass, preferably 4% by mass, and 3.5% by mass.
- % Preferably 3% by weight, preferably 2.5% by weight, preferably 2% by weight, preferably 1.5% by weight, preferably 1% by weight, preferably 0.95% by weight, 0.9% by weight % Is preferred, 0.85% by weight is preferred, 0.8% by weight is preferred, 0.75% by weight is preferred, 0.7% by weight is preferred, 0.65% by weight is preferred and 0.6% by weight is preferred. Preferably, 0.55 mass% is preferable, 0.5 mass% is preferable, 0.45 mass% is preferable, and 0.4 mass% is preferable.
- the content in order to obtain a sufficient pretilt angle or a small residual amount of the polymerizable compound or a high voltage holding ratio (VHR), the content is preferably 0.2 to 0.6% by mass. In the case where emphasis is placed on suppression of the content, the content is preferably 0.01 to 0.4% by mass. In order to obtain a particularly fast response speed, it is also preferable to increase the content to 2% by mass. Moreover, when it contains multiple polymeric compounds represented by general formula (RM), it is preferable that each content is 0.01 to 0.4 mass%. Therefore, in order to solve all these problems, it is particularly preferable to adjust the polymerizable compound represented by the general formula (RM) in the range of 0.1 to 0.6% by mass.
- the polymerizable compound represented by the general formula (RM) specifically, compounds represented by the general formulas (RM-1) to (RM-10) are preferable, and PSA type using these compounds
- the liquid crystal display element has a small residual amount of the polymerizable compound, has a sufficient pretilt angle, and has no or very few defects such as alignment failure and display failure due to a change in pretilt.
- each of R M1 and R M2 independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom, and represents an alkyl group having 1 carbon atom or a hydrogen atom. Is more preferable.
- the liquid crystal composition according to the present invention may contain one or more compounds having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy ⁇ greater than +2.
- the ⁇ of the compound is a value extrapolated from the measured value of dielectric anisotropy of a composition obtained by adding the compound to a dielectrically neutral composition at 25 ° C.
- the compound is used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc., and in particular, a liquid crystal containing a polymerizable compound The reactivity of the polymerizable compound in the composition can be accelerated.
- a compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy ⁇ greater than +2 has a preferable lower limit of 0.1% with respect to the total amount of the liquid crystal composition of the present invention. 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 10% is there.
- the upper limit value of the preferable content is, for example, 20%, 15%, 10%, 9%, 8% with respect to the total amount of the liquid crystal composition of the present invention. 7% 6% 5% 4% 3%
- a compound selected from the group represented by formula (M-7) as a compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy greater than +2 that can be used in the liquid crystal composition of the present invention Is mentioned.
- X M71 to X M76 each independently represents a fluorine atom or a hydrogen atom
- R M71 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 4 represents an alkoxy group
- Y M71 represents a fluorine atom or OCF 3.
- the content of the compound represented by the general formula (M-7) is an upper limit and a lower limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. There is a value.
- the lower limit of the preferable content of the compound represented by the formula (M-7) with respect to the total amount of the liquid crystal composition of the present invention is 1%, 2%, 4%, 5% Yes, 8%, 10%, 13%, 15%, 18%, 20%.
- the upper limit of the preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% 8% and 5%.
- examples of the compound represented by the general formula (M-7) include compounds represented by the formula (M-7.1) to the formula (M-7.4). It is preferable that it is a compound represented by 2).
- examples of the compound represented by the general formula (M-7) include compounds represented by the formula (M-7.11) to the formula (M-7.14), and the formula (M-7.11). And a compound represented by the formula (M-7.12).
- examples of the compound represented by the general formula (M-7) include compounds represented by the formula (M-7.21) to the formula (M-7.24), and the formula (M-7.21). And a compound represented by Formula (M-7.22).
- the liquid crystal composition of the present invention may contain a normal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, light stabilizer or infrared absorber in addition to the above-mentioned compounds.
- antioxidant examples include hindered phenols represented by general formula (H-1) to general formula (H-4).
- R H1 is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. It represents a 10 alkenyl group or alkenyloxy group having 2 to 10 carbon atoms from which one of the -CH 2 that is present in the radical - or non-adjacent two or more -CH 2 - are each independently - O— or —S— may be substituted, and one or more hydrogen atoms present in the group may be independently substituted with fluorine atoms or chlorine atoms.
- alkyl group having 2 to 7 carbon atoms an alkoxy 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.
- one or two or more non-adjacent —CH 2 — in the 1,4-cyclohexylene group is —O— or —S—. May be substituted.
- each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
- the antioxidant When the antioxidant is contained in the liquid crystal composition of the present invention, 10 ppm by mass or more is preferable, 20 ppm by mass or more is preferable, and 50 ppm by mass or more is preferable.
- the upper limit when the antioxidant is contained is 10,000 ppm by mass, preferably 1000 ppm by mass, preferably 500 ppm by mass, and preferably 100 ppm by mass.
- 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 according to the present invention a case where the entire liquid crystal composition exhibits a positive dielectric anisotropy and a case where the entire liquid crystal composition exhibits a negative dielectric anisotropy are assumed. However, it is preferable that the entire liquid crystal composition exhibits negative dielectric anisotropy.
- 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 is a 160 mPa ⁇ s to 50, preferably preferably from 160 mPa ⁇ s to 55, a 160 mPa ⁇ s to 60, 80 To 150 mPa ⁇ s, preferably 90 to 140 mPa ⁇ s, preferably 90 to 130 mPa ⁇ s, and preferably 100 to 130 mPa ⁇ s.
- the liquid crystal composition of the present invention has a dielectric anisotropy ( ⁇ ) at 20 ° C. of ⁇ 2.0 to ⁇ 8.0, preferably ⁇ 2.0 to ⁇ 6.0, -5.0 is more preferred, -2.5 to -4.0 is more preferred, and -2.5 to -3.5 is particularly preferred.
- the upper limit of the total content of compounds having an alkenyl group is preferably 10%, preferably 8%, and preferably 6%. Preferably, it is 5%, preferably 4%, preferably 3%, preferably 2%, preferably 1%, preferably 0%,
- the total range of the content of the compound having an alkenyl group is preferably 0 to 10%, preferably 0 to 8%, preferably 0 to 5%, and 0 to 4%. It is preferably 0 to 3%, more preferably 0 to 2%.
- the liquid crystal composition of the present invention contains compounds of the formulas (B31) and (CB31), which are essential components, and further includes the general formula (N-01), the general formula (N-02), and the general formula (N-03). ), A general formula (N-04), a general formula (N-05) and a compound selected from the group of compounds represented by the general formula (N-06). It is preferable to contain one or more compounds selected from the group of compounds represented by (-01) to (NU-06), and it contains the compounds of formula (B31) and formula (CB31) as essential components.
- the liquid crystal composition of the present invention contains compounds of the formulas (B31) and (CB31), which are essential components, and further includes the general formula (N-01), the general formula (N-02), and the general formula (N-03). ), A general formula (N-04), a general formula (N-05) and a compound selected from the group of compounds represented by the general formula (N-06).
- the liquid crystal composition of the present invention contains compounds of the formulas (B31) and (CB31), which are essential components, and further includes the general formula (N-01), the general formula (N-02), and the general formula (N-03). ) And one or more compounds selected from the compound group represented by the general formula (N-04), and further from the compound group represented by the general formulas (NU-01) to (NU-06) 1 type or 2 types or more of the compounds chosen,
- the upper limit of the total of the content of the component is 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, It is more preferable that they are 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%,
- the lower limit of the total content of the constituent components is 78% by mass, 80% %, 81%, 83%, 85%, 85%, 86%, 8
- the liquid crystal composition containing a polymerizable compound in the liquid crystal composition of the present invention contains the compounds of the formulas (B31) and (CB31) as essential components, and further includes the general formula (N-01), the general formula One compound selected from the group of compounds represented by formula (N-02), general formula (N-03), general formula (N-04), general formula (N-05) and general formula (N-06) Or two or more kinds, and further containing one or more compounds selected from the group of compounds represented by the general formulas (NU-01) to (NU-06), and further represented by the general formula (RM) 1 type or 2 types or more are contained, and the upper limit of the total of the content of the component is 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 Mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, It is preferably 9% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, and 8
- the liquid crystal display device using the liquid crystal composition of the present invention has a remarkable feature of high-speed response.
- a sufficient tilt angle can be obtained, and there is no unreacted polymerizable compound.
- VHR voltage holding ratio
- the tilt angle and the residual amount of the polymerizable compound can be easily controlled, it is easy to optimize and reduce the energy cost for production, which is optimal for improving production efficiency and stable mass production.
- the liquid crystal display device using the liquid crystal composition of the present invention is particularly useful for a liquid crystal display device for active matrix driving, and a liquid crystal display device for PSA mode, PSVA mode, VA mode, PS-IPS mode or PS-FFS mode Can be used.
- the liquid crystal display element includes a first substrate and a second substrate disposed opposite to each other, a common electrode provided on the first substrate or the second substrate, the first substrate,
- the pixel electrode includes a thin film transistor provided over a second substrate and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate.
- an alignment film for controlling the alignment direction of the liquid crystal molecules may be provided on the opposing surface side of at least one of the first substrate and / or the second substrate so as to contact the liquid crystal layer.
- a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected in accordance with the driving mode of the liquid crystal display element, and a rubbing alignment film (for example, polyimide) or a photo-alignment film (decomposable polyimide, etc.)
- a rubbing alignment film for example, polyimide
- a photo-alignment film decomposable polyimide, etc.
- the known alignment film can be used.
- a color filter may be provided as appropriate on the first substrate or the second substrate, and a color filter may be provided on the pixel electrode or the common electrode.
- the two substrates of the liquid crystal cell used in the liquid crystal display device according to the present invention can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon.
- a transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
- the color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.
- a method for producing a color filter by a pigment dispersion method will be described as an example.
- a curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created.
- a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.
- first substrate and the second substrate face each other so that the common electrode and the pixel electrode layer are inside.
- the distance between the first substrate and the second substrate may be adjusted via a spacer.
- it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 ⁇ m. More preferably, the thickness is 1.5 to 10 ⁇ m.
- a polarizing plate it is preferable to adjust the product of the refractive index anisotropy ⁇ n of the liquid crystal and the cell thickness d so that the contrast is maximized.
- the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good.
- a retardation film for widening the viewing angle can also be used.
- the spacer examples include glass particles, plastic particles, alumina particles, and a photoresist material.
- a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
- a normal vacuum injection method or an ODF method can be used as a method of sandwiching the liquid crystal composition between the two substrates.
- a liquid crystal composition containing a polymerizable compound is used in the liquid crystal composition, and the polymerizable compound in the liquid crystal composition is polymerized. it can.
- the polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention it is desirable to polymerize at an appropriate polymerization rate in order to obtain good alignment performance of the liquid crystal.
- a method of polymerizing by irradiating energy rays singly or in combination or sequentially is preferable.
- ultraviolet rays When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used.
- the polymerization is performed with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays.
- the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization.
- a means for polymerization In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the liquid crystal composition.
- the alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the PSVA liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
- the temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited.
- the liquid crystal composition of the present invention when applied to a liquid crystal display element including a substrate having an alignment film, it is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained.
- Polymerization is preferably performed at a temperature close to room temperature, that is, typically 15 to 35 ° C.
- the liquid crystal composition of the present invention when applied to a liquid crystal display element having a substrate that does not have an alignment film, the irradiation time applied to the liquid crystal display element having a substrate having the alignment film described above.
- a temperature range wider than the temperature range may be used.
- a lamp for generating ultraviolet rays a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.
- a wavelength of the ultraviolet-rays to irradiate it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed.
- the intensity of the irradiated ultraviolet light is preferably 0.1 mW / cm 2 to 100 W / cm 2, more preferably 2 mW / cm 2 to 50 W / cm 2 .
- the amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm 2 to 500 J / cm 2, and more preferably 100 mJ / cm 2 to 200 J / cm 2 .
- the intensity may be changed.
- the time for irradiation with ultraviolet rays is appropriately selected depending on the intensity of ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.
- the measured characteristics are as follows.
- VHR VHR (UV): Voltage holding ratio (%) after ultraviolet irradiation (irradiation conditions 1 and 2) (Manufacturing method and evaluation method of liquid crystal display element)
- a liquid crystal composition containing a polymerizable compound is applied with a polyimide alignment film that induces vertical alignment at a cell gap of 3.3 ⁇ m, and then vacuum injection is applied to a liquid crystal cell including an ITO-attached substrate in which the polyimide alignment film is rubbed. Injected with.
- JALS2096 manufactured by JSR Corporation was used as a material for forming a vertical alignment film.
- the liquid crystal cell into which the liquid crystal composition containing the polymerizable compound was injected was irradiated with ultraviolet rays through a filter that cuts out ultraviolet rays of 325 nm or less using a high-pressure mercury lamp with a voltage of 20 V applied at a frequency of 100 Hz.
- the ultraviolet irradiation condition was set as irradiation condition 1. Under this irradiation condition 1, a pretilt angle is given to the liquid crystal molecules in the liquid crystal cell.
- the illuminance measured under the condition of a center wavelength of 313 nm was adjusted to 3 mW / cm 2 and further irradiated with ultraviolet rays for 90 minutes to obtain a liquid crystal display element.
- the ultraviolet irradiation condition was set as irradiation condition 2.
- irradiation condition 2 the residual amount of the polymerizable compound in the liquid crystal cell that has not reacted under irradiation condition 1 is reduced.
- pretilt angle of the liquid crystal display element was measured and set as the pretilt angle (initial).
- a voltage of 30 V was applied to the liquid crystal display element at a frequency of 100 Hz for 24 hours.
- the pretilt angle was measured to obtain a pretilt angle (after the test).
- the pretilt angle was measured using an OPTIPRO made by Shintec.
- pretilt angle change amount is to 0 [°]
- the pretilt angle change amount exceeds 0.5 [°]
- a display failure due to the change in the pretilt angle will occur. More likely.
- the residual amount [ppm] of the polymerizable compound in the liquid crystal display element after irradiation with ultraviolet rays under irradiation conditions 1 and 2 was measured.
- a method for measuring the residual amount of the polymerizable compound will be described. First, the liquid crystal display element was disassembled, and an acetonitrile solution of the taken out liquid crystal composition was prepared. The peak area of each component was measured using a high performance liquid chromatograph. The amount of the polymerizable compound was determined from the peak area ratio of the liquid crystal compound and the peak area of the polymerizable compound as an index. The residual amount of the polymerizable compound was determined from this value and the amount of the polymerizable compound initially added.
- the detection limit of the residual amount of the polymerizable compound was 100 ppm.
- Liquid crystal compositions of Example 1 (LC-1), Comparative Example 1 (LC-A), Comparative Example 2 (LC-B), and Comparative Example 3 (LC-C) 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.
- Example 1 T ni is high, ⁇ n is large, ⁇ is negative, ⁇ 1 is small, K 33 is large, and ⁇ 1 / K 33 is small. VA using this liquid crystal composition
- VHR UV
- ⁇ 1 / K 33 of Comparative Example 1 (LC-A), Comparative Example 2 (LC-B), and Comparative Example 3 (LC-C) is large, and the response of Example 1 (LC-1) It was confirmed that the problem of the present invention could not be solved because it was significantly slower than the speed.
- LC-1 liquid crystal composition of Example 1
- R M1 and R M2 are methyl groups
- LC-1 liquid crystal composition
- R M1 and R M2 are methyl groups
- LC-1 wherein R M1 and R M2 are methyl groups
- a polymerizable compound-containing liquid crystal composition to which 0.3% by mass was added was prepared, and a PSA type liquid crystal display device was produced.
- the polymerizable compound remaining in the PSA type liquid crystal display element was below the detection lower limit.
- VHR (UV) was as high as 95%.
- the PSA type liquid crystal display element was irradiated with ultraviolet rays under irradiation condition 1, and further irradiated with ultraviolet rays under irradiation condition 2.
- the measurement conditions of the response speed were 6V for Von, 1V for Voff, 25 ° C for measurement temperature, and DMS703, manufactured by AUTRONIC-MELCHERS, as the measuring instrument.
- the liquid crystal display element using this was confirmed to have a display defect due to low VHR (UV).
- a polymerizable compound-containing liquid crystal composition to which 0.3% by mass was added was prepared, and a PSA type liquid crystal display device was produced.
- VHR (UV) was a low value of 89%.
- LC-E Comparative Example 5
- R M1 and R M2 are methyl groups
- LC-F Comparative Example 6
- R M1 and R M2 are methyl groups
- Example 2 A liquid crystal composition of Example 2 (LC-2) was prepared and measured for physical properties. The composition of the liquid crystal composition and the results of its physical property values are shown in Table 3.
- Example 2 T ni is high, ⁇ n is large, ⁇ is negative, ⁇ 1 is small, K 33 is large, and ⁇ 1 / K 33 is small. VA using this liquid crystal composition
- a liquid crystal display element of a type was manufactured, it was confirmed that the response speed was sufficiently high and VHR (UV) was a very high value of 94%.
- a polymerizable compound-containing liquid crystal composition to which 0.4 mass% was added was prepared to prepare a PSA type liquid crystal display element.
- VHR (UV) was 96%. Further, the polymerizable compound remaining in the PSA type liquid crystal display element was confirmed to be below the lower limit of detection by an HPLC analyzer.
- the PSA type liquid crystal display element was manufactured by irradiating with ultraviolet rays under irradiation condition 1 and further irradiating with ultraviolet rays under irradiation condition 2.
- Example 3 A liquid crystal composition of Example 3 (LC-3) was prepared and measured for physical properties.
- Table 4 shows the composition of the liquid crystal composition and the results of its physical properties.
- Example 3 T ni is high, ⁇ n is very large, ⁇ is negative, ⁇ 1 is small, K 33 is large, and ⁇ 1 / K 33 is small. As a result, it was confirmed that the response speed was very fast and VHR (UV) was a very high value of 95%.
- a polymerizable compound-containing liquid crystal composition to which 0.35% by mass was added was prepared, and a PSA type liquid crystal display device was produced.
- the PSA type liquid crystal display element was irradiated with ultraviolet rays under irradiation condition 1, and further irradiated with ultraviolet rays under irradiation condition 2.
- LC-3 wherein R M1 and R M2 are methyl groups
- LC-3 wherein R M1 and R M2 represent a methyl group
- a polymerizable compound-containing liquid crystal composition to which 0.35% by mass was added was prepared, and a PSA type liquid crystal display device was produced.
- VHR (UV) was 96%.
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Abstract
Description
しかしながら、いずれの液晶組成物も特に大型の液晶表示素子に求められる応答速度と信頼性を両立することができていなかった。一方、特許文献6において、(式1)で示される指数が大きい液晶材料を使用することでホメオトロピック液晶セルの応答速度を向上させることが開示されているが、十分満足できるとは言えないものであった。
また、近年開発されたPSA(Polymer Sustained Alignment)型液晶表示装置は、液晶分子のプレチルト角を制御するためにセル内にポリマー構造物を形成した構造を有するものであり、高速応答性や高いコントラストから主にテレビ用途の液晶表示素子として開発、改良が進められている。
以上のようなことから、PSA型液晶表示素子に使用される液晶組成物は、紫外線照射による劣化がないこと又はほとんど劣化しないことが求められており、なおかつ、液晶表示素子としたときに焼き付きが発生しないこと、応答速度が速いことなどが求められる。
R21は、炭素原子数1から8のアルキル基であることが好ましく、炭素原子数1から5のアルキル基がより好ましく、炭素原子数1から4のアルキル基が更に好ましい。但し、Z1が単結合以外を表す場合は、R21は、炭素原子数1~3のアルキル基が好ましい。
R22は、炭素原子数1~8のアルキル基又は炭素原子数1から8のアルコキシ基であることが好ましく、炭素原子数1~5のアルキル基又は炭素原子数1から4のアルコキシ基がより好ましく、炭素原子数1~4のアルコキシ基が更に好ましい。
R21及びR22は、アルケニル基であることもでき、式(R1)から式(R5)のいずれかで表される基(各式中の黒点は環構造中の炭素原子を表す。)から選ばれることが好ましく、式(R1)又は式(R2)が好ましいが、R21及びR22がアルケニル基である化合物の含有量はできる限り少ない方が良く、含有しない方が好ましい場合が多い。
mは、1であることが好ましい。
本発明の液晶組成物は、一般式(N-01)、一般式(N-02)、一般式(N-03)及び一般式(N-04)で表される化合物群から選ばれる化合物の含有量の合計が10質量%から80質量%であることが好ましく、20質量%から75質量%であることが好ましく、30質量%から73質量%であることが好ましく、35質量%から70質量%であることが好ましい。以下、含有量を%で記載するが、これは質量%を意味する。
一般式(N-05)で表される化合物は、種々の物性を調整したい場合に有効であるが、特に大きな屈折率異方性(Δn)を得るために使用することができる。
一般式(N-06)で表される化合物は、種々の物性を調整したい場合に有効であるが、特に大きな屈折率異方性(Δn)、高いT、大きなΔεを得るために使用することができる。
また、一般式(RM)で表される重合性化合物を複数含有する場合は、それぞれの含有量が0.01から0.4質量%であることが好ましい。従って、これら全ての課題を解決するためには、一般式(RM)で表される重合性化合物を0.1から0.6質量%の範囲で調整することが特に好ましい。
ターフェニル構造又はテトラフェニル構造を有し、誘電率異方性Δεが+2より大きい化合物は、本発明の液晶組成物の総量に対して、好ましい含有量の下限値は、0.1%であり、0.5%であり、1%であり、1.5%であり、2%であり、2.5%であり、3%であり、4%であり、5%であり、10%である。好ましい含有量の上限値は、本発明の液晶組成物の総量に対して、例えば本発明の一つの形態では20%であり、15%であり、10%であり、9%であり、8%であり、7%であり、6%であり、5%であり、4%であり、3%である。
本発明の液晶組成物の粘度を低く保ち、応答速度が速い液晶組成物とする場合は上記の下限値を低めに、上限値を低めにすることが好ましい。さらに、焼き付きの発生しにくい液晶組成物とする場合は上記の下限値を低めに、上限値を低めにすることが好ましい。また、駆動電圧を低く保つために誘電率異方性を大きくする場合は、上記の下限値を高めに、上限値を高めにすることが好ましい。液晶組成物中に含有させた重合性化合物の反応性を加速させる場合は上記の下限値を低めに、上限値を低めにすることが好ましい。
本発明の液晶組成物に用いることができるターフェニル構造又はテトラフェニル構造を有し、誘電率異方性が+2より大きい化合物として、式(M-8.51)から式(M-8.54)で表される化合物であることが好ましく、中でも式(M-8.52)で表される化合物を含有することが好ましい。
組み合わせることができる化合物の種類に特に制限は無いが、これらの化合物の中から1種~2種類含有することが好ましく、1種~3種類含有することがより好ましく、1種~4種類含有することが更に好ましい。
本発明の液晶組成物は、20℃における屈折率異方性(Δn)が0.08から0.14であるが、0.09から0.13がより好ましく、0.09から0.12が特に好ましい。更に詳述すると、薄いセルギャップに対応する場合は0.10から0.13であることが好ましく、厚いセルギャップに対応する場合は0.08から0.10であることが好ましい。
-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基
nO- CnH2n+1O- 炭素数nの直鎖状のアルコキシ基
-V -CH=CH2
V- CH2=CH-
-V- -CH=CH-
-O1V -O-CH2-CH=CH2
-V1 -CH=CH-CH3
1V- CH3-CH=CH-
-2V -CH2-CH2-CH=CH2
V2- CH2=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH2-
-F -F
-OCF3 -OCF3
(連結基)
-CF2O- -CF2-O-
-OCF2- -O-CF2-
-1O- -CH2-O-
-O1- -O-CH2-
-2- -CH2-CH2-
-COO- -COO-
-OCO- -OCO-
(環構造)
Δn :20℃における屈折率異方性
γ1 :20℃における回転粘性(mPa・s)
Δε :20℃における誘電率異方性
K33 :20℃における弾性定数K33(pN)
VHR(UV) :紫外線照射(照射条件1および2)後の電圧保持率(%)
(液晶表示素子の製造方法および評価方法)
まず、重合性化合物を含有する液晶組成物をセルギャップ3.3μmで垂直配向を誘起するポリイミド配向膜を塗布した後、前記ポリイミド配向膜をラビング処理したITO付き基板を含む液晶セルに真空注入法で注入した。垂直配向膜形成材料として、JSR社製のJALS2096を用いた。
(液晶組成物の調製と評価結果)
実施例1(LC-1)、比較例1(LC-A)、比較例2(LC-B)及び比較例3(LC-C)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。
実施例1(LC-1)の液晶組成物を99.7質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は検出下限以下であることを確認した。プレチルト角の変化を確認したところ、その変化量は、ほぼ0[°]であった。VHR(UV)は94%と高い値であった。
実施例1(LC-1)の液晶組成物を99.7質量%に対して、式(RM-2)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は検出下限以下であることを確認した。プレチルト角の変化を確認したところ、その変化量は、ほぼ0[°]であった。VHR(UV)は96%と高い値であった。
実施例1(LC-1)の液晶組成物を99.7質量%に対して、式(RM-4)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は検出下限以下であることを確認した。プレチルト角の変化を確認したところ、その変化量は、ほぼ0[°]であった。VHR(UV)は95%と高い値であった。
なお、PSA型液晶表示素子は照射条件1で紫外線を照射し、更に照射条件2で紫外線を照射した。応答速度の測定条件は、Vonは6V、Voffは1V、測定温度は25℃で、測定機器はAUTRONIC-MELCHERS社のDMS703を用いた。
比較例5(LC-E)はγ1/K33が実施例1(LC-1)よりも大きく、VHR(UV)が、84%と顕著に低かった。これを用いた液晶表示素子はVHR(UV)が低いことに起因する表示不良が確認された。比較例6(LC-F)はγ1/K33が小さいが、VHR(UV)が、77%と顕著に低かった。これを用いた液晶表示素子はVHR(UV)が低いことに起因する表示不良が確認された。
比較例4(LC-D)の液晶組成物を99.7質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良が少し発生し、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は130ppmであることを確認した。VHR(UV)は89%と低い値であった。
比較例5(LC-E)の液晶組成物を99.7質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良が少し発生し、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は150ppmであることを確認した。VHR(UV)は88%と低い値であった。
比較例6(LC-F)の液晶組成物を99.7質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.3質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良が少し発生し、高速応答であることを確認した。また、PSA型液晶表示素子に残留している重合性化合物は230ppmであることを確認した。VHR(UV)は82%と低い値であった。
比較例4(LC-D)、比較例5(LC-E)および比較例6(LC-F)のプレチルト角の変化を測定したところ、0.5[°]以上変化しており、実施例よりも顕著に劣っており、表示不良の1つである焼き付きを確認した。
実施例2(LC-2)の液晶組成物を99.6質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.4質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であること、VHRが十分に高いことを確認した。VHR(UV)は95%であった。また、PSA型液晶表示素子に残留している重合性化合物はHPLC分析装置によって検出下限以下であることを確認した。
実施例2(LC-2)の液晶組成物を99.6質量%に対して、式(RM-2)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.4質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であること、VHRが十分に高いことを確認した。VHR(UV)は96%であった。また、PSA型液晶表示素子に残留している重合性化合物はHPLC分析装置によって検出下限以下であることを確認した。
なお、PSA型液晶表示素子は照射条件1で紫外線を照射し、更に照射条件2で紫外線を照射して作製した。
実施例3(LC-3)の液晶組成物を99.65質量%に対して、式(RM-1)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.35質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であること、VHRが十分に高いことを確認した。VHR(UV)は96%であった。また、PSA型液晶表示素子に残留している重合性化合物はHPLC分析装置によって検出下限以下であることを確認した。なお、PSA型液晶表示素子は照射条件1で紫外線を照射し、更に照射条件2で紫外線を照射した。
実施例3(LC-3)の液晶組成物を99.65質量%に対して、式(RM-2)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.35質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答であること、VHRが十分に高いことを確認した。VHR(UV)は97%であった。また、PSA型液晶表示素子に残留している重合性化合物は検出下限以下であることを確認した。プレチルト角の変化を確認したところ、その変化量は、ほぼ0[°]であった。
実施例3(LC-3)の液晶組成物を99.65質量%に対して、式(RM-4)で表される重合性化合物(但し、式中、RM1及びRM2は、メチル基を表す。)を0.35質量%添加した重合性化合物含有液晶組成物を調製し、PSA型液晶表示素子を作製した。その結果、配向ムラなどの表示不良がなく、高速応答で、残留している重合性化合物は検出下限以下であり、プレチルト角の変化はほぼ0[°]であった。VHR(UV)は96%であった。
Claims (10)
- 一般式(N-01)、一般式(N-02)、一般式(N-03)及び一般式(N-04)
- 一般式(NU-01)から一般式(NU-06)
- アルケニル基を有する化合物の含有量の合計が0質量%から5質量%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。
- ターフェニル構造又はテトラフェニル構造を有し、誘電率異方性Δεが+2より大きい化合物を1種又は2種以上含有する請求項1から4のいずれか1項に記載の液晶組成物。
- 一般式(RM)
- 請求項1から7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7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7のいずれか1項に記載の液晶組成物を用いたVA型、PSA型、PSVA型、PS-IPS型又はPS-FFS型の液晶表示素子。
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CN202010069100.5A CN111234844B (zh) | 2016-11-22 | 2017-11-09 | 液晶组合物和液晶显示元件 |
CN201780018249.7A CN109072079B (zh) | 2016-11-22 | 2017-11-09 | 液晶组合物和液晶显示元件 |
KR1020187026876A KR101988816B1 (ko) | 2016-11-22 | 2017-11-09 | 액정 조성물 및 액정 표시 소자 |
US16/304,948 US20190203120A1 (en) | 2016-11-22 | 2017-11-09 | Liquid crystal composition and liquid crystal display device |
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WO2019116902A1 (ja) * | 2017-12-11 | 2019-06-20 | Dic株式会社 | 液晶表示素子 |
WO2019116901A1 (ja) * | 2017-12-11 | 2019-06-20 | Dic株式会社 | 液晶表示素子 |
CN111187629A (zh) * | 2018-11-14 | 2020-05-22 | Dic株式会社 | 液晶组合物和液晶显示元件 |
JP2020097678A (ja) * | 2018-12-18 | 2020-06-25 | Dic株式会社 | 液晶組成物及び液晶表示素子 |
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CN108239545B (zh) * | 2016-12-23 | 2022-02-25 | 江苏和成显示科技有限公司 | 具有负介电各向异性的液晶组合物及其显示器件 |
CN110484281B (zh) * | 2019-07-31 | 2021-04-20 | 北京八亿时空液晶科技股份有限公司 | 一种负性液晶组合物及其应用 |
JP7392434B2 (ja) * | 2019-12-02 | 2023-12-06 | Dic株式会社 | 液晶組成物及び液晶表示素子 |
CN113234453B (zh) * | 2021-05-27 | 2023-11-10 | 重庆汉朗精工科技有限公司 | 液晶组合物和液晶显示器 |
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KR20180107289A (ko) | 2018-10-01 |
JP6369663B1 (ja) | 2018-08-08 |
CN111234844A (zh) | 2020-06-05 |
KR101988816B1 (ko) | 2019-06-12 |
JPWO2018096932A1 (ja) | 2018-11-29 |
US20190203120A1 (en) | 2019-07-04 |
CN109072079B (zh) | 2020-02-14 |
CN111234844B (zh) | 2023-03-14 |
CN109072079A (zh) | 2018-12-21 |
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