WO2017065078A1 - Nematic liquid crystal composition and liquid crystal display element using same - Google Patents
Nematic liquid crystal composition and liquid crystal display element using same Download PDFInfo
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- WO2017065078A1 WO2017065078A1 PCT/JP2016/079760 JP2016079760W WO2017065078A1 WO 2017065078 A1 WO2017065078 A1 WO 2017065078A1 JP 2016079760 W JP2016079760 W JP 2016079760W WO 2017065078 A1 WO2017065078 A1 WO 2017065078A1
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N CC(C)(C)c1cc(C)cc(C(C)(C)C)c1O Chemical compound CC(C)(C)c1cc(C)cc(C(C)(C)C)c1O NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C)(*)C1CCC(C)CC1 Chemical compound CCC(C)(*)C1CCC(C)CC1 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
- C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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- G—PHYSICS
- G02—OPTICS
- 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
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- G—PHYSICS
- G02—OPTICS
- 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
Definitions
- the present invention relates to a nematic liquid crystal composition containing a polymerizable compound and a liquid crystal display device using the same.
- a PSA (Polymer Sustained Alignment) type liquid crystal display element has a polymer structure formed in a cell to control the pretilt angle of liquid crystal molecules, and is practical as a liquid crystal display element having features such as high-speed response and high contrast. It has become.
- a PSA-type liquid crystal display device is a liquid crystal display device manufactured using a polymerizable compound-containing liquid crystal composition comprising a liquid crystal compound and a polymerizable compound, and polymerizes the polymerizable compound in a state where liquid crystal molecules are aligned by voltage application. And by fixing the alignment of the liquid crystal molecules.
- the polymerization reaction rate of the polymerizable compound is very important for productivity. It is also very important to adjust the pretilt angle that affects the response speed and contrast of the PSA type liquid crystal display element and the residual amount of the polymerizable compound that affects the reliability such as display unevenness and image sticking.
- the polymerization reaction rate of the polymerizable compound depends on the wavelength and irradiation intensity of the UV irradiation lamp, development of a polymerizable compound-containing liquid crystal composition containing the polymerizable compound adapted to the specifications of the UV irradiation lamp is required. However, sufficient response was difficult.
- a composition containing a liquid crystal compound having a terphenyl ring (Patent Document 1) or a composition containing a liquid crystal compound having a naphthalene ring and a phenyl ring ( Patent Document 2) introduces a technique for reducing the polymerization reaction rate.
- VHR voltage holding ratio
- liquid crystal composition containing a polymerizable compound that suppresses adverse effects such as high-speed response, high contrast, display unevenness, and image sticking of the liquid crystal display element at the same time as adjusting the polymerization reaction speed adapted to the specifications of the UV irradiation lamp
- the problem to be solved by the present invention is that the viscosity ( ⁇ ) is sufficiently small, the rotational viscosity ( ⁇ 1) is sufficiently small, the polymerizable compound reacts sufficiently fast, and there is no residue of the polymerizable compound after UV irradiation.
- a liquid crystal display element such as a PSA type in which VHR is good and display unevenness or image sticking does not occur or is extremely suppressed.
- R 11 and R 12 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 carbon atoms.
- To 10 alkenyloxy groups, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms
- X 11 to X 20 are each independently a hydrogen atom.
- L 11 and L 12 are each independently —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —.
- m 11 and m 12 each independently represent 0 or 1
- m 11 + m 12 represents 1 or 2.
- the viscosity ( ⁇ ) of the composition of the present invention is sufficiently low, the liquid crystal display device using the composition has a sufficiently high response speed and can display 3D, and there is no residual polymerizable compound. Since it is sufficiently suppressed, VHR is good and display unevenness or image sticking does not occur or is extremely suppressed. Further, since the polymerization reaction rate of the polymerizable compound is sufficiently high, the energy cost for production can be reduced, the production efficiency can be improved, and uniform and stable alignment control can be obtained, which is very useful.
- composition of the present invention has the general formula (I)
- the compound represented by the general formula (I) has a structure having a naphthalene ring, a phenyl ring, and one or more cyclohexane rings.
- R 11 and R 12 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 carbon. Represents an alkenyloxy group having 2 to 10 atoms, and one or more hydrogen atoms present in these groups may be substituted by a fluorine atom, but an alkyl group having 1 to 5 carbon atoms, Preferred are 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, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms.
- An alkoxyl group or an alkenyl group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms is more
- X 11 to X 20 each independently represents a hydrogen atom, a methyl group, —CF 3 group, a fluorine atom or a chlorine atom, preferably a hydrogen atom, a methyl group or a fluorine atom, and preferably a hydrogen atom or a fluorine atom It is more preferable that two or three of X 11 to X 20 are fluorine atoms, and the other is a hydrogen atom, and two of X 11 to X 20 are fluorine atoms. The other is particularly preferably a hydrogen atom.
- L 11 and L 12 are each independently —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond represents a, -OCH 2 -, - CH 2 O -, - it is or a single bond - CH 2 CH 2 - that or a single bond preferably, -CH 2 CH 2 is a structure containing no oxygen atom Is more preferable, and a single bond is more preferable.
- n 11 and m 12 each independently represent 0 or 1, and m 11 + m 12 represents 1 or 2, but m 11 + m 12 is preferably 1.
- the compound represented by general formula (I) contains 1 type, or 2 or more types, it is preferable to contain 1 type to 5 types, it is more preferable to contain 1 type to 3 types, and 1 type is contained. Is particularly preferred. Further, the content thereof is 0.1% to 50% by mass, preferably 0.1% to 10% by mass, and 0.3% to 8% by mass with respect to the composition. The range is more preferably 0.5% by mass to 5% by mass, 0.5% to 3% by mass, and 0.5% to 2% by mass. May be.
- the compound represented by general formula (I) is preferably a compound represented by general formula (N-002) to general formula (N-079).
- the compounds represented by the general formula (N-002) to the general formula (N-079) the compounds represented by the general formula (N-030) to the general formula (N-042), 058) to general formula (N-062), general formula (N-071) to general formula (N-074), general formula (N-077) to general formula (N— 079) is preferred, and compounds represented by general formula (N-030) to general formula (N-035) are more preferred.
- composition of the present invention contains one or more polymerizable compounds.
- the polymerizable compound preferably has a mesogenic skeleton, specifically, the general formula (M)
- R 201 is, P 201 -Sp 201 - represents, R 202 is, P 202 -Sp 202 - represents a.
- P 201 and P 202 each independently represent formula (R-1) to formula (R-15)
- P 201 and P 202 may be the same or different.
- Sp 201 and Sp 202 each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more —CH 2 — in the alkylene group is not directly adjacent to an oxygen atom. May be substituted with —O—, —OCO— or —COO—, but each independently represents a single bond or a carbon number in which one methylene may be substituted with —O—, —OCO— or —COO—.
- at least one is preferably a single bond, one is a single bond and the other is an alkylene group having 1 to 4 carbon atoms, or — O— (CH 2 ) s — is preferable.
- an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4. It is also preferable that both Sp 201 and Sp 202 are single bonds.
- M 201 , M 202 and M 203 are each independently a phenyl group, 1,4-phenylene group, benzene-1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1, 4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, the group being unsubstituted or an alkyl group having 1 to 12 carbon atoms, 1 carbon atom May be substituted with an alkoxyl group of ⁇ 12, halogen, cyano group or nitro group, but each independently is unsubstituted or substituted with an alkyl group
- n 201 , n 202 and n 203 each independently represents an integer of 0 to 3, and the total number of n 201 and n 203 is 2 or more, but n 202 is preferably 0, 1 or 2 0 or 1 is more preferable.
- n 201 and n 203 are each independently preferably 0, 1 or 2, more preferably 1 or 2, and the total number of n 201 and n 203 is preferably 2 or 3.
- a plurality of existing P 201 , P 202 , Sp 201 , Sp 202 , Z 201, and M 202 may be the same or different.
- the composition of the present invention contains at least one polymerizable compound represented by formula (M), preferably 1 to 5 types, more preferably 1 to 3 types.
- the orientation control power with respect to a liquid-crystal composition becomes weak.
- the content of the polymerizable compound represented by the general formula (M) is too large, the energy required for the polymerization of the polymerizable compound increases, and the amount of the polymerizable compound that remains without being polymerized increases.
- the content is preferably 0.01 to 2.00% by mass, and more preferably 0.05 to 1.00% by mass. 0.10 to 0.50% by mass is particularly preferable.
- the ring structure between Sp 201 and Sp 202 is the formula (XXa-1) to the 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 preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
- 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 phenyl group in the formula may be further substituted by —F, —Cl, —CF 3 , —CH 3 , or any one of formulas (R-1) to (R-15). .
- n 202 is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M52) is preferable.
- the hydrogen atom in the phenyl group and naphthalene group in the formula is further substituted with —F, —Cl, —CF 3 , —CH 3 , or any one of formulas (R-1) to (R-15). May be.
- the polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
- n 201 is 1, n 202 is 1, and n 203 is 2, for example, a polymerizable compound such as formula (M301) to formula (M320) is preferable.
- the hydrogen atom in the phenyl group and naphthalene group in the formula may be further substituted with —F, —Cl, —CF 3 , —CH 3 .
- the polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
- composition of the present invention further has the general formula (N-1)
- R N11 and R N12 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 carbon atoms
- R N11 and R N12 in present in one -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O- and / or -S
- one or two or more hydrogen atoms present in R N11 and R N12 may each independently be substituted with a fluorine atom or a chlorine atom
- a N11 represents 1 , 4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 -.
- -O- 1,4 Phenylene group
- -N 1,4 Phenylene group
- n N11 1 or 2
- Z N11 is - OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond
- a plurality of existing A N11 are the same. Or may be different.
- the compound represented by the general formula (N-1) is contained in one or more kinds, preferably 1 to 10 kinds, more preferably 1 to 6 kinds,
- the content is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 50% by mass with respect to the composition.
- R N11 and R N12 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. Or an alkenyloxy group having 2 to 5 carbon atoms, R N11 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N12 is 1 carbon atom. And more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms.
- a N11 is 1,4-cyclohexylene group or 1,4-phenylene group is preferred.
- Z N11 is, -CH 2 O -, - CH 2 CH 2 - or preferably a single bond, more preferably -CH 2 O-or a single bond.
- the compound represented by the general formula (N-1) is represented by the general formula (N-1-1) to the general formula (N-1-4), the general formula (N-1-10) or the general formula.
- R N111 and R N112 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N121 and R N122 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N131 and R N132 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
- R N141 and R N142 each independently represents the same meaning as R N11 and R N12 in the general formula (N-1).
- R N1101 and R N1102 each independently represent the same meaning as R N11 and R N12 in formula (N-1).
- R N1111 and R N1112 each independently represent the same meaning as R N11 and R N12 in formula (N-1)) are preferable.
- the compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
- the compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
- the compound represented by the general formula (N-1-1) is specifically selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14).
- the compounds represented by formulas (N-4-1.1) to (N-1-1.4) are preferred, and the compounds represented by formulas (N-1-1.1) and A compound represented by the formula (N-1-1.3) is preferred.
- the compounds represented by formulas (N-1-1.1) to (N-1-1.14) can be used alone or in combination.
- the lower limit of the preferred content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, 20%, 23% 25% 27% 30% 33% 35%
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
- the compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-2) with respect to the total amount of the composition of the present invention is 5%, 7%, 10%, %, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37 %, 40%, and 42%.
- the upper limit of the preferable content is 50%, 48%, 45%, 43%, 40%, 38%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% %, 8%, 7%, 6%, 5%.
- the compound represented by the general formula (N-1-2) is specifically a compound group represented by the formula (N-1-2.1) to the formula (N-1-2.13).
- the compound is selected from the formulas (N-1-2.3) to (N-1-2.7), (N-1-2.10), and (N-1-2). .11) and the compound represented by formula (N-1-2.13).
- the compound represented by formula (N-1-2.3) to formula (N-1 is preferably a compound represented by -2.7), formula (N-1-2.10 in the case of emphasizing improvements in T NI), the formula (N-1-2.11) and formula (N-1 -2.13) is preferred.
- the compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) can be used alone or in combination.
- the lower limit of the preferable content of these compounds alone or with respect to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23 %, 25%, 27%, 30%, 33%, and 35%.
- the upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
- the compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-3) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-3) is specifically a group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11).
- a compound selected from the group consisting of formulas (N-1-3.1) to (N-1-3.7) is preferable, and a compound represented by formula (N-1-3.1) is preferable.
- Formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compound represented by formula (N-1-3.6) Is preferred.
- the compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred.
- the lower limit of the preferred content of these compounds alone or with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15%, 17%, 20% %.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-4) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 10% %, 13%, 15%, 17%, and 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.
- the compound represented by the general formula (N-1-4) is specifically selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14)
- the compounds represented by formulas (N-1-4.1) to (N-1-4.4) are preferred, and the compounds represented by formulas (N-1-4.1) and A compound represented by the formula (N-1-4.2) is preferable.
- the compounds represented by formulas (N-1-4.1) to (N-1-4.4) can be used singly or in combination, but the compounds of the present invention
- the lower limit of the preferable content of these compounds alone or with respect to the total amount is 3%, 5%, 7%, 10%, 13%, 15%, 17% And 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.
- the compound represented by the general formula (N-1) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferable content of the compound represented by the general formula (N-1-10) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-10) is specifically a group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.15).
- a compound selected from the group consisting of formulas (N-1-10.1) to (N-1-10.5) is preferable.
- a compound represented by the formula (N-1-10.2) are preferable.
- the compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination.
- the lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-11) can be used alone, but two or more compounds are used in combination. You can also. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence.
- the kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
- the lower limit of the preferred content of the compound represented by formula (N-1-11) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%.
- the upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
- the compound represented by the general formula (N-1-11) specifically includes a compound group represented by the formula (N-1-11.1) to the formula (N-1-11.15).
- the compound is preferably a compound selected from formulas (N-1-11.1) to (N-1-11.15), and preferably represented by formula (N-1-111.2).
- a compound represented by formula (N-1-11.4) is preferable.
- the compounds represented by the formula (N-1-11.2 and the formula (N-1-11.4) can be used alone or in combination.
- the lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%.
- the upper limit of the amount is 35%, 30%, 28%, 25%, 23%, 20%, 18% with respect to the total amount of the composition of the present invention. Yes, 15%, 13%.
- composition of the present invention has a general formula (L-1) to a general formula (L-6) as a compound having a dielectric anisotropy ( ⁇ ) of almost 0.
- R L11 to R L62 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms
- X L61 and X L62 each independently represent a hydrogen atom or fluorine It is preferable to contain a compound selected from the group consisting of compounds represented by the formula:
- composition of the present invention preferably contains the compounds of general formula (I), general formula (M) and general formula (N-1) at the same time, and includes general formula (I), general formula (M) and general formula (N-1). More preferably, the compound of (N-1) and the general formula (L-1) are simultaneously contained.
- the composition of the present invention comprises a compound represented by general formula (I), a compound represented by general formula (M), a compound represented by general formula (N-1), and general formula (L-1) to
- the total amount of compounds selected from the compound group represented by formula (L-6) is preferably 85% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and 95% by mass. To 100% by mass, and more preferably 98% to 100% by mass.
- the compound having an alkenyl group is preferably 12% by mass or less, More preferably, it is not contained at all, and the cyclohexane ring or benzene ring in the liquid crystal compound may be substituted with a fluorine atom, but is not preferably substituted with a chlorine atom.
- the composition of the present invention has a dielectric anisotropy ( ⁇ ) at 25 ° C. of ⁇ 2.0 to ⁇ 8.0, preferably ⁇ 2.0 to ⁇ 6.0, and ⁇ 2.0 to ⁇ 5.0 is more preferable, and ⁇ 2.5 to ⁇ 4.0 is even more preferable.
- the 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 particularly preferably 0.09 to 0.12. preferable. More specifically, when it corresponds to a thin cell gap, it is preferably 0.10 to 0.125, and when it corresponds to a thick cell gap, it is preferably 0.08 to 0.10.
- the 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 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.
- composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T ni ) of 60 ° C to 120 ° C, more preferably 68 ° C to 100 ° C, and particularly preferably 68 ° C to 85 ° C.
- T ni nematic phase-isotropic liquid phase transition temperature
- the polymerization proceeds even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to accelerate the polymerization.
- the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
- composition of the present invention may further contain a compound represented by the general formula (Q).
- R Q represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or two or more non-adjacent CH 2 groups in the group are —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O—, —OCF 2 — may be substituted.
- MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond.
- the compound represented by the general formula (Q) is preferably a compound represented by the following general formula (Qa) to general formula (Qd).
- R Q1 is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms.
- R Q2 is preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group.
- R Q3 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group, a linear alkoxy group, or a branched alkoxy group.
- L Q is preferably a linear alkylene group or branched alkylene group having 1 to 8 carbon atoms.
- the composition of the present invention preferably contains one or more compounds represented by the general formula (Q), preferably contains 1 to 5 types, and preferably contains 1 to 3 types. More preferably, it is more preferable to contain 1 type. Further, the content is preferably 0.001% by mass to 1% by mass, more preferably 0.001% by mass to 0.1% by mass, and further preferably 0.001% by mass to 0.05% by mass. .
- a stabilizer may be added to improve storage stability.
- examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, ⁇ -naphthylamines, ⁇ -naphthols, nitroso compounds, and the like. It is done.
- composition of the present invention may contain a normal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, polymerizable monomer and the like in addition to the above-mentioned compounds.
- composition of the present invention is useful for a liquid crystal display device, particularly useful for a liquid crystal display device for driving an active matrix, and used for a liquid crystal display device for a PSA mode, a PSVA mode, a VA-IPS mode or a polymer stabilization mode. be able to.
- the composition of the present invention is a liquid crystal display element in which the polymerizable compound contained therein is polymerized by ultraviolet irradiation to impart liquid crystal alignment ability, and the amount of transmitted light is controlled using the birefringence of the liquid crystal composition.
- a liquid crystal display element it is useful for an AM-LCD (active matrix liquid crystal display element) and an IPS-LCD (in-plane switching liquid crystal display element), but is particularly useful for an AM-LCD and is a transmissive or reflective liquid crystal display. It can be used for an element.
- the two substrates of the liquid crystal cell used in the liquid crystal display element 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.
- the substrate is opposed so that the transparent electrode layer is on the inside.
- the thickness of the obtained light control layer is 1 to 100 ⁇ m. More preferably, the thickness is 1.5 to 10 ⁇ m.
- the 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 composition of the present invention between two substrates.
- an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially.
- the method of polymerizing by is preferred.
- a polarized light source or a non-polarized light source may be used.
- at least the substrate on the irradiated 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 composition of the present invention.
- 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 MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
- the temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically 15 to 35 ° C.
- 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.
- T ni Nematic phase-isotropic liquid phase transition temperature (° C.)
- ⁇ n Refractive index anisotropy at 20 ° C.
- ⁇ Dielectric anisotropy at 20 ° C.
- ⁇ 1 Rotational viscosity at 20 ° C. (mPa ⁇ s)
- K 33 Elastic constant of bending at 20 ° C.
- Pre-tilt angle Pre-tilt angle after UV irradiation by 20 J [°] / AUTRONIC-MELCHERS, TBA105 VHR / Initial: Voltage holding ratio before UV irradiation (1 V, 60 Hz, 60 ° C.) / Toyo Technica VHR-1 After VHR / UV20J: Voltage holding ratio after UV20J irradiation (1 V, 60 Hz, 60 ° C.) / Toyo Technica VHR-1 (Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 1) Polymeric compound-containing liquid crystal compositions of MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were prepared, and their physical property values were prepared. Was measured. Table 1 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
- MLC-A1 (Comparative Example 1)
- MLC-A2 (Comparative Example 2)
- MLC-A3 (Comparative Example 3)
- MLC-A4 (Example 1) were each homeotropically aligned with a cell gap of 3.0 ⁇ m. It injected by the vacuum injection method to the cell with ITO which apply
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. It was confirmed that these PSVA liquid crystal display elements all showed an appropriate pretilt angle of about 88 ° and a response speed correlated with a physical property value.
- VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 2.
- Example 1 MLC-A4 has a significantly higher VHR after UV irradiation than MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2) and MLC-A3 (Comparative Example 3). In addition, it has been found that both of the characteristics that the remaining amount of the polymerizable compound is reduced are combined. Further, when a burn-in test was performed on these PSVA liquid crystal display elements, MLC-A1, MLC-A2 and MLC-A3 showed a burn-in which is considered to be caused by a low VHR or residual polymerizable compound after UV irradiation. . On the other hand, MLC-A4 did not generate any burn-in.
- LC-A4 which is a polymerizable compound-containing liquid crystal composition of the present invention, has excellent UV resistance, a small residual amount of the polymerizable compound, and does not cause display defects such as image sticking. It was found to be a liquid crystal composition-containing liquid crystal composition.
- Polymerizable compound-containing liquid crystal compositions of MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were prepared and their physical properties were measured. Was measured. Table 3 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
- MLC-B1 Comparative Example 4
- MLC-B2 Example 2
- MLC-B3 Example 3
- MLC-B4 Example 4
- ITO Indium Tin Oxide
- UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm).
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values. For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 4.
- the polymerizable compound-containing liquid crystal composition of the present invention MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
- Polymeric compound-containing liquid crystal compositions of MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were prepared, and their physical properties were measured. Was measured.
- the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values are shown in Table 5.
- MLC-C1 Comparative Example 5
- MLC-C2 Example 5
- MLC-C3 Example 6
- MLC-C4 Example 7
- ITO Indium Tin Oxide
- UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm).
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values. For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 6.
- the polymerizable compound-containing liquid crystal composition of the present invention MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
- Polymeric compound-containing liquid crystal compositions of MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were prepared and their physical properties were measured. Was measured. Table 7 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
- MLC-D1 Comparative Example 6
- MLC-D2 Example 8
- MLC-D3 Example 9
- MLC-D4 Example 10
- ITO ITO
- UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less.
- the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm).
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values. For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 8.
- the polymerizable compound-containing liquid crystal composition of the present invention MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
- Polymerizable compound-containing liquid crystal compositions of MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were prepared, and their physical property values were prepared. Was measured. Table 9 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
- MLC-E1 Comparative Example 7
- MLC-E2 Example 11
- MLC-E3 Example 12
- MLC-E4 Example 13
- ITO Indium Tin Oxide
- UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm).
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values. For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 10.
- the polymerizable compound-containing liquid crystal composition of the present invention MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
- Polymerizable compound-containing liquid crystal compositions of MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were prepared, and their physical property values were prepared. Was measured. Table 11 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
- MLC-F1 Comparative Example 8
- MLC-F2 Example 14
- MLC-F3 Example 15
- MLC-F4 Example 16
- PSVA liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values. For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 12.
- the polymerizable compound-containing liquid crystal composition of the present invention MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
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Abstract
The present invention provides a liquid crystal composition which has sufficiently low viscosity (η), sufficiently low rotational viscosity (γ1) and sufficiently high reaction rate of a polymerizable compound, while being free from or sufficiently suppressed in residue of the polymerizable compound after UV irradiation. This liquid crystal composition is useful since a liquid crystal display element such as PSA, which has a sufficiently short response time and achieves uniform and stable alignment control at a lower energy cost, while having good VHR and being free from or extremely suppressed in the occurrence of display unevenness or image burn-in, is able to be produced from this liquid crystal composition.
Description
本発明は重合性化合物を含有するネマチック液晶組成物及びこれを用いた液晶表示素子に関する。
The present invention relates to a nematic liquid crystal composition containing a polymerizable compound and a liquid crystal display device using the same.
PSA(Polymer Sustained Alignment)型液晶表示素子は、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ものであり、高速応答や高コントラスト等の特徴を有する液晶表示素子として実用化されている。
A PSA (Polymer Sustained Alignment) type liquid crystal display element has a polymer structure formed in a cell to control the pretilt angle of liquid crystal molecules, and is practical as a liquid crystal display element having features such as high-speed response and high contrast. It has become.
PSA型液晶表示素子は、液晶化合物及び重合性化合物からなる重合性化合物含有液晶組成物を用いて製造される液晶表示素子であり、電圧印加により液晶分子を配向させた状態で重合性化合物を重合させ、液晶分子の配向を固定することにより製造される。PSA型液晶表示素子の重合性化合物を重合させる工程において、重合性化合物の重合反応速度は生産性にとって非常に重要である。PSA型液晶表示素子の応答速度やコントラスト等に影響を与えるプレチルト角の調整や、表示ムラ及び焼き付きといった信頼性に影響を及ぼす重合性化合物の残留量の調整も非常に重要である。重合性化合物の重合反応速度はUV照射ランプの波長や照射強度に依存するため、UV照射ランプの仕様に適合させた重合性化合物を含有する重合性化合物含有液晶組成物の開発が求められているが、十分な対応は困難であった。
A PSA-type liquid crystal display device is a liquid crystal display device manufactured using a polymerizable compound-containing liquid crystal composition comprising a liquid crystal compound and a polymerizable compound, and polymerizes the polymerizable compound in a state where liquid crystal molecules are aligned by voltage application. And by fixing the alignment of the liquid crystal molecules. In the step of polymerizing the polymerizable compound of the PSA type liquid crystal display element, the polymerization reaction rate of the polymerizable compound is very important for productivity. It is also very important to adjust the pretilt angle that affects the response speed and contrast of the PSA type liquid crystal display element and the residual amount of the polymerizable compound that affects the reliability such as display unevenness and image sticking. Since the polymerization reaction rate of the polymerizable compound depends on the wavelength and irradiation intensity of the UV irradiation lamp, development of a polymerizable compound-containing liquid crystal composition containing the polymerizable compound adapted to the specifications of the UV irradiation lamp is required. However, sufficient response was difficult.
製造方法とは別に、液晶組成物の面から改良するアプローチとして、ターフェニル環を有する液晶化合物を含有する組成物(特許文献1)やナフタレン環とフェニル環を有する液晶化合物を含有する組成物(特許文献2)を用いることで重合反応速度を短縮する技術が紹介されているが、ターフェニル環を有する液晶化合物を用いると、製造された液晶表示素子において、電圧保持率(VHR)の低下による表示ムラや焼き付きといった信頼性に影響を及ぼすことがあった。
Apart from the production method, as an approach to improve from the aspect of the liquid crystal composition, a composition containing a liquid crystal compound having a terphenyl ring (Patent Document 1) or a composition containing a liquid crystal compound having a naphthalene ring and a phenyl ring ( Patent Document 2) introduces a technique for reducing the polymerization reaction rate. However, when a liquid crystal compound having a terphenyl ring is used, in the manufactured liquid crystal display element, the voltage holding ratio (VHR) is reduced. The reliability of display unevenness and burn-in may be affected.
以上のように、UV照射ランプの仕様に適合させた重合反応速度の調整と同時に液晶表示素子の高速応答や高コントラスト、表示ムラや焼き付き等の悪影響が抑えられた重合性化合物を含有する液晶組成物及びこれを用いた液晶表示素子が求められていた。
As described above, a liquid crystal composition containing a polymerizable compound that suppresses adverse effects such as high-speed response, high contrast, display unevenness, and image sticking of the liquid crystal display element at the same time as adjusting the polymerization reaction speed adapted to the specifications of the UV irradiation lamp There has been a demand for a liquid crystal display device using the same.
本発明が解決しようとする課題は、粘度(η)が十分に小さく、回転粘性(γ1)が十分に小さく、重合性化合物が十分に速く反応し、UV照射後の重合性化合物の残留がないか、十分に抑制された重合性化合物を含有する液晶組成物を提供し、更にこれを用いた、応答速度が十分に速く、3D表示も可能で、均一かつ安定な配向制御がより少ないエネルギーコストで得られると同時に、更に、VHRが良好であって、表示ムラや焼き付きが発生しないか、極めて抑制されるPSA型等の液晶表示素子を提供することにある。
The problem to be solved by the present invention is that the viscosity (η) is sufficiently small, the rotational viscosity (γ1) is sufficiently small, the polymerizable compound reacts sufficiently fast, and there is no residue of the polymerizable compound after UV irradiation. Or a liquid crystal composition containing a sufficiently suppressed polymerizable compound, and using this, the response speed is sufficiently fast, 3D display is possible, and uniform and stable alignment control is less energy cost. And a liquid crystal display element such as a PSA type in which VHR is good and display unevenness or image sticking does not occur or is extremely suppressed.
本発明者は、種々の重合性化合物及び液晶化合物を検討した結果、特定の構造を有する重合性化合物及び液晶化合物で構成される組成物が前述の課題を解決できることを見出し、本発明を完成するに至った。
As a result of studying various polymerizable compounds and liquid crystal compounds, the present inventors have found that a composition composed of a polymerizable compound having a specific structure and a liquid crystal compound can solve the above-mentioned problems, and completes the present invention. It came to.
すなわち、一般式(I)
That is, general formula (I)
(式中、R11及びR12は、それぞれ独立的に、炭素原子数1から10のアルキル基、炭素原子数1から10のアルコキシル基、炭素原子数2から10のアルケニル基又は炭素原子数2から10のアルケニルオキシ基を表し、これらの基中に存在する1個又は2個以上の水素原子はフッ素原子によって置換されていても良く、X11からX20は、それぞれ独立的に、水素原子、メチル基、-CF3基、フッ素原子又は塩素原子を表し、L11及びL12は、それぞれ独立的に、-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-又は単結合を表し、m11及びm12は、それぞれ独立的に、0又は1を表し、かつm11+m12が1又は2を表す。)で表される化合物を1種又は2種以上含有し、重合性化合物を1種又は2種以上含有することを特徴とする組成物、これを用いた液晶表示素子及び一般式(I)で表される化合物を提供する。
Wherein R 11 and R 12 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 carbon atoms. To 10 alkenyloxy groups, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms, and X 11 to X 20 are each independently a hydrogen atom. , Methyl group, —CF 3 group, fluorine atom or chlorine atom, and L 11 and L 12 are each independently —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —. , -CH 2 CH 2- , -CF 2 CF 2 -or a single bond, m 11 and m 12 each independently represent 0 or 1, and m 11 + m 12 represents 1 or 2. Compound represented by A composition containing one or more kinds of polymerizable compounds and one or more polymerizable compounds, a liquid crystal display device using the composition, and a compound represented by the general formula (I) To do.
本発明の組成物は、粘度(η)が十分に低いため、これを用いた液晶表示素子は応答速度が十分に速く、3D表示も可能であり、なおかつ、重合性化合物の残留がないか、十分に抑制されるため、更に、VHRが良好であって、表示ムラや焼き付きが発生しないか、極めて抑制される。また、重合性化合物の重合反応速度が十分に速いため、製造のためのエネルギーコストを削減し、生産効率を向上でき、均一かつ安定な配向制御が得られるため、非常に有用である。
Since the viscosity (η) of the composition of the present invention is sufficiently low, the liquid crystal display device using the composition has a sufficiently high response speed and can display 3D, and there is no residual polymerizable compound. Since it is sufficiently suppressed, VHR is good and display unevenness or image sticking does not occur or is extremely suppressed. Further, since the polymerization reaction rate of the polymerizable compound is sufficiently high, the energy cost for production can be reduced, the production efficiency can be improved, and uniform and stable alignment control can be obtained, which is very useful.
本発明の組成物は、一般式(I)
The composition of the present invention has the general formula (I)
で表される化合物を1種又は2種以上含有する。一般式(I)で表される化合物は、ナフタレン環、フェニル環及び1つ以上のシクロヘキサン環を有する構造となっている。
1 type or 2 types or more are contained. The compound represented by the general formula (I) has a structure having a naphthalene ring, a phenyl ring, and one or more cyclohexane rings.
一般式(I)において、R11及びR12は、それぞれ独立的に、炭素原子数1から10のアルキル基、炭素原子数1から10のアルコキシル基、炭素原子数2から10のアルケニル基又は炭素原子数2から10のアルケニルオキシ基を表し、これらの基中に存在する1個又は2個以上の水素原子はフッ素原子によって置換されていても良いが、炭素原子数1から5のアルキル基、炭素原子数1から5のアルコキシル基、炭素原子数2から5のアルケニル基又は炭素原子数2から5のアルケニルオキシ基が好ましく、炭素原子数1から5のアルキル基、炭素原子数1から5のアルコキシル基又は炭素原子数2から5のアルケニル基が好ましく、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のアルコキシル基が更に好ましい。
In the general formula (I), R 11 and R 12 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 carbon. Represents an alkenyloxy group having 2 to 10 atoms, and one or more hydrogen atoms present in these groups may be substituted by a fluorine atom, but an alkyl group having 1 to 5 carbon atoms, Preferred are 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, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. An alkoxyl group or an alkenyl group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms is more preferable.
X11からX20は、それぞれ独立的に、水素原子、メチル基、-CF3基、フッ素原子又は塩素原子を表すが、水素原子、メチル基又はフッ素原子であることが好ましく、水素原子又はフッ素原子であることが更に好ましく、X11からX20の内の2つ又は3つがフッ素原子で、その他が水素原子であることが更に好ましく、X11からX20の内の2つがフッ素原子で、その他が水素原子であることが特に好ましい。
X 11 to X 20 each independently represents a hydrogen atom, a methyl group, —CF 3 group, a fluorine atom or a chlorine atom, preferably a hydrogen atom, a methyl group or a fluorine atom, and preferably a hydrogen atom or a fluorine atom It is more preferable that two or three of X 11 to X 20 are fluorine atoms, and the other is a hydrogen atom, and two of X 11 to X 20 are fluorine atoms. The other is particularly preferably a hydrogen atom.
L11及びL12は、それぞれ独立的に、-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-又は単結合を表すが、-OCH2-、-CH2O-、-CH2CH2-又は単結合であることが好ましく、酸素原子を含まない構造である-CH2CH2-又は単結合であることがより好ましく、単結合であることが更に好ましい。
L 11 and L 12 are each independently —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond represents a, -OCH 2 -, - CH 2 O -, - it is or a single bond - CH 2 CH 2 - that or a single bond preferably, -CH 2 CH 2 is a structure containing no oxygen atom Is more preferable, and a single bond is more preferable.
m11及びm12は、それぞれ独立的に、0又は1を表し、m11+m12が1又は2を表すが、m11+m12が1であることが好ましい。
m 11 and m 12 each independently represent 0 or 1, and m 11 + m 12 represents 1 or 2, but m 11 + m 12 is preferably 1.
一般式(I)で表される化合物は1種又は2種以上を含有するが、1種から5種含有することが好ましく、1種から3種含有することが更に好ましく、1種含有することが特に好ましい。また、その含有量は組成物に対して、0.1質量%から50質量%であるが、0.1質量%から10質量%であることが好ましく、0.3質量%から8質量%の範囲であることが更に好ましく、0.5質量%から5質量%であることが特に好ましく、0.5質量%から3質量%であっても良く、0.5質量%から2質量%であっても良い。
Although the compound represented by general formula (I) contains 1 type, or 2 or more types, it is preferable to contain 1 type to 5 types, it is more preferable to contain 1 type to 3 types, and 1 type is contained. Is particularly preferred. Further, the content thereof is 0.1% to 50% by mass, preferably 0.1% to 10% by mass, and 0.3% to 8% by mass with respect to the composition. The range is more preferably 0.5% by mass to 5% by mass, 0.5% to 3% by mass, and 0.5% to 2% by mass. May be.
更に詳述すると、一般式(I)で表される化合物は、一般式(N-002)から一般式(N-079)で表される化合物であることが好ましい。
More specifically, the compound represented by general formula (I) is preferably a compound represented by general formula (N-002) to general formula (N-079).
一般式(N-002)から一般式(N-079)で表される化合物の中では、一般式(N-030)から一般式(N-042)で表される化合物、一般式(N-058)から一般式(N-062)で表される化合物、一般式(N-071)から一般式(N-074)で表される化合物、一般式(N-077)から一般式(N-079)で表される化合物であることが好ましく、一般式(N-030)から一般式(N-035)で表される化合物であることが更に好ましい。
Among the compounds represented by the general formula (N-002) to the general formula (N-079), the compounds represented by the general formula (N-030) to the general formula (N-042), 058) to general formula (N-062), general formula (N-071) to general formula (N-074), general formula (N-077) to general formula (N— 079) is preferred, and compounds represented by general formula (N-030) to general formula (N-035) are more preferred.
本発明の組成物は、重合性化合物を1種又は2種以上含有する。
The composition of the present invention contains one or more polymerizable compounds.
該重合性化合物は、メソゲン骨格を有するものが好ましく、具体的には、一般式(M)
The polymerizable compound preferably has a mesogenic skeleton, specifically, the general formula (M)
で表される化合物が挙げられる。
The compound represented by these is mentioned.
式中、R201は、P201-Sp201-を表し、R202は、P202-Sp202-を表す。
P201及びP202はそれぞれ独立的に、式(R-1)から式(R-15) Wherein, R 201 is, P 201 -Sp 201 - represents, R 202 is, P 202 -Sp 202 - represents a.
P 201 and P 202 each independently represent formula (R-1) to formula (R-15)
P201及びP202はそれぞれ独立的に、式(R-1)から式(R-15) Wherein, R 201 is, P 201 -Sp 201 - represents, R 202 is, P 202 -Sp 202 - represents a.
P 201 and P 202 each independently represent formula (R-1) to formula (R-15)
のいずれかを表すが、式(R-1)又は式(R-2)であることが好ましい。P201及びP202は、同じであっても異なっていても良い。
Is preferably represented by formula (R-1) or formula (R-2). P 201 and P 202 may be the same or different.
Sp201及びSp202は、それぞれ独立的に単結合又は炭素数1~15のアルキレン基を表し、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-、-OCO-又は-COO-で置換されてよいが、それぞれ独立的に単結合又は、ひとつのメチレンが-O-、-OCO-又は-COO-で置換されてよい炭素数1~7のアルキレン基であることが好ましく、PSAモードの液晶表示素子においては少なくとも一方が単結合であることが好ましく、一方が単結合でもう一方が炭素原子数1~4のアルキレン基又は-O-(CH2)s-であることが好ましく、この場合、炭素原子数1~4のアルキレン基が好ましく、sは1~4が好ましい。また、Sp201及びSp202は共に単結合であることも好ましい。
Sp 201 and Sp 202 each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more —CH 2 — in the alkylene group is not directly adjacent to an oxygen atom. May be substituted with —O—, —OCO— or —COO—, but each independently represents a single bond or a carbon number in which one methylene may be substituted with —O—, —OCO— or —COO—. In the PSA mode liquid crystal display element, at least one is preferably a single bond, one is a single bond and the other is an alkylene group having 1 to 4 carbon atoms, or — O— (CH 2 ) s — is preferable. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4. It is also preferable that both Sp 201 and Sp 202 are single bonds.
M201、M202及びM203は、それぞれ独立的にフェニル基、1,4-フェニレン基、ベンゼン-1,2,4-トリイル基、ベンゼン-1,2,4,6-テトライル基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフチル基、ナフタレン-2,6-ジイル基、インダン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基又は1,3-ジオキサン-2,5-ジイル基を表し、基は無置換であるか又は炭素原子数1~12のアルキル基、炭素原子数1~12のアルコキシル基、ハロゲン、シアノ基又はニトロ基で置換されていても良いが、それぞれ独立的に、無置換又は、炭素原子数1~3のアルキル基あるいはハロゲンに置換されている、1,4-フェニレン基、ベンゼン-1,2,4-トリイル基、ベンゼン-1,2,4,6-テトライル基、1,4-シクロヘキシレン基、ナフタレン-2,6-ジイル基、又は1,3-ジオキサン-2,5-ジイル基であることが好ましく、無置換又は炭素原子数1~3のアルキル基あるいはハロゲンに置換されている1,4-フェニレン基、ベンゼン-1,2,4-トリイル基、ベンゼン-1,2,4,6-テトライル基又はナフタレン-2,6-ジイル基であることが更に好ましい。
M 201 , M 202 and M 203 are each independently a phenyl group, 1,4-phenylene group, benzene-1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1, 4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, the group being unsubstituted or an alkyl group having 1 to 12 carbon atoms, 1 carbon atom May be substituted with an alkoxyl group of ˜12, halogen, cyano group or nitro group, but each independently is unsubstituted or substituted with an alkyl group of 1 to 3 carbon atoms or halogen, 4- Phenylene group, benzene-1,2,4-triyl group, benzene-1,2,4,6-tetrayl group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, or 1,3-dioxane -2,5-diyl group, 1,4-phenylene group, benzene-1,2,4-triyl group which is unsubstituted or substituted by alkyl group having 1 to 3 carbon atoms or halogen, More preferred is a benzene-1,2,4,6-tetrayl group or a naphthalene-2,6-diyl group.
Z201及びZ202は、それぞれ独立的に-O-、-S-、-CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRa-、-NRa-CO-、-SCH2-、-CH2S-、-CH=CRa-COO-、-CH=CRa-OCO-、-COO-CRa=CH-、-OCO-CRa=CH-、-COO-CRa=CH-COO-、-COO-CRa=CH-OCO-、-OCO-CRa=CH-COO-、-OCO-CRa=CH-OCO-、-(CH2)z-C(=O)-O-、-(CH2)z-O-(C=O)-、-O-(C=O)-(CH2)z-、-(C=O)-O-(CH2)z-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、C≡C-又は単結合(式中、Raはそれぞれ独立して水素原子又は炭素原子数1~4のアルキル基を表し、前記式中、zは1~4の整数を表す。)を表すが、-COO-、-OCO-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-C≡C-又は単結合が好ましく、-COO-、-OCO-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-又は単結合が更に好ましい。
Z 201 and Z 202 are each independently —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —OCOOCH 2 —, —CH 2 OCOO—, —OCH 2 CH 2 O—, —CO—NR a —, —NR a —CO—, —SCH 2 —, —CH 2 S—, —CH = CR a -COO-, -CH = CR a -OCO-, -COO-CR a = CH-, -OCO-CR a = CH-, -COO-CR a = CH-COO-, -COO-CR a = CH-OCO -, - OCO -CR a = CH-COO -, - OCO-CR a = CH-OCO -, - (CH 2) z -C (= O) -O -, - (CH 2) z —O— (C═O) —, —O— (C═O) — (CH 2 ) z—, — (C═O) —O— ( CH 2 ) z—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —CF 2 —, —CF 2 O—, —OCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, C≡C— or a single bond (wherein R a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, In the above formula, z represents an integer of 1 to 4, and represents —COO—, —OCO—, —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—, —C≡C— Or a single bond is preferred, —COO—, —OCO—, —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 -Or a single bond is more preferred.
n201、n202及びn203は、それぞれ独立的に0から3の整数を表し、n201とn203の総数は2以上であるが、n202は、0、1又は2であることが好ましく、0又は1であることが更に好ましい。n201及びn203は、それぞれ独立的に0、1又は2であることが好ましく、1又は2であることが更に好ましく、n201とn203の総数は、2又は3が好ましい。
n 201 , n 202 and n 203 each independently represents an integer of 0 to 3, and the total number of n 201 and n 203 is 2 or more, but n 202 is preferably 0, 1 or 2 0 or 1 is more preferable. n 201 and n 203 are each independently preferably 0, 1 or 2, more preferably 1 or 2, and the total number of n 201 and n 203 is preferably 2 or 3.
複数する存在するP201、P202、Sp201、Sp202、Z201及びM202は同一であっても良く異なっていても良い。
A plurality of existing P 201 , P 202 , Sp 201 , Sp 202 , Z 201, and M 202 may be the same or different.
本発明の組成物は、一般式(M)で表される重合性化合物を少なくとも1種含有するが、1種~5種含有することが好ましく、1種~3種含有することが更に好ましい。一般式(M)で表される重合性化合物の含有量が少ない場合、重合性化合物を反応させて製造した液晶表示素子において液晶組成物に対する配向規制力が弱くなる。逆に、一般式(M)で表される重合性化合物の含有量が多すぎる場合、重合性化合物の重合時の必要エネルギーが上昇し、重合せず残存してしまう重合性化合物の量が増加し、残存する重合性化合物が表示不良の原因となるため、その含有量は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。
The composition of the present invention contains at least one polymerizable compound represented by formula (M), preferably 1 to 5 types, more preferably 1 to 3 types. When there is little content of the polymeric compound represented by general formula (M), in the liquid crystal display element manufactured by making a polymeric compound react, the orientation control power with respect to a liquid-crystal composition becomes weak. On the contrary, when the content of the polymerizable compound represented by the general formula (M) is too large, the energy required for the polymerization of the polymerizable compound increases, and the amount of the polymerizable compound that remains without being polymerized increases. In addition, since the remaining polymerizable compound causes display defects, the content is preferably 0.01 to 2.00% by mass, and more preferably 0.05 to 1.00% by mass. 0.10 to 0.50% by mass is particularly preferable.
更に具体的には、一般式(M)においてn201及びn203が1の場合、Sp201及びSp202の間の環構造は、式(XXa-1)から式(XXa-5)であることが好ましく、式(XXa-1)から式(XXa-3)であることが更に好ましく、式(XXa-1)又は式(XXa-2)であることが特に好ましい。但し、式の両端はSp201又はSp202に結合するものとする。
More specifically, when n 201 and n 203 are 1 in the general formula (M), the ring structure between Sp 201 and Sp 202 is the formula (XXa-1) to the formula (XXa-5). Are more preferable, 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. However, both ends of the equation shall be connected to Sp 201 or Sp 202 .
これらの骨格を含む一般式(M)で表される重合性化合物は重合後の配向規制力がPSAモードの液晶表示素子に好ましい。
The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
一般式(M)の具体的な化合物として、式(XX-1)から一般式(XX-10)で表される化合物が好ましく、式(XX-1)から式(XX-4)が更に好ましい。
As specific compounds of general formula (M), compounds represented by general formula (XX-1) to general formula (XX-10) are preferred, and formulas (XX-1) to (XX-4) are more preferred. .
式中、Spxxは炭素原子数1~8のアルキレン基又は-O-(CH2)s-(式中、sは2から7の整数を表し、酸素原子は環に結合するものとする。)を表す。
In the formula, 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. ).
式中のフェニル基中の水素原子は、更に、-F、-Cl、-CF3、-CH3、式(R-1)から式(R-15)のいずれかによって置換されていても良い。
The hydrogen atom in the phenyl group in the formula may be further substituted by —F, —Cl, —CF 3 , —CH 3 , or any one of formulas (R-1) to (R-15). .
一般式(M)においてn202が1の場合、例えば、式(M31)から式(M52)のような重合性化合物が好ましい。
In the general formula (M), when n 202 is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M52) is preferable.
式中のフェニル基及びナフタレン基中の水素原子は、更に、-F、-Cl、-CF3、-CH3、式(R-1)から式(R-15)のいずれかによって置換されていても良い。
The hydrogen atom in the phenyl group and naphthalene group in the formula is further substituted with —F, —Cl, —CF 3 , —CH 3 , or any one of formulas (R-1) to (R-15). May be.
これらの骨格を含む一般式(M)で表される重合性化合物は重合後の配向規制力がPSAモードの液晶表示素子に好ましい。
The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
一般式(M)においてn201が1、n202が1、かつn203が2である場合、例えば、式(M301)から式(M320)のような重合性化合物が好ましい。
In the general formula (M), when n 201 is 1, n 202 is 1, and n 203 is 2, for example, a polymerizable compound such as formula (M301) to formula (M320) is preferable.
式中のフェニル基及びナフタレン基中の水素原子は、更に、-F、-Cl、-CF3、-CH3によって置換されていても良い。
The hydrogen atom in the phenyl group and naphthalene group in the formula may be further substituted with —F, —Cl, —CF 3 , —CH 3 .
これらの骨格を含む一般式(M)で表される重合性化合物は重合後の配向規制力がPSAモードの液晶表示素子に好ましい。
The polymerizable compound represented by the general formula (M) containing these skeletons is preferable for a PSA mode liquid crystal display element because of its orientation regulating force after polymerization.
本発明の組成物は、更に、一般式(N-1)
The composition of the present invention further has the general formula (N-1)
(式中、RN11及びRN12は、それぞれ独立的に炭素原子数1から10のアルキル基、炭素原子数1から10のアルコキシル基、炭素原子数2から10のアルケニル基又は炭素原子数2から10のアルケニルオキシ基を表し、RN11及びRN12中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-はそれぞれ独立的に-O-及び/又は-S-に置換されても良く、また、RN11及びRN12中に存在する1個又は2個以上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に置換されても良く、AN11は、1,4-シクロヘキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は-O-に置き換えられてもよい。)又は1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられてもよい。)を表し、nN11は、1又は2を表し、ZN11は、-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-又は単結合を表し、複数する存在するAN11は同一であっても良く異なっていても良い。)で表される化合物を含有することが好ましい。
(Wherein R N11 and R N12 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 carbon atoms) represents 10 alkenyloxy group, R N11 and R N12 in present in one -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O- and / or -S And one or two or more hydrogen atoms present in R N11 and R N12 may each independently be substituted with a fluorine atom or a chlorine atom, and A N11 represents 1 , 4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 -. may be replaced by -O-) or 1,4 Phenylene group (in this group . Present one -CH = or nonadjacent two or more -CH = can which may be replaced by -N =) represents, n N11 represents 1 or 2, Z N11 is - OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond, and a plurality of existing A N11 are the same. Or may be different.) It is preferable to contain a compound represented by:
この場合、一般式(N-1)で表される化合物は1種又は2種以上含有するが、1種から10種含有することが好ましく、1種から6種含有することが更に好ましく、その含有量は組成物に対して10質量%から90質量%であることが好ましく、10質量%から70質量%であることが更に好ましく、20質量%から50質量%であることが特に好ましい。
In this case, the compound represented by the general formula (N-1) is contained in one or more kinds, preferably 1 to 10 kinds, more preferably 1 to 6 kinds, The content is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 20% by mass to 50% by mass with respect to the composition.
一般式(N-1)の式中、RN11及びRN12は、それぞれ独立的に炭素原子数1から5のアルキル基、炭素原子数1から5のアルコキシル基、炭素原子数2から5のアルケニル基又は炭素原子数2から5のアルケニルオキシ基であることが好ましく、RN11が炭素原子数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り、RN12が炭素原子数1から5のアルキル基又は炭素原子数1から5のアルコキシル基であることが更に好ましい。
In the general formula (N-1), R N11 and R N12 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. Or an alkenyloxy group having 2 to 5 carbon atoms, R N11 is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N12 is 1 carbon atom. And more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group having 1 to 5 carbon atoms.
AN11は、1,4-シクロヘキシレン基又は1,4-フェニレン基が好ましい。
A N11 is 1,4-cyclohexylene group or 1,4-phenylene group is preferred.
ZN11は、-CH2O-、-CH2CH2-又は単結合であることが好ましく、-CH2O-又は単結合であることが更に好ましい。
Z N11 is, -CH 2 O -, - CH 2 CH 2 - or preferably a single bond, more preferably -CH 2 O-or a single bond.
一般式(N-1)で表される化合物は、具体的には、一般式(N-1-1)~一般式(N-1-4)、一般式(N-1-10)又は一般式(N-1-11)
Specifically, the compound represented by the general formula (N-1) is represented by the general formula (N-1-1) to the general formula (N-1-4), the general formula (N-1-10) or the general formula. Formula (N-1-11)
(式中、RN111及びRN112はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)
( Wherein , R N111 and R N112 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
(式中、RN121及びRN122はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)
(In the formula, R N121 and R N122 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
(式中、RN131及びRN132はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)
( Wherein , R N131 and R N132 each independently represent the same meaning as R N11 and R N12 in formula (N-1)).
(式中、RN141及びRN142はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)
(Wherein, R N141 and R N142 each independently represents the same meaning as R N11 and R N12 in the general formula (N-1).)
(式中、RN1101及びRN1102はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)
(In the formula, R N1101 and R N1102 each independently represent the same meaning as R N11 and R N12 in formula (N-1).)
(式中、RN1111及びRN1112はそれぞれ独立して、一般式(N-1)におけるRN11及びRN12と同じ意味を表す。)で表される化合物であることが好ましい。
( Wherein , R N1111 and R N1112 each independently represent the same meaning as R N11 and R N12 in formula (N-1)) are preferable.
一般式(N-1)で表される化合物の内、一般式(N-1-1)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量を少なめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-1)で表される化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、33%であり、35%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、50%であり、40%であり、38%であり、35%であり、33%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、10%であり、8%であり、7%であり、6%であり、5%であり、3%である。
一般式(N-1-1)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。 The lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
The compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
一般式(N-1-1)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。 The lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
The compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量を少なめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-1)で表される化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、33%であり、35%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、50%であり、40%であり、38%であり、35%であり、33%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、10%であり、8%であり、7%であり、6%であり、5%であり、3%である。
The lower limit of the preferable content of the compound represented by the general formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
一般式(N-1-1)で表される化合物は、具体的には、式(N-1-4.1)から式(N-1-4.14)で表される化合物群から選ばれる化合物であることが好ましく、式(N-4-1.1)~(N-1-1.4)で表される化合物であることが好ましく、式(N-1-1.1)及び式(N-1-1.3)で表される化合物が好ましい。
The compound represented by the general formula (N-1-1) is specifically selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14). The compounds represented by formulas (N-4-1.1) to (N-1-1.4) are preferred, and the compounds represented by formulas (N-1-1.1) and A compound represented by the formula (N-1-1.3) is preferred.
式(N-1-1.1)~(N-1-1.14)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、33%であり、35%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、50%であり、40%であり、38%であり、35%であり、33%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、10%であり、8%であり、7%であり、6%であり、5%であり、3%である。
The compounds represented by formulas (N-1-1.1) to (N-1-1.14) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, 20%, 23% 25% 27% 30% 33% 35% The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
一般式(N-1)で表される化合物の内、一般式(N-1-2)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を少なめに設定すると効果が高く、TNIを重視する場合は含有量を多めに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-2)で表される化合物の好ましい含有量の下限値は、5%であり、7%であり、10%であり、13%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、33%であり、35%であり、37%であり、40%であり、42%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、50%であり、48%であり、45%であり、43%であり、40%であり、38%であり、35%であり、33%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、10%であり、8%であり、7%であり、6%であり、5%である。
The lower limit of the preferable content of the compound represented by the general formula (N-1-2) with respect to the total amount of the composition of the present invention is 5%, 7%, 10%, %, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37 %, 40%, and 42%. The upper limit of the preferable content is 50%, 48%, 45%, 43%, 40%, 38%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10% %, 8%, 7%, 6%, 5%.
さらに、一般式(N-1-2)で表される化合物は、具体的には、式(N-1-2.1)から式(N-1-2.13)で表される化合物群から選ばれる化合物であることが好ましく、式(N-1-2.3)から式(N-1-2.7)、式(N-1-2.10)、式(N-1-2.11)及び式(N-1-2.13)で表される化合物であることが好ましく、Δεの改良を重視する場合には式(N-1-2.3)から式(N-1-2.7)で表される化合物が好ましく、TNIの改良を重視する場合には式(N-1-2.10)、式(N-1-2.11)及び式(N-1-2.13)で表される化合物であることが好ましい。
Further, the compound represented by the general formula (N-1-2) is specifically a compound group represented by the formula (N-1-2.1) to the formula (N-1-2.13). Preferably, the compound is selected from the formulas (N-1-2.3) to (N-1-2.7), (N-1-2.10), and (N-1-2). .11) and the compound represented by formula (N-1-2.13). When importance is attached to the improvement of Δε, the compound represented by formula (N-1-2.3) to formula (N-1 is preferably a compound represented by -2.7), formula (N-1-2.10 in the case of emphasizing improvements in T NI), the formula (N-1-2.11) and formula (N-1 -2.13) is preferred.
式(N-1-2.1)から式(N-1-2.13)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%であり、23%であり、25%であり、27%であり、30%であり、33%であり、35%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、50%であり、40%であり、38%であり、35%であり、33%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、10%であり、8%であり、7%であり、6%であり、5%であり、3%である。
The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23 %, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 28% with respect to the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% %, 5%, 3%.
一般式(N-1)で表される化合物の内、一般式(N-1-3)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量をおおめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-3)で表される化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The lower limit of the preferable content of the compound represented by the general formula (N-1-3) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
さらに、一般式(N-1-3)で表される化合物は、具体的には、式(N-1-3.1)から式(N-1-3.11)で表される化合物群から選ばれる化合物であることが好ましく、式(N-1-3.1)~(N-1-3.7)で表される化合物であることが好ましく、式(N-1-3.1)、式(N-1-3.2)、式(N-1-3.3)、式(N-1-3.4)及び式(N-1-3.6)で表される化合物が好ましい。
Further, the compound represented by the general formula (N-1-3) is specifically a group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11). A compound selected from the group consisting of formulas (N-1-3.1) to (N-1-3.7) is preferable, and a compound represented by formula (N-1-3.1) is preferable. ), Formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compound represented by formula (N-1-3.6) Is preferred.
式(N-1-3.1)~式(N-1-3.4)及び式(N-1-3.6)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、式(N-1-3.1)及び式(N-1-3.2)の組み合わせ、式(N-1-3.3)、式(N-1-3.4)及び式(N-1-3.6)から選ばれる2種又は3種の組み合わせが好ましい。本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15%, 17%, 20% %. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
一般式(N-1)で表される化合物の内、一般式(N-1-4)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量を少なめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-4)で表される化合物の好ましい含有量の下限値は、3%であり、5%であり、7%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、11%であり、10%であり、8%である。
The lower limit of the preferable content of the compound represented by the general formula (N-1-4) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 10% %, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.
一般式(N-1-4)で表される化合物は、具体的には、式(N-1-4.1)から式(N-1-4.14)で表される化合物群から選ばれる化合物であることが好ましく、式(N-1-4.1)~(N-1-4.4)で表される化合物であることが好ましく、式(N-1-4.1)及び式(N-1-4.2)で表される化合物が好ましい。
The compound represented by the general formula (N-1-4) is specifically selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14) The compounds represented by formulas (N-1-4.1) to (N-1-4.4) are preferred, and the compounds represented by formulas (N-1-4.1) and A compound represented by the formula (N-1-4.2) is preferable.
式(N-1-4.1)~(N-1-4.4)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、3%であり、5%であり、7%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%であり、11%であり、10%であり、8%である。
The compounds represented by formulas (N-1-4.1) to (N-1-4.4) can be used singly or in combination, but the compounds of the present invention The lower limit of the preferable content of these compounds alone or with respect to the total amount is 3%, 5%, 7%, 10%, 13%, 15%, 17% And 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, and 8%.
一般式(N-1)で表される化合物の内、一般式(N-1-10)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Of the compounds represented by the general formula (N-1), the compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. it can. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量をおおめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-10)で表される化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The lower limit of the preferable content of the compound represented by the general formula (N-1-10) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
さらに、一般式(N-1-10)で表される化合物は、具体的には、式(N-1-10.1)から式(N-1-10.15)で表される化合物群から選ばれる化合物であることが好ましく、式(N-1-10.1)~(N-1-10.5)で表される化合物であることが好ましく、式(N-1-10.1)及び式(N-1-10.2)で表される化合物が好ましい。
Further, the compound represented by the general formula (N-1-10) is specifically a group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.15). A compound selected from the group consisting of formulas (N-1-10.1) to (N-1-10.5) is preferable. ) And a compound represented by the formula (N-1-10.2) are preferable.
式(N-1-10.1)及び式(N-1-10.2)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
一般式(N-1-11)で表される化合物の内、一般式(N-1-11)で表される化合物は単独で使用することもできるが、2以上の化合物を組み合わせて使用することもできる。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、低温での溶解性、転移温度、電気的な信頼性、複屈折率などの求められる性能に応じて適宜組み合わせて使用する。使用する化合物の種類は、例えば本発明の一つの実施形態としては1種類であり、2種類であり、3種類であり、4種類であり、5種類以上である。
Among the compounds represented by the general formula (N-1-11), the compound represented by the general formula (N-1-11) can be used alone, but two or more compounds are used in combination. You can also. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.
Δεの改善を重視する場合には含有量を高めに設定することが好ましく、低温での溶解性を重視する場合は含有量を多めに設定すると効果が高く、TNIを重視する場合は含有量をおおめに設定すると効果が高い。さらに、滴下痕や焼き付き特性を改良する場合は、含有量の範囲を中間に設定することが好ましい。
It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.
本発明の組成物の総量に対しての一般式(N-1-11)で表される化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The lower limit of the preferred content of the compound represented by formula (N-1-11) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% %, 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.
さらに、一般式(N-1-11)で表される化合物は、具体的には、式(N-1-11.1)から式(N-1-11.15)で表される化合物群から選ばれる化合物であることが好ましく、式(N-1-11.1)~(N-1-11.15)で表される化合物であることが好ましく、式(N-1-11.2及び式(N-1-11.4)で表される化合物が好ましい。
Further, the compound represented by the general formula (N-1-11) specifically includes a compound group represented by the formula (N-1-11.1) to the formula (N-1-11.15). The compound is preferably a compound selected from formulas (N-1-11.1) to (N-1-11.15), and preferably represented by formula (N-1-111.2). And a compound represented by formula (N-1-11.4) is preferable.
式(N-1-11.2及び式(N-1-11.4)で表される化合物は単独で使用することも、組み合わせて使用することも可能であるが、本発明の組成物の総量に対しての単独又はこれら化合物の好ましい含有量の下限値は、5%であり、10%であり、13%であり、15%であり、17%であり、20%である。好ましい含有量の上限値は、本発明の組成物の総量に対して、35%であり、30%であり、28%であり、25%であり、23%であり、20%であり、18%であり、15%であり、13%である。
The compounds represented by the formula (N-1-11.2 and the formula (N-1-11.4) can be used alone or in combination. The lower limit of the preferable content of these compounds alone or with respect to the total amount is 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the amount is 35%, 30%, 28%, 25%, 23%, 20%, 18% with respect to the total amount of the composition of the present invention. Yes, 15%, 13%.
本発明の組成物は、誘電率異方性(Δε)がほぼ0の化合物として、一般式(L-1)~一般式(L-6)
The composition of the present invention has a general formula (L-1) to a general formula (L-6) as a compound having a dielectric anisotropy (Δε) of almost 0.
(式中、RL11~RL62はお互い独立して炭素原子数1から10のアルキル基又は炭素原子数2から10のアルケニル基を表し、XL61及びXL62はお互い独立して水素原子又はフッ素原子を表すが、少なくとも一方は水素原子を表す。)で表される化合物群から選ばれる化合物を含有することが好ましい。
(Wherein R L11 to R L62 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and X L61 and X L62 each independently represent a hydrogen atom or fluorine It is preferable to contain a compound selected from the group consisting of compounds represented by the formula:
一般式(L-1)~一般式(L-6)で表される化合物群から選ばれる化合物を1種又は2種以上含有するが、1種から10種が好ましく、1種から6種が更に好ましく、その含有量は10から90質量%であるが、20質量%から70質量%であることが更に好ましく、30質量%から60質量%であることが特に好ましい。
Contains one or more compounds selected from the compound group represented by formula (L-1) to formula (L-6), preferably 1 to 10 species, preferably 1 to 6 species. More preferably, the content is 10 to 90% by mass, more preferably 20% to 70% by mass, and particularly preferably 30% to 60% by mass.
一般式(L-1)~一般式(L-6)で表される化合物群から選ばれる化合物の内、一般式(L-1)、(L-3)、(L-4)及び(L-6)で表される化合物が好ましく、一般式(L-1)で表される化合物が特に好ましい。
Of the compounds selected from the group of compounds represented by formulas (L-1) to (L-6), formulas (L-1), (L-3), (L-4) and (L The compound represented by -6) is preferable, and the compound represented by the general formula (L-1) is particularly preferable.
本発明の組成物は、一般式(I)、一般式(M)及び一般式(N-1)の化合物を同時に含有することが好ましく、一般式(I)、一般式(M)、一般式(N-1)及び一般式(L-1)の化合物を同時に含有することが更に好ましい。
The composition of the present invention preferably contains the compounds of general formula (I), general formula (M) and general formula (N-1) at the same time, and includes general formula (I), general formula (M) and general formula (N-1). More preferably, the compound of (N-1) and the general formula (L-1) are simultaneously contained.
本発明の組成物は、一般式(I)で表される化合物、一般式(M)で表される化合物、一般式(N-1)で表される化合物及び一般式(L-1)~一般式(L-6)で表される化合物群から選ばれる化合物の総計が85質量%から100質量%であることが好ましく、90質量%から100質量%であることがより好ましく、95質量%から100質量%であることが更に好ましく、98質量%から100質量%であることが更に好ましい。
The composition of the present invention comprises a compound represented by general formula (I), a compound represented by general formula (M), a compound represented by general formula (N-1), and general formula (L-1) to The total amount of compounds selected from the compound group represented by formula (L-6) is preferably 85% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and 95% by mass. To 100% by mass, and more preferably 98% to 100% by mass.
本発明の組成物に含まれる液晶化合物において、焼き付きや表示ムラ等の表示不良を抑制するため、又は、全く発生させないためには、アルケニル基を有する化合物を12質量%以下にすることが好ましく、全く含まないことがより好ましく、また、液晶化合物の中のシクロヘキサン環又はベンゼン環はフッ素原子で置換されていても良いが、塩素原子で置換されていることは好ましくない。
In the liquid crystal compound contained in the composition of the present invention, in order to suppress display defects such as image sticking and display unevenness, or in order not to generate at all, the compound having an alkenyl group is preferably 12% by mass or less, More preferably, it is not contained at all, and the cyclohexane ring or benzene ring in the liquid crystal compound may be substituted with a fluorine atom, but is not preferably substituted with a chlorine atom.
本発明の組成物は、25℃における誘電率異方性(Δε)が-2.0から-8.0であるが、-2.0から-6.0が好ましく、-2.0から-5.0がより好ましく、-2.5から-4.0が更に好ましい。
The composition of the present invention has a dielectric anisotropy (Δε) at 25 ° C. of −2.0 to −8.0, preferably −2.0 to −6.0, and −2.0 to − 5.0 is more preferable, and −2.5 to −4.0 is even more preferable.
本発明の組成物は、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0.125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。
The composition of the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. preferable. More specifically, when it corresponds to a thin cell gap, it is preferably 0.10 to 0.125, and when it corresponds to a thick cell gap, it is preferably 0.08 to 0.10.
本発明の組成物は、20℃における粘度(η)が10から30mPa・sであるが、10から25mPa・sであることがより好ましく、10から22mPa・sであることが特に好ましい。
The composition of the present invention has a viscosity (η) at 20 ° C. of 10 to 30 mPa · s, more preferably 10 to 25 mPa · s, and particularly preferably 10 to 22 mPa · s.
本発明の組成物は、20℃における回転粘性(γ1)が60から130mPa・sであるが、60から110mPa・sであることがより好ましく、60から100mPa・sであることが特に好ましい。
The composition of the present invention has a rotational viscosity (γ 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.
本発明の組成物は、ネマチック相-等方性液体相転移温度(Tni)が60℃から120℃であるが、68℃から100℃がより好ましく、68℃から85℃が特に好ましい。
The composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T ni ) of 60 ° C to 120 ° C, more preferably 68 ° C to 100 ° C, and particularly preferably 68 ° C to 85 ° C.
本発明の組成物は、重合開始剤が存在しない場合でも重合は進行するが、重合を促進するために重合開始剤を含有しても良い。重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド類等が挙げられる。
In the composition of the present invention, the polymerization proceeds even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to accelerate the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
本発明の組成物は、更に、一般式(Q)で表される化合物を含有しても良い。
The composition of the present invention may further contain a compound represented by the general formula (Q).
式中、RQは、炭素原子数1から22の直鎖アルキル基又は分岐鎖アルキル基を表し、基中の1つ又は非隣接の2つ以上のCH2基は、-O-、-CH=CH-、-CO-、-OCO-、-COO-、-C≡C-、-CF2O-、-OCF2-によって置換されていても良い。
In the formula, R Q represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or two or more non-adjacent CH 2 groups in the group are —O—, —CH ═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF 2 O—, —OCF 2 — may be substituted.
MQは、トランス-1,4-シクロへキシレン基、1,4-フェニレン基又は単結合を表す。
MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond.
一般式(Q)で表される化合物は、具体的には、下記の一般式(Q-a)から一般式(Q-d)で表される化合物が好ましい。
Specifically, the compound represented by the general formula (Q) is preferably a compound represented by the following general formula (Qa) to general formula (Qd).
式中、RQ1は、炭素原子数1から10の直鎖アルキル基又は分岐鎖アルキル基が好ましい。
In the formula, R Q1 is preferably a linear alkyl group or a branched alkyl group having 1 to 10 carbon atoms.
RQ2は、炭素原子数1から20の直鎖アルキル基又は分岐鎖アルキル基が好ましい。
R Q2 is preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group.
RQ3は、炭素原子数1から8の直鎖アルキル基、分岐鎖アルキル基、直鎖アルコキシ基又は分岐鎖アルコキシ基が好ましい。
R Q3 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group, a linear alkoxy group, or a branched alkoxy group.
LQは炭素原子数1から8の直鎖アルキレン基又は分岐鎖アルキレン基が好ましい。
L Q is preferably a linear alkylene group or branched alkylene group having 1 to 8 carbon atoms.
一般式(Q-a)から一般式(Q-d)で表される化合物中、一般式(Q-c)及び一般式(Q-d)で表される化合物が更に好ましい。
Of the compounds represented by general formula (Qa) to general formula (Qd), compounds represented by general formula (Qc) and general formula (Qd) are more preferable.
本発明の組成物は、一般式(Q)で表される化合物を1種又は2種以上含有することが好ましく、1種から5種含有することが好ましく、1種から3種含有することが更に好ましく、1種含有することが更に好ましい。また、その含有量は0.001質量%から1質量%であることが好ましく、0.001質量%から0.1質量%が更に好ましく、0.001質量%から0.05質量%が更に好ましい。
The composition of the present invention preferably contains one or more compounds represented by the general formula (Q), preferably contains 1 to 5 types, and preferably contains 1 to 3 types. More preferably, it is more preferable to contain 1 type. Further, the content is preferably 0.001% by mass to 1% by mass, more preferably 0.001% by mass to 0.1% by mass, and further preferably 0.001% by mass to 0.05% by mass. .
また、保存安定性を向上させるために、安定剤を添加しても良い。使用できる安定剤としては、例えば、ヒドロキノン類、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β-ナフチルアミン類、β-ナフトール類、ニトロソ化合物等が挙げられる。
In addition, a stabilizer may be added to improve storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done.
本発明の組成物は、上述の化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶、酸化防止剤、紫外線吸収剤、重合性モノマーなどを含有しても良い。
The composition of the present invention may contain a normal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, polymerizable monomer and the like in addition to the above-mentioned compounds.
本発明の組成物は、液晶表示素子に有用であり、特にアクティブマトリクス駆動用液晶表示素子に有用であり、PSAモード、PSVAモード、VA-IPSモード又は高分子安定化モード用液晶表示素子に用いることができる。
The composition of the present invention is useful for a liquid crystal display device, particularly useful for a liquid crystal display device for driving an active matrix, and used for a liquid crystal display device for a PSA mode, a PSVA mode, a VA-IPS mode or a polymer stabilization mode. be able to.
本発明の組成物は、これに含まれる重合性化合物が紫外線照射により重合することで液晶配向能が付与され、液晶組成物の複屈折を利用して光の透過光量を制御する液晶表示素子に使用される。液晶表示素子として、AM-LCD(アクティブマトリックス液晶表示素子)及びIPS-LCD(インプレーンスイッチング液晶表示素子)に有用であるが、AM-LCDに特に有用であり、透過型あるいは反射型の液晶表示素子に用いることができる。
The composition of the present invention is a liquid crystal display element in which the polymerizable compound contained therein is polymerized by ultraviolet irradiation to impart liquid crystal alignment ability, and the amount of transmitted light is controlled using the birefringence of the liquid crystal composition. used. As a liquid crystal display element, it is useful for an AM-LCD (active matrix liquid crystal display element) and an IPS-LCD (in-plane switching liquid crystal display element), but is particularly useful for an AM-LCD and is a transmissive or reflective liquid crystal display. It can be used for an element.
液晶表示素子に使用される液晶セルの2枚の基板はガラス又はプラスチックの如き柔軟性をもつ透明な材料を用いることができ、一方はシリコン等の不透明な材料でも良い。透明電極層を有する透明基板は、例えば、ガラス板等の透明基板上にインジウムスズオキシド(ITO)をスパッタリングすることにより得ることができる。
The two substrates of the liquid crystal cell used in the liquid crystal display element 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.
カラーフィルターは、例えば、顔料分散法、印刷法、電着法又は、染色法等によって作成することができる。顔料分散法によるカラーフィルターの作成方法を一例に説明すると、カラーフィルター用の硬化性着色組成物を、該透明基板上に塗布し、パターニング処理を施し、そして加熱又は光照射により硬化させる。この工程を、赤、緑、青の3色についてそれぞれ行うことで、カラーフィルター用の画素部を作成することができる。その他、該基板上に、TFT、薄膜ダイオード、金属絶縁体金属比抵抗素子等の能動素子を設けた画素電極を設置してもよい。
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. In addition, 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.
前記基板を、透明電極層が内側となるように対向させる。その際、スペーサーを介して、基板の間隔を調整してもよい。このときは、得られる調光層の厚さが1~100μmとなるように調整するのが好ましい。1.5から10μmが更に好ましく、偏光板を使用する場合は、コントラストが最大になるように液晶の屈折率異方性Δnとセル厚dとの積を調整することが好ましい。又、二枚の偏光板がある場合は、各偏光板の偏光軸を調整して視野角やコントラトが良好になるように調整することもできる。更に、視野角を広げるための位相差フィルムも使用することもできる。スペーサーとしては、例えば、ガラス粒子、プラスチック粒子、アルミナ粒子、フォトレジスト材料等が挙げられる。その後、エポキシ系熱硬化性組成物等のシール剤を、液晶注入口を設けた形で該基板にスクリーン印刷し、該基板同士を貼り合わせ、加熱しシール剤を熱硬化させる。
The substrate is opposed so that the transparent electrode layer is on the inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. In this case, it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 μm. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, 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.
2枚の基板間に本発明の組成物を狭持させる方法は、通常の真空注入法又はODF法などを用いることができる。
As a method of sandwiching the composition of the present invention between two substrates, a normal vacuum injection method or an ODF method can be used.
重合性化合物を重合させる方法としては、液晶の良好な配向性能を得るためには、適度な重合速度が望ましいので、紫外線又は電子線等の活性エネルギー線を単一又は併用又は順番に照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、重合性化合物の重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場又は温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、更に活性エネルギー線を照射して重合させるという手段を用いても良い。特に紫外線露光する際には、本発明の組成物に交流電界を印加しながら紫外線露光することが好ましい。印加する交流電界は、周波数10Hzから10kHzの交流が好ましく、周波数60Hzから10kHzがより好ましく、電圧は液晶表示素子の所望のプレチルト角に依存して選ばれる。つまり、印加する電圧により液晶表示素子のプレチルト角を制御することができる。MVAモードの液晶表示素子においては、配向安定性及びコントラストの観点からプレチルト角を80度から89.9度に制御することが好ましい。
As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when polymerizing a polymerizable compound, at least the substrate on the irradiated surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, 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. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the composition of the present invention. 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 MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
照射時の温度は、本発明の組成物の液晶状態が保持される温度範囲内であることが好ましい。室温に近い温度、即ち、典型的には15~35℃で重合させることが好ましい。紫外線を発生させるランプとしては、メタルハライドランプ、高圧水銀ランプ、超高圧水銀ランプ等を用いることができる。また、照射する紫外線の波長としては、液晶組成物の吸収波長域でない波長領域の紫外線を照射することが好ましく、必要に応じて、紫外線をカットして使用することが好ましい。照射する紫外線の強度は、0.1mW/cm2~100W/cm2が好ましく、2mW/cm2~50W/cm2が更に好ましい。照射する紫外線のエネルギー量は、適宜調整することができるが、10mJ/cm2から500J/cm2が好ましく、100mJ/cm2から200J/cm2が更に好ましい。紫外線を照射する際に、強度を変化させても良い。紫外線を照射する時間は照射する紫外線強度により適宜選択されるが、10秒から3600秒が好ましく、10秒から600秒が更に好ましい。
The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically 15 to 35 ° C. As 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. Moreover, as 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 . When irradiating with ultraviolet rays, 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.
以下に実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
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 炭素原子数nの直鎖状のアルキル基
n- CnH2n+1- 炭素原子数nの直鎖状のアルキル基
-On -OCnH2n+1 炭素原子数nの直鎖状のアルコキシル基
nO- CnH2n+1O- 炭素原子数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=CH2
V2- CH2=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH3
(連結基)
-n- -CnH2n-
-nO- -CnH2n-O-
-On- -O-CnH2n-
-COO- -C(=O)-O-
-OCO- -O-C(=O)-
-CF2O- -CF2-O-
-OCF2- -O-CF2-
(環構造) The following abbreviations are used for the description of compounds in the examples.
(Side chain)
-n -C n H 2n + 1 linear alkyl group with n carbon atoms n- C n H 2n + 1 -linear alkyl group with n carbon atoms -On -OC n H 2n + 1 carbon Straight-chain alkoxyl group having n atoms
nO- C n H 2n + 1 O- linear alkoxyl group having n carbon atoms -V -CH = CH 2
V- CH 2 = CH-
-V1 -CH = CH-CH 3
1V- CH 3 -CH = CH-
-2V -CH 2 -CH 2 -CH = CH 2
V2- CH 2 = CH-CH 2 -CH 2-
-2V1 -CH 2 -CH 2 -CH = CH-CH 3
1V2- CH 3 -CH = CH-CH 2 -CH 3
(Linking group)
-n- -C n H 2n-
-nO- -C n H 2n -O-
-On- -OC n H 2n -
-COO- -C (= O) -O-
-OCO- -OC (= O)-
-CF2O- -CF 2 -O-
-OCF2- -O-CF 2-
(Ring structure)
(側鎖)
-n -CnH2n+1 炭素原子数nの直鎖状のアルキル基
n- CnH2n+1- 炭素原子数nの直鎖状のアルキル基
-On -OCnH2n+1 炭素原子数nの直鎖状のアルコキシル基
nO- CnH2n+1O- 炭素原子数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=CH2
V2- CH2=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH3
(連結基)
-n- -CnH2n-
-nO- -CnH2n-O-
-On- -O-CnH2n-
-COO- -C(=O)-O-
-OCO- -O-C(=O)-
-CF2O- -CF2-O-
-OCF2- -O-CF2-
(環構造) The following abbreviations are used for the description of compounds in the examples.
(Side chain)
-n -C n H 2n + 1 linear alkyl group with n carbon atoms n- C n H 2n + 1 -linear alkyl group with n carbon atoms -On -OC n H 2n + 1 carbon Straight-chain alkoxyl group having n atoms
nO- C n H 2n + 1 O- linear alkoxyl group having n carbon atoms -V -CH = CH 2
V- CH 2 = CH-
-V1 -CH = CH-CH 3
1V- CH 3 -CH = CH-
-2V -CH 2 -CH 2 -CH = CH 2
V2- CH 2 = CH-CH 2 -CH 2-
-2V1 -CH 2 -CH 2 -CH = CH-CH 3
1V2- CH 3 -CH = CH-CH 2 -CH 3
(Linking group)
-n- -C n H 2n-
-nO- -C n H 2n -O-
-On- -OC n H 2n -
-COO- -C (= O) -O-
-OCO- -OC (= O)-
-CF2O- -CF 2 -O-
-OCF2- -O-CF 2-
(Ring structure)
実施例中、測定した特性は以下の通りである。
In the examples, the measured characteristics are as follows.
Tni :ネマチック相-等方性液体相転移温度(℃)
Δn :20℃における屈折率異方性
Δε :20℃における誘電率異方性
γ1 :20℃における回転粘性(mPa・s)
K33 :20℃における曲がりの弾性定数
プレチルト角 :UVを20J照射した後のプレチルト角[°]
/AUTRONIC-MELCHERS社・TBA105
VHR・初期 :UV照射前の電圧保持率(1V、60Hz、60℃)
/東陽テクニカ・VHR-1
VHR・UV20J後 :UV20J照射後の電圧保持率(1V、60Hz、60℃)
/東陽テクニカ・VHR-1
(比較例1、比較例2、比較例3及び実施例1)
MLC-A1(比較例1)、MLC-A2(比較例2)、MLC-A3(比較例3)及びMLC-A4(実施例1)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有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。 T ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: Refractive index anisotropy at 20 ° C. Δε: Dielectric anisotropy at 20 ° C. γ 1 : Rotational viscosity at 20 ° C. (mPa · s)
K 33 : Elastic constant of bending at 20 ° C. Pre-tilt angle: Pre-tilt angle after UV irradiation by 20 J [°]
/ AUTRONIC-MELCHERS, TBA105
VHR / Initial: Voltage holding ratio before UV irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
After VHR / UV20J: Voltage holding ratio after UV20J irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
(Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 1)
Polymeric compound-containing liquid crystal compositions of MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were prepared, and their physical property values were prepared. Was measured. Table 1 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
Δn :20℃における屈折率異方性
Δε :20℃における誘電率異方性
γ1 :20℃における回転粘性(mPa・s)
K33 :20℃における曲がりの弾性定数
プレチルト角 :UVを20J照射した後のプレチルト角[°]
/AUTRONIC-MELCHERS社・TBA105
VHR・初期 :UV照射前の電圧保持率(1V、60Hz、60℃)
/東陽テクニカ・VHR-1
VHR・UV20J後 :UV20J照射後の電圧保持率(1V、60Hz、60℃)
/東陽テクニカ・VHR-1
(比較例1、比較例2、比較例3及び実施例1)
MLC-A1(比較例1)、MLC-A2(比較例2)、MLC-A3(比較例3)及びMLC-A4(実施例1)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有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。 T ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: Refractive index anisotropy at 20 ° C. Δε: Dielectric anisotropy at 20 ° C. γ 1 : Rotational viscosity at 20 ° C. (mPa · s)
K 33 : Elastic constant of bending at 20 ° C. Pre-tilt angle: Pre-tilt angle after UV irradiation by 20 J [°]
/ AUTRONIC-MELCHERS, TBA105
VHR / Initial: Voltage holding ratio before UV irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
After VHR / UV20J: Voltage holding ratio after UV20J irradiation (1 V, 60 Hz, 60 ° C.)
/ Toyo Technica VHR-1
(Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 1)
Polymeric compound-containing liquid crystal compositions of MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were prepared, and their physical property values were prepared. Was measured. Table 1 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
次に、MLC-A1(比較例1)、MLC-A2(比較例2)、MLC-A3(比較例3)及びMLC-A4(実施例1)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子は、すべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表2に示す。 Next, MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. It was confirmed that these PSVA liquid crystal display elements all showed an appropriate pretilt angle of about 88 ° and a response speed correlated with a physical property value.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 2.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表2に示す。 Next, MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2), MLC-A3 (Comparative Example 3) and MLC-A4 (Example 1) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. It was confirmed that these PSVA liquid crystal display elements all showed an appropriate pretilt angle of about 88 ° and a response speed correlated with a physical property value.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 2.
実施例1であるMLC-A4は、MLC-A1(比較例1)、MLC-A2(比較例2)およびMLC-A3(比較例3)と比較して、UV照射後のVHRが顕著に高く、かつ、重合性化合物の残存量が少なくなるという、両方の特徴を兼ね備えていることが分かった。更に、これらのPSVA液晶表示素子に焼きつき試験を実施したところ、MLC-A1、MLC-A2およびMLC-A3はUV照射後の低いVHRや残存重合性化合物に起因すると思われる焼きつきを示した。一方で、MLC-A4は焼きつきが全く発生しなかった。以上より、本発明の重合性化合物含有液晶組成物であるLC-A4は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
(比較例4、実施例2、実施例3及び実施例4)
MLC-B1(比較例4)、MLC-B2(実施例2)、MLC-B3(実施例3)及びMLC-B4(実施例4)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表3のとおりであった。 In Example 1, MLC-A4 has a significantly higher VHR after UV irradiation than MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2) and MLC-A3 (Comparative Example 3). In addition, it has been found that both of the characteristics that the remaining amount of the polymerizable compound is reduced are combined. Further, when a burn-in test was performed on these PSVA liquid crystal display elements, MLC-A1, MLC-A2 and MLC-A3 showed a burn-in which is considered to be caused by a low VHR or residual polymerizable compound after UV irradiation. . On the other hand, MLC-A4 did not generate any burn-in. From the above, LC-A4, which is a polymerizable compound-containing liquid crystal composition of the present invention, has excellent UV resistance, a small residual amount of the polymerizable compound, and does not cause display defects such as image sticking. It was found to be a liquid crystal composition-containing liquid crystal composition.
(Comparative Example 4, Example 2, Example 3 and Example 4)
Polymerizable compound-containing liquid crystal compositions of MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were prepared and their physical properties were measured. Was measured. Table 3 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
(比較例4、実施例2、実施例3及び実施例4)
MLC-B1(比較例4)、MLC-B2(実施例2)、MLC-B3(実施例3)及びMLC-B4(実施例4)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表3のとおりであった。 In Example 1, MLC-A4 has a significantly higher VHR after UV irradiation than MLC-A1 (Comparative Example 1), MLC-A2 (Comparative Example 2) and MLC-A3 (Comparative Example 3). In addition, it has been found that both of the characteristics that the remaining amount of the polymerizable compound is reduced are combined. Further, when a burn-in test was performed on these PSVA liquid crystal display elements, MLC-A1, MLC-A2 and MLC-A3 showed a burn-in which is considered to be caused by a low VHR or residual polymerizable compound after UV irradiation. . On the other hand, MLC-A4 did not generate any burn-in. From the above, LC-A4, which is a polymerizable compound-containing liquid crystal composition of the present invention, has excellent UV resistance, a small residual amount of the polymerizable compound, and does not cause display defects such as image sticking. It was found to be a liquid crystal composition-containing liquid crystal composition.
(Comparative Example 4, Example 2, Example 3 and Example 4)
Polymerizable compound-containing liquid crystal compositions of MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were prepared and their physical properties were measured. Was measured. Table 3 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
次に、MLC-B1(比較例4)、MLC-B2(実施例2)、MLC-B3(実施例3)及びMLC-B4(実施例4)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子はすべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表4に示す。 Next, MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 4.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表4に示す。 Next, MLC-B1 (Comparative Example 4), MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 4.
以上より、本発明の重合性化合物含有液晶組成物であるMLC-B2(実施例2)、MLC-B3(実施例3)及びMLC-B4(実施例4)は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
(比較例5、実施例5、実施例6及び実施例7)
MLC-C1(比較例5)、MLC-C2(実施例5)、MLC-C3(実施例6)及びMLC-C4(実施例7)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表5のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 5, Example 5, Example 6 and Example 7)
Polymeric compound-containing liquid crystal compositions of MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were prepared, and their physical properties were measured. Was measured. The composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values are shown in Table 5.
(比較例5、実施例5、実施例6及び実施例7)
MLC-C1(比較例5)、MLC-C2(実施例5)、MLC-C3(実施例6)及びMLC-C4(実施例7)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表5のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-B2 (Example 2), MLC-B3 (Example 3) and MLC-B4 (Example 4) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 5, Example 5, Example 6 and Example 7)
Polymeric compound-containing liquid crystal compositions of MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were prepared, and their physical properties were measured. Was measured. The composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values are shown in Table 5.
次に、MLC-C1(比較例5)、MLC-C2(実施例5)、MLC-C3(実施例6)及びMLC-C4(実施例7)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子はすべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表6に示す。 Next, MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 6.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表6に示す。 Next, MLC-C1 (Comparative Example 5), MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 6.
以上より、本発明の重合性化合物含有液晶組成物であるMLC-C2(実施例5)、MLC-C3(実施例6)及びMLC-C4(実施例7)は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
(比較例6、実施例8、実施例9及び実施例10)
MLC-D1(比較例6)、MLC-D2(実施例8)、MLC-D3(実施例9)及びMLC-D4(実施例10)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表7のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 6, Example 8, Example 9 and Example 10)
Polymeric compound-containing liquid crystal compositions of MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were prepared and their physical properties were measured. Was measured. Table 7 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
(比較例6、実施例8、実施例9及び実施例10)
MLC-D1(比較例6)、MLC-D2(実施例8)、MLC-D3(実施例9)及びMLC-D4(実施例10)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表7のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-C2 (Example 5), MLC-C3 (Example 6) and MLC-C4 (Example 7) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 6, Example 8, Example 9 and Example 10)
Polymeric compound-containing liquid crystal compositions of MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were prepared and their physical properties were measured. Was measured. Table 7 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical properties.
次に、MLC-D1(比較例6)、MLC-D2(実施例8)、MLC-D3(実施例9)及びMLC-D4(実施例10)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子はすべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表8に示す。 Next, MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 8.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表8に示す。 Next, MLC-D1 (Comparative Example 6), MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 8.
以上より、本発明の重合性化合物含有液晶組成物であるMLC-D2(実施例8)、MLC-D3(実施例9)及びMLC-D4(実施例10)は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
(比較例7、実施例11、実施例12及び実施例13)
MLC-E1(比較例7)、MLC-E2(実施例11)、MLC-E3(実施例12)及びMLC-E4(実施例13)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表9のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 7, Example 11, Example 12 and Example 13)
Polymerizable compound-containing liquid crystal compositions of MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were prepared, and their physical property values were prepared. Was measured. Table 9 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
(比較例7、実施例11、実施例12及び実施例13)
MLC-E1(比較例7)、MLC-E2(実施例11)、MLC-E3(実施例12)及びMLC-E4(実施例13)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表9のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-D2 (Example 8), MLC-D3 (Example 9) and MLC-D4 (Example 10) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 7, Example 11, Example 12 and Example 13)
Polymerizable compound-containing liquid crystal compositions of MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were prepared, and their physical property values were prepared. Was measured. Table 9 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
次に、MLC-E1(比較例7)、MLC-E2(実施例11)、MLC-E3(実施例12)及びMLC-E4(実施例13)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子はすべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表10に示す。 Next, MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 10.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表10に示す。 Next, MLC-E1 (Comparative Example 7), MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 10.
以上より、本発明の重合性化合物含有液晶組成物であるMLC-E2(実施例11)、MLC-E3(実施例12)及びMLC-E4(実施例13)は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
(比較例8、実施例14、実施例15及び実施例16)
MLC-F1(比較例8)、MLC-F2(実施例14)、MLC-F3(実施例15)及びMLC-F4(実施例16)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表11のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 8, Example 14, Example 15 and Example 16)
Polymerizable compound-containing liquid crystal compositions of MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were prepared, and their physical property values were prepared. Was measured. Table 11 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
(比較例8、実施例14、実施例15及び実施例16)
MLC-F1(比較例8)、MLC-F2(実施例14)、MLC-F3(実施例15)及びMLC-F4(実施例16)の重合性化合物含有液晶組成物を調製し、その物性値を測定した。重合性化合物含有液晶組成物の構成とその物性値の結果は表11のとおりであった。 From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-E2 (Example 11), MLC-E3 (Example 12) and MLC-E4 (Example 13) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
(Comparative Example 8, Example 14, Example 15 and Example 16)
Polymerizable compound-containing liquid crystal compositions of MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were prepared, and their physical property values were prepared. Was measured. Table 11 shows the composition of the polymerizable compound-containing liquid crystal composition and the results of its physical property values.
次に、MLC-F1(比較例8)、MLC-F2(実施例14)、MLC-F3(実施例15)及びMLC-F4(実施例16)をそれぞれセルギャップ3.0μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで9.0Vの矩形波を印加しながら、高圧水銀灯により300nm以下の紫外線をカットするフィルターを介してUV照射した。このとき、セル表面の照射強度は100mW/cm2(365nm)となるように調整した。これにより、重合性化合物含有液晶組成物中の重合性化合物を重合させた、高分子安定化垂直配向(PSVA)液晶表示素子を得た。これらのPSVA液晶表示素子はすべて88°程度の適切なプレチルト角を示し、物性値と相関する応答速度を示すことが確認された。
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表12に示す。 Next, MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 12.
これらのPSVA液晶表示素子について、UV照射前後のVHRおよびUV照射後に残存した重合性化合物量を測定した。結果を表12に示す。 Next, MLC-F1 (Comparative Example 8), MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) were each homeotropically aligned with a cell gap of 3.0 μm. It injected by the vacuum injection method to the cell with ITO which apply | coated the polyimide alignment film to induce. While applying a rectangular wave of 9.0 V at a frequency of 1 kHz, UV irradiation was performed through a high-pressure mercury lamp through a filter that cuts off ultraviolet rays of 300 nm or less. At this time, the irradiation intensity on the cell surface was adjusted to 100 mW / cm 2 (365 nm). As a result, a polymer-stabilized vertical alignment (PSVA) liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized was obtained. All of these PSVA liquid crystal display elements exhibited an appropriate pretilt angle of about 88 °, and were confirmed to exhibit a response speed correlated with physical property values.
For these PSVA liquid crystal display elements, VHR before and after UV irradiation and the amount of polymerizable compound remaining after UV irradiation were measured. The results are shown in Table 12.
以上より、本発明の重合性化合物含有液晶組成物であるMLC-F2(実施例14)、MLC-F3(実施例15)及びMLC-F4(実施例16)は高い耐UV性を持ち、かつ、重合性化合物の残存量が少なく、焼きつきなどの表示不良を起こさない、優れた重合性化合物含有液晶組成物であることが分かった。
From the above, the polymerizable compound-containing liquid crystal composition of the present invention, MLC-F2 (Example 14), MLC-F3 (Example 15) and MLC-F4 (Example 16) have high UV resistance, and It was found that the polymerizable compound-containing liquid crystal composition has a small amount of the remaining polymerizable compound and does not cause display defects such as image sticking.
Claims (10)
- 一般式(I)
- 前記重合性化合物が、一般式(M)
- 一般式(N-1)
- 一般式(L-1)~一般式(L-6)
- 前記一般式(N-1)が、一般式(N-1-1)~一般式(N-1-4)、一般式(N-1-10)又は一般式(N-1-11)
である請求項3に記載の組成物。 The general formula (N-1) is the general formula (N-1-1) to the general formula (N-1-4), the general formula (N-1-10), or the general formula (N-1-11).
The composition according to claim 3. - 一般式(I)で表される化合物の含有量が0.1質量%から10.0質量%である請求項1又は2に記載の組成物。 The composition according to claim 1 or 2, wherein the content of the compound represented by the general formula (I) is from 0.1% by mass to 10.0% by mass.
- 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又は2に記載の組成物。 The dielectric anisotropy (Δε) at 25 ° C. is in the range of −2.0 to −8.0, and the refractive index anisotropy (Δn) at 20 ° C. is in the range of 0.08 to 0.14. The viscosity (η) at 20 ° C. is in the range of 10 to 30 mPa · s, the rotational viscosity at 20 ° C. (γ 1 ) is in the range of 60 to 130 mPa · s, and the nematic phase-isotropic liquid phase transition temperature (T The composition according to claim 1 or 2, wherein ni ) is in the range of 60 ° C to 120 ° C.
- 一般式(I)
- 請求項1から8のいずれか1項に記載の組成物を用いた液晶表示素子。 The liquid crystal display element using the composition of any one of Claim 1 to 8.
- 請求項1から8のいずれか1項に記載の組成物を用いたPSAモード、PSVAモード又はVA-IPSモード用液晶表示素子。 A liquid crystal display element for PSA mode, PSVA mode or VA-IPS mode using the composition according to any one of claims 1 to 8.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000119653A (en) * | 1998-10-16 | 2000-04-25 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display using same |
JP2001040354A (en) * | 1999-07-28 | 2001-02-13 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display prepared by using same |
JP2003193054A (en) * | 2001-12-27 | 2003-07-09 | Chisso Corp | Liquid-crystal composition and liquid crystal display element |
JP2004137258A (en) * | 2002-09-27 | 2004-05-13 | Dainippon Ink & Chem Inc | 1, 7, 8-trifluoro-2-naphthol and method for producing liquid crystal compound by using the same |
JP2012025667A (en) * | 2010-07-20 | 2012-02-09 | Dic Corp | Fluoronaphthalene derivative and liquid crystal composition containing the same |
JP2015180728A (en) * | 2013-10-08 | 2015-10-15 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using the same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2732765B2 (en) * | 1992-11-30 | 1998-03-30 | シャープ株式会社 | Ferroelectric liquid crystal display device |
CA2269561C (en) * | 1998-04-22 | 2007-06-05 | Dainippon Ink And Chemicals, Inc. | Naphthalene derivative and liquid crystal composition comprising the same |
TWI319762B (en) * | 2002-09-27 | 2010-01-21 | 1,7,8-trifluoro-2-naphthol and manufacturing methods for liquid crystal compositions containing the same | |
JP4941801B2 (en) * | 2004-08-27 | 2012-05-30 | Dic株式会社 | Liquid crystal composition, display element and liquid crystal compound containing trifluoronaphthalene derivative, production method and production intermediate thereof |
CN105189702A (en) * | 2013-03-21 | 2015-12-23 | Dic株式会社 | Polymerizable-compound-containing liquid crystal composition and liquid crystal display element using same |
CN103254907B (en) * | 2013-04-23 | 2016-01-20 | 石家庄诚志永华显示材料有限公司 | Negative dielectric anisotropy liquid crystal composition |
-
2016
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000119653A (en) * | 1998-10-16 | 2000-04-25 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display using same |
JP2001040354A (en) * | 1999-07-28 | 2001-02-13 | Dainippon Ink & Chem Inc | Nematic liquid crystal composition and liquid crystal display prepared by using same |
JP2003193054A (en) * | 2001-12-27 | 2003-07-09 | Chisso Corp | Liquid-crystal composition and liquid crystal display element |
JP2004137258A (en) * | 2002-09-27 | 2004-05-13 | Dainippon Ink & Chem Inc | 1, 7, 8-trifluoro-2-naphthol and method for producing liquid crystal compound by using the same |
JP2012025667A (en) * | 2010-07-20 | 2012-02-09 | Dic Corp | Fluoronaphthalene derivative and liquid crystal composition containing the same |
JP2015180728A (en) * | 2013-10-08 | 2015-10-15 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using the same |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170283698A1 (en) * | 2016-03-31 | 2017-10-05 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
JPWO2018043144A1 (en) * | 2016-09-01 | 2018-08-30 | Dic株式会社 | Liquid crystal display element |
CN110317613A (en) * | 2018-03-28 | 2019-10-11 | 江苏和成显示科技有限公司 | A kind of liquid-crystal composition and liquid crystal display device |
CN110317613B (en) * | 2018-03-28 | 2022-03-11 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device |
CN110734770A (en) * | 2018-07-20 | 2020-01-31 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
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