WO2019160029A1 - Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device - Google Patents
Polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device Download PDFInfo
- Publication number
- WO2019160029A1 WO2019160029A1 PCT/JP2019/005316 JP2019005316W WO2019160029A1 WO 2019160029 A1 WO2019160029 A1 WO 2019160029A1 JP 2019005316 W JP2019005316 W JP 2019005316W WO 2019160029 A1 WO2019160029 A1 WO 2019160029A1
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- WIPO (PCT)
- Prior art keywords
- group
- liquid crystal
- carbon atoms
- polymerizable liquid
- polymerizable
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 153
- 239000010408 film Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000012788 optical film Substances 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 158
- 125000004432 carbon atom Chemical group C* 0.000 claims description 58
- 125000001424 substituent group Chemical group 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
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- 229910052755 nonmetal Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
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- 239000001257 hydrogen Substances 0.000 claims 1
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- 238000004090 dissolution Methods 0.000 abstract description 12
- -1 methylhexylene group Chemical group 0.000 description 29
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- 239000003795 chemical substances by application Substances 0.000 description 23
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- 238000000034 method Methods 0.000 description 12
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
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- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
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- 125000002950 monocyclic group Chemical group 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- 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
-
- 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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display device.
- a polymerizable compound exhibiting reverse wavelength dispersion has features such as being able to accurately convert the light wavelength in a wide wavelength range and being able to reduce the thickness of the retardation film because it has a high refractive index. Therefore, it has been actively researched.
- T-type molecular design guidelines have been adopted for polymerizable compounds exhibiting reverse wavelength dispersion, and the wavelength of the major axis is shortened and the wavelength of the minor axis located at the center of the molecule is lengthened. Is required to do.
- JP 2010-031223 A International Publication No. 2014/010325 JP 2016-081035 A
- the inventors of the present invention have studied the polymerizable compound having reverse wavelength dispersion described in Patent Documents 1 to 3, and depending on the type of the polymerizable compound, the stability after dissolution may be inferior, and as a result, It has been clarified that it may be difficult to produce an optically anisotropic film having a good surface shape.
- the present invention provides a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display that are excellent in stability after dissolution and can form a good planar optically anisotropic film. It is an object to provide an apparatus.
- the present inventors have found that two types of polymerizable compounds having different ring structures in the molecular long axis (side chain) as polymerizable compounds exhibiting reverse wavelength dispersion.
- the present inventors have found that a polymerizable liquid crystal composition in which a liquid crystal compound is used in combination is excellent in stability after dissolution and can form a good planar optical anisotropic film, thereby completing the present invention. That is, it has been found that the above-described problem can be achieved by the following configuration.
- a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (1) described later and a polymerizable liquid crystal compound represented by formula (2) described later.
- D 1 and D 2 in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with Ar.
- D 3 and D 4 in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with SP 1 or SP 2.
- An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].
- a polarizing plate comprising the optical film according to [8] and a polarizer.
- An image display device having the optical film according to [8] or the polarizing plate according to [9].
- a polymerizable liquid crystal composition, an optically anisotropic film, an optical film, a polarizing plate, and an image display that are excellent in stability after dissolution and can form a good planar optically anisotropic film.
- An apparatus can be provided.
- FIG. 1A is a schematic cross-sectional view showing an example of the optical film of the present invention.
- FIG. 1B is a schematic cross-sectional view showing an example of the optical film of the present invention.
- FIG. 1C is a schematic cross-sectional view showing an example of the optical film of the present invention.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the bonding direction of a divalent group (for example, —O—CO—) represented is not particularly limited unless the bonding position is clearly specified.
- D 1 in 1) is —CO—O—, assuming that the position bonded to the Ar side is * 1, and the position bonded to the G 1 side is * 2, D 1 is * 1- It may be CO-O- * 2 or * 1-O-CO- * 2.
- the polymerizable liquid crystal composition of the present invention is represented by a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter also abbreviated as “polymerizable liquid crystal compound (1)”) and the following formula (2).
- a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound hereinafter also abbreviated as “polymerizable liquid crystal compound (2)”.
- L 1 -SP 1 -D 3 -G 3 -G 1 -D 1 -Ar-D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 (1) L 1 -SP 1 -D 3 -A 3 -A 1 -D 1 -Ar-D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 (2)
- the polymerizable liquid crystal composition using the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in which a part of the ring structure included in the side chain is different is dissolved. It is excellent in stability and can form a good planar optical anisotropic film.
- the present inventors presume as follows. That is, from the results of Comparative Examples 1 to 3 described later, it can be seen that when the polymerizable liquid crystal compound (1) is blended alone, the stability after dissolution is poor. This is considered to be because the polymerizable liquid crystal compound (1) is a compound having a crystal structure having high crystallinity and low solubility by itself.
- the polymerizable liquid crystal composition in which the polymerizable liquid crystal compound (2) is blended together with the polymerizable liquid crystal compound (1) has similar structures, and the polymerizable liquid crystal compound (1) is packed.
- the polymerizable liquid crystal compound (2) is mixed and packing is inhibited, the stability after dissolution is improved, and as a result, it is considered that a good planar optical anisotropic film can be formed.
- each component of the polymerizable liquid crystal composition of the present invention will be described in detail.
- the polymerizable liquid crystal compound (1) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (1).
- G 1 , G 2 , G 3 and G 4 each independently represent a cyclohexane ring which may have a substituent.
- D 1 , D 2 , D 3 and D 4 are each independently a single bond, or —CO—, —O—, —S—, —C ( ⁇ S) —.
- -CR 1 R 2 -, - CR 3 CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more thereof
- R 1 ⁇ R 5 are each independently Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
- SP 1 and SP 2 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. Or a divalent linkage in which one or more of —CH 2 — constituting the branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—.
- Q represents a substituent.
- L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group.
- Ar is an aromatic ring represented by the following formula (Ar-3)
- at least one of L 1 and L 2 and L 3 and L 4 in the following formula (Ar-3) is a polymerizable group. Represents.
- the cyclohexane ring represented by G 1 , G 2 , G 3 and G 4 is preferably a trans-1,4-cyclohexylene group.
- the substituent that the cyclohexane ring represented by G 1 , G 2 , G 3, and G 4 may have is Y 1 in formula (Ar-1) described later. Examples of the substituent which may be used are the same as those described above.
- examples of the divalent linking group represented by D 1 , D 2 , D 3 and D 4 include —CO—O—, —C ( ⁇ S) O—, —CR 1 R 2 -, - CR 1 R 2 -CR 1 R 2 -, - O-CR 1 R 2 -, - CR 1 R 2 -O-CR 1 R 2 -, - CO-O-CR 1 R 2 -, - O —CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—CR 1 R 2 —, —CR 1 R 2 —CO—O—CR 1 R 2 —, —NR 5 —CR 1 R 2 — And -CO-NR 5 -and the like.
- R 1 , R 2 and R 5 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
- both D 1 and D 2 in the above formula (1) are —CO—O— * for easy synthesis and liquid crystallinity.
- * represents the coupling
- D 3 and D 4 in the above formula (1) are all —O—, —CO—O— *, —CO—NR 5 — *, and —CO -O- * is more preferable.
- * represents a bonding position to SP 1 or SP 2.
- Examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP 1 and SP 2 in the above formula (1) include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and hexylene. Preferred examples include a group, a methylhexylene group, and a heptylene group.
- SP 1 and SP 2 are as described above, wherein one or more of —CH 2 — constituting a linear or branched alkylene group having 1 to 12 carbon atoms is —O—, —S—, —NH.
- It may be a divalent linking group substituted with —, —N (Q) —, or —CO—, and examples of the substituent represented by Q include Y in formula (Ar-1) described later. Examples are the same as the substituents 1 may have.
- examples of the monovalent organic group represented by L 1 and L 2 include an alkyl group, an aryl group, and a heteroaryl group.
- the alkyl group may be linear, branched or cyclic, but is preferably linear.
- the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aryl group may be monocyclic or polycyclic but is preferably monocyclic.
- the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
- the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
- the hetero atom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom.
- the heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
- the alkyl group, aryl group and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents as those which Y 1 in formula (Ar-1) described later may have.
- the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
- a generally known radical polymerizable group can be used, and preferable examples include an acryloyl group or a methacryloyl group.
- the acryloyl group is generally fast in the polymerization rate, and the acryloyl group is preferable from the viewpoint of improving the productivity.
- the methacryloyl group can be similarly used as the polymerizable group.
- cationic polymerizable group generally known cationic polymerizable can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and And vinyloxy groups.
- an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
- particularly preferred polymerizable groups include the following.
- L 1 and L 2 are each preferably a polymerizable group, and more preferably an acryloyl group or a methacryloyl group, because the film strength after crosslinking is improved.
- Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
- * represents a bonding position with D 1 or D 2 in the above formula (1).
- Q 1 represents N or CH
- Q 2 represents —S—, —O—, or —N (R 6 ) —
- R 6 represents Y 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Y 1 may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic complex having 3 to 12 carbon atoms. Represents a cyclic group.
- alkyl group having 1 to 6 carbon atoms represented by R 6 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group and the like.
- aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
- Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 include heteroaryl groups such as thienyl group, thiazolyl group, furyl group, and pyridyl group.
- Examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom.
- As the alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group).
- an alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable.
- An alkoxy group having a number of 1 to 4 is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom and a chlorine atom are preferable.
- Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon A monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —OR 7 , —NR 8 R 9 , or , -SR 10 , R 7 to R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to each other to form an aromatic ring. Good.
- the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group or an ethyl group.
- Isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, methyl group, ethyl group, tert-butyl group
- the group is particularly preferred.
- Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and ethylcyclohexyl.
- Monocyclic saturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, cyclodecadienyl
- Monocyclic unsaturated hydrocarbon groups such as dienes; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 2,6 ] decyl group, Tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1.
- dodecyl group polycyclic saturated hydrocarbon group such as adamantyl group, and the like.
- the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group, and the like.
- the aryl group (particularly a phenyl group) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
- the alkyl group having 1 to 6 carbon atoms represented by R 7 to R 10 specifically includes, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. Group, tert-butyl group, n-pentyl group, n-hexyl group and the like.
- a 3 and A 4 are each independently from —O—, —N (R 11 ) —, —S—, and —CO—.
- X represents a hydrogen atom or a nonmetallic atom belonging to Groups 14 to 16 to which a substituent may be bonded.
- Examples of the non-metal atoms of Group 14 to 16 represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent.
- substituents include Is, for example, an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (eg, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, a hydroxyl group, etc. Is mentioned.
- D 5 and D 6 are each independently a single bond, or —CO—, —O—, —S—, —C ( ⁇ S) —, —CR 1.
- examples of the divalent linking group include the same groups as those described for D 1 to D 4 in the above formula (1).
- each of SP 3 and SP 4 independently represents a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms.
- Q represents a substituent. Examples of the substituent include the same substituents as those which Y 1 in formula (Ar-1) may have.
- L 3 and L 4 each independently represent a monovalent organic group
- L 3 and L 4 and at least one of L 1 and L 2 in the formula (1) Represents a polymerizable group.
- the monovalent organic group include the same as those described for L 1 and L 2 in the above formula (1).
- the polymerizable group include the same as those described in L 1 and L 2 in the formula (1).
- Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and has 2 to 30 carbon atoms.
- Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and an aromatic group.
- the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
- Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
- Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).
- Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q 3 include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert, -Butyl group, n-pentyl group, n-hexyl group and the like, and examples of the substituent are the same as those which Y 1 in the above formula (Ar-1) may have. Can be mentioned.
- polymerizable liquid crystal compound represented by the above formula (1) include, for example, the following formulas (I-1) to (I-8), (II-n), (III-n) and (III) IV-1) to (IV-5) and a side chain represented by any of the following formulas (M-101) to (M-105) L 1 -SP 1 -D 3 -G 3 -G 1 -D 1- *, or * -D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 ) Of these, compounds (1-1) to (1-12) shown in Table 1 below are preferred. In the structure of the core and the side chain, * represents the bonding position between the core and the side chain. In the following description, the following formula (II-n) refers to a structure represented by the formula (II-2) when n in the formula is 2. The same applies to the following formula (III-n).
- the polymerizable liquid crystal compound (2) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (2).
- D 1 , D 2 , D 3 and D 4 , SP 1 and SP 2 , L 1 and L 2 , and Ar are the same as those described in the above formula (1).
- a 1 , A 2 , A 3 and A 4 each independently have a cyclohexane ring which may have a substituent, or may have a substituent 6 Represents a membered unsaturated ring. However, at least one of A 1 and A 3 represents a 6-membered unsaturated ring which may have a substituent.
- the cyclohexane rings represented by A 1 , A 2 , A 3 and A 4 are the same as those described as G 1 , G 2 , G 3 and G 4 in the above formula (1).
- examples of the 6-membered unsaturated ring represented by A 1 , A 2 , A 3 and A 4 include a benzene ring, a cyclohexene ring, and a cyclohexadiene ring.
- examples of the substituent that the cyclohexene ring and the 6-membered unsaturated ring may have include the same substituents that Y 1 in the above-described formula (Ar-1) may have.
- a 1 and A 3 represents an optionally substituted 6-membered unsaturated ring, but the reverse from the viewpoint of enhancing the wavelength dispersion, one of a 1 and a 3 represents a cyclohexane ring is preferable that the other represents a benzene ring, one of a 1 and a 3 are trans-1,4- More preferably, it represents a silene group and the other represents a 1,4-phenylene group. Further, from the viewpoint of enhancing reverse wavelength dispersion, A 2 and A 4 in the above formula (2) both preferably represent a cyclohexane ring, and more preferably represent a trans-1,4-cyclohexylene group. preferable.
- polymerizable liquid crystal compound represented by the above formula (2) include, for example, the above formulas (I-1) to (I-8), (II-n), (III-n) and A core (* -Ar- *) represented by any one of (IV-1) to (IV-5), the above formulas (M-101) to (M-105) and the following formula (M-1- 1) to (M-1-6), (M-2-1), (M-3-1), (M-4-1), (M-4-2) and (M-5-1)
- a side chain represented by any one of (L 1 -SP 1 -D 3 -A 3 -A 1 -D 1- * or * -D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 ), and compounds (2-1-1) to (2-12-2) shown in Table 2 below are preferred.
- * represents the bonding position between the core and the side chain.
- the content of the polymerizable liquid crystal compound (2) is not particularly limited, but is 0.05 to 15% by mass relative to the total mass of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2).
- the content is 0.1 to 10% by mass because the durability is good.
- the polymerizable liquid crystal composition of the present invention contains, in addition to the above-described polymerizable liquid crystal compounds (1) and (2), other polymerizable compounds having one or more polymerizable groups, as long as the solubility is not inhibited. Also good.
- the polymerizable group that the other polymerizable compound has is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, an acryloyl group and a methacryloyl group are preferable.
- the other polymerizable compound is preferably another polymerizable compound having 1 to 4 polymerizable groups because the wet heat durability of the formed optically anisotropic film is further improved. More preferred is another polymerizable compound having two groups.
- Examples of other polymerizable compounds include compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
- Other polymerizable compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP2014-077068A. More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be given.
- those having the structures of formulas (1) to (3) described in JP-A-2014-198814 can also be preferably used, and more specifically, [0020] ] To [0035], [0042] to [0050], and specific examples described in paragraphs [0056] to [0057].
- the content in the case of containing such other polymerizable compound is less than 60% by mass with respect to the total mass including the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) described above. It is preferably 50% by mass or less, more preferably 2 to 40% by mass.
- the polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
- the polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
- Examples of the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substituted aromatics, and the like.
- Group acyloin compounds described in US Pat. No. 2,722,512
- polynuclear quinone compounds described in US Pat. Nos.
- the polymerization initiator is an oxime type polymerization initiator. Specific examples thereof include those described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents.
- the polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
- a solvent from the viewpoint of workability for forming an optically anisotropic film.
- the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons.
- hexane alicyclic hydrocarbons (for example, cyclohexane), aromatic hydrocarbons (for example, toluene, xylene, trimethylbenzene), halogenated carbons (for example, dichloromethane, dichloroethane, dichlorobenzene) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cello) Rub etc.), cellosolve acetates, sulfoxides (eg dimethyl sulfoxide etc.), amides (eg dimethylformamide, dimethylacetamide etc.) and the like. These may be used alone or in combination of two or more.
- the polymerizable liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic film smooth and facilitating alignment control.
- a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect with respect to the amount added, and from the viewpoint of preventing crying (bloom, bleed), a fluorine-based leveling agent.
- the leveling agent include compounds described in paragraphs [0079] to [0102] of JP 2007-069471, and general formulas described in JP 2013-047204 A ( I) (especially compounds described in paragraphs [0020] to [0032]), a compound represented by general formula (I) described in JP 2012-211306 A (particularly [0022] To the compound described in paragraph [0029], a liquid crystal alignment accelerator represented by the general formula (I) described in JP-A No.
- the polymerizable liquid crystal composition of the present invention can contain an alignment controller as required.
- the alignment control agent can form various alignment states such as homeotropic alignment (vertical alignment), inclined alignment, hybrid alignment, cholesteric alignment, etc. in addition to homogeneous alignment, It can be realized with precise control.
- a low-molecular alignment control agent or a high-molecular alignment control agent can be used as an alignment control agent that promotes homogeneous alignment.
- the low molecular orientation control agent include paragraphs [0009] to [0083] of JP-A No. 2002-20363, paragraphs [0111] to [0120] of JP-A No. 2006-106662, and JP-A 2012.
- the description in paragraphs [0021] to [0029] of Japanese Patent Publication No. 211306 can be referred to, and the contents thereof are incorporated herein.
- the polymer orientation control agent for example, refer to paragraphs [0021] to [0057] of JP-A No. 2004-198511 and paragraphs [0121] to [0167] of JP-A No. 2006-106662. The contents of which are incorporated herein by reference.
- Examples of the alignment control agent that forms or promotes homeotropic alignment include boronic acid compounds and onium salt compounds, and specifically, paragraphs [0023] to [0032] in JP-A-2008-225281. [0052] to [0058] paragraphs of JP2012-208397, paragraphs [0024] to [0055] of JP2008-026730A, and [0043] to [0055] of JP2016-193869A. Reference can be made to compounds described in paragraphs and the like, the contents of which are incorporated herein.
- the cholesteric orientation can be realized by adding a chiral agent to the polymerizable composition of the present invention, and the turning direction of the cholesteric orientation can be controlled by the direction of the chirality.
- the pitch of cholesteric orientation can be controlled according to the orientation regulating force of the chiral agent.
- the content is preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass with respect to the total solid content in the polymerizable liquid crystal composition. More preferred. When the content is within this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without realizing precipitation, phase separation, alignment defects and the like while realizing a desired alignment state.
- These alignment control agents can further impart a polymerizable functional group, in particular, a polymerizable functional group that can be polymerized with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.
- the polymerizable liquid crystal composition of the present invention may contain components other than those described above.
- An agent, a crosslinking agent, etc. are mentioned.
- the optically anisotropic film of the present invention is an optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition of the present invention described above.
- Examples of the method for forming the optically anisotropic film include a method in which the polymerizable liquid crystal composition of the present invention described above is used to obtain a desired alignment state and then fixed by polymerization.
- the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in polymerization by light irradiation.
- the irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2 , more preferably 20 mJ / cm 2 to 5 J / cm 2 , and still more preferably 30 mJ / cm 2 to 3 J / cm 2. 50 to 1000 mJ / cm 2 is particularly preferable.
- the optically anisotropic film can be formed on any support in the optical film of the present invention described later or on the polarizer in the polarizing plate of the present invention described later.
- the optically anisotropic film of the present invention preferably satisfies the following formula (3). 0.50 ⁇ Re (450) / Re (550) ⁇ 1.00 (3)
- Re (450) represents in-plane retardation of the optically anisotropic film at a wavelength of 450 nm
- Re (550) represents in-plane letter of the optically anisotropic film at a wavelength of 550 nm.
- the measurement wavelength of retardation is not specified, the measurement wavelength is 550 nm.
- the optically anisotropic film of the present invention is preferably a positive A plate or a positive C plate, more preferably a positive A plate.
- the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
- the refractive index in the slow axis direction in the film plane (direction in which the refractive index in the plane is maximum) is nx
- the refractive index in the direction perpendicular to the slow axis in the plane is ny
- the refractive index in the thickness direction is nz
- the positive A plate satisfies the relationship of the formula (A1)
- the positive C plate satisfies the relationship of the formula (C1).
- the positive A plate shows a positive value for Rth
- the positive C plate shows a negative value for Rth.
- Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, More preferably, it is 130 to 150 nm, and particularly preferably 130 to 140 nm.
- the “ ⁇ / 4 plate” is a plate having a ⁇ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). It is a board which has.
- the optical film of the present invention is an optical film having the optical anisotropic film of the present invention.
- FIG. 1A, FIG. 1B, and FIG. 1C are schematic cross-sectional views showing examples of the optical film of the present invention.
- FIG. 1 is a schematic diagram, and the thickness relationship and positional relationship of each layer do not necessarily match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. It is a member.
- the optical film 10 shown in FIG. 1 has a support 16, an alignment film 14, and an optical anisotropic film 12 in this order.
- the optical film 10 may have a hard coat layer 18 on the side opposite to the side on which the alignment film 14 of the support 16 is provided.
- the optically anisotropic film 12 may have a hard coat layer 18 on the side opposite to the side where the alignment film 14 is provided.
- optically anisotropic film included in the optical film of the present invention is the optically anisotropic film of the present invention described above.
- the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m.
- the optical film of the present invention may have a support as a base material for forming the optically anisotropic film.
- a support is preferably transparent, and specifically has a light transmittance of 80% or more.
- Examples of such a support include a glass substrate and a polymer film, and examples of the material of the polymer film include a cellulose polymer; an acrylic polymer having an acrylate polymer such as a polymethyl methacrylate and a lactone ring-containing polymer.
- the thickness of the support is not particularly limited, but is preferably 5 to 60 ⁇ m, and more preferably 5 to 30 ⁇ m.
- the optical film of the present invention has the above-mentioned arbitrary support, it is preferable to have an alignment film between the support and the optically anisotropic film. Note that the above-described support may also serve as an alignment film.
- the alignment film generally contains a polymer as a main component.
- the polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
- the polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
- a photo-alignment film as the alignment film because it is possible to prevent the deterioration of the surface state by not contacting the alignment film surface when forming the alignment film.
- the photo-alignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; described in JP 2012-155308 A
- a liquid crystal alignment film formed of a liquid crystal aligning agent having a photo-alignable group, such as trade name LPP-JP265CP manufactured by Rollic Technologies, Inc. can be used.
- the thickness of the alignment film is not particularly limited. However, from the viewpoint of forming an optically anisotropic film having a uniform thickness by reducing surface irregularities that may exist on the support.
- the thickness is preferably from 01 to 10 ⁇ m, more preferably from 0.01 to 1 ⁇ m, still more preferably from 0.01 to 0.5 ⁇ m.
- the optical film of the present invention preferably has a hard coat layer in order to impart the physical strength of the film.
- the support may have a hard coat layer on the side opposite to the side on which the alignment film is provided (see FIG. 1B), and the side on which the alignment film of the optical anisotropic film is provided; May have a hard coat layer on the opposite side (see FIG. 1C).
- the hard coat layer those described in paragraphs [0190] to [0196] of JP-A-2009-98658 can be used.
- the optical film of the present invention may have another optical anisotropic film in addition to the optical anisotropic film of the present invention. That is, the optical film of the present invention may have a laminated structure of the optical anisotropic film of the present invention and another optical anisotropic film.
- Such other optically anisotropic film does not contain any one or both of the above-described polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and other polymerizable compounds described above (particularly, Any optically anisotropic film obtained by using a liquid crystal compound) is not particularly limited.
- liquid crystal compounds can be classified into a rod type and a disk type from the shape.
- Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992).
- any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is preferably used.
- Two or more kinds of rod-like liquid crystal compounds, two or more kinds of disk-like liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a disk-like liquid crystal compound may be used.
- the liquid crystal compound described above it is more preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound having a polymerizable group, and the liquid crystal compound has two or more polymerizable groups in one molecule. Further preferred. When the liquid crystal compound is a mixture of two or more, it is preferable that at least one liquid crystal compound has two or more polymerizable groups in one molecule.
- the rod-like liquid crystal compound for example, those described in claim 1 of JP-T-11-53019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used.
- liquid crystal compound for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. However, it is not limited to these.
- the optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet rays).
- the ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention.
- a support is preferably mentioned.
- the UV absorber any conventionally known UV absorber can be used.
- a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber is used from the viewpoint of high ultraviolet absorption and obtaining ultraviolet absorption capability (ultraviolet cut capability) used in an image display device. preferable.
- two or more ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
- Specific examples of the ultraviolet absorber include compounds described in paragraphs [0258] to [0259] of JP2012-18395A, and paragraphs [0055] to [0105] of JP2007-72163A. And the like.
- Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 can be used as a commercial item.
- the polarizing plate of the present invention has the above-described optical film of the present invention and a polarizer.
- the polarizing plate of the present invention can be used as a circularly polarizing plate when the above-described optically anisotropic film of the present invention is a ⁇ / 4 plate (positive A plate).
- the slow axis of the ⁇ / 4 plate and the absorption axis of the polarizer described later Is preferably 30 to 60 °, more preferably 40 to 50 °, still more preferably 42 to 48 °, and particularly preferably 45 °.
- the “slow axis” of the ⁇ / 4 plate means the direction in which the refractive index is maximum in the plane of the ⁇ / 4 plate
- the “absorption axis” of the polarizer means the direction having the highest absorbance. To do.
- the polarizer which the polarizing plate of this invention has is not specifically limited if it is a member which has a function which converts light into specific linearly polarized light,
- a conventionally well-known absorption type polarizer and reflection type polarizer can be utilized.
- As the absorption polarizer an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, and the like are used.
- Iodine polarizers and dye polarizers include coating polarizers and stretchable polarizers, both of which can be applied. Polarized light produced by adsorbing iodine or dichroic dye to polyvinyl alcohol and stretching. A child is preferred.
- Patent No. 5048120, Patent No. 5143918, Patent No. 4691205, Patent No. 4751481 and Japanese Patent No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used.
- the reflective polarizer a polarizer in which thin films having different birefringence are stacked, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate are combined, or the like is used.
- a polyvinyl alcohol resin (a polymer containing —CH 2 —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, in terms of better adhesion.
- a polyvinyl alcohol resin a polymer containing —CH 2 —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, in terms of better adhesion.
- the thickness of the polarizer is not particularly limited, but is preferably 3 ⁇ m to 60 ⁇ m, more preferably 5 ⁇ m to 30 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
- an adhesive layer may be disposed between the optically anisotropic film and the polarizer in the optical film of the present invention.
- the adhesive that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based adhesive.
- the image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
- the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, a plasma display panel, and the like. Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic EL display device using an organic EL display panel as a display element, and is a liquid crystal display device. More preferred.
- the liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-described polarizing plate of the present invention and a liquid crystal cell.
- the polarizing plate of the present invention is preferably used as the polarizing plate on the front side, and the polarizing plate of the present invention is used as the polarizing plate on the front side and the rear side. Is more preferable.
- the liquid crystal cell which comprises a liquid crystal display device is explained in full detail.
- the liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic). It is not limited to.
- a TN mode liquid crystal cell rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
- the TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
- a VA mode liquid crystal cell rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
- the VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle.
- VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the
- a liquid crystal cell in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98).
- any of a PVA (Patterned Vertical Alignment) type, a photo-alignment type (Optical Alignment), and a PSA (Polymer-Stained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-T 2008-538819.
- JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light during black display in an oblique direction and improving the viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.
- Organic EL display device As an organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, a polarizer, a ⁇ / 4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL device. An embodiment having the display panel in this order is preferable.
- the organic EL display panel is a display panel configured using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode).
- the configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
- dimethyl 4,4′-dicyclohexanedicarboxylate 130 g
- potassium hydroxide pellets 166.3 g
- polyethylene glycol 2000 Tokyo
- Tokyo Polyethylene glycol 2000 (Tokyo) (Made by Kasei Kogyo Co., Ltd.) 10 mL was mixed, a Dean-Stark tube was attached, and it heated and stirred at 120 degreeC.
- the external temperature was set to 180 ° C., and heating and refluxing were continued for 20 hours while the solvent was distilled off.
- the progress of the reaction was confirmed by NMR (Nuclear Magnetic Resonance).
- the organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. After adding 40 mL of hexane to the residue to precipitate crystals, the mixture was cooled to 5 ° C. and stirred for 30 minutes under ice water, and then the crude product was collected by filtration. The obtained crude product was suspended in 40 mL of hexane, stirred for 30 minutes, filtered, and dried by blowing to obtain 5.39 g of compound (S-1-d) (yield 36%). .
- a polymerizable liquid crystal compound (1-9) represented by the following formula was synthesized according to the method described in paragraphs [0161] to [0163] of JP 2010-084032 A.
- reaction mixture was dried over magnesium sulfate and purified by silica gel column chromatography to obtain 32.0 g of compound (S-2-a). 17.3 g of aluminum chloride and 100 mL of dichloroethane were cooled to 5 to 10 ° C., and 12.9 g of compound (S-2-a) was added. 5.1 g of acetyl chloride was added dropwise at 5-10 ° C., and the mixture was stirred at 5-10 ° C. for 1 hour. 100 mL of water was added to stop the reaction, and the organic layer was dried over magnesium sulfate. Purification by silica gel column chromatography gave 9.3 g (yield 60%) of compound (S-2-b).
- N, N-diisopropylethylamine (0.94 ml, 5.4 mmol) was added dropwise, and the mixture was stirred at room temperature for 6 hours. After stirring, 10 ml of 1N hydrochloric acid and 10 ml of ethyl acetate were added to stop the reaction, and liquid separation was performed. The organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.0 g (1.1 mmol) of a polymerizable liquid crystal compound (2-1-7) (yield 88%).
- DIPEA N, N-diisopropylethylamine
- solubility The solubility of the synthesized polymerizable liquid crystal compound was measured by the following method. The results are shown in Table 3 and Table 4 below.
- the evaluation of the solubility of Examples 1 to 8 was carried out by mixing the polymerizable liquid crystal compounds described in Table 3 and Table 4 in the ratios described in Table 3 and Table 4 below. The mixture was evaluated. First, 1.0 g of the total amount of the polymerizable liquid crystal compound was weighed in a 10 mL sample bottle, and 1.5 g of a solvent was added until the solid content became 40% by mass. Thereafter, the mixture was shaken well by hand at 50 ° C., and allowed to stand at room temperature (23 ° C.) for 10 minutes.
- Examples 1 to 8 and Comparative Examples 1 to 3 [Production of optical film]
- a polymerizable composition (coating solution for optically anisotropic film) having the following composition was prepared and applied by spin coating to a glass substrate with a rubbed polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.). did.
- the coating film was aligned at 200 ° C. to form a liquid crystal layer. Then, it cooled to 135 degreeC, the orientation fixation by 1000 mJ / cm ⁇ 2 > ultraviolet irradiation was performed, the optically anisotropic film was formed, and the optical film for wavelength dispersion measurement was obtained.
- the mixing ratio of the polymerizable liquid crystal compounds (1-1) and (1-3) as the polymerizable liquid crystal compound (1) is 1: 1
- the mixing ratio of the polymerizable liquid crystal compound (2-1-5) and (2-3-1) as 1) is 1: 1.
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Abstract
Description
また、逆波長分散性を示す重合性化合物としては、一般にT型の分子設計指針が取られており、分子長軸の波長を短波長化し、分子中央に位置する短軸の波長を長波長化することが要求されている。
そのため、分子中央に位置する短軸の骨格(以下、「逆波長分散発現部」ともいう。)と、分子長軸との連結には、吸収波長のないシクロアルキレン骨格を利用することが知られている(例えば、特許文献1~3参照)。 A polymerizable compound exhibiting reverse wavelength dispersion has features such as being able to accurately convert the light wavelength in a wide wavelength range and being able to reduce the thickness of the retardation film because it has a high refractive index. Therefore, it has been actively researched.
In general, T-type molecular design guidelines have been adopted for polymerizable compounds exhibiting reverse wavelength dispersion, and the wavelength of the major axis is shortened and the wavelength of the minor axis located at the center of the molecule is lengthened. Is required to do.
For this reason, it is known to use a cycloalkylene skeleton having no absorption wavelength for the connection between the short-axis skeleton located in the center of the molecule (hereinafter also referred to as “reverse wavelength dispersion expression part”) and the molecular long axis. (For example, see Patent Documents 1 to 3).
すなわち、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that two types of polymerizable compounds having different ring structures in the molecular long axis (side chain) as polymerizable compounds exhibiting reverse wavelength dispersion. The present inventors have found that a polymerizable liquid crystal composition in which a liquid crystal compound is used in combination is excellent in stability after dissolution and can form a good planar optical anisotropic film, thereby completing the present invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.
[2] 後述する式(1)および(2)中のD1およびD2が、いずれも、-CO-O-*であり、*は、Arとの結合位置を表す、[1]に記載の重合性液晶組成物。
[3] 後述する式(1)および(2)中のD3およびD4が、いずれも、-CO-O-*であり、*は、SP1またはSP2との結合位置を表す、[1]または[2]に記載の重合性液晶組成物。
[4] 後述する式(1)および(2)中のL1およびL2が、いずれも、重合性基を表す、[1]~[3]のいずれかに記載の重合性液晶組成物。
[5] 後述する式(2)中のA1およびA3が、いずれか一方がシクロヘキサン環を表し、他方がベンゼン環を表す、[1]~[4]のいずれかに記載の重合性液晶組成物。
[6] 後述する式(2)中のA2およびA4が、いずれも、シクロヘキサン環を表す、[1]~[5]のいずれかに記載の重合性液晶組成物。 [1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by formula (1) described later and a polymerizable liquid crystal compound represented by formula (2) described later.
[2] Described in [1], D 1 and D 2 in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with Ar. Polymerizable liquid crystal composition.
[3] D 3 and D 4 in formulas (1) and (2) described later are both —CO—O— *, and * represents a bonding position with SP 1 or SP 2. [3] The polymerizable liquid crystal composition according to [1] or [2].
[4] The polymerizable liquid crystal composition according to any one of [1] to [3], wherein L 1 and L 2 in formulas (1) and (2) described later each represents a polymerizable group.
[5] The polymerizable liquid crystal according to any one of [1] to [4], wherein one of A 1 and A 3 in formula (2) described later represents a cyclohexane ring and the other represents a benzene ring. Composition.
[6] The polymerizable liquid crystal composition according to any one of [1] to [5], wherein A 2 and A 4 in formula (2) described later each represent a cyclohexane ring.
[8] [7]に記載の光学異方性膜を有する光学フィルム。
[9] [8]に記載の光学フィルムと、偏光子とを有する、偏光板。
[10] [8]に記載の光学フィルム、または、[9]に記載の偏光板を有する、画像表示装置。 [7] An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [6].
[8] An optical film having the optically anisotropic film according to [7].
[9] A polarizing plate comprising the optical film according to [8] and a polarizer.
[10] An image display device having the optical film according to [8] or the polarizing plate according to [9].
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、本明細書において、表記される二価の基(例えば、-O-CO-)の結合方向は、結合位置を明記している場合を除き、特に制限されず、例えば、後述する式(1)中のD1が-CO-O-である場合、Ar側に結合している位置を*1、G1側に結合している位置を*2とすると、D1は、*1-CO-O-*2であってもよく、*1-O-CO-*2であってもよい。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, in this specification, the bonding direction of a divalent group (for example, —O—CO—) represented is not particularly limited unless the bonding position is clearly specified. When D 1 in 1) is —CO—O—, assuming that the position bonded to the Ar side is * 1, and the position bonded to the G 1 side is * 2, D 1 is * 1- It may be CO-O- * 2 or * 1-O-CO- * 2.
本発明の重合性液晶組成物は、下記式(1)で表される重合性液晶化合物(以下、「重合性液晶化合物(1)」とも略す。)と、下記式(2)で表される重合性液晶化合物(以下、「重合性液晶化合物(2)」とも略す。)とを含有する重合性液晶組成物である。
L1-SP1-D3-G3-G1-D1-Ar-D2-G2-G4-D4-SP2-L2 ・・・(1)
L1-SP1-D3-A3-A1-D1-Ar-D2-A2-A4-D4-SP2-L2 ・・・(2) [Polymerizable liquid crystal composition]
The polymerizable liquid crystal composition of the present invention is represented by a polymerizable liquid crystal compound represented by the following formula (1) (hereinafter also abbreviated as “polymerizable liquid crystal compound (1)”) and the following formula (2). A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound (hereinafter also abbreviated as “polymerizable liquid crystal compound (2)”).
L 1 -SP 1 -D 3 -G 3 -G 1 -D 1 -Ar-D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 (1)
L 1 -SP 1 -D 3 -A 3 -A 1 -D 1 -Ar-D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 (2)
これは、詳細には明らかではないが、本発明者らは以下のように推測している。
すなわち、後述する比較例1~3の結果から、重合性液晶化合物(1)を単独で配合すると、溶解後の安定性が劣ることが分かる。これは、重合性液晶化合物(1)は、単独では結晶性が高く、溶解性の低い結晶構造を採る化合物であるためであると考えられる。
そのため、重合性液晶化合物(1)とともに、重合性液晶化合物(2)を配合した重合性液晶組成物は、互いの構造が類似しており、重合性液晶化合物(1)がパッキングしていく際に、重合性液晶化合物(2)が混ざり込み、パッキングが阻害されるため、溶解後の安定性が改善し、その結果、良好な面状の光学異方性膜を形成できたと考えられる。
以下、本発明の重合性液晶組成物の各成分について詳細に説明する。 In the present invention, as described above, the polymerizable liquid crystal composition using the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) in which a part of the ring structure included in the side chain is different is dissolved. It is excellent in stability and can form a good planar optical anisotropic film.
Although this is not clear in detail, the present inventors presume as follows.
That is, from the results of Comparative Examples 1 to 3 described later, it can be seen that when the polymerizable liquid crystal compound (1) is blended alone, the stability after dissolution is poor. This is considered to be because the polymerizable liquid crystal compound (1) is a compound having a crystal structure having high crystallinity and low solubility by itself.
Therefore, the polymerizable liquid crystal composition in which the polymerizable liquid crystal compound (2) is blended together with the polymerizable liquid crystal compound (1) has similar structures, and the polymerizable liquid crystal compound (1) is packed. In addition, since the polymerizable liquid crystal compound (2) is mixed and packing is inhibited, the stability after dissolution is improved, and as a result, it is considered that a good planar optical anisotropic film can be formed.
Hereinafter, each component of the polymerizable liquid crystal composition of the present invention will be described in detail.
本発明の重合性液晶組成物に含まれる重合性液晶化合物(1)は、下記式(1)で表される重合性液晶化合物である。
L1-SP1-D3-G3-G1-D1-Ar-D2-G2-G4-D4-SP2-L2 ・・・(1) [Polymerizable liquid crystal compound (1)]
The polymerizable liquid crystal compound (1) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (1).
L 1 -SP 1 -D 3 -G 3 -G 1 -D 1 -Ar-D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 (1)
また、上記式(1)中、D1、D2、D3およびD4は、それぞれ独立に、単結合、または、-CO-、-O-、-S-、-C(=S)-、-CR1R2-、-CR3=CR4-、-NR5-、もしくは、これらの2つ以上の組み合わせからなる2価の連結基を表し、R1~R5は、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
また、上記式(1)中、SP1およびSP2は、それぞれ独立に、単結合、炭素数1~12の直鎖状もしくは分岐状のアルキレン基、または、炭素数1~12の直鎖状もしくは分岐状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、もしくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
また、上記式(1)中、L1およびL2は、それぞれ独立に1価の有機基を表し、L1およびL2の少なくとも一方は重合性基を表す。ただし、Arが、下記式(Ar-3)で表される芳香環である場合は、L1およびL2ならびに下記式(Ar-3)中のL3およびL4の少なくとも1つが重合性基を表す。 In the above formula (1), G 1 , G 2 , G 3 and G 4 each independently represent a cyclohexane ring which may have a substituent.
In the above formula (1), D 1 , D 2 , D 3 and D 4 are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —. , -CR 1 R 2 -, - CR 3 = CR 4 -, - NR 5 -, or a divalent linking group formed from these two or more thereof, R 1 ~ R 5 are each independently Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
In the above formula (1), SP 1 and SP 2 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. Or a divalent linkage in which one or more of —CH 2 — constituting the branched alkylene group is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—. Represents a group, Q represents a substituent.
In the above formula (1), L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar-3), at least one of L 1 and L 2 and L 3 and L 4 in the following formula (Ar-3) is a polymerizable group. Represents.
また、上記式(1)中、G1、G2、G3およびG4が示すシクロヘキサン環が有していてもよい置換基としては、後述する式(Ar-1)中のY1が有していてもよい置換基と同様のものが挙げられる。 In the above formula (1), the cyclohexane ring represented by G 1 , G 2 , G 3 and G 4 is preferably a trans-1,4-cyclohexylene group.
In the above formula (1), the substituent that the cyclohexane ring represented by G 1 , G 2 , G 3, and G 4 may have is Y 1 in formula (Ar-1) described later. Examples of the substituent which may be used are the same as those described above.
また、同様の理由から、上記式(1)中のD3およびD4が、いずれも、-O-、-CO-O-*、-CO-NR5-*であることが好ましく、-CO-O-*であることがより好ましい。なお、*はSP1またはSP2との結合位置を表す。 Among these, it is preferable that both D 1 and D 2 in the above formula (1) are —CO—O— * for easy synthesis and liquid crystallinity. In addition, * represents the coupling | bonding position with Ar.
For the same reason, it is preferable that D 3 and D 4 in the above formula (1) are all —O—, —CO—O— *, —CO—NR 5 — *, and —CO -O- * is more preferable. Note that * represents a bonding position to SP 1 or SP 2.
ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとして、アクリロイル基またはメタクリロイル基を挙げることができる。この場合、重合速度はアクリロイル基が一般的に速いことが知られており、生産性向上の観点からアクリロイル基が好ましいが、メタクリロイル基も重合性基として同様に使用することができる。
カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、および、ビニルオキシ基などを挙げることができる。中でも、脂環式エーテル基、または、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、または、ビニルオキシ基が特に好ましい。
特に好ましい重合性基の例としては下記が挙げられる。 In the above formula (1), the polymerizable group represented by at least one of L 1 and L 2 is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and preferable examples include an acryloyl group or a methacryloyl group. In this case, it is known that the acryloyl group is generally fast in the polymerization rate, and the acryloyl group is preferable from the viewpoint of improving the productivity. However, the methacryloyl group can be similarly used as the polymerizable group.
As the cationic polymerizable group, generally known cationic polymerizable can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and And vinyloxy groups. Among these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
Examples of particularly preferred polymerizable groups include the following.
R6が示す炭素数1~6のアルキル基としては、具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基などが挙げられる。
Y1が示す炭素数6~12の芳香族炭化水素基としては、例えば、フェニル基、2,6-ジエチルフェニル基、ナフチル基などのアリール基が挙げられる。
Y1が示す炭素数3~12の芳香族複素環基としては、例えば、チエニル基、チアゾリル基、フリル基、ピリジル基などのヘテロアリール基が挙げられる。
また、Y1が有していてもよい置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子などが挙げられる。
アルキル基としては、例えば、炭素数1~18の直鎖状、分岐鎖状または環状のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、シクロヘキシル基等)がより好ましく、炭素数1~4のアルキル基であることが更に好ましく、メチル基またはエチル基であるのが特に好ましい。
アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、メトキシエトキシ基等)がより好ましく、炭素数1~4のアルコキシ基であることが更に好ましく、メトキシ基またはエトキシ基であるのが特に好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でも、フッ素原子、塩素原子であるのが好ましい。 Here, in the formula (Ar-1), Q 1 represents N or CH, Q 2 represents —S—, —O—, or —N (R 6 ) —, and R 6 represents Y 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y 1 may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic complex having 3 to 12 carbon atoms. Represents a cyclic group.
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group and the like.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y 1 include heteroaryl groups such as thienyl group, thiazolyl group, furyl group, and pyridyl group.
Examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, and a halogen atom.
As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group). N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group. Is particularly preferred.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable. An alkoxy group having a number of 1 to 4 is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom and a chlorine atom are preferable.
炭素数1~20の1価の脂肪族炭化水素基としては、炭素数1~15のアルキル基が好ましく、炭素数1~8のアルキル基がより好ましく、具体的には、メチル基、エチル基、イソプロピル基、tert-ペンチル基(1,1-ジメチルプロピル基)、tert-ブチル基、1,1-ジメチル-3,3-ジメチル-ブチル基が更に好ましく、メチル基、エチル基、tert-ブチル基が特に好ましい。
炭素数3~20の1価の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、メチルシクロヘキシル基、エチルシクロヘキシル基等の単環式飽和炭化水素基;シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基、シクロオクテニル基、シクロデセニル基、シクロペンタジエニル基、シクロヘキサジエニル基、シクロオクタジエニル基、シクロデカジエン等の単環式不飽和炭化水素基;ビシクロ[2.2.1]ヘプチル基、ビシクロ[2.2.2]オクチル基、トリシクロ[5.2.1.02,6]デシル基、トリシクロ[3.3.1.13,7]デシル基、テトラシクロ[6.2.1.13,6.02,7]ドデシル基、アダマンチル基等の多環式飽和炭化水素基;等が挙げられる。
炭素数6~20の1価の芳香族炭化水素基としては、具体的には、例えば、フェニル基、2,6-ジエチルフェニル基、ナフチル基、ビフェニル基などが挙げられ、炭素数6~12のアリール基(特にフェニル基)が好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でも、フッ素原子、塩素原子、臭素原子であるのが好ましい。
一方、R7~R10が示す炭素数1~6のアルキル基としては、具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基などが挙げられる。 In the above formulas (Ar-1) to (Ar-5), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon A monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —OR 7 , —NR 8 R 9 , or , -SR 10 , R 7 to R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to each other to form an aromatic ring. Good.
The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group or an ethyl group. , Isopropyl group, tert-pentyl group (1,1-dimethylpropyl group), tert-butyl group, 1,1-dimethyl-3,3-dimethyl-butyl group are more preferable, methyl group, ethyl group, tert-butyl group The group is particularly preferred.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and ethylcyclohexyl. Monocyclic saturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, cyclodecadienyl Monocyclic unsaturated hydrocarbon groups such as dienes; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 2,6 ] decyl group, Tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1. 1 3,6 . 0 2,7 ] dodecyl group, polycyclic saturated hydrocarbon group such as adamantyl group, and the like.
Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group, and the like. Of the aryl group (particularly a phenyl group).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
On the other hand, the alkyl group having 1 to 6 carbon atoms represented by R 7 to R 10 specifically includes, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. Group, tert-butyl group, n-pentyl group, n-hexyl group and the like.
R11が示す置換基としては、上記式(Ar-1)中のY1が有していてもよい置換基と同様のものが挙げられる。 In the above formulas (Ar-2) and (Ar-3), A 3 and A 4 are each independently from —O—, —N (R 11 ) —, —S—, and —CO—. Represents a group selected from the group consisting of R 11 and represents a hydrogen atom or a substituent.
Examples of the substituent represented by R 11 include the same substituents as those which Y 1 in the above formula (Ar-1) may have.
また、Xが示す第14~16族の非金属原子としては、例えば、酸素原子、硫黄原子、置換基を有する窒素原子、置換基を有する炭素原子が挙げられ、置換基としては、具体的には、例えば、アルキル基、アルコキシ基、アルキル置換アルコキシ基、環状アルキル基、アリール基(例えば、フェニル基、ナフチル基など)、シアノ基、アミノ基、ニトロ基、アルキルカルボニル基、スルホ基、水酸基等が挙げられる。 Further, in the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom belonging to
Examples of the non-metal atoms of
ここで、2価の連結基としては、上記式(1)中のD1~D4において説明したものと同様のものが挙げられる。 In the formula (Ar-3), D 5 and D 6 are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —, —CR 1. R 2 —, —CR 3 ═CR 4 —, —NR 5 —, or a divalent linking group consisting of a combination of two or more thereof, each of R 1 to R 5 independently represents a hydrogen atom, A fluorine atom or an alkyl group having 1 to 4 carbon atoms is represented.
Here, examples of the divalent linking group include the same groups as those described for D 1 to D 4 in the above formula (1).
1価の有機基としては、上記式(1)中のL1およびL2において説明したものと同様のものが挙げられる。
また、重合性基としては、上記式(1)中のL1およびL2において説明したものと同様のものが挙げられる。 In the formula (Ar-3), L 3 and L 4 each independently represent a monovalent organic group, and L 3 and L 4 and at least one of L 1 and L 2 in the formula (1) Represents a polymerizable group.
Examples of the monovalent organic group include the same as those described for L 1 and L 2 in the above formula (1).
Further, the polymerizable group include the same as those described in L 1 and L 2 in the formula (1).
また、上記式(Ar-4)~(Ar-5)中、Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、または、芳香族炭化水素環および芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
ここで、AxおよびAyにおける芳香環は、置換基を有していてもよく、AxとAyとが結合して環を形成していてもよい。
また、Q3は、水素原子、または、置換基を有していてもよい炭素数1~6のアルキル基を表す。
AxおよびAyとしては、特許文献2(国際公開第2014/010325号)の[0039]~[0095]段落に記載されたものが挙げられる。
また、Q3が示す炭素数1~6のアルキル基としては、具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、および、n-ヘキシル基などが挙げられ、置換基としては、上記式(Ar-1)中のY1が有していてもよい置換基と同様のものが挙げられる。 In the above formulas (Ar-4) to (Ar-5), Ax has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and has 2 to 30 carbon atoms. Represents an organic group.
In the above formulas (Ar-4) to (Ar-5), Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and an aromatic group. And an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 2 (International Publication No. 2014/010325).
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q 3 include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert, -Butyl group, n-pentyl group, n-hexyl group and the like, and examples of the substituent are the same as those which Y 1 in the above formula (Ar-1) may have. Can be mentioned.
なお、以下の説明において、下記式(II-n)は、式中のnが2である場合を式(II-2)で表される構造という。下記式(III-n)についても同様である。 Specific examples of the polymerizable liquid crystal compound represented by the above formula (1) include, for example, the following formulas (I-1) to (I-8), (II-n), (III-n) and (III) IV-1) to (IV-5) and a side chain represented by any of the following formulas (M-101) to (M-105) L 1 -SP 1 -D 3 -G 3 -G 1 -D 1- *, or * -D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 ) Of these, compounds (1-1) to (1-12) shown in Table 1 below are preferred. In the structure of the core and the side chain, * represents the bonding position between the core and the side chain.
In the following description, the following formula (II-n) refers to a structure represented by the formula (II-2) when n in the formula is 2. The same applies to the following formula (III-n).
本発明の重合性液晶組成物に含まれる重合性液晶化合物(2)は、下記式(2)で表される重合性液晶化合物である。
L1-SP1-D3-A3-A1-D1-Ar-D2-A2-A4-D4-SP2-L2 ・・・(2) [Polymerizable liquid crystal compound (2)]
The polymerizable liquid crystal compound (2) contained in the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound represented by the following formula (2).
L 1 -SP 1 -D 3 -A 3 -A 1 -D 1 -Ar-D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 (2)
また、上記式(2)中、A1、A2、A3およびA4は、それぞれ独立に、置換基を有していてもよいシクロヘキサン環、または、置換基を有していてもよい6員不飽和環を表す。ただし、A1およびA3の少なくとも一方は、置換基を有していてもよい6員不飽和環を表す。 In the above formula (2), D 1 , D 2 , D 3 and D 4 , SP 1 and SP 2 , L 1 and L 2 , and Ar are the same as those described in the above formula (1). There are also preferred embodiments.
In the above formula (2), A 1 , A 2 , A 3 and A 4 each independently have a cyclohexane ring which may have a substituent, or may have a substituent 6 Represents a membered unsaturated ring. However, at least one of A 1 and A 3 represents a 6-membered unsaturated ring which may have a substituent.
また、上記式(2)中、A1、A2、A3およびA4が示す6員不飽和環としては、ベンゼン環、シクロヘキセン環、および、シクロヘキサジエン環が挙げられる。
また、シクロヘキセン環および6員不飽和環が有していてよい置換基としては、上述した式(Ar-1)中のY1が有していてもよい置換基と同様のものが挙げられる。 In the above formula (2), the cyclohexane rings represented by A 1 , A 2 , A 3 and A 4 are the same as those described as G 1 , G 2 , G 3 and G 4 in the above formula (1). .
In the above formula (2), examples of the 6-membered unsaturated ring represented by A 1 , A 2 , A 3 and A 4 include a benzene ring, a cyclohexene ring, and a cyclohexadiene ring.
In addition, examples of the substituent that the cyclohexene ring and the 6-membered unsaturated ring may have include the same substituents that Y 1 in the above-described formula (Ar-1) may have.
また、逆波長分散性を高める観点から、上記式(2)中のA2およびA4が、いずれも、シクロヘキサン環を表すことが好ましく、トランス-1,4-シクロヘキシレン基を表すことがより好ましい。 In the above formula (2), among A 1 , A 2 , A 3 and A 4 , at least one of A 1 and A 3 represents an optionally substituted 6-membered unsaturated ring, but the reverse from the viewpoint of enhancing the wavelength dispersion, one of a 1 and a 3 represents a cyclohexane ring is preferable that the other represents a benzene ring, one of a 1 and a 3 are trans-1,4- More preferably, it represents a silene group and the other represents a 1,4-phenylene group.
Further, from the viewpoint of enhancing reverse wavelength dispersion, A 2 and A 4 in the above formula (2) both preferably represent a cyclohexane ring, and more preferably represent a trans-1,4-cyclohexylene group. preferable.
なお、下記式(M-1-5)、(M-1-6)、(M-2-1)、(M-3-1)、(M-4-1)および(M-4-2)は、それぞれ、以下に示す2つの構造が混合した側鎖を表す。 Specific examples of the polymerizable liquid crystal compound represented by the above formula (2) include, for example, the above formulas (I-1) to (I-8), (II-n), (III-n) and A core (* -Ar- *) represented by any one of (IV-1) to (IV-5), the above formulas (M-101) to (M-105) and the following formula (M-1- 1) to (M-1-6), (M-2-1), (M-3-1), (M-4-1), (M-4-2) and (M-5-1) A side chain represented by any one of (L 1 -SP 1 -D 3 -A 3 -A 1 -D 1- * or * -D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 ), and compounds (2-1-1) to (2-12-2) shown in Table 2 below are preferred. In the structure of the core and the side chain, * represents the bonding position between the core and the side chain.
The following formulas (M-1-5), (M-1-6), (M-2-1), (M-3-1), (M-4-1) and (M-4-2) ) Each represents a side chain in which two structures shown below are mixed.
本発明の重合性液晶組成物は、溶解性を阻害しない限り、上述した重合性液晶化合物(1)および(2)以外に、重合性基を1個以上有する他の重合性化合物を含んでいてもよい。
ここで、他の重合性化合物が有する重合性基は特に限定されず、例えば、アクリロイル基、メタクリロイル基、ビニル基、スチリル基、アリル基等が挙げられる。なかでも、アクリロイル基、メタクリロイル基を有しているのが好ましい。 [Other polymerizable compounds]
The polymerizable liquid crystal composition of the present invention contains, in addition to the above-described polymerizable liquid crystal compounds (1) and (2), other polymerizable compounds having one or more polymerizable groups, as long as the solubility is not inhibited. Also good.
Here, the polymerizable group that the other polymerizable compound has is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, an acryloyl group and a methacryloyl group are preferable.
また、他の重合性化合物としては、特開2014-077068号公報の[0030]~[0033]段落に記載された式(M1)、(M2)、(M3)で表される化合物が挙げられ、より具体的には、同公報の[0046]~[0055]段落に記載された具体例が挙げられる。
また、他の重合性化合物としては、特開2014-198814号公報に記載の式(1)~(3)の構造のものも好ましく用いることができ、より具体的には、同公報の[0020]~[0035]、[0042]~[0050]、[0056]~[0057]段落に記載された具体例が挙げられる。 Examples of other polymerizable compounds include compounds described in paragraphs [0073] to [0074] of JP-A-2016-053709.
Other polymerizable compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs [0030] to [0033] of JP2014-077068A. More specifically, specific examples described in paragraphs [0046] to [0055] of the same publication can be given.
As other polymerizable compounds, those having the structures of formulas (1) to (3) described in JP-A-2014-198814 can also be preferably used, and more specifically, [0020] ] To [0035], [0042] to [0050], and specific examples described in paragraphs [0056] to [0057].
本発明の重合性液晶組成物は、重合開始剤を含有していることが好ましい。
使用する重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であるのが好ましい。
光重合開始剤としては、例えば、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)およびオキサジアゾール化合物(米国特許第4212970号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、特開平10-29997号公報記載)等が挙げられる。
また、本発明においては、重合開始剤がオキシム型の重合開始剤であることも好ましく、その具体例としては、国際公開第2017/170443号の[0049]~[0052]段落に記載された開始剤が挙げられる。 (Polymerization initiator)
The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics, and the like. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US patent) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970), acylphosphine Oxide compounds (Japanese Patent Publication No. 6) No. 3-40799, JP-B-5-29234, JP-A-10-95788, JP-A-10-29997) and the like.
In the present invention, it is also preferable that the polymerization initiator is an oxime type polymerization initiator. Specific examples thereof include those described in paragraphs [0049] to [0052] of International Publication No. 2017/170443. Agents.
本発明の重合性液晶組成物は、光学異方性膜を形成する作業性等の観点から、溶媒を含有するのが好ましい。
溶媒としては、具体的には、例えば、ケトン類(例えば、アセトン、2-ブタノン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノンなど)、エーテル類(例えば、ジオキサン、テトラヒドロフランなど)、脂肪族炭化水素類(例えば、ヘキサンなど)、脂環式炭化水素類(例えば、シクロヘキサンなど)、芳香族炭化水素類(例えば、トルエン、キシレン、トリメチルベンゼンなど)、ハロゲン化炭素類(例えば、ジクロロメタン、ジクロロエタン、ジクロロベンゼン、クロロトルエンなど)、エステル類(例えば、酢酸メチル、酢酸エチル、酢酸ブチルなど)、水、アルコール類(例えば、エタノール、イソプロパノール、ブタノール、シクロヘキサノールなど)、セロソルブ類(例えば、メチルセロソルブ、エチルセロソルブなど)、セロソルブアセテート類、スルホキシド類(例えば、ジメチルスルホキシドなど)、アミド類(例えば、ジメチルホルムアミド、ジメチルアセトアミドなど)等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。 〔solvent〕
The polymerizable liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability for forming an optically anisotropic film.
Specific examples of the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons. (For example, hexane), alicyclic hydrocarbons (for example, cyclohexane), aromatic hydrocarbons (for example, toluene, xylene, trimethylbenzene), halogenated carbons (for example, dichloromethane, dichloroethane, dichlorobenzene) , Chlorotoluene, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cello) Rub etc.), cellosolve acetates, sulfoxides (eg dimethyl sulfoxide etc.), amides (eg dimethylformamide, dimethylacetamide etc.) and the like. These may be used alone or in combination of two or more. You may use together.
本発明の重合性液晶組成物は、光学異方性膜の表面を平滑に保ち、配向制御を容易にする観点から、レベリング剤を含有することが好ましい。
このようなレベリング剤としては、添加量に対するレベリング効果が高い理由から、フッ素系レベリング剤またはケイ素系レベリング剤であることが好ましく、泣き出し(ブルーム、ブリード)を起こしにくい観点から、フッ素系レベリング剤であることがより好ましい。
レベリング剤としては、具体的には、例えば、特開2007-069471号公報の[0079]~[0102]段落の記載に記載された化合物、特開2013-047204号公報に記載された一般式(I)で表される化合物(特に[0020]~[0032]段落に記載された化合物)、特開2012-211306号公報に記載された一般式(I)で表される化合物(特に[0022]~[0029]段落に記載された化合物)、特開2002-129162号公報に記載された一般式(I)で表される液晶配向促進剤(特に[0076]~[0078]および[0082]~[0084]段落に記載された化合物)、特開2005-099248号公報に記載された一般式(I)、(II)および(III)で表される化合物(特に[0092]~[0096]段落に記載された化合物)などが挙げられる。なお、後述する配向制御剤としての機能を兼ね備えてもよい。 (Leveling agent)
The polymerizable liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of keeping the surface of the optically anisotropic film smooth and facilitating alignment control.
Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect with respect to the amount added, and from the viewpoint of preventing crying (bloom, bleed), a fluorine-based leveling agent. It is more preferable that
Specific examples of the leveling agent include compounds described in paragraphs [0079] to [0102] of JP 2007-069471, and general formulas described in JP 2013-047204 A ( I) (especially compounds described in paragraphs [0020] to [0032]), a compound represented by general formula (I) described in JP 2012-211306 A (particularly [0022] To the compound described in paragraph [0029], a liquid crystal alignment accelerator represented by the general formula (I) described in JP-A No. 2002-129162 (particularly [0076] to [0078] and [0082] to [0084] Paragraphs), compounds represented by general formulas (I), (II) and (III) described in JP-A-2005-099248 (particularly 0092] ~ [0096] compounds described in Paragraph), and the like. In addition, you may have the function as an orientation control agent mentioned later.
本発明の重合性液晶組成物は、必要に応じて、配向制御剤を含有することができる。
配向制御剤により、ホモジニアス配向の他、ホメオトロピック配向(垂直配向)、傾斜配向、ハイブリッド配向、コレステリック配向等の種々の配向状態を形成することができ、また、特定の配向状態をより均一かつより精密に制御して実現することができる。 (Orientation control agent)
The polymerizable liquid crystal composition of the present invention can contain an alignment controller as required.
The alignment control agent can form various alignment states such as homeotropic alignment (vertical alignment), inclined alignment, hybrid alignment, cholesteric alignment, etc. in addition to homogeneous alignment, It can be realized with precise control.
低分子の配向制御剤としては、例えば、特開2002-20363号公報の[0009]~[0083]段落、特開2006-106662号公報の[0111]~[0120]段落、および、特開2012-211306公報の[0021]~[0029]段落の記載を参酌することができ、この内容は本願明細書に組み込まれる。
また、高分子の配向制御剤としては、例えば、特開2004-198511号公報の[0021]~[0057]段落、および、特開2006-106662号公報の[0121]~[0167]段落を参酌することができ、この内容は本願明細書に組み込まれる。 As an alignment control agent that promotes homogeneous alignment, for example, a low-molecular alignment control agent or a high-molecular alignment control agent can be used.
Examples of the low molecular orientation control agent include paragraphs [0009] to [0083] of JP-A No. 2002-20363, paragraphs [0111] to [0120] of JP-A No. 2006-106662, and JP-A 2012. The description in paragraphs [0021] to [0029] of Japanese Patent Publication No. 211306 can be referred to, and the contents thereof are incorporated herein.
Further, as the polymer orientation control agent, for example, refer to paragraphs [0021] to [0057] of JP-A No. 2004-198511 and paragraphs [0121] to [0167] of JP-A No. 2006-106662. The contents of which are incorporated herein by reference.
これらの配向制御剤は、さらに重合性官能基、特に、本発明の重合性液晶組成物を構成する重合性液晶化合物と重合可能な重合性官能基を付与することができる。 When the alignment control agent is contained, the content is preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass with respect to the total solid content in the polymerizable liquid crystal composition. More preferred. When the content is within this range, it is possible to obtain a uniform and highly transparent optically anisotropic film without realizing precipitation, phase separation, alignment defects and the like while realizing a desired alignment state.
These alignment control agents can further impart a polymerizable functional group, in particular, a polymerizable functional group that can be polymerized with the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition of the present invention.
本発明の重合性液晶組成物は、上述した成分以外の成分を含有してもよく、例えば、上述した重合性液晶化合物以外の液晶化合物、界面活性剤、チルト角制御剤、配向助剤、可塑剤、および、架橋剤などが挙げられる。 [Other ingredients]
The polymerizable liquid crystal composition of the present invention may contain components other than those described above. For example, liquid crystal compounds other than the above-described polymerizable liquid crystal compounds, surfactants, tilt angle control agents, alignment aids, plasticizers. An agent, a crosslinking agent, etc. are mentioned.
本発明の光学異方性膜は、上述した本発明の重合性液晶組成物を重合して得られる光学異方性膜である。
光学異方性膜の形成方法としては、例えば、上述した本発明の重合性液晶組成物を用いて、所望の配向状態とした後に、重合により固定化する方法などが挙げられる。
ここで、重合条件は特に限定されないが、光照射による重合においては、紫外線を用いることが好ましい。照射量は、10mJ/cm2~50J/cm2であることが好ましく、20mJ/cm2~5J/cm2であることがより好ましく、30mJ/cm2~3J/cm2であることが更に好ましく、50~1000mJ/cm2であることが特に好ましい。また、重合反応を促進するため、加熱条件下で実施してもよい。
なお、本発明においては、光学異方性膜は、後述する本発明の光学フィルムにおける任意の支持体上や、後述する本発明の偏光板における偏光子上に形成することができる。 [Optically anisotropic film]
The optically anisotropic film of the present invention is an optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition of the present invention described above.
Examples of the method for forming the optically anisotropic film include a method in which the polymerizable liquid crystal composition of the present invention described above is used to obtain a desired alignment state and then fixed by polymerization.
Here, the polymerization conditions are not particularly limited, but it is preferable to use ultraviolet rays in polymerization by light irradiation. The irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2 , more preferably 20 mJ / cm 2 to 5 J / cm 2 , and still more preferably 30 mJ / cm 2 to 3 J / cm 2. 50 to 1000 mJ / cm 2 is particularly preferable. Moreover, in order to accelerate | stimulate a polymerization reaction, you may implement on heating conditions.
In the present invention, the optically anisotropic film can be formed on any support in the optical film of the present invention described later or on the polarizer in the polarizing plate of the present invention described later.
0.50<Re(450)/Re(550)<1.00 ・・・(3)
ここで、上記式(3)中、Re(450)は、光学異方性膜の波長450nmにおける面内レターデーションを表し、Re(550)は、光学異方性膜の波長550nmにおける面内レターデーションを表す。なお、本明細書において、レターデーションの測定波長を明記していない場合は、測定波長は550nmとする。
また、面内レターデーションおよび厚み方向のレターデーションの値は、AxoScan OPMF-1(オプトサイエンス社製)を用い、測定波長の光を用いて測定した値をいう。
具体的には、AxoScan OPMF-1にて、平均屈折率((Nx+Ny+Nz)/3)と膜厚(d(μm))を入力することにより、
遅相軸方向(°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2-nz)×d
が算出される。
なお、R0(λ)は、AxoScan OPMF-1で算出される数値として表示されるものであるが、Re(λ)を意味している。 The optically anisotropic film of the present invention preferably satisfies the following formula (3).
0.50 <Re (450) / Re (550) <1.00 (3)
In the above formula (3), Re (450) represents in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Represents the foundation. In addition, in this specification, when the measurement wavelength of retardation is not specified, the measurement wavelength is 550 nm.
Further, the values of in-plane retardation and retardation in the thickness direction are values measured using AxoScan OPMF-1 (manufactured by Optoscience) and using light having a measurement wavelength.
Specifically, by inputting an average refractive index ((Nx + Ny + Nz) / 3) and a film thickness (d (μm)) in AxoScan OPMF-1.
Slow axis direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) / 2−nz) × d
Is calculated.
Note that R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, and means Re (λ).
フィルム面内の遅相軸方向(面内での屈折率が最大となる方向)の屈折率をnx、面内の遅相軸と面内で直交する方向の屈折率をny、厚み方向の屈折率をnzとしたとき、ポジティブAプレートは式(A1)の関係を満たすものであり、ポジティブCプレートは式(C1)の関係を満たすものである。なお、ポジティブAプレートはRthが正の値を示し、ポジティブCプレートはRthが負の値を示す。
式(A1) nx>ny≒nz
式(C1) nz>nx≒ny
なお、上記「≒」とは、両者が完全に同一である場合だけでなく、両者が実質的に同一である場合も包含する。
「実質的に同一」とは、ポジティブAプレートでは、例えば、(ny-nz)×d(ただし、dはフィルムの厚みである)が、-10~10nm、好ましくは-5~5nmの場合も「ny≒nz」に含まれ、(nx-nz)×dが、-10~10nm、好ましくは-5~5nmの場合も「nx≒nz」に含まれる。また、ポジティブCプレートでは、例えば、(nx-ny)×d(ただし、dはフィルムの厚みである)が、0~10nm、好ましくは0~5nmの場合も「nx≒ny」に含まれる。 Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the slow axis direction in the film plane (direction in which the refractive index in the plane is maximum) is nx, the refractive index in the direction perpendicular to the slow axis in the plane is ny, and the refractive index in the thickness direction. When the rate is nz, the positive A plate satisfies the relationship of the formula (A1), and the positive C plate satisfies the relationship of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Formula (A1) nx> ny≈nz
Formula (C1) nz> nx≈ny
The above “≈” includes not only the case where both are completely the same, but also the case where both are substantially the same.
“Substantially the same” means that, for a positive A plate, for example, (ny-nz) × d (where d is the thickness of the film) is −10 to 10 nm, preferably −5 to 5 nm. It is included in “ny≈nz”, and (nx−nz) × d is also included in “nx≈nz” when −10 to 10 nm, preferably −5 to 5 nm. In the positive C plate, for example, (nx−ny) × d (where d is the thickness of the film) includes 0 to 10 nm, preferably 0 to 5 nm, in “nx≈ny”.
ここで、「λ/4板」とは、λ/4機能を有する板であり、具体的には、ある特定の波長の直線偏光を円偏光に(または円偏光を直線偏光に)変換する機能を有する板である。 When the optically anisotropic film of the present invention is a positive A plate, from the viewpoint of functioning as a λ / 4 plate, Re (550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, More preferably, it is 130 to 150 nm, and particularly preferably 130 to 140 nm.
Here, the “λ / 4 plate” is a plate having a λ / 4 function, and specifically, a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). It is a board which has.
本発明の光学フィルムは、本発明の光学異方性膜を有する光学フィルムである。
図1A、図1Bおよび図1C(以下、これらの図面を特に区別を要しない場合は「図1」と略す。)は、それぞれ本発明の光学フィルムの一例を示す模式的な断面図である。
なお、図1は模式図であり、各層の厚みの関係や位置関係などは必ずしも実際のものとは一致せず、図1に示す支持体、配向膜およびハードコート層は、いずれも任意の構成部材である。
図1に示す光学フィルム10は、支持体16と、配向膜14と、光学異方性膜12とをこの順で有する。
また、光学フィルム10は、図1Bに示すように、支持体16の配向膜14が設けられた側とは反対側にハードコート層18を有していてもよく、図1Cに示すように、光学異方性膜12の配向膜14が設けられた側とは反対側にハードコート層18を有していてもよい。
以下、本発明の光学フィルムに用いられる種々の部材について詳細に説明する。 [Optical film]
The optical film of the present invention is an optical film having the optical anisotropic film of the present invention.
FIG. 1A, FIG. 1B, and FIG. 1C (hereinafter, these drawings are abbreviated as “FIG. 1” unless they need to be distinguished in particular) are schematic cross-sectional views showing examples of the optical film of the present invention.
Note that FIG. 1 is a schematic diagram, and the thickness relationship and positional relationship of each layer do not necessarily match the actual ones, and the support, alignment film, and hard coat layer shown in FIG. It is a member.
The
1B, the
Hereinafter, various members used in the optical film of the present invention will be described in detail.
本発明の光学フィルムが有する光学異方性膜は、上述した本発明の光学異方性膜である。
本発明の光学フィルムにおいては、上記光学異方性膜の厚みについては特に限定されないが、0.1~10μmであるのが好ましく、0.5~5μmであるのがより好ましい。 (Optically anisotropic film)
The optically anisotropic film included in the optical film of the present invention is the optically anisotropic film of the present invention described above.
In the optical film of the present invention, the thickness of the optically anisotropic film is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
本発明の光学フィルムは、上述したように、光学異方性膜を形成するための基材として支持体を有していてもよい。
このような支持体は、透明であるのが好ましく、具体的には、光透過率が80%以上であるのが好ましい。 [Support]
As described above, the optical film of the present invention may have a support as a base material for forming the optically anisotropic film.
Such a support is preferably transparent, and specifically has a light transmittance of 80% or more.
また、後述する偏光子がこのような支持体を兼ねる態様であってもよい。 Examples of such a support include a glass substrate and a polymer film, and examples of the material of the polymer film include a cellulose polymer; an acrylic polymer having an acrylate polymer such as a polymethyl methacrylate and a lactone ring-containing polymer. Polymers; Thermoplastic norbornene polymers; Polycarbonate polymers; Polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; Styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin); Polyethylene, polypropylene, ethylene / propylene copolymer Polyolefin polymers such as polymers; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamide; imide polymers; sulfone polymers; Phon polymers; Polyether ether ketone polymers; Polyphenylene sulfide polymers; Vinylidene chloride polymers; Vinyl alcohol polymers; Vinyl butyral polymers; Arylate polymers; Polyoxymethylene polymers; Epoxy polymers; A mixed polymer may be mentioned.
Moreover, the mode which the polarizer mentioned later serves also as such a support body may be sufficient.
本発明の光学フィルムは、上述した任意の支持体を有する場合、支持体と光学異方性膜との間に、配向膜を有しているのが好ましい。なお、上述した支持体が配向膜を兼ねる態様であってもよい。 (Alignment film)
When the optical film of the present invention has the above-mentioned arbitrary support, it is preferable to have an alignment film between the support and the optically anisotropic film. Note that the above-described support may also serve as an alignment film.
本発明において利用されるポリマー材料は、ポリビニルアルコール又はポリイミド、及びその誘導体が好ましい。特に変性又は未変性のポリビニルアルコールが好ましい。
本発明に使用可能な配向膜については、例えば、国際公開第01/88574号の43頁24行~49頁8行に記載された配向膜;特許第3907735号公報の段落[0071]~[0095]に記載の変性ポリビニルアルコール;特開2012-155308号公報に記載された液晶配向剤により形成される液晶配向膜;等が挙げられる。 The alignment film generally contains a polymer as a main component. The polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
With respect to the alignment film that can be used in the present invention, for example, an alignment film described in International Publication No. 01/88574, page 43, line 24 to page 49, line 8; Japanese Patent No. 3907735, paragraphs [0071] to [0095] Modified liquid alcohol described in JP-A-2012-155308, a liquid crystal alignment film formed with a liquid crystal alignment agent described in JP 2012-155308 A, and the like.
光配向膜としては特に限定はされないが、国際公開第2005/096041号の段落[0024]~[0043]に記載されたポリアミド化合物やポリイミド化合物などのポリマー材料;特開2012-155308号公報に記載された光配向性基を有する液晶配向剤により形成される液晶配向膜;Rolic Technologies社製の商品名LPP-JP265CPなどを用いることができる。 In the present invention, it is also preferable to use a photo-alignment film as the alignment film because it is possible to prevent the deterioration of the surface state by not contacting the alignment film surface when forming the alignment film.
The photo-alignment film is not particularly limited, but is a polymer material such as a polyamide compound or a polyimide compound described in paragraphs [0024] to [0043] of International Publication No. 2005/096041; described in JP 2012-155308 A A liquid crystal alignment film formed of a liquid crystal aligning agent having a photo-alignable group, such as trade name LPP-JP265CP manufactured by Rollic Technologies, Inc. can be used.
本発明の光学フィルムは、フィルムの物理的強度を付与するために、ハードコート層を有しているのが好ましい。具体的には、支持体の配向膜が設けられた側とは反対側にハードコート層を有していてもよく(図1B参照)、光学異方性膜の配向膜が設けられた側とは反対側にハードコート層を有していてもよい(図1C参照)。
ハードコート層としては特開2009-98658号公報の段落[0190]~[0196]に記載のものを使用することができる。 [Hard coat layer]
The optical film of the present invention preferably has a hard coat layer in order to impart the physical strength of the film. Specifically, the support may have a hard coat layer on the side opposite to the side on which the alignment film is provided (see FIG. 1B), and the side on which the alignment film of the optical anisotropic film is provided; May have a hard coat layer on the opposite side (see FIG. 1C).
As the hard coat layer, those described in paragraphs [0190] to [0196] of JP-A-2009-98658 can be used.
本発明の光学フィルムは、本発明の光学異方性膜とは別に、他の光学異方性膜を有していてもよい。
すなわち、本発明の光学フィルムは、本発明の光学異方性膜と他の光学異方性膜との積層構造を有していてもよい。
このような他の光学異方性膜は、上述した重合性液晶化合物(1)および重合性液晶化合物(2)のいずれか一方または両方を配合せず、上述した他の重合性化合物(特に、液晶化合物)を用いて得られる光学異方性膜であれば特に限定されない。
ここで、一般的に、液晶化合物はその形状から、棒状タイプと円盤状タイプに分類できる。さらにそれぞれ低分子と高分子タイプがある。高分子とは一般に重合度が100以上のものを指す(高分子物理・相転移ダイナミクス,土井 正男 著,2頁,岩波書店,1992)。本発明では、いずれの液晶化合物を用いることもできるが、棒状液晶化合物またはディスコティック液晶化合物(円盤状液晶化合物)を用いるのが好ましい。2種以上の棒状液晶化合物、2種以上の円盤状液晶化合物、または棒状液晶化合物と円盤状液晶化合物との混合物を用いてもよい。上述の液晶化合物の固定化のために、重合性基を有する棒状液晶化合物または円盤状液晶化合物を用いて形成することがより好ましく、液晶化合物が1分子中に重合性基を2以上有することがさらに好ましい。液晶化合物が二種類以上の混合物の場合には、少なくとも1種類の液晶化合物が1分子中に2以上の重合性基を有していることが好ましい。
棒状液晶化合物としては、例えば、特表平11-513019号公報の請求項1や特開2005-289980号公報の段落[0026]~[0098]に記載のものを好ましく用いることができ、ディスコティック液晶化合物としては、例えば、特開2007-108732号公報の段落[0020]~[0067]や特開2010-244038号公報の段落[0013]~[0108]に記載のものを好ましく用いることができるが、これらに限定されない。 [Other optically anisotropic films]
The optical film of the present invention may have another optical anisotropic film in addition to the optical anisotropic film of the present invention.
That is, the optical film of the present invention may have a laminated structure of the optical anisotropic film of the present invention and another optical anisotropic film.
Such other optically anisotropic film does not contain any one or both of the above-described polymerizable liquid crystal compound (1) and polymerizable liquid crystal compound (2), and other polymerizable compounds described above (particularly, Any optically anisotropic film obtained by using a liquid crystal compound) is not particularly limited.
Here, in general, liquid crystal compounds can be classified into a rod type and a disk type from the shape. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is preferably used. Two or more kinds of rod-like liquid crystal compounds, two or more kinds of disk-like liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a disk-like liquid crystal compound may be used. In order to fix the liquid crystal compound described above, it is more preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound having a polymerizable group, and the liquid crystal compound has two or more polymerizable groups in one molecule. Further preferred. When the liquid crystal compound is a mixture of two or more, it is preferable that at least one liquid crystal compound has two or more polymerizable groups in one molecule.
As the rod-like liquid crystal compound, for example, those described in claim 1 of JP-T-11-53019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used. As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. However, it is not limited to these.
本発明の光学フィルムは、外光(特に紫外線)の影響を考慮して、紫外線(UV)吸収剤を含むことが好ましい。
紫外線吸収剤は、本発明の光学異方性膜に含有されてしてもよいし、本発明の光学フィルムを構成する光学異方性膜以外の部材に含有されていてもよい。光学異方性膜以外の部材としては、例えば、支持体が好適に挙げられる。
紫外線吸収剤としては、紫外線吸収性を発現できる従来公知のものがいずれも使用できる。このような紫外線吸収剤のうち、紫外線吸収性が高く、画像表示装置で用いられる紫外線吸収能(紫外線カット能)を得る観点から、ベンゾトリアゾール系またはヒドロキシフェニルトリアジン系の紫外線吸収剤を用いることが好ましい。
また、紫外線の吸収幅を広くするために、最大吸収波長の異なる紫外線吸収剤を2種以上併用することができる。
紫外線吸収剤としては、具体的には、例えば、特開2012-18395公報の[0258]~[0259]段落に記載された化合物、特開2007-72163号公報の[0055]~[0105]段落に記載された化合物などが挙げられる。
また、市販品として、Tinuvin400、Tinuvin405、Tinuvin460、Tinuvin477、Tinuvin479、および、Tinuvin1577(いずれもBASF社製)等を用いることができる。 [Ultraviolet absorber]
The optical film of the present invention preferably contains an ultraviolet (UV) absorber in consideration of the influence of external light (particularly ultraviolet rays).
The ultraviolet absorber may be contained in the optically anisotropic film of the present invention, or may be contained in a member other than the optically anisotropic film constituting the optical film of the present invention. As a member other than the optically anisotropic film, for example, a support is preferably mentioned.
As the UV absorber, any conventionally known UV absorber can be used. Of these ultraviolet absorbers, a benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorber is used from the viewpoint of high ultraviolet absorption and obtaining ultraviolet absorption capability (ultraviolet cut capability) used in an image display device. preferable.
Moreover, in order to widen the absorption width of ultraviolet rays, two or more ultraviolet absorbers having different maximum absorption wavelengths can be used in combination.
Specific examples of the ultraviolet absorber include compounds described in paragraphs [0258] to [0259] of JP2012-18395A, and paragraphs [0055] to [0105] of JP2007-72163A. And the like.
Moreover, Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577 (all are BASF Corporation) etc. can be used as a commercial item.
本発明の偏光板は、上述した本発明の光学フィルムと、偏光子とを有するものである。
また、本発明の偏光板は、上述した本発明の光学異方性膜がλ/4板(ポジティブAプレート)である場合、円偏光板として用いることができる。
また、本発明の偏光板は、上述した本発明の光学異方性膜がλ/4板(ポジティブAプレート)である場合、λ/4板の遅相軸と後述する偏光子の吸収軸とのなす角が30~60°であることが好ましく、40~50°であることがより好ましく、42~48°であることが更に好ましく、45°であることが特に好ましい。
ここで、λ/4板の「遅相軸」は、λ/4板の面内において屈折率が最大となる方向を意味し、偏光子の「吸収軸」は、吸光度の最も高い方向を意味する。 [Polarizer]
The polarizing plate of the present invention has the above-described optical film of the present invention and a polarizer.
The polarizing plate of the present invention can be used as a circularly polarizing plate when the above-described optically anisotropic film of the present invention is a λ / 4 plate (positive A plate).
In the polarizing plate of the present invention, when the above-described optically anisotropic film of the present invention is a λ / 4 plate (positive A plate), the slow axis of the λ / 4 plate and the absorption axis of the polarizer described later Is preferably 30 to 60 °, more preferably 40 to 50 °, still more preferably 42 to 48 °, and particularly preferably 45 °.
Here, the “slow axis” of the λ / 4 plate means the direction in which the refractive index is maximum in the plane of the λ / 4 plate, and the “absorption axis” of the polarizer means the direction having the highest absorbance. To do.
本発明の偏光板が有する偏光子は、光を特定の直線偏光に変換する機能を有する部材であれば特に限定されず、従来公知の吸収型偏光子および反射型偏光子を利用することができる。
吸収型偏光子としては、ヨウ素系偏光子、二色性染料を利用した染料系偏光子、およびポリエン系偏光子などが用いられる。ヨウ素系偏光子および染料系偏光子には、塗布型偏光子と延伸型偏光子があり、いずれも適用できるが、ポリビニルアルコールにヨウ素または二色性染料を吸着させ、延伸して作製される偏光子が好ましい。
また、基材上にポリビニルアルコール層を形成した積層フィルムの状態で延伸および染色を施すことで偏光子を得る方法として、特許第5048120号公報、特許第5143918号公報、特許第4691205号公報、特許第4751481号公報、特許第4751486号公報を挙げることができ、これらの偏光子に関する公知の技術も好ましく利用することができる。
反射型偏光子としては、複屈折の異なる薄膜を積層した偏光子、ワイヤーグリッド型偏光子、選択反射域を有するコレステリック液晶と1/4波長板とを組み合わせた偏光子などが用いられる。
なかでも、密着性がより優れる点で、ポリビニルアルコール系樹脂(-CH2-CHOH-を繰り返し単位として含むポリマー。特に、ポリビニルアルコールおよびエチレン-ビニルアルコール共重合体からなる群から選択される少なくとも1つ)を含む偏光子であることが好ましい。 [Polarizer]
The polarizer which the polarizing plate of this invention has is not specifically limited if it is a member which has a function which converts light into specific linearly polarized light, A conventionally well-known absorption type polarizer and reflection type polarizer can be utilized. .
As the absorption polarizer, an iodine polarizer, a dye polarizer using a dichroic dye, a polyene polarizer, and the like are used. Iodine polarizers and dye polarizers include coating polarizers and stretchable polarizers, both of which can be applied. Polarized light produced by adsorbing iodine or dichroic dye to polyvinyl alcohol and stretching. A child is preferred.
Further, as a method for obtaining a polarizer by stretching and dyeing in the state of a laminated film in which a polyvinyl alcohol layer is formed on a substrate, Patent No. 5048120, Patent No. 5143918, Patent No. 4691205, Patent No. 4751481 and Japanese Patent No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used.
As the reflective polarizer, a polarizer in which thin films having different birefringence are stacked, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate are combined, or the like is used.
Among them, a polyvinyl alcohol resin (a polymer containing —CH 2 —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, in terms of better adhesion. Are preferably included.
本発明の偏光板は、本発明の光学フィルムにおける光学異方性膜と、偏光子との間に、粘着剤層が配置されていてもよい。
光学異方性膜と偏光子との積層のために用いられる粘着剤層としては、例えば、動的粘弾性測定装置で測定した貯蔵弾性率G’と損失弾性率G”との比(tanδ=G”/G’)が0.001~1.5である物質のことを表し、いわゆる、粘着剤やクリープしやすい物質等が含まれる。本発明に用いることのできる粘着剤としては、例えば、ポリビニルアルコール系粘着剤が挙げられるが、これに限定されない。 (Adhesive layer)
In the polarizing plate of the present invention, an adhesive layer may be disposed between the optically anisotropic film and the polarizer in the optical film of the present invention.
As the pressure-sensitive adhesive layer used for laminating the optically anisotropic film and the polarizer, for example, the ratio of the storage elastic modulus G ′ and the loss elastic modulus G ″ measured with a dynamic viscoelasticity measuring apparatus (tan δ = G ″ / G ′) represents a material having a value of 0.001 to 1.5, and includes a so-called pressure-sensitive adhesive, a substance that easily creeps, and the like. Examples of the adhesive that can be used in the present invention include, but are not limited to, a polyvinyl alcohol-based adhesive.
本発明の画像表示装置は、本発明の光学フィルムまたは本発明の偏光板を有する、画像表示装置である。
本発明の画像表示装置に用いられる表示素子は特に限定されず、例えば、液晶セル、有機エレクトロルミネッセンス(以下、「EL」と略す。)表示パネル、プラズマディスプレイパネル等が挙げられる。
これらのうち、液晶セル、有機EL表示パネルであるのが好ましく、液晶セルであるのがより好ましい。すなわち、本発明の画像表示装置としては、表示素子として液晶セルを用いた液晶表示装置、表示素子として有機EL表示パネルを用いた有機EL表示装置であるのが好ましく、液晶表示装置であるのがより好ましい。 [Image display device]
The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, a plasma display panel, and the like.
Among these, a liquid crystal cell and an organic EL display panel are preferable, and a liquid crystal cell is more preferable. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, and an organic EL display device using an organic EL display panel as a display element, and is a liquid crystal display device. More preferred.
本発明の画像表示装置の一例である液晶表示装置は、上述した本発明の偏光板と、液晶セルとを有する液晶表示装置である。
なお、本発明においては、液晶セルの両側に設けられる偏光板のうち、フロント側の偏光板として本発明の偏光板を用いるのが好ましく、フロント側およびリア側の偏光板として本発明の偏光板を用いるのがより好ましい。
以下に、液晶表示装置を構成する液晶セルについて詳述する。 [Liquid Crystal Display]
The liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-described polarizing plate of the present invention and a liquid crystal cell.
In the present invention, among the polarizing plates provided on both sides of the liquid crystal cell, the polarizing plate of the present invention is preferably used as the polarizing plate on the front side, and the polarizing plate of the present invention is used as the polarizing plate on the front side and the rear side. Is more preferable.
Below, the liquid crystal cell which comprises a liquid crystal display device is explained in full detail.
液晶表示装置に利用される液晶セルは、VA(Vertical Alignment)モード、OCB(Optically Compensated Bend)モード、IPS(In-Plane-Switching)モード、又はTN(Twisted Nematic)であることが好ましいが、これらに限定されるものではない。
TNモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に水平配向し、更に60~120゜にねじれ配向している。TNモードの液晶セルは、カラーTFT液晶表示装置として最も多く利用されており、多数の文献に記載がある。
VAモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に垂直に配向している。VAモードの液晶セルには、(1)棒状液晶性分子を電圧無印加時に実質的に垂直に配向させ、電圧印加時に実質的に水平に配向させる狭義のVAモードの液晶セル(特開平2-176625号公報記載)に加えて、(2)視野角拡大のため、VAモードをマルチドメイン化した(MVAモードの)液晶セル(SID97、Digest of tech.Papers(予稿集)28(1997)845記載)、(3)棒状液晶性分子を電圧無印加時に実質的に垂直配向させ、電圧印加時にねじれマルチドメイン配向させるモード(n-ASMモード)の液晶セル(日本液晶討論会の予稿集58~59(1998)記載)及び(4)SURVIVALモードの液晶セル(LCDインターナショナル98で発表)が含まれる。また、PVA(Patterned Vertical Alignment)型、光配向型(Optical Alignment)、及びPSA(Polymer-Sustained Alignment)のいずれであってもよい。これらのモードの詳細については、特開2006-215326号公報、及び特表2008-538819号公報に詳細な記載がある。
IPSモードの液晶セルは、棒状液晶分子が基板に対して実質的に平行に配向しており、基板面に平行な電界が印加することで液晶分子が平面的に応答する。IPSモードは電界無印加状態で黒表示となり、上下一対の偏光板の吸収軸は直交している。光学補償シートを用いて、斜め方向での黒表示時の漏れ光を低減させ、視野角を改良する方法が、特開平10-54982号公報、特開平11-202323号公報、特開平9-292522号公報、特開平11-133408号公報、特開平11-305217号公報、特開平10-307291号公報などに開示されている。 <Liquid crystal cell>
The liquid crystal cell used in the liquid crystal display device is preferably in a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic). It is not limited to.
In a TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °. The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied. The VA mode liquid crystal cell includes: (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle. ), (3) A liquid crystal cell (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98). Further, any of a PVA (Patterned Vertical Alignment) type, a photo-alignment type (Optical Alignment), and a PSA (Polymer-Stained Alignment) may be used. Details of these modes are described in JP-A-2006-215326 and JP-T 2008-538819.
In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. The IPS mode displays black when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light during black display in an oblique direction and improving the viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.
本発明の画像表示装置の一例である有機EL表示装置としては、例えば、視認側から、偏光子と、本発明の光学異方性膜からなるλ/4板(ポジティブAプレート)と、有機EL表示パネルとをこの順で有する態様が好適に挙げられる。
また、有機EL表示パネルは、電極間(陰極および陽極間)に有機発光層(有機エレクトロルミネッセンス層)を挟持してなる有機EL素子を用いて構成された表示パネルである。有機EL表示パネルの構成は特に制限されず、公知の構成が採用される。 [Organic EL display device]
As an organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, a polarizer, a λ / 4 plate (positive A plate) made of the optically anisotropic film of the present invention, and an organic EL device. An embodiment having the display panel in this order is preferable.
The organic EL display panel is a display panel configured using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration is adopted.
下記式(I-1)で表される化合物(I-1)の合成は、Justus Liebigs Annalen der Chemie,726,103-109(1969)に記載の方法を参考にして行った。
The synthesis of the compound (I-1) represented by the following formula (I-1) was performed with reference to the method described in Justus Liebigs Analder der Chemie, 726, 103-109 (1969).
下記式(I-4)で表される化合物(I-4)の合成は、ベンゾキノンを2-t-ブチルベンゾキノンに変更した以外は、化合物(I-1)と同様の方法で合成した。
Compound (I-4) represented by the following formula (I-4) was synthesized in the same manner as compound (I-1) except that benzoquinone was changed to 2-t-butylbenzoquinone.
反応終了後、室温(23℃)まで冷却した後に、ろ過にて触媒を除いた。
次いで、酢酸を減圧留去した後、酢酸エチル、および、炭酸水素ナトリウム水溶液を添加した。その後、撹拌し、分液して水層を除去し、更に、有機層を10%食塩水で洗浄した。この溶液に硫酸ナトリウムを加えて乾燥し、溶媒を濃縮することで、4,4’-ジシクロヘキサンジカルボン酸ジメチル(S-1-b)(130g)を得た。
これ以上の精製は行わず、引き続き、4,4’-ジシクロヘキサンジカルボン酸ジメチル(130g)、水酸化カリウムペレット(Aldrich製、純度90%)86.3g、クメン1300mL、および、ポリエチレングリコール2000(東京化成工業社製)10mLを混合し、ディーンスターク管をつけて120℃にて加熱撹拌した。メタノールを留去した後に、外設を180℃として、溶媒を留去しながら20時間加熱還流を続けた。NMR(Nuclear Magnetic Resonance)にて反応進行を確認し、反応終了後、冷却し、反応液にエタノール1300mLを添加し、析出しているカリウム塩をろ取した。
次いで、このカリウム塩を水1300mlに溶解し、氷冷下で濃塩酸を系のpHが3になるまで添加し、析出したカルボン酸をろ取し、粗体を回収した。
回収した粗体をアセトン500mLに懸濁し、50℃で30分撹拌した後に、室温に冷却し、ろ取し、ジシクロヘキサンジカルボン酸(S-1-c)の結晶を93.9g(収率80%)得た。 As shown in the above scheme, 125 g (0.462 mol) of dimethyl 4,4-biphenyldicarboxylate (S-1-a) was added to 1000 mL of acetic acid, and 12.5 g of palladium carbon catalyst (wet product) was added. The catalytic hydrogenation reaction was carried out in an autoclave at 130 ° C. and 2 MPa.
After completion of the reaction, the reaction mixture was cooled to room temperature (23 ° C.), and then the catalyst was removed by filtration.
Then, after acetic acid was distilled off under reduced pressure, ethyl acetate and an aqueous sodium hydrogen carbonate solution were added. Thereafter, the mixture was stirred and separated to remove the aqueous layer, and the organic layer was washed with 10% brine. Sodium sulfate was added to this solution for drying, and the solvent was concentrated to obtain dimethyl 4,4′-dicyclohexanedicarboxylate (S-1-b) (130 g).
Without further purification, dimethyl 4,4′-dicyclohexanedicarboxylate (130 g), potassium hydroxide pellets (manufactured by Aldrich, purity 90%) 86.3 g, cumene 1300 mL, and polyethylene glycol 2000 (Tokyo) (Made by Kasei Kogyo Co., Ltd.) 10 mL was mixed, a Dean-Stark tube was attached, and it heated and stirred at 120 degreeC. After the methanol was distilled off, the external temperature was set to 180 ° C., and heating and refluxing were continued for 20 hours while the solvent was distilled off. The progress of the reaction was confirmed by NMR (Nuclear Magnetic Resonance). After completion of the reaction, the reaction mixture was cooled, 1300 mL of ethanol was added to the reaction solution, and the precipitated potassium salt was collected by filtration.
Next, this potassium salt was dissolved in 1300 ml of water, concentrated hydrochloric acid was added under ice cooling until the pH of the system became 3, and the precipitated carboxylic acid was collected by filtration to recover a crude product.
The recovered crude product was suspended in 500 mL of acetone, stirred at 50 ° C. for 30 minutes, cooled to room temperature, and collected by filtration to obtain 93.9 g of a crystal of dicyclohexanedicarboxylic acid (S-1-c) (yield: 80 %)Obtained.
混合物に、4-メチルスルホニルオキシブチルアクリレート9.61g(43.2mmol)を加え、100℃にて5時間撹拌した。室温まで冷却した後、1N塩酸水30ml、トルエン50mlを加え、40℃にて撹拌後、分液を行った。有機層を、5%炭酸水素ナトリウム水溶液、1%炭酸水素ナトリウム水溶液、1%炭酸水素ナトリウム水溶液で順次洗浄したのちに、溶媒を減圧留去した。残渣にヘキサン40mLを加えて結晶を析出させたのちに5℃まで冷却し、氷水下で30分間撹拌したのちに、粗体をろ取した。得られた粗体をヘキサン40mLにけん濁させ、30分撹拌したのちに、ろ取し、送風乾燥することで、化合物(S-1-d)を5.39g得た(収率36%)。 As shown in the above scheme, 10.0 g (39.3 mmol) of the compound (S-1-c), 50 mL of N, N-dimethylacetamide (DMAc), 8.0 ml (78.6 mmol) of triethylamine, and 2,6 -433 mg of di-t-butyl-4-methylphenol was mixed at room temperature (23 ° C).
To the mixture, 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 30 ml of 1N hydrochloric acid and 50 ml of toluene were added, and the mixture was stirred at 40 ° C. and then separated. The organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution, 1% aqueous sodium hydrogen carbonate solution and 1% aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. After adding 40 mL of hexane to the residue to precipitate crystals, the mixture was cooled to 5 ° C. and stirred for 30 minutes under ice water, and then the crude product was collected by filtration. The obtained crude product was suspended in 40 mL of hexane, stirred for 30 minutes, filtered, and dried by blowing to obtain 5.39 g of compound (S-1-d) (yield 36%). .
特開2010-084032号公報の[0161]~[0163]段落に記載された方法に従い、下記式で表される重合性液晶化合物(1-9)を合成した。
A polymerizable liquid crystal compound (1-9) represented by the following formula was synthesized according to the method described in paragraphs [0161] to [0163] of JP 2010-084032 A.
塩化アルミニウム17.3gとジクロロエタン100mLを5~10℃に冷却し、化合物(S-2-a)12.9gを添加した。5~10℃でアセチルクロリド5.1gを滴下し、5-10℃で1時間撹拌した。水100mLを加え、反応を停止し、有機層を硫酸マグネシウムで乾燥した。シリカゲルカラムクロマトグラフィーにより精製し、化合物(S-2-b)9.3g(収率60%)を得た。
次亜塩素酸ナトリウム75.0gと水酸化ナトリウム13.9gの溶解液にテトラブチルアンモニウムクロライド0.28gおよび硫酸ナトリウム2.8gを添加した後、化合物(S-2-b)8.6gを加え、60℃で3時間撹拌した。室温まで冷却後、30%硫酸により、pHを2に調整し、析出したカルボン酸をろ取し、粗体を回収した。回収した粗体をアセトン50mLに懸濁し、50℃で30分撹拌した後に、室温に冷却し、ろ取し、化合物(S-2-c)7.8g(収率90%)得た。 As shown in the above scheme, a suspension of 60.0 g of aluminum chloride and 30.0 g of acetyl chloride in 120 mL of carbon disulfide was cooled to −50 ° C., and 30.0 g of cyclohexene was added dropwise. After stirring at −20 ° C. or lower for 15 minutes, the solution portion was removed, and 300 mL of benzene was added, followed by stirring at 45 ° C. for 3 hours. The reaction solution was ice-cooled, quenched with 100 mL of 1N hydrochloric acid, and the organic layer was washed with 1N hydrochloric acid and 10% aqueous NaOH. The reaction mixture was dried over magnesium sulfate and purified by silica gel column chromatography to obtain 32.0 g of compound (S-2-a).
17.3 g of aluminum chloride and 100 mL of dichloroethane were cooled to 5 to 10 ° C., and 12.9 g of compound (S-2-a) was added. 5.1 g of acetyl chloride was added dropwise at 5-10 ° C., and the mixture was stirred at 5-10 ° C. for 1 hour. 100 mL of water was added to stop the reaction, and the organic layer was dried over magnesium sulfate. Purification by silica gel column chromatography gave 9.3 g (yield 60%) of compound (S-2-b).
After adding 0.28 g of tetrabutylammonium chloride and 2.8 g of sodium sulfate to a solution of 75.0 g of sodium hypochlorite and 13.9 g of sodium hydroxide, 8.6 g of compound (S-2-b) was added. , And stirred at 60 ° C. for 3 hours. After cooling to room temperature, the pH was adjusted to 2 with 30% sulfuric acid, the precipitated carboxylic acid was collected by filtration, and the crude product was recovered. The recovered crude product was suspended in 50 mL of acetone and stirred at 50 ° C. for 30 minutes, then cooled to room temperature and collected by filtration to obtain 7.8 g of compound (S-2-c) (yield 90%).
化合物(S-1-e)の合成に用いた化合物(I-1)を化合物(I-4)に代えた以外は、重合性液晶化合物(2-1-5)と同じ方法で、下記式で表される重合性液晶化合物(2-3-1)を合成した。
Except that the compound (I-1) used for the synthesis of the compound (S-1-e) was replaced with the compound (I-4), the same method as in the polymerizable liquid crystal compound (2-1-5) was used. A polymerizable liquid crystal compound represented by the formula (2-3-1) was synthesized.
化合物(I-1)に代えて、特開2010-084032号公報の[0161]段落に記載された化合物Iを用いた以外は、重合性液晶化合物(2-1-7)と同じ方法で、下記式で表される重合性液晶化合物(2-9-2)を合成した。
In the same manner as the polymerizable liquid crystal compound (2-1-7) except that the compound I described in paragraph [0161] of JP 2010-084032 A was used instead of the compound (I-1), A polymerizable liquid crystal compound (2-9-2) represented by the following formula was synthesized.
合成した重合性液晶化合物の溶解性の測定を以下に示す方法で行った。結果を下記表3および表4に示す。なお、下記3および表4中、実施例1~8の溶解性の評価は、下記表3および表4中に記載する重合性液晶化合物を下記表3および表4中に記載の比率で混合した混合物で評価した。
まず、10mLのサンプル瓶に重合性液晶化合物を総量として1.0g秤量し、固形分が40質量%になるまで溶媒を1.5g加えた。その後、50℃にて手でよく振り混ぜ、室温(23℃)で10分間放置した後、目視で観察してクリアであれば終了して、溶解性40質量%と判定した。
一方、溶け残りがあれば固形分が35質量%になるように溶媒を加えた(+0.36g)。その後、50℃にて手でよく振り混ぜ、室温(23℃)で10分間放置した後、目視で観察してクリアであれば終了して、35質量%と判定した。
また、更に溶け残りがあれば30質量%になるように溶媒を加えた。同様の操作を5質量%刻みで行い、5質量%になるまで繰り返して、溶け残りがある場合は溶解性5質量%未満(<5質量%)と判定し、終了した。溶解性測定の溶媒として、CPN(シクロペンタノン)を使用した。
A:CPNに対する溶解性が20%以上
B:CPNに対する溶解性が10%以上20%未満
C:CPNに対する溶解性が5%以上10%未満
D:CPNに対する溶解性が5%以下 [Solubility]
The solubility of the synthesized polymerizable liquid crystal compound was measured by the following method. The results are shown in Table 3 and Table 4 below. In the following 3 and Table 4, the evaluation of the solubility of Examples 1 to 8 was carried out by mixing the polymerizable liquid crystal compounds described in Table 3 and Table 4 in the ratios described in Table 3 and Table 4 below. The mixture was evaluated.
First, 1.0 g of the total amount of the polymerizable liquid crystal compound was weighed in a 10 mL sample bottle, and 1.5 g of a solvent was added until the solid content became 40% by mass. Thereafter, the mixture was shaken well by hand at 50 ° C., and allowed to stand at room temperature (23 ° C.) for 10 minutes.
On the other hand, if there was any undissolved residue, the solvent was added so that the solid content was 35% by mass (+0.36 g). Thereafter, the mixture was shaken well by hand at 50 ° C., left at room temperature (23 ° C.) for 10 minutes, and then visually observed to finish if it was clear, and determined to be 35% by mass.
Further, if there was any undissolved residue, a solvent was added so that it would be 30% by mass. The same operation was performed in increments of 5% by mass, and repeated until 5% by mass. If there was undissolved, it was determined that the solubility was less than 5% by mass (<5% by mass), and the process was completed. CPN (cyclopentanone) was used as a solvent for solubility measurement.
A: Solubility in CPN is 20% or more B: Solubility in CPN is 10% or more and less than 20% C: Solubility in CPN is 5% or more and less than 10% D: Solubility in CPN is 5% or less
実施例および比較例で合成した重合性液晶化合物の溶解安定性の測定を以下に示す方法で行った。結果を下記表3および表4に示す。なお、下記3および表4中、実施例1~8の溶解安定性の評価は、下記表3および表4中に記載する重合性液晶化合物を下記表3および表4中に記載の比率で混合した混合物で評価した。
具体的には、10mLのサンプル瓶に重合性液晶化合物を総量として1.0g秤量し、所定の固形分(表3では15質量%、表4では30質量%)になるまで溶媒を加えた後、50℃にて手でよく振り混ぜ、室温(23℃)で10分間放置した後、目視で観察した。
その後、溶解液のはいったサンプル瓶を23℃にて28日間経時させた。液を作成して14日後および28日後に析出の有無を目視で確認した。
溶解安定性測定の溶媒として、CPN(シクロペンタノン)を使用した。
A:析出はみられず、液はクリアである。
B:析出物はみられないが、液にわずかに濁りがある。
C:わずかに析出物がみられる。
D:大量の析出物がみられる。
E:液全体が固化している。 [Solution stability]
The dissolution stability of the polymerizable liquid crystal compounds synthesized in Examples and Comparative Examples was measured by the following method. The results are shown in Table 3 and Table 4 below. In the following 3 and Table 4, the dissolution stability of Examples 1 to 8 was evaluated by mixing the polymerizable liquid crystal compounds described in Table 3 and Table 4 in the ratios described in Table 3 and Table 4 below. The mixture was evaluated.
Specifically, after weighing 1.0 g of the polymerizable liquid crystal compound as a total amount in a 10 mL sample bottle and adding a solvent until a predetermined solid content (15% by mass in Table 3, 30% by mass in Table 4) is obtained. The mixture was shaken well by hand at 50 ° C., allowed to stand at room temperature (23 ° C.) for 10 minutes, and then visually observed.
Thereafter, the sample bottle containing the dissolved solution was aged at 23 ° C. for 28 days. The presence or absence of precipitation was visually confirmed 14 days and 28 days after the liquid was prepared.
CPN (cyclopentanone) was used as a solvent for dissolution stability measurement.
A: No precipitation is observed, and the liquid is clear.
B: Although no precipitate is observed, the liquid is slightly turbid.
C: Slight deposits are observed.
D: A large amount of precipitate is observed.
E: The whole liquid is solidified.
〔光学フィルムの作製〕
下記の組成を有する重合性組成物(光学異方性膜用塗布液)を調製し、ラビング処理されたポリイミド配向膜(日産化学工業(株)製SE-150)付ガラス基板にスピンコートにより塗布した。塗膜を200℃で配向処理し、液晶層を形成した。その後、135℃まで冷却して1000mJ/cm2の紫外線照射による配向固定化を行い、光学異方性膜を形成し、波長分散測定用の光学フィルムを得た。 [Examples 1 to 8 and Comparative Examples 1 to 3]
[Production of optical film]
A polymerizable composition (coating solution for optically anisotropic film) having the following composition was prepared and applied by spin coating to a glass substrate with a rubbed polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.). did. The coating film was aligned at 200 ° C. to form a liquid crystal layer. Then, it cooled to 135 degreeC, the orientation fixation by 1000 mJ / cm < 2 > ultraviolet irradiation was performed, the optically anisotropic film was formed, and the optical film for wavelength dispersion measurement was obtained.
光学異方性膜用塗布液
―――――――――――――――――――――――――――――――――
・重合性液晶化合物(1)(下記表3または下記表4に記載の化合物)
・重合性液晶化合物(2)(下記表3または下記表4に記載の化合物)
・光重合開始剤(イルガキュア819、BASF社製) 0.45質量部
・下記含フッ素化合物A 0.12質量部
・シクロペンタノン 85.00質量部
―――――――――――――――――――――――――――――――――
ここで、上記重合性液晶性化合物(1)および(2)の含有量は、合計で15質量部であり、それぞれを下記表3および下記表4に示す比率(%)で配合した。
なお、下記表4中、重合性液晶性化合物(1)としての重合性液晶化合物(1-1)と(1-3)との混合比は1:1であり、重合性液晶性化合物(2)としての重合性液晶化合物(2-1-5)と(2-3-1)との混合比は1:1である。 ―――――――――――――――――――――――――――――――――
Coating liquid for optically anisotropic film ―――――――――――――――――――――――――――――――――
Polymerizable liquid crystal compound (1) (compound described in Table 3 or Table 4 below)
Polymerizable liquid crystal compound (2) (compound described in Table 3 or Table 4 below)
Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass The following fluorine-containing compound A 0.12 parts by mass Cyclopentanone 85.00 parts by mass ―――――――――――――――――――――
Here, content of the said polymeric liquid crystalline compound (1) and (2) is 15 mass parts in total, and each was mix | blended by the ratio (%) shown in following Table 3 and following Table 4. FIG.
In Table 4 below, the mixing ratio of the polymerizable liquid crystal compounds (1-1) and (1-3) as the polymerizable liquid crystal compound (1) is 1: 1, and the polymerizable liquid crystal compound (2 The mixing ratio of the polymerizable liquid crystal compound (2-1-5) and (2-3-1) as 1) is 1: 1.
作製した光学フィルムについて、面状を偏光顕微鏡および目視で確認し、以下の基準で評価した。
A:輝点やスジ状の欠陥はみられない
B:輝点やスジ状の欠陥が一部みられる
C:輝点やスジ状の欠陥が多い
D:全面に欠陥発生、または、配向しない [Surface]
About the produced optical film, planar shape was confirmed with the polarizing microscope and visual observation, and the following references | standards evaluated.
A: No bright spots or streak-like defects are observed B: Some bright spots or streak-like defects are observed C: Many bright spots or streak-like defects are present D: Defects are not generated or oriented on the entire surface
これに対し、重合性液晶化合物(1)および重合性液晶化合物(2)の混合物は、溶解安定性が良好となり、これを用いて形成した光学フィルムの面状も良好となることが分かった(実施例1~8)。 From the results shown in Table 3 and Table 4 above, it was found that when the polymerizable liquid crystal compound (2) was not blended, that is, the single product of the polymerizable liquid crystal compound (1) was inferior in dissolution stability (Comparative Examples 1 to 3).
On the other hand, it was found that the mixture of the polymerizable liquid crystal compound (1) and the polymerizable liquid crystal compound (2) has good dissolution stability, and the surface shape of an optical film formed using the mixture is also good ( Examples 1 to 8).
Claims (10)
- 下記式(1)で表される重合性液晶化合物と、下記式(2)で表される重合性液晶化合物とを含有する、重合性液晶組成物。
L1-SP1-D3-G3-G1-D1-Ar-D2-G2-G4-D4-SP2-L2 ・・・(1)
L1-SP1-D3-A3-A1-D1-Ar-D2-A2-A4-D4-SP2-L2 ・・・(2)
前記式(1)中、G1、G2、G3およびG4は、それぞれ独立に、置換基を有していてもよいシクロヘキサン環を表す。
前記式(2)中、A1、A2、A3およびA4は、それぞれ独立に、置換基を有していてもよいシクロヘキサン環、または、置換基を有していてもよい6員不飽和環を表す。ただし、A1およびA3の少なくとも一方は、置換基を有していてもよい6員不飽和環を表す。
前記式(1)および(2)中、D1、D2、D3およびD4は、それぞれ独立に、単結合、または、-CO-、-O-、-S-、-C(=S)-、-CR1R2-、-CR3=CR4-、-NR5-、もしくは、これらの2つ以上の組み合わせからなる2価の連結基を表し、R1~R5は、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
また、SP1およびSP2は、それぞれ独立に、単結合、炭素数1~12の直鎖状もしくは分岐状のアルキレン基、または、炭素数1~12の直鎖状もしくは分岐状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、もしくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
また、L1およびL2は、それぞれ独立に1価の有機基を表し、L1およびL2の少なくとも一方は重合性基を表す。ただし、Arが、下記式(Ar-3)で表される芳香環である場合は、L1およびL2ならびに下記式(Ar-3)中のL3およびL4の少なくとも1つが重合性基を表す。
また、Arは、下記式(Ar-1)~(Ar-5)で表される基からなる群から選択されるいずれかの芳香環を表す。
また、Q1は、NまたはCHを表す。
また、Q2は、-S-、-O-、または、-N(R6)-を表し、R6は、水素原子または炭素数1~6のアルキル基を表す。
また、Y1は、置換基を有してもよい、炭素数6~12の芳香族炭化水素基、または、炭素数3~12の芳香族複素環基を表す。
また、Z1、Z2およびZ3は、それぞれ独立に、水素原子、炭素数1~20の1価の脂肪族炭化水素基、炭素数3~20の1価の脂環式炭化水素基、炭素数6~20の1価の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、-OR7、-NR8R9、または、-SR10を表し、R7~R10は、それぞれ独立に、水素原子または炭素数1~6のアルキル基を表し、Z1およびZ2は、互いに結合して芳香環を形成してもよい。
また、A3およびA4は、それぞれ独立に、-O-、-N(R11)-、-S-、および、-CO-からなる群から選択される基を表し、R11は、水素原子または置換基を表す。
また、Xは、水素原子または置換基が結合していてもよい第14~16族の非金属原子を表す。
また、D5およびD6は、それぞれ独立に、単結合、または、-CO-、-O-、-S-、-C(=S)-、-CR1R2-、-CR3=CR4-、-NR5-、もしくは、これらの2つ以上の組み合わせからなる2価の連結基を表し、R1~R5は、それぞれ独立に、水素原子、フッ素原子、または、炭素数1~4のアルキル基を表す。
また、SP3およびSP4は、それぞれ独立に、単結合、炭素数1~12の直鎖状もしくは分岐状のアルキレン基、または、炭素数1~12の直鎖状もしくは分岐状のアルキレン基を構成する-CH2-の1個以上が-O-、-S-、-NH-、-N(Q)-、もしくは、-CO-に置換された2価の連結基を表し、Qは、置換基を表す。
また、L3およびL4は、それぞれ独立に1価の有機基を表し、L3およびL4ならびに前記式(1)または(2)中のL1およびL2の少なくとも1つが重合性基を表す。
また、Axは、芳香族炭化水素環および芳香族複素環からなる群から選ばれる少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
また、Ayは、水素原子、置換基を有していてもよい炭素数1~12のアルキル基、または、芳香族炭化水素環および芳香族複素環からなる群から選択される少なくとも1つの芳香環を有する、炭素数2~30の有機基を表す。
また、AxおよびAyにおける芳香環は、置換基を有していてもよく、AxとAyとが結合して環を形成していてもよい。
また、Q3は、水素原子、または、置換基を有していてもよい炭素数1~6のアルキル基を表す。 A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound represented by the following formula (1) and a polymerizable liquid crystal compound represented by the following formula (2).
L 1 -SP 1 -D 3 -G 3 -G 1 -D 1 -Ar-D 2 -G 2 -G 4 -D 4 -SP 2 -L 2 (1)
L 1 -SP 1 -D 3 -A 3 -A 1 -D 1 -Ar-D 2 -A 2 -A 4 -D 4 -SP 2 -L 2 (2)
In the formula (1), G 1 , G 2 , G 3 and G 4 each independently represent a cyclohexane ring which may have a substituent.
In the formula (2), A 1 , A 2 , A 3 and A 4 are each independently a cyclohexane ring which may have a substituent, or a 6-membered group which may have a substituent. Represents a saturated ring. However, at least one of A 1 and A 3 represents a 6-membered unsaturated ring which may have a substituent.
In the formulas (1) and (2), D 1 , D 2 , D 3 and D 4 are each independently a single bond, or —CO—, —O—, —S—, —C (═S ) —, —CR 1 R 2 —, —CR 3 ═CR 4 —, —NR 5 —, or a divalent linking group consisting of two or more thereof, wherein R 1 to R 5 are each Independently, it represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
SP 1 and SP 2 each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. A divalent linking group in which one or more of —CH 2 — constituting is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Represents a substituent.
L 1 and L 2 each independently represent a monovalent organic group, and at least one of L 1 and L 2 represents a polymerizable group. However, when Ar is an aromatic ring represented by the following formula (Ar-3), at least one of L 1 and L 2 and L 3 and L 4 in the following formula (Ar-3) is a polymerizable group. Represents.
Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-5).
Q 1 represents N or CH.
Q 2 represents —S—, —O—, or —N (R 6 ) —, and R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y 1 represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms.
Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, —OR 7 , —NR 8 R 9 , or —SR 10 , wherein R 7 to R 10 each represents Independently, it represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may combine with each other to form an aromatic ring.
A 3 and A 4 each independently represents a group selected from the group consisting of —O—, —N (R 11 ) —, —S—, and —CO—, and R 11 represents hydrogen Represents an atom or substituent.
X represents a hydrogen atom or a non-metal atom of Groups 14 to 16 to which a substituent may be bonded.
D 5 and D 6 are each independently a single bond, or —CO—, —O—, —S—, —C (═S) —, —CR 1 R 2 —, —CR 3 ═CR. 4 -, - NR 5 -, or a divalent linking group formed from these two or more thereof, R 1 - R 5 are each independently a hydrogen atom, a fluorine atom or a C 1 - 4 represents an alkyl group.
SP 3 and SP 4 each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. A divalent linking group in which one or more of —CH 2 — constituting is substituted with —O—, —S—, —NH—, —N (Q) —, or —CO—; Represents a substituent.
L 3 and L 4 each independently represent a monovalent organic group, and at least one of L 3 and L 4 and L 1 and L 2 in the formula (1) or (2) represents a polymerizable group. Represent.
Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
Ay represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. And an organic group having 2 to 30 carbon atoms.
Further, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring.
Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. - 前記式(1)および(2)中のD1およびD2が、いずれも、-CO-O-*であり、*は、Arとの結合位置を表す、請求項1に記載の重合性液晶組成物。 The polymerizable liquid crystal according to claim 1, wherein D 1 and D 2 in the formulas (1) and (2) are both —CO—O— *, and * represents a bonding position with Ar. Composition.
- 前記式(1)および(2)中のD3およびD4が、いずれも、-CO-O-*であり、*は、SP1またはSP2との結合位置を表す、請求項1または2に記載の重合性液晶組成物。 Formula (1) and (2) D 3 and D 4 in the are both a -CO-O- *, * represents a bonding position to SP 1 or SP 2, claim 1 or 2 The polymerizable liquid crystal composition described in 1.
- 前記式(1)および(2)中のL1およびL2が、いずれも、重合性基を表す、請求項1~3のいずれか1項に記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein L 1 and L 2 in the formulas (1) and (2) both represent a polymerizable group.
- 前記式(2)中のA1およびA3が、いずれか一方がシクロヘキサン環を表し、他方がベンゼン環を表す、請求項1~4のいずれか1項に記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein one of A 1 and A 3 in the formula (2) represents a cyclohexane ring and the other represents a benzene ring.
- 前記式(2)中のA2およびA4が、いずれも、シクロヘキサン環を表す、請求項1~5のいずれか1項に記載の重合性液晶組成物。 The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein A 2 and A 4 in the formula (2) each represent a cyclohexane ring.
- 請求項1~6のいずれか1項に記載の重合性液晶組成物を重合して得られる光学異方性膜。 An optically anisotropic film obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 6.
- 請求項7に記載の光学異方性膜を有する光学フィルム。 An optical film having the optically anisotropic film according to claim 7.
- 請求項8に記載の光学フィルムと、偏光子とを有する、偏光板。 A polarizing plate comprising the optical film according to claim 8 and a polarizer.
- 請求項8に記載の光学フィルム、または、請求項9に記載の偏光板を有する、画像表示装置。 An image display device comprising the optical film according to claim 8 or the polarizing plate according to claim 9.
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