JP6672815B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element Download PDFInfo
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- JP6672815B2 JP6672815B2 JP2016006005A JP2016006005A JP6672815B2 JP 6672815 B2 JP6672815 B2 JP 6672815B2 JP 2016006005 A JP2016006005 A JP 2016006005A JP 2016006005 A JP2016006005 A JP 2016006005A JP 6672815 B2 JP6672815 B2 JP 6672815B2
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- Prior art keywords
- liquid crystal
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- polyamic acid
- solvent
- solution
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 190
- 239000003795 chemical substances by application Substances 0.000 title claims description 98
- 229920005575 poly(amic acid) Polymers 0.000 claims description 89
- 239000002904 solvent Substances 0.000 claims description 73
- 239000004642 Polyimide Substances 0.000 claims description 67
- 229920001721 polyimide Polymers 0.000 claims description 67
- 229920000642 polymer Polymers 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 98
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- 239000000758 substrate Substances 0.000 description 41
- 238000003786 synthesis reaction Methods 0.000 description 40
- 230000015572 biosynthetic process Effects 0.000 description 38
- -1 polysiloxane Polymers 0.000 description 35
- 238000007639 printing Methods 0.000 description 35
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 31
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 26
- 150000004985 diamines Chemical class 0.000 description 25
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 230000018044 dehydration Effects 0.000 description 20
- 238000006297 dehydration reaction Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000007363 ring formation reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 10
- 210000002858 crystal cell Anatomy 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 6
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 6
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 6
- 239000012024 dehydrating agents Substances 0.000 description 6
- 238000006358 imidation reaction Methods 0.000 description 6
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000007645 offset printing Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- UENRXLSRMCSUSN-UHFFFAOYSA-M 3,5-diaminobenzoate Chemical compound NC1=CC(N)=CC(C([O-])=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-M 0.000 description 4
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 3
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- IEXIHWCBQMQDHC-KEIUHOJNSA-N 5,9-hexacosadienoic acid Chemical compound CCCCCCCCCCCCCCCC\C=C\CC\C=C\CCCC(O)=O IEXIHWCBQMQDHC-KEIUHOJNSA-N 0.000 description 3
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007774 anilox coating Methods 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- JMJRYTGVHCAYCT-UHFFFAOYSA-N oxan-4-one Chemical compound O=C1CCOCC1 JMJRYTGVHCAYCT-UHFFFAOYSA-N 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
- XIIAYQZJNBULGD-UHFFFAOYSA-N (5alpha)-cholestane Natural products C1CC2CCCCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 XIIAYQZJNBULGD-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
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- BLHZUMDWLLFLJC-UHFFFAOYSA-N 4-methylfuran-2-carbaldehyde Chemical compound CC1=COC(C=O)=C1 BLHZUMDWLLFLJC-UHFFFAOYSA-N 0.000 description 2
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 2
- ITCGQBAPLXQYCA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-8-methyl-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C2=CC(C)=CC=C2C1C1CC(=O)OC1=O ITCGQBAPLXQYCA-UHFFFAOYSA-N 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- XIIAYQZJNBULGD-LDHZKLTISA-N cholestane Chemical compound C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XIIAYQZJNBULGD-LDHZKLTISA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 2
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- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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Landscapes
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、液晶配向剤、液晶配向膜及び液晶素子に関する。 The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal device.
従来、液晶素子としては、電極構造や、使用する液晶分子の物性等が異なる種々の駆動方式のものが開発されており、例えばTN型やSTN型、VA型、面内スイッチング型(IPS型)、FFS型、光学補償ベント型(OCB型)等の各種液晶素子が知られている。これら液晶素子は、液晶分子を配向させるための液晶配向膜を有する。液晶配向膜の材料としては、耐熱性、機械的強度、液晶との親和性等の各種特性が良好である点から、ポリアミック酸やポリイミドなどが使用されている。 2. Description of the Related Art Conventionally, as a liquid crystal element, various driving methods having different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type). , FFS type, optical compensation bent type (OCB type) and other various liquid crystal elements are known. These liquid crystal elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid, polyimide, or the like is used because of its excellent properties such as heat resistance, mechanical strength, and affinity for liquid crystal.
液晶配向剤において、重合体成分は溶剤に溶解されており、液晶配向剤を基板に塗布し加熱することにより液晶配向膜が形成される。ここで、液晶配向剤の溶剤としては、重合体の溶解性が高い有機溶媒、例えばN−メチル−2−ピロリドンやγ−ブチロラクトンなどの非プロトン性極性溶媒が一般に使用される。また、液晶配向剤を基板に塗布する際の液晶配向剤の塗布性(印刷性)を良好にするために、非プロトン性極性溶媒と共に、例えばブチルセロソルブなどといった、表面張力が比較的低い有機溶媒が併用されている(例えば、特許文献1や特許文献2参照)。 In the liquid crystal alignment agent, a polymer component is dissolved in a solvent, and a liquid crystal alignment film is formed by applying the liquid crystal alignment agent to a substrate and heating the substrate. Here, as a solvent for the liquid crystal aligning agent, an organic solvent having high polymer solubility, for example, an aprotic polar solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone is generally used. In addition, in order to improve the applicability (printability) of the liquid crystal aligning agent when applying the liquid crystal aligning agent to the substrate, an organic solvent having a relatively low surface tension such as butyl cellosolve is used together with the aprotic polar solvent. They are used in combination (for example, see Patent Documents 1 and 2).
液晶配向剤を基板に塗布する方法としては、スピンコート法やオフセット印刷法、インクジェット法など種々の方法が適用される。例えばオフセット印刷法は、APR(登録商標)などの樹脂からなる印刷版に液晶配向剤を塗布し、印刷版により液晶配向剤を基板上に転写する転写印刷装置を用いて一般に行われる(例えば、特許文献3参照)。 As a method of applying the liquid crystal aligning agent to the substrate, various methods such as a spin coating method, an offset printing method, and an inkjet method are applied. For example, the offset printing method is generally performed using a transfer printing apparatus that applies a liquid crystal aligning agent to a printing plate made of a resin such as APR (registered trademark) and transfers the liquid crystal aligning agent onto a substrate using the printing plate (for example, Patent Document 3).
液晶配向剤の塗布性の改善を目的として一般に使用されているブチルセロソルブは、APR樹脂を膨潤させやすい傾向にある。そのため、ブチルセロソルブを含む液晶配向剤をオフセット印刷により基板に塗布する場合に、印刷版への塗布が繰り返し行われることによって印刷版が膨潤し、印刷性が低下することが懸念される。また、液晶配向剤の溶剤成分としては、連続して印刷を行った場合にも印刷機上に重合体が析出しにくく、印刷性(連続印刷性)が良好であることが求められる。 Butyl cellosolve, which is generally used for the purpose of improving the coating property of the liquid crystal alignment agent, tends to swell the APR resin. For this reason, when a liquid crystal aligning agent containing butyl cellosolve is applied to a substrate by offset printing, there is a concern that the printing plate may swell due to repeated application to the printing plate, resulting in reduced printability. Further, as a solvent component of the liquid crystal aligning agent, it is required that a polymer hardly precipitates on a printing machine even when printing is performed continuously and that printability (continuous printability) is good.
本発明は上記課題に鑑みなされたものであり、印刷版を膨潤させにくく、かつ印刷性が良好な液晶配向剤を提供することを一つの目的とする。 The present invention has been made in view of the above problems, and has as its object to provide a liquid crystal aligning agent that hardly swells a printing plate and has good printability.
本発明者らは、上記のような従来技術の課題を達成するべく鋭意検討した結果、溶剤として特定の有機溶媒を使用することにより上記課題を解決可能であることを見出し、本発明を完成するに至った。具体的には、本発明により以下の液晶配向剤、液晶配向膜及び液晶素子が提供される。 The present inventors have conducted intensive studies to achieve the above-described problems of the related art, and as a result, found that the problems can be solved by using a specific organic solvent as a solvent, and completed the present invention. Reached. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element.
本発明は一つの側面において、重合体成分と、リン原子を有する溶剤、N,N−ジメチルプロピレン尿素、テトラヒドロ−4H−ピラン−4−オン、テトラメチレンスルホキシド、3−メチルシクロヘキサノン、4−メチルシクロヘキサノン、下記式(1)で表される化合物、下記式(2)で表される化合物、下記式(3)で表される化合物、及び下記式(10)で表される化合物よりなる群から選ばれる少なくとも一種である特定溶剤と、を含有する液晶配向剤を提供する。 In one aspect, the present invention provides a polymer component, a solvent having a phosphorus atom, N, N-dimethylpropylene urea, tetrahydro-4H-pyran-4-one, tetramethylene sulfoxide, 3-methylcyclohexanone, 4-methylcyclohexanone. Selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (10). And at least one specific solvent.
液晶配向剤の溶剤成分として上記の特定溶剤を用いることにより、印刷版が膨潤しにくい液晶配向剤を得ることができる。また、連続して印刷を行った場合にも印刷機上に重合体が析出しにくく、印刷性を良好にすることができる。 By using the above-mentioned specific solvent as a solvent component of the liquid crystal aligning agent, a liquid crystal aligning agent that hardly swells the printing plate can be obtained. Further, even when printing is performed continuously, the polymer hardly precipitates on the printing press, and the printability can be improved.
本発明は他の一つの側面において、上記液晶配向剤により形成された液晶配向膜を提供する。また、他の一つの側面において、上記液晶配向剤により形成された液晶配向膜を具備する液晶素子を提供する。 In another aspect, the present invention provides a liquid crystal alignment film formed by the liquid crystal alignment agent. In another aspect, the present invention provides a liquid crystal element including a liquid crystal alignment film formed of the liquid crystal alignment agent.
本発明の液晶配向膜は、上記特定溶剤を含む液晶配向剤を用いて形成されていることから、均一な塗膜を形成できるとともに膜質が良好である。また、上記液晶配向剤を用いて液晶素子を製造した場合、製造プロセスにおいて印刷不良を減らすことができ、結果として製品の歩留まり向上を図ることができる。 Since the liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent containing the specific solvent, a uniform coating film can be formed and the film quality is good. Further, when a liquid crystal element is manufactured using the liquid crystal alignment agent, printing defects can be reduced in the manufacturing process, and as a result, the yield of products can be improved.
以下に、本発明の液晶配向剤に含まれる各成分、及び必要に応じて任意に配合されるその他の成分について説明する。 Hereinafter, each component contained in the liquid crystal aligning agent of the present invention, and other components that are arbitrarily added as necessary will be described.
<重合体成分>
本発明の液晶配向剤は重合体成分を含有する。重合体の主骨格は特に限定されず、例えばポリアミック酸、ポリアミック酸エステル、ポリイミド、ポリシロキサン、ポリエステル、ポリアミド、ポリベンゾオキサゾール前駆体、ポリベンゾオキサゾール、セルロース誘導体、ポリアセタール、ポリスチレン誘導体、ポリ(スチレン−フェニルマレイミド)誘導体、ポリ(メタ)アクリレートなどの主骨格が挙げられる。なお、(メタ)アクリレートは、アクリレート及びメタクリレートを含むことを意味する。
<Polymer component>
The liquid crystal aligning agent of the present invention contains a polymer component. The main skeleton of the polymer is not particularly limited. For example, polyamic acid, polyamic acid ester, polyimide, polysiloxane, polyester, polyamide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene- Phenylmaleimide) derivatives and poly (meth) acrylate. In addition, (meth) acrylate means including acrylate and methacrylate.
特定溶剤による印刷性の改善効果が高い点で、液晶配向剤の重合体成分は上記の中でも、ポリアミック酸、ポリアミック酸エステル、ポリイミド及びポリオルガノシロキサンよりなる群から選ばれる少なくとも一種であることが好ましい。なお、液晶配向剤の調製に際し、重合体としては1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。 In that the effect of improving the printability by the specific solvent is high, the polymer component of the liquid crystal aligning agent is preferably at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, and polyorganosiloxanes. . In preparing the liquid crystal alignment agent, one type of polymer may be used alone, or two or more types may be used in combination.
[ポリアミック酸]
本発明におけるポリアミック酸は、例えばテトラカルボン酸二無水物とジアミンとを反応させることにより得ることができる。
[Polyamic acid]
The polyamic acid in the present invention can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.
(テトラカルボン酸二無水物)
ポリアミック酸の合成に用いるテトラカルボン酸二無水物としては、例えば脂肪族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、芳香族テトラカルボン酸二無水物などを挙げることができる。これらの具体例としては、脂肪族テトラカルボン酸二無水物として、例えば1,2,3,4−ブタンテトラカルボン酸二無水物などを;
脂環式テトラカルボン酸二無水物として、例えば1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、5−(2,5−ジオキソテトラヒドロ−3−フラニル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸無水物、3,5,6−トリカルボキシ−2−カルボキシメチルノルボルナン−2:3,5:6−二無水物、2,4,6,8−テトラカルボキシビシクロ[3.3.0]オクタン−2:4,6:8−二無水物、4,9−ジオキサトリシクロ[5.3.1.02,6]ウンデカン−3,5,8,10−テトラオン、シクロヘキサンテトラカルボン酸二無水物などを;
芳香族テトラカルボン酸二無水物として、例えばピロメリット酸二無水物などを;それぞれ挙げることができるほか、特開2010−97188号公報に記載のテトラカルボン酸二無水物を用いることができる。なお、テトラカルボン酸二無水物は、1種を単独で又は2種以上組み合わせて使用することができる。
(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] Furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, , 4,6,8-Tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 2,6 ] Undecane-3,5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride and the like;
As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride and the like can be mentioned; in addition, the tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
合成に使用するテトラカルボン酸二無水物としては、電気特性を良好にできる点、及び特定溶剤を含む溶剤に対する重合体の溶解性をより高くでき、印刷性の改善効果をより高くできる点で、脂環式テトラカルボン酸二無水物を含むものであることが好ましい。また、脂環式テトラカルボン酸二無水物の中でも、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、2,4,6,8−テトラカルボキシビシクロ[3.3.0]オクタン−2:4,6:8−二無水物、及び1,2,3,4−シクロブタンテトラカルボン酸二無水物よりなる群から選択される少なくとも一種を含むものであることが好ましく、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、2,4,6,8−テトラカルボキシビシクロ[3.3.0]オクタン−2:4,6:8−二無水物、及び1,2,3,4−シクロブタンテトラカルボン酸二無水物よりなる群から選択される少なくとも一種を含むものであることが特に好ましい。 As the tetracarboxylic dianhydride used in the synthesis, the point that the electric properties can be improved, and the solubility of the polymer in a solvent containing a specific solvent can be increased, and the effect of improving the printability can be increased, Preferably, it contains an alicyclic tetracarboxylic dianhydride. In addition, among alicyclic tetracarboxylic dianhydrides, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: It preferably contains at least one selected from the group consisting of 8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 2,3,5-tricarboxycyclopentylacetic acid dianhydride. Thing, 2, , 6,8-Tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride It is particularly preferred that the composition contains at least one of the compounds described above.
テトラカルボン酸二無水物として、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、2,4,6,8−テトラカルボキシビシクロ[3.3.0]オクタン−2:4,6:8−二無水物、及び1,2,3,4−シクロブタンテトラカルボン酸二無水物よりなる群から選択される少なくとも一種を含む場合、それら化合物の合計の含有量は、ポリアミック酸の合成に使用するテトラカルボン酸二無水物の全量に対して、10モル%以上であることが好ましく、20〜100モル%であることがより好ましい。 As the tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8- When at least one selected from the group consisting of dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride is contained, the total content of those compounds is determined by the amount of tetracarboxylic acid used in the synthesis of polyamic acid. It is preferably at least 10 mol%, more preferably 20 to 100 mol%, based on the total amount of the carboxylic dianhydride.
(ジアミン)
ポリアミック酸の合成に使用するジアミンとしては、例えば脂肪族ジアミン、脂環式ジアミン、芳香族ジアミン、ジアミノオルガノシロキサンなどを挙げることができる。これらジアミンの具体例としては、脂肪族ジアミンとして、例えばメタキシリレンジアミン、1,3−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、1,3−ビス(アミノメチル)シクロヘキサンなどを;脂環式ジアミンとして、例えば1,4−ジアミノシクロヘキサン、4,4’−メチレンビス(シクロヘキシルアミン)などを;
(Diamine)
Examples of the diamine used in the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diaminoorganosiloxane. Specific examples of these diamines include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis (aminomethyl) cyclohexane. As alicyclic diamines, for example, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine) and the like;
芳香族ジアミンとして、例えばp−フェニレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルスルフィド、1,5−ジアミノナフタレン、2,2’−ジメチル−4,4’−ジアミノビフェニル、4,4’−ジアミノ−2,2’−ビス(トリフルオロメチル)ビフェニル、4,4’−ジアミノジフェニルエーテル、1,3−ビス(4−アミノフェノキシ)プロパン、9,9−ビス(4−アミノフェニル)フルオレン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、4,4’−(p−フェニレンジイソプロピリデン)ビスアニリン、1,4−ビス(4−アミノフェノキシ)ベンゼン、2,6−ジアミノピリジン、3,6−ジアミノカルバゾール、N,N’−ビス(4−アミノフェニル)−ベンジジン、1,4−ビス−(4−アミノフェニル)−ピペラジン、1−(4−アミノフェニル)−2,3−ジヒドロ−1,3,3−トリメチル−1H−インデン−5−アミン、1−(4−アミノフェニル)−2,3−ジヒドロ−1,3,3−トリメチル−1H−インデン−6−アミン、3,5−ジアミノ安息香酸、コレスタニルオキシ−3,5−ジアミノベンゼン、コレステニルオキシ−3,5−ジアミノベンゼン、コレスタニルオキシ−2,4−ジアミノベンゼン、3,5−ジアミノ安息香酸コレスタニル、3,5−ジアミノ安息香酸コレステニル、3,5−ジアミノ安息香酸ラノスタニル、3,6−ビス(4−アミノベンゾイルオキシ)コレスタン、4−(4’−トリフルオロメトキシベンゾイロキシ)シクロヘキシル−3,5−ジアミノベンゾエート、1,1−ビス(4−((アミノフェニル)メチル)フェニル)−4−ヘプチルシクロヘキサン、1,1−ビス(4−((アミノフェニル)メチル)フェニル)−4−(4−ヘプチルシクロヘキシル)シクロヘキサン、2,4−ジアミノ−N,N―ジアリルアニリン、4−アミノベンジルアミン、N−[4−(2−アミノエチル)フェニル]ベンゼン−1,4−ジアミン、N−[4−(アミノメチル)フェニル]ベンゼン−1,4−ジアミン、桂皮酸構造含有ジアミン及び下記式(D−1)、
で表される化合物などを;
ジアミノオルガノシロキサンとして、例えば、1,3−ビス(3−アミノプロピル)−テトラメチルジシロキサンなどを、それぞれ挙げることができるほか、特開2010−97188号公報に記載のジアミンを用いることができる。なお、これらのジアミンは、1種を単独で又は2種以上組み合わせて使用することができる。
As the aromatic diamine, for example, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) propane, 9,9-bis (4-amino Phenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) Benzene, 2,6-diaminopyridine, 3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) Benzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyl Oxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6 -Bis (4-aminobenzoyloxy) cholestan, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-dia Nobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptyl Cyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, N- [4- (2-aminoethyl) phenyl] benzene-1,4-diamine, N- [4- ( Aminomethyl) phenyl] benzene-1,4-diamine, cinnamic acid structure-containing diamine and the following formula (D-1):
A compound represented by;
Examples of the diaminoorganosiloxane include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and the diamine described in JP-A-2010-97188 can be used. In addition, these diamines can be used individually by 1 type or in combination of 2 or more types.
上記式(D−1)で表される化合物の具体例としては、例えば下記式(D−1−1)〜式(D−1−4)のそれぞれで表される化合物などが挙げられる。
ポリアミック酸の合成に用いるジアミンは、芳香族ジアミンを、全ジアミンに対して30モル%以上含むものであることが好ましく、50モル%以上含むものであることがより好ましく、80モル%以上含むものであることが特に好ましい。 The diamine used in the synthesis of the polyamic acid preferably contains at least 30 mol%, more preferably at least 50 mol%, and particularly preferably at least 80 mol%, of the aromatic diamine based on the total diamine. .
(ポリアミック酸の合成)
ポリアミック酸は、上記のようなテトラカルボン酸二無水物とジアミンとを、必要に応じて分子量調整剤とともに反応させることによって得ることができる。ポリアミック酸の合成反応に供されるテトラカルボン酸二無水物とジアミンとの使用割合は、ジアミンのアミノ基1当量に対して、テトラカルボン酸二無水物の酸無水物基が0.2〜2当量となる割合が好ましい。分子量調整剤としては、例えば無水マレイン酸、無水フタル酸、無水イタコン酸などの酸一無水物、アニリン、シクロヘキシルアミン、n−ブチルアミンなどのモノアミン化合物、フェニルイソシアネート、ナフチルイソシアネートなどのモノイソシアネート化合物等を挙げることができる。分子量調整剤の使用割合は、使用するテトラカルボン酸二無水物及びジアミンの合計100重量部に対して20重量部以下とすることが好ましい。
(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above-described tetracarboxylic dianhydride with a diamine, if necessary, together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and the diamine used for the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 with respect to 1 equivalent of the amino group of the diamine. The equivalent ratio is preferred. Examples of the molecular weight modifier include maleic anhydride, phthalic anhydride, acid monoanhydrides such as itaconic anhydride, aniline, cyclohexylamine, monoamine compounds such as n-butylamine, phenyl isocyanate, monoisocyanate compounds such as naphthyl isocyanate and the like. Can be mentioned. The proportion of the molecular weight modifier used is preferably 20 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used.
ポリアミック酸の合成反応は、好ましくは有機溶媒中において行われる。このときの反応温度は−20℃〜150℃が好ましく、反応時間は0.1〜24時間が好ましい。
反応に使用する有機溶媒としては、例えば非プロトン性極性溶媒、フェノール系溶媒、アルコール、ケトン、エステル、エーテル、ハロゲン化炭化水素、炭化水素などを挙げることができる。特に好ましい有機溶媒は、N−メチル−2−ピロリドン、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、ジメチルスルホキシド、γ−ブチロラクトン、テトラメチル尿素、ヘキサメチルホスホルトリアミド、m−クレゾール、キシレノール、ハロゲン化フェノール及び下記に示す特定溶剤よりなる群から選択される1種以上を溶媒として使用するか、あるいはこれらの1種以上と他の有機溶媒(例えば、ブチルセロソルブ、ジエチレングリコールジエチルエーテルなど)との混合物を使用することが好ましい。有機溶媒の使用量(a)は、テトラカルボン酸二無水物及びジアミンの合計量(b)が、反応溶液の全量(a+b)に対して、0.1〜50重量%になる量とすることが好ましい。
以上のようにして、ポリアミック酸を溶解してなる反応溶液が得られる。この反応溶液はそのまま液晶配向剤の調製に供してもよく、反応溶液中に含まれるポリアミック酸を単離したうえで液晶配向剤の調製に供してもよい。
The synthesis reaction of the polyamic acid is preferably performed in an organic solvent. The reaction temperature at this time is preferably from -20C to 150C, and the reaction time is preferably from 0.1 to 24 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol Or one or more selected from the group consisting of halogenated phenols and the following specific solvents, or a mixture of one or more of these with another organic solvent (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.) It is preferred to use a mixture. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferred.
As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. This reaction solution may be directly used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution.
[ポリイミド]
本発明におけるポリイミドは、上記の如くして合成されたポリアミック酸を脱水閉環してイミド化することにより得ることができる。ポリイミドは、その前駆体であるポリアミック酸が有していたアミック酸構造のすべてを脱水閉環した完全イミド化物であってもよく、アミック酸構造の一部のみを脱水閉環し、アミック酸構造とイミド環構造が併存する部分イミド化物であってもよい。本発明におけるポリイミドは、そのイミド化率が30%以上であることが好ましく、40〜99%であることがより好ましく、50〜99%であることが更に好ましい。このイミド化率は、ポリイミドのアミック酸構造の数とイミド環構造の数との合計に対するイミド環構造の数の占める割合を百分率で表したものである。ここで、イミド環の一部がイソイミド環であってもよい。
[Polyimide]
The polyimide in the present invention can be obtained by dehydrating and cyclizing the polyamic acid synthesized as described above to imidize it. Polyimide may be a complete imidized product obtained by dehydrating and ring-closing all of the amic acid structure that the precursor polyamic acid had, and dehydrating and ring-closing only a part of the amic acid structure to form an amic acid structure and an imide. It may be a partially imidized compound having a ring structure. The imidation ratio of the polyimide in the present invention is preferably 30% or more, more preferably 40 to 99%, and still more preferably 50 to 99%. The imidation ratio is a percentage of the number of imide ring structures to the total number of amic acid structures and imide ring structures of the polyimide. Here, a part of the imide ring may be an isoimide ring.
ポリアミック酸の脱水閉環は、好ましくはポリアミック酸を加熱する方法により、又はポリアミック酸を有機溶媒に溶解し、この溶液中に脱水剤及び脱水閉環触媒を添加し必要に応じて加熱する方法により行われる。このうち、後者の方法によることが好ましい。
ポリアミック酸の溶液中に脱水剤及び脱水閉環触媒を添加する方法において、脱水剤としては、例えば無水酢酸、無水プロピオン酸、無水トリフルオロ酢酸などの酸無水物を用いることができる。脱水剤の使用量は、ポリアミック酸のアミック酸構造の1モルに対して0.01〜20モルとすることが好ましい。脱水閉環触媒としては、例えばピリジン、コリジン、ルチジン、トリエチルアミン等の3級アミンを用いることができる。脱水閉環触媒の使用量は、使用する脱水剤1モルに対して0.01〜10モルとすることが好ましい。脱水閉環反応に用いられる有機溶媒としては、ポリアミック酸の合成に用いられるものとして例示した有機溶媒を挙げることができる。脱水閉環反応の反応温度は、好ましくは0〜180℃であり、反応時間は、好ましくは1.0〜120時間である。
The dehydration and ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid or by dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution and heating as necessary. . Of these, the latter method is preferred.
In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of a polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used in the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, and the reaction time is preferably 1.0 to 120 hours.
このようにしてポリイミドを含有する反応溶液が得られる。この反応溶液は、そのまま液晶配向剤の調製に供してもよく、反応溶液から脱水剤及び脱水閉環触媒を除いたうえで液晶配向剤の調製に供してもよく、ポリイミドを単離したうえで液晶配向剤の調製に供してもよい。これらの精製操作は公知の方法に従って行うことができる。その他、ポリイミドは、ポリアミック酸エステルのイミド化によって得ることもできる。 Thus, a reaction solution containing the polyimide is obtained. This reaction solution may be directly used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution. It may be used for preparing an alignment agent. These purification operations can be performed according to a known method. In addition, polyimide can also be obtained by imidizing a polyamic acid ester.
[ポリアミック酸エステル]
本発明におけるポリアミック酸エステルは、例えば、[I]上記合成反応により得られたポリアミック酸とエステル化剤(例えば、メタノールやエタノール、N,N−ジメチルホルムアミドジエチルアセタールなど)とを反応させる方法、[II]テトラカルボン酸ジエステルとジアミンとを、有機溶媒中、適当な脱水触媒(例えば、4−(4,6−ジメトキシ−1,3,5−トリアジン−2−イル)−4−メチルモルホリニウムハライド、リン系縮合剤など)の存在下で反応させる方法、[III]テトラカルボン酸ジエステルジハロゲン化物とジアミンとを、有機溶媒中、適当な塩基(例えば、ピリジン、トリエチルアミン、水酸化ナトリウムなど)の存在下で反応させる方法、などによって得ることができる。
液晶配向剤に含有させるポリアミック酸エステルは、アミック酸エステル構造のみを有していてもよく、アミック酸構造とアミック酸エステル構造とが併存する部分エステル化物であってもよい。なお、ポリアミック酸エステルを溶解してなる反応溶液は、そのまま液晶配向剤の調製に供してもよく、反応溶液中に含まれるポリアミック酸エステルを単離したうえで液晶配向剤の調製に供してもよい。
[Polyamic acid ester]
The polyamic acid ester in the present invention is, for example, [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent (for example, methanol, ethanol, N, N-dimethylformamide diethyl acetal, etc.), II] A tetracarboxylic diester and a diamine are treated with an appropriate dehydration catalyst (eg, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium) in an organic solvent. [III] tetracarboxylic diester dihalide and diamine in an organic solvent in a suitable base (eg, pyridine, triethylamine, sodium hydroxide, etc.). The reaction can be carried out in the presence.
The polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product having both an amic acid structure and an amic acid ester structure. The reaction solution obtained by dissolving the polyamic acid ester may be directly used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. Good.
以上のようにして得られるポリアミック酸、ポリアミック酸エステル及びポリイミドは、これを濃度10重量%の溶液としたときに、10〜800mPa・sの溶液粘度を持つものであることが好ましく、15〜500mPa・sの溶液粘度を持つものであることがより好ましい。なお、上記重合体の溶液粘度(mPa・s)は、当該重合体の良溶媒(例えばγ−ブチロラクトン、N−メチル−2−ピロリドンなど)を用いて調製した濃度10重量%の重合体溶液につき、E型回転粘度計を用いて25℃において測定した値である。
本発明の液晶配向剤に含有させるポリアミック酸、ポリアミック酸エステル及びポリイミドについて、ゲルパーミエーションクロマトグラフィー(GPC)により測定したポリスチレン換算の重量平均分子量は、500〜100,000であることが好ましく、1,000〜50,000であることがより好ましい。
The polyamic acid, polyamic acid ester, and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s when used as a solution having a concentration of 10% by weight, and preferably have a solution viscosity of 15 to 500 mPa. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone) for the polymer. , Measured at 25 ° C. using an E-type rotational viscometer.
The polyamic acid, polyamic acid ester and polyimide contained in the liquid crystal aligning agent of the present invention preferably have a polystyrene equivalent weight average molecular weight of 500 to 100,000 as measured by gel permeation chromatography (GPC), preferably 1 to 100,000. More preferably, the molecular weight is from 000 to 50,000.
[ポリオルガノシロキサン]
本発明におけるポリオルガノシロキサンは、例えば加水分解性のシラン化合物を、好ましくは適当な有機溶媒、水及び触媒の存在下において、加水分解又は加水分解・縮合することにより得ることができる。
[Polyorganosiloxane]
The polyorganosiloxane in the present invention can be obtained, for example, by hydrolyzing or hydrolyzing / condensing a hydrolyzable silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst.
ポリオルガノシロキサンの合成に使用する加水分解性のシラン化合物としては、例えばテトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、トリメトキシシリルプロピルコハク酸無水物、ジメチルジメトキシシラン、ジメチルジエトキシシラン等のアルコキシシラン化合物;3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、メルカプトメチルトリメトキシシラン、メルカプトメチルトリエトキシシラン、3−ウレイドプロピルトリメトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、N−(3−シクロヘキシルアミノ)プロピルトリメトキシシラン等の窒素・硫黄含有アルコキシシラン化合物;3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シラン化合物;3−(メタ)アクリロキシプロピルトリメトキシシラン、3−(メタ)アクリロキシプロピルメチルジメトキシシラン、3−(メタ)アクリロキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、p−スチリルトリメトキシシラン等の不飽和結合含有アルコキシシラン化合物、などを挙げることができる。加水分解性シラン化合物は、これらのうちの1種を単独で又は2種以上を組み合わせて使用することができる。なお、「(メタ)アクリロキシ」は、「アクリロキシ」及び「メタクリロキシ」を含む意味である。 Examples of hydrolyzable silane compounds used for the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and trimethoxysilylpropyl. Alkoxysilane compounds such as succinic anhydride, dimethyldimethoxysilane and dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureido Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltri Nitrogen / sulfur-containing alkoxysilane compounds such as toxicoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Epoxy group-containing silane compounds such as ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxy Examples include silane, 3- (meth) acryloxypropylmethyldiethoxysilane, unsaturated bond-containing alkoxysilane compounds such as vinyltrimethoxysilane and p-styryltrimethoxysilane. One of these hydrolyzable silane compounds can be used alone or in combination of two or more. In addition, "(meth) acryloxy" has a meaning including "acryloxy" and "methacryloxy".
上記の加水分解・縮合反応は、上記の如きシラン化合物の1種又は2種以上と水とを、好ましくは適当な触媒及び有機溶媒の存在下で反応させることにより行う。反応に際し、水の使用割合は、シラン化合物(合計量)1モルに対して、好ましくは1〜30モルである。使用する触媒としては、例えば酸、アルカリ金属化合物、有機塩基(例えばトリエチルアミンやテトラメチルアンモニウムヒドロキシドなど)、チタン化合物、ジルコニウム化合物などを挙げることができる。触媒の使用量は、触媒の種類、温度などの反応条件などにより異なり、適宜に設定されるべきであるが、例えばシラン化合物の合計量に対して、好ましくは0.01〜3倍モルである。使用する有機溶媒としては、例えば炭化水素、ケトン、エステル、エーテル、アルコールなどが挙げられ、これらのうち、非水溶性又は難水溶性の有機溶媒を用いることが好ましい。有機溶媒の使用割合は、反応に使用するシラン化合物の合計100重量部に対して、好ましくは50〜1,000重量部である。 The above hydrolysis / condensation reaction is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. In the reaction, the use ratio of water is preferably 1 to 30 mol per 1 mol of the silane compound (total amount). Examples of the catalyst used include acids, alkali metal compounds, organic bases (eg, triethylamine and tetramethylammonium hydroxide), titanium compounds, zirconium compounds, and the like. The amount of the catalyst used depends on the type of the catalyst, the reaction conditions such as the temperature and the like, and should be appropriately set. For example, the amount is preferably 0.01 to 3 times the mol of the total amount of the silane compound. . Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, alcohols and the like, and among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The proportion of the organic solvent used is preferably 50 to 1,000 parts by weight based on 100 parts by weight of the total of the silane compounds used in the reaction.
上記の加水分解・縮合反応は、例えば油浴などにより加熱して実施することが好ましい。その際、加熱温度は130℃以下とすることが好ましく、加熱時間は、0.5〜12時間とすることが好ましい。反応終了後において、反応液から分取した有機溶媒層につき、溶媒を除去することによりポリシロキサンを得ることができる。 The above hydrolysis / condensation reaction is preferably carried out by heating, for example, in an oil bath or the like. At that time, the heating temperature is preferably 130 ° C. or lower, and the heating time is preferably 0.5 to 12 hours. After the completion of the reaction, the polysiloxane can be obtained by removing the solvent from the organic solvent layer separated from the reaction solution.
TN型、STN型又は垂直配向型の液晶表示素子用の液晶配向剤に適用する場合、ポリオルガノシロキサンの側鎖に、液晶配向性基や光配向性構造を有する基などの特定基を導入してもよい。これら特定基を側鎖に有するポリオルガノシロキサンを合成する方法は特に限定されないが、例えば、エポキシ基含有シラン化合物、又はエポキシ基含有シラン化合物とその他のシラン化合物との混合物を加水分解縮合してエポキシ基を有するポリオルガノシロキサンを合成し、次いで、得られたエポキシ基含有のポリオルガノシロキサンと、上記特定基を有するカルボン酸とを反応させる方法などが挙げられる。エポキシ基含有ポリオルガノシロキサンとカルボン酸との反応は公知の方法に従って行うことができる。 When applied to a liquid crystal aligning agent for a TN type, STN type or vertical alignment type liquid crystal display element, a specific group such as a liquid crystal alignment group or a group having a photo alignment structure is introduced into a side chain of polyorganosiloxane. You may. The method for synthesizing the polyorganosiloxane having these specific groups in the side chain is not particularly limited.For example, an epoxy group is obtained by hydrolyzing and condensing an epoxy group-containing silane compound or a mixture of an epoxy group-containing silane compound and another silane compound. A method of synthesizing a polyorganosiloxane having a group, and then reacting the resulting epoxy group-containing polyorganosiloxane with the carboxylic acid having the specific group. The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be performed according to a known method.
ポリオルガノシロキサンは、GPCで測定したポリスチレン換算の重量平均分子量(Mw)が500〜100,000の範囲にあることが好ましく、1,000〜30,000の範囲にあることがより好ましく、1,000〜20,000であることが更に好ましい。ポリオルガノシロキサンの重量平均分子量が上記範囲にあると、液晶配向膜を製造する際に取り扱いやすく、また得られた液晶配向膜は十分な材料強度及び特性を有するものとなる。 The polyorganosiloxane has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC of preferably from 500 to 100,000, more preferably from 1,000 to 30,000, More preferably, it is from 000 to 20,000. When the weight average molecular weight of the polyorganosiloxane is within the above range, it is easy to handle when producing a liquid crystal alignment film, and the obtained liquid crystal alignment film has sufficient material strength and properties.
本発明の液晶配向剤において、ポリアミック酸、ポリアミック酸エステル、ポリイミド及びポリオルガノシロキサンよりなる群から選ばれる重合体の含有割合(2種以上含有する場合には合計量)は、液晶配向剤中の重合体成分の合計量に対して、50重量%以上であることが好ましく、60重量%以上であることがより好ましい。また、本発明の効果をより好適に得る観点から、重合体成分としては、ポリアミック酸、ポリアミック酸エステル及びポリイミドよりなる群から選ばれる少なくとも一種を含むことが好ましい。液晶配向剤中におけるポリアミック酸、ポリアミック酸エステル及びポリイミドの合計の含有割合は、液晶配向剤中の重合体成分の合計量に対して、40重量%以上であることが好ましく、60重量%以上であることがより好ましい。 In the liquid crystal aligning agent of the present invention, the content ratio of the polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane (the total amount when two or more kinds are contained) is determined by It is preferably at least 50% by weight, more preferably at least 60% by weight, based on the total amount of the polymer components. Further, from the viewpoint of more suitably obtaining the effects of the present invention, the polymer component preferably contains at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. The total content of polyamic acid, polyamic acid ester and polyimide in the liquid crystal aligning agent is preferably at least 40% by weight, more preferably at least 60% by weight, based on the total amount of the polymer components in the liquid crystal aligning agent. More preferably, there is.
<溶剤>
本発明の液晶配向剤は、重合体成分が、溶剤中に分散又は溶解してなる液状の組成物である。当該液晶配向剤は、溶剤として、リン原子を有する溶剤(以下、「リン含有溶剤」ともいう。)、N,N−ジメチルプロピレン尿素、テトラヒドロ−4H−ピラン−4−オン、テトラメチレンスルホキシド、3−メチルシクロヘキサノン、4−メチルシクロヘキサノン、上記式(1)で表される化合物、上記式(2)で表される化合物、上記式(3)で表される化合物、及び上記式(10)で表される化合物よりなる群から選ばれる少なくとも一種である特定溶剤を含有する。
<Solvent>
The liquid crystal alignment agent of the present invention is a liquid composition in which a polymer component is dispersed or dissolved in a solvent. The liquid crystal aligning agent includes, as a solvent, a solvent having a phosphorus atom (hereinafter, also referred to as a “phosphorus-containing solvent”), N, N-dimethylpropyleneurea, tetrahydro-4H-pyran-4-one, tetramethylene sulfoxide, -Methylcyclohexanone, 4-methylcyclohexanone, a compound represented by the above formula (1), a compound represented by the above formula (2), a compound represented by the above formula (3), and a compound represented by the above formula (10) At least one specific solvent selected from the group consisting of the compounds.
[リン含有溶剤]
リン含有溶剤は、少なくとも1個のリン原子を分子内に有する化合物であれば特に限定されないが、下記式(p−1)〜式(p−4)のそれぞれで表される化合物よりなる群から選ばれる少なくとも一種であることが好ましい。
The phosphorus-containing solvent is not particularly limited as long as it is a compound having at least one phosphorus atom in a molecule, and is selected from the group consisting of compounds represented by the following formulas (p-1) to (p-4). Preferably, it is at least one selected.
ここで、本明細書において「炭化水素基」とは、鎖状炭化水素基、脂環式炭化水素基及び芳香族炭化水素基を含む意味である。「鎖状炭化水素基」とは、主鎖に環状構造を含まず、鎖状構造のみで構成された直鎖状炭化水素基及び分岐状炭化水素基を意味する。ただし、飽和でも不飽和でもよい。「脂環式炭化水素基」とは、環構造としては脂環式炭化水素の構造のみを含み、芳香環構造を含まない炭化水素基を意味する。ただし、脂環式炭化水素の構造のみで構成されている必要はなく、その一部に鎖状構造を有するものも含む。「芳香族炭化水素基」とは、環構造として芳香環構造を含む炭化水素基を意味する。ただし、芳香環構造のみで構成されている必要はなく、その一部に鎖状構造や脂環式炭化水素の構造を含んでいてもよい。また、本明細書において「有機基」とは、炭素原子を含む基を意味し、構造中にヘテロ原子を含んでいてもよい。 Here, in the present specification, the “hydrocarbon group” is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group that are composed of only a chain structure without a cyclic structure in the main chain. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of the alicyclic hydrocarbon, but also includes those having a chain structure in part. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to include only an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. Moreover, in this specification, an "organic group" means a group containing a carbon atom, and may contain a hetero atom in the structure.
上記式(p−1)において、R1の炭素数1〜10の1価の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖状又は分岐状のアルキル基;ビニル基、アリル基等のアルケニル基;エチニル基等のアルキニル基;シクロペンチル基、シクロヘキシル基、メチルシクロヘキシル基等のシクロアルキル基;フェニル基、トリル基、キシリル基等のアリール基;ベンジル基、フェネチル基、スチリル基等のアラルキル基、などが挙げられる。R1は、これらの中でも炭素数1〜3のアルキル基であることが好ましい。 In the above formula (p-1), examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Linear or branched alkyl groups such as octyl group, nonyl group and decyl group; alkenyl groups such as vinyl group and allyl group; alkynyl groups such as ethynyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and methylcyclohexyl group Groups; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group, phenethyl group and styryl group. R 1 is preferably an alkyl group having 1 to 3 carbon atoms among these.
R2の1価の有機基としては、例えば炭素数1〜10の1価の炭化水素基、当該炭化水素基の炭素−炭素結合間にヘテロ原子含有基を含む基、当該炭化水素基とヘテロ原子含有基とが結合した基、これらの基の少なくとも1個の水素原子を置換基で置き換えた基、シアノ基、ホルミル基などが挙げられる。
ここで、ヘテロ原子含有基とは、ヘテロ原子を有する2価以上の基を意味し、例えば−O−、−CO−、−COO−、−CONRa−(Raは、水素原子又は炭素数1〜6のアルキル基、以下同じ。)、−NRa−、3価の窒素原子、−NRaCONRa−、−OCONRa−、−S−、−COS−、−OCOO−、−SO2−等が挙げられる。置換基としては、例えばハロゲン原子、ニトロ基、シアノ基、水酸基等が挙げられる。R2は、上記の中でも、炭素数1〜6のアルキル基又は炭素数6若しくは7のアリール基であることが好ましい。
Examples of the monovalent organic group represented by R 2 include a monovalent hydrocarbon group having 1 to 10 carbon atoms, a group containing a hetero atom-containing group between carbon-carbon bonds of the hydrocarbon group, Examples include a group bonded to an atom-containing group, a group in which at least one hydrogen atom of these groups is replaced with a substituent, a cyano group, a formyl group, and the like.
Here, the heteroatom-containing group means a divalent or higher group having a hetero atom, for example -O -, - CO -, - COO -, - CONR a - (R a is a hydrogen atom or a carbon atoms 1-6 alkyl group, hereinafter the same), -. NR a -, 3 -valent nitrogen atom, -NR a CONR a -, - OCONR a -, - S -, - COS -, - OCOO -, - SO 2 -And the like. Examples of the substituent include a halogen atom, a nitro group, a cyano group, a hydroxyl group and the like. Among them, R 2 is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 or 7 carbon atoms.
R3の炭素数1〜6のアルキル基は、直鎖状でも分岐状でもよい。2個のR3が相互に結合して形成される1価の窒素含有複素環基としては、窒素含有複素環が有する窒素原子に結合する水素原子を取り除いた基などが挙げられる。当該窒素含有複素環の具体例としては、例えばピロリジン環、ピペリジン環等が挙げられ、これらの環部分に例えばハロゲン原子、アルキル基等の置換基を有していてもよい。R3は、好ましくは炭素数1〜3のアルキル基であり、より好ましくはメチル基である。X1及びY1は酸素原子であることが好ましい。m,n,k及びjは2又は3が好ましく、3がより好ましい。 The alkyl group having 1 to 6 carbon atoms of R 3 may be linear or branched. Examples of the monovalent nitrogen-containing heterocyclic group formed by bonding two R 3 to each other include a group in which a hydrogen atom bonded to a nitrogen atom of the nitrogen-containing heterocycle has been removed. Specific examples of the nitrogen-containing heterocyclic ring include, for example, a pyrrolidine ring and a piperidine ring, and these ring portions may have a substituent such as a halogen atom or an alkyl group. R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. X 1 and Y 1 are preferably oxygen atoms. m, n, k and j are preferably 2 or 3, and more preferably 3.
リン含有溶剤としては、印刷性の改善効果がより高い点で、上記式(p−1)〜式(p−4)のうち、上記式(p−1)で表される化合物及び上記式(p−3)で表される化合物よりなる群から選ばれる少なくとも一種であることが好ましく、上記式(p−1)で表される化合物であることがより好ましい。 As the phosphorus-containing solvent, among the above formulas (p-1) to (p-4), the compound represented by the above formula (p-1) and the above formula ( It is preferably at least one selected from the group consisting of compounds represented by p-3), and more preferably a compound represented by the formula (p-1).
リン含有溶剤の好ましい具体例としては、例えば下記式(p−1−1)〜式(p−1−7)、式(p−3−1)及び式(p−3−2)のそれぞれで表される化合物等が挙げられる。
リン含有溶剤としては、印刷性がより良好である点で、上記の中でも、上記式(p−1−1)〜式(p−1−4)及び式(p−3−1)のそれぞれで表される化合物が特に好ましい。なお、リン含有溶剤は、1種を単独で又は2種以上を組み合わせて使用することができる。 As the phosphorus-containing solvent, in terms of better printability, among the above, each of the above formulas (p-1-1) to (p-1-4) and formula (p-3-1) The compounds represented are particularly preferred. The phosphorus-containing solvent can be used alone or in combination of two or more.
[上記式(1)で表される化合物]
上記式(1)において、R4の炭素数1〜6のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基等が挙げられ、これらは直鎖状でも分岐状でもよい。上記式(1)で表される化合物の具体例としては、例えば4−ホルミルモルホリン、4−アセチルモルホリン等が挙げられ、中でも4−ホルミルモルホリンであることが特に好ましい。なお、上記式(1)で表される化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。
[Compound represented by the above formula (1)]
In the above formula (1), examples of the alkyl group having 1 to 6 carbon atoms for R 4 include a methyl group, an ethyl group, a propyl group and a butyl group, and these may be linear or branched. Specific examples of the compound represented by the above formula (1) include, for example, 4-formylmorpholine and 4-acetylmorpholine, among which 4-formylmorpholine is particularly preferable. In addition, the compound represented by the above formula (1) can be used alone or in combination of two or more.
[上記式(2)で表される化合物]
上記式(2)において、R5の炭素数1〜6のアルキル基の例示は、上記式(1)のR4の説明を適用することができる。R6の炭素数2〜4のアルカンジイル基としては、例えばエチレン基、プロパンジイル基、ブタンジイル基が挙げられ、これらは直鎖状でも分岐状でもよい。上記式(2)で表される化合物の具体例としては、例えば3−メチル−2−オキサゾリドン、3−エチル−2−オキサゾリドン、3−イソプロピル−2−オキサゾリドン、N−メチル−2−オキサジナノン等が挙げられ、中でも3−メチル−2−オキサゾリドンであることが特に好ましい。なお、上記式(2)で表される化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。
[Compound represented by the above formula (2)]
In the above formula (2), the description of R 4 in the above formula (1) can be applied to the examples of the alkyl group having 1 to 6 carbon atoms of R 5 . Examples of the alkanediyl group having 2 to 4 carbon atoms for R 6 include an ethylene group, a propanediyl group, and a butanediyl group, and these may be linear or branched. Specific examples of the compound represented by the above formula (2) include, for example, 3-methyl-2-oxazolidone, 3-ethyl-2-oxazolidone, 3-isopropyl-2-oxazolidone, N-methyl-2-oxazinanone, and the like. Among them, 3-methyl-2-oxazolidone is particularly preferable. In addition, the compound represented by the above formula (2) can be used alone or in combination of two or more.
[上記式(3)で表される化合物]
上記式(3)において、R7〜R10の1価の有機基としては、例えば炭素数1〜10のアルキル基、当該アルキル基の炭素−炭素結合間にヘテロ原子含有基を含む基、当該アルキル基とヘテロ原子含有基とが結合した基、これらの基の少なくとも1個の水素原子を置換基で置き換えた基などが挙げられる。ヘテロ原子含有基及び置換基の具体例については、上記式(p−1)中のR2の説明を適用することができる。なお、R7〜R10は、互いに同じでも異なっていてもよい。R7〜R10は、好ましくは水素原子、炭素数1〜5のアルキル基又は−CORb(Rbは、水素原子又は炭素数1〜3のアルキル基)である。R7及びR10の一方は、−CORbであることが好ましい。
[Compound represented by the above formula (3)]
In the above formula (3), examples of the monovalent organic group represented by R 7 to R 10 include an alkyl group having 1 to 10 carbon atoms, a group including a hetero atom-containing group between carbon-carbon bonds of the alkyl group, Examples include a group in which an alkyl group and a hetero atom-containing group are bonded, a group in which at least one hydrogen atom in these groups is replaced with a substituent, and the like. For the specific examples of the hetero atom-containing group and the substituent, the description of R 2 in the above formula (p-1) can be applied. Note that R 7 to R 10 may be the same or different from each other. R 7 to R 10 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or —COR b (R b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Preferably, one of R 7 and R 10 is —COR b .
上記式(3)で表される化合物の具体例としては、例えば2−フルアルデヒド、3−フルアルデヒド、5−メチル−2−フルアルデヒド、5−メチル−3−フルアルデヒド、4−メチル−2−フルアルデヒド、4−メチル−2−フルアルデヒド、5−ヒドロキシメチル−2−フルアルデヒド等が挙げられ、中でも5−メチル−2−フルアルデヒドであることが特に好ましい。なお、上記式(3)で表される化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。 Specific examples of the compound represented by the above formula (3) include, for example, 2-furaldehyde, 3-furaldehyde, 5-methyl-2-furaldehyde, 5-methyl-3-furaldehyde, 4-methyl-2 -Furaldehyde, 4-methyl-2-furaldehyde, 5-hydroxymethyl-2-furaldehyde and the like, among which 5-methyl-2-furaldehyde is particularly preferred. In addition, the compound represented by the above formula (3) can be used alone or in combination of two or more.
[上記式(10)で表される化合物]
上記式(10)において、R11〜R13の炭素数1〜3のアルキル基としては、例えばメチル基、エチル基、n−プロピル基、イソプロピル基が挙げられ、中でもメチル基が好ましい。上記式(10)で表される化合物の具体例としては、例えばラクトアミド、N,N−ジメチルラクトアミド、N,N−ジエチルラクトアミド、N−メチル−N−プロピルラクトアミド、N−エチルラクトアミド、N−イソプロピルラクトアミド等が挙げられ、中でもN,N−ジメチルラクトアミドが特に好ましい。なお、上記式(10)で表される化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。
[Compound represented by the above formula (10)]
In the above formula (10), examples of the alkyl group having 1 to 3 carbon atoms of R 11 to R 13 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among them, a methyl group is preferable. Specific examples of the compound represented by the above formula (10) include, for example, lactoamide, N, N-dimethyllactoamide, N, N-diethyllactoamide, N-methyl-N-propyllactoamide, N-ethyllactoamide , N-isopropyllactoamide and the like, among which N, N-dimethyllactoamide is particularly preferred. In addition, the compound represented by the above formula (10) can be used alone or in combination of two or more.
特定溶剤としては、印刷性(特に連続印刷性)がより良好である点で、上記の中でも、リン含有溶剤、N,N−ジメチルプロピレン尿素、上記式(1)で表される化合物、及び上記式(2)で表される化合物よりなる群から選ばれる少なくとも一種であることが好ましい。なお、特定溶剤としては、1種を単独で又は2種以上を組み合わせて使用することができる。 As the specific solvent, among the above, the phosphorus-containing solvent, N, N-dimethylpropylene urea, the compound represented by the above formula (1), and the It is preferably at least one selected from the group consisting of the compounds represented by the formula (2). In addition, as a specific solvent, one type can be used alone or two or more types can be used in combination.
[その他の溶剤]
本発明の液晶配向剤は、特定溶剤以外の溶剤(以下、「その他の溶剤」ともいう。)を含有していてもよい。その他の溶剤の具体例としては、例えばN−エチル−2−ピロリドン、N−(n−プロピル)−2−ピロリドン、N−イソプロピル−2−ピロリドン、N−(n−ブチル)−2−ピロリドン、N−(t−ブチル)−2−ピロリドン、N−(n−ペンチル)−2−ピロリドン、N−メトキシプロピル−2−ピロリドン、N−エトキシエチル−2−ピロリドン、N−メトキシブチル−2−ピロリドン、3−ブトキシ−N,N−ジメチルプロパンアミド、3−メトキシ−N,N−ジメチルプロパンアミド、3−ヘキシルオキシ−N,N−ジメチルプロパンアミド、イソプロポキシ−N−イソプロピル−プロピオンアミド、n−ブトキシ−N−イソプロピル−プロピオンアミド、1,3−ジメチル−2−イミダゾリジノン、N,N’−ジメチルプロピレン尿素、テトラメチル尿素、N−メチル−2−ピロリドン、γ−ブチロラクトン、δ−バレロラクトン、γ−バレロラクトン、γ−カプロラクトン、N,N−ジエチルアセトアミド、γ−ブチロラクタム、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、エチレングリコールモノメチルエーテル、乳酸ブチル、酢酸ブチル、メチルメトキシプロピオネ−ト、エチルエトキシプロピオネ−ト、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコール−n−プロピルエーテル、エチレングリコール−i−プロピルエーテル、エチレングリコール−n−ブチルエーテル(ブチルセロソルブ)、エチレングリコールジメチルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル(DPM)、ジイソブチルケトン、イソアミルプロピオネート、イソアミルイソブチレート、エチレンカーボネート、プロピレンカーボネート等が挙げられる。なお、その他の溶剤は、上記のものを1種単独で又は2種以上を混合して使用することができる。
[Other solvents]
The liquid crystal aligning agent of the present invention may contain a solvent other than the specific solvent (hereinafter, also referred to as “other solvents”). Specific examples of other solvents include, for example, N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone , 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n- Butoxy-N-isopropyl-propionamide, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylpropyl Urea, tetramethylurea, N-methyl-2-pyrrolidone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, γ-caprolactone, N, N-diethylacetamide, γ-butyrolactam, N, N-dimethylformamide N, N-dimethylacetamide, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether , Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Recall monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate, propylene carbonate, etc. Can be The other solvents can be used alone or in combination of two or more.
特定溶剤について、液晶配向剤に含有させる溶剤の全部を特定溶剤としてもよいし、一部を特定溶剤としてもよい。特定溶剤の含有割合(2種以上使用する場合にはその合計量、以下同じ)は、液晶配向剤に含有させる溶剤の全体量に対して、好ましくは1〜80重量%であり、より好ましくは5〜70重量%であり、更に好ましくは10〜60重量%であり、特に好ましくは20〜60重量%である。 With respect to the specific solvent, all of the solvents contained in the liquid crystal alignment agent may be used as the specific solvent, or a part of the solvent may be used as the specific solvent. The content ratio of the specific solvent (the total amount when two or more types are used, the same applies hereinafter) is preferably 1 to 80% by weight, more preferably the total amount of the solvent to be contained in the liquid crystal aligning agent. The content is 5 to 70% by weight, more preferably 10 to 60% by weight, and particularly preferably 20 to 60% by weight.
<その他の成分>
本発明の液晶配向剤は、上記の如き重合体成分及び溶剤を含有するが、必要に応じてその他の成分を含有していてもよい。かかるその他の成分としては、例えば分子内に少なくとも一つのエポキシ基を有する化合物、官能性シラン化合物、光重合性化合物、界面活性剤、充填剤、消泡剤、増感剤、分散剤、酸化防止剤、密着助剤、帯電防止剤、レベリング剤、抗菌剤等が挙げられる。これらの配合割合は、配合する化合物に応じて、本発明の効果を妨げない範囲で適宜設定することができる。
<Other ingredients>
The liquid crystal aligning agent of the present invention contains the above-mentioned polymer component and solvent, but may contain other components as necessary. Examples of such other components include compounds having at least one epoxy group in the molecule, functional silane compounds, photopolymerizable compounds, surfactants, fillers, defoamers, sensitizers, dispersants, and antioxidants. Agents, adhesion aids, antistatic agents, leveling agents, antibacterial agents and the like. These blending ratios can be appropriately set according to the compound to be blended, as long as the effects of the present invention are not impaired.
本発明の液晶配向剤における固形分濃度(液晶配向剤の溶媒以外の成分の合計重量が液晶配向剤の全重量に占める割合)は、粘性、揮発性などを考慮して適宜に選択されるが、好ましくは1〜10重量%の範囲である。すなわち、本発明の液晶配向剤は、後述するように基板表面に塗布され、好ましくは加熱されることにより、液晶配向膜である塗膜又は液晶配向膜となる塗膜が形成されるが、このとき、固形分濃度が1重量%未満である場合には、塗膜の膜厚が過小となって良好な液晶配向膜を得にくくなる。一方、固形分濃度が10重量%を超える場合には、塗膜の膜厚が過大となって良好な液晶配向膜を得にくく、また、液晶配向剤の粘性が増大して塗布特性が低下する傾向にある。 The solid content concentration (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) in the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like. , Preferably in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film serving as a liquid crystal alignment film or a coating film serving as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film becomes too small and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solids concentration exceeds 10% by weight, the thickness of the coating film becomes excessively large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases to deteriorate the coating characteristics. There is a tendency.
特に好ましい固形分濃度の範囲は、基板に液晶配向剤を塗布する際に用いる方法によって異なる。例えばスピンコート法による場合には固形分濃度1.5〜4.5重量%の範囲が特に好ましい。オフセット印刷法による場合には、固形分濃度を3〜9重量%の範囲とし、それにより溶液粘度を12〜50mPa・sの範囲とすることが特に好ましい。インクジェット法による場合には、固形分濃度を1〜5重量%の範囲とし、それにより、溶液粘度を3〜15mPa・sの範囲とすることが特に好ましい。液晶配向剤を調製する際の温度は、好ましくは10〜50℃であり、より好ましくは20〜30℃である。 The particularly preferable range of the solid content concentration differs depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the offset printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of using the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at the time of preparing the liquid crystal alignment agent is preferably 10 to 50C, more preferably 20 to 30C.
<液晶配向膜及び液晶素子>
本発明の液晶配向膜は、上記のように調製された液晶配向剤により形成される。また、本発明の液晶素子は、上記の液晶配向剤を用いて形成された液晶配向膜を具備する。液晶素子における液晶の駆動モードは特に限定されず、TN型、STN型、IPS型、FFS型、VA型、MVA型、PSA型などの種々の駆動モードに適用することができる。本発明の液晶素子は、例えば以下の工程1〜工程3を含む方法により製造することができる。工程1は、所望の駆動モードによって使用基板が異なる。工程2及び工程3は各駆動モードに共通である。
<Liquid crystal alignment film and liquid crystal element>
The liquid crystal alignment film of the present invention is formed by the liquid crystal alignment agent prepared as described above. Further, a liquid crystal element of the present invention includes a liquid crystal alignment film formed using the above liquid crystal alignment agent. The driving mode of the liquid crystal in the liquid crystal element is not particularly limited, and can be applied to various driving modes such as a TN mode, an STN mode, an IPS mode, an FFS mode, a VA mode, an MVA mode, and a PSA mode. The liquid crystal element of the present invention can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, a substrate to be used is different depending on a desired driving mode. Steps 2 and 3 are common to each drive mode.
[工程1:塗膜の形成]
先ず、基板上に本発明の液晶配向剤を塗布し、次いで塗布面を加熱することにより基板上に塗膜を形成する。
(1−1)TN型、STN型、VA型、MVA型又はPSA型の液晶素子を製造する場合、パターニングされた透明導電膜が設けられている基板二枚を一対として、それぞれの基板における透明性導電膜の形成面上に液晶配向剤を、好ましくはオフセット印刷法、スピンコート法、ロールコーター法又はインクジェット印刷法によりそれぞれ塗布する。基板としては、例えばフロートガラス、ソーダガラスなどのガラス;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、ポリ(脂環式オレフィン)などのプラスチックからなる透明基板を用いることができる。基板の一面に設けられる透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社登録商標)、酸化インジウム−酸化スズ(In2O3−SnO2)からなるITO膜などを用いることができる。
[Step 1: Formation of coating film]
First, the liquid crystal aligning agent of the present invention is applied on a substrate, and then the coated surface is heated to form a coating film on the substrate.
(1-1) When manufacturing a TN-type, STN-type, VA-type, MVA-type or PSA-type liquid crystal element, two substrates provided with a patterned transparent conductive film are paired, and a transparent substrate is used for each substrate. A liquid crystal aligning agent is preferably applied on the surface on which the conductive conductive film is formed, preferably by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. As the substrate, for example, a transparent substrate made of glass such as float glass and soda glass; and a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. Examples of the transparent conductive film provided on one surface of the substrate include a NESA film made of tin oxide (SnO 2 ) (registered trademark of PPG, USA) and an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ). Can be used.
液晶配向剤の塗布後、塗布した配向剤の液垂れ防止などの目的で、好ましくは予備加熱(プレベーク)が実施される。プレベーク温度は、好ましくは30〜200℃であり、プレベーク時間は、好ましくは0.25〜10分である。その後、溶剤を完全に除去する目的で、また必要に応じて重合体に存在するアミック酸構造を熱イミド化することを目的として焼成(ポストベーク)工程が実施される。このときの焼成温度(ポストベーク温度)は、好ましくは80〜300℃であり、ポストベーク時間は、好ましくは5〜200分である。このようにして形成される膜の膜厚は、好ましくは0.001〜1μm、より好ましくは0.005〜0.5μmである。 After the application of the liquid crystal alignment agent, preheating (prebake) is preferably performed for the purpose of preventing the applied alignment agent from dripping. The pre-bake temperature is preferably 30 to 200 ° C., and the pre-bake time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, for thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., and the post-bake time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.
(1−2)IPS型又はFFS型液晶表示素子を製造する場合、櫛歯型にパターニングされた透明導電膜又は金属膜からなる電極が設けられている基板の電極形成面と、電極が設けられていない対向基板の一面とに液晶配向剤をそれぞれ塗布し、次いで各塗布面を加熱することにより塗膜を形成する。このとき使用される基板及び透明導電膜の材質、塗布方法、塗布後の加熱条件、膜厚等については上記(1−1)と同様である。金属膜としては、例えばクロムなどの金属からなる膜を使用することができる。
上記(1−1)及び(1−2)のいずれの場合も、基板上に液晶配向剤を塗布した後、有機溶媒を除去することによって、液晶配向膜又は液晶配向膜となる塗膜が形成される。
(1-2) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape and an electrode are provided. A liquid crystal aligning agent is applied to one surface of the opposite substrate that has not been coated, and then each applied surface is heated to form a coating film. At this time, the materials and application methods of the substrate and the transparent conductive film, the heating conditions after application, the film thickness, and the like are the same as in (1-1) above. As the metal film, for example, a film made of a metal such as chromium can be used.
In any of the above (1-1) and (1-2), a liquid crystal alignment film or a coating film to be a liquid crystal alignment film is formed by applying a liquid crystal alignment agent on a substrate and then removing an organic solvent. Is done.
[工程2:配向能付与処理]
TN型、STN型、IPS型又はFFS型の液晶表示素子を製造する場合、上記工程1で形成した塗膜に液晶配向能を付与する処理を実施する。これにより、液晶分子の配向能が塗膜に付与されて液晶配向膜となる。配向能付与処理としては、例えばナイロン、レーヨン、コットンなどの繊維からなる布を巻き付けたロールで塗膜を一定方向に擦るラビング処理、塗膜に対して偏光又は非偏光の放射線を照射する光配向処理などが挙げられる。一方、VA型液晶表示素子を製造する場合には、上記工程1で形成した塗膜をそのまま液晶配向膜として使用することができるが、該塗膜に対し配向能付与処理を施してもよい。VA型の液晶表示素子に好適な液晶配向膜は、PSA(Polymer sustained alignment)型の液晶表示素子にも好適に用いることができる。
[Step 2: treatment for imparting alignment ability]
When manufacturing a TN-type, STN-type, IPS-type or FFS-type liquid crystal display device, a process of imparting liquid crystal alignment capability to the coating film formed in the above step 1 is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. The orientation imparting treatment includes, for example, rubbing treatment in which the coating is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, and the like, and optical alignment in which the coating is irradiated with polarized or unpolarized radiation. Processing. On the other hand, in the case of manufacturing a VA liquid crystal display element, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment. A liquid crystal alignment film suitable for a VA liquid crystal display element can be suitably used for a PSA (Polymer sustained alignment) liquid crystal display element.
[工程3:液晶セルの構築]
上記のようにして液晶配向膜が形成された基板を2枚準備し、対向配置した2枚の基板間に液晶を配置することにより液晶セルを製造する。液晶セルを製造するには、例えば、(1)液晶配向膜が対向するように間隙を介して2枚の基板を対向配置し、2枚の基板の周辺部をシール剤を用いて貼り合わせ、基板表面及びシール剤により区画されたセルギャップ内に液晶を注入充填した後、注入孔を封止する方法、(2)液晶配向膜を形成した一方の基板上の所定の場所にシール剤を塗布し、さらに液晶配向膜面上の所定の数箇所に液晶を滴下した後、液晶配向膜が対向するように他方の基板を貼り合わせるとともに液晶を基板の全面に押し広げる方法(ODF方式)等が挙げられる。製造した液晶セルにつき、さらに、用いた液晶が等方相をとる温度まで加熱した後、室温まで徐冷することにより、液晶充填時の流動配向を除去することが望ましい。
[Step 3: Construction of Liquid Crystal Cell]
A liquid crystal cell is manufactured by preparing two substrates on each of which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates that are opposed to each other. In order to manufacture a liquid crystal cell, for example, (1) two substrates are opposed to each other with a gap therebetween so that a liquid crystal alignment film faces each other, and the peripheral portions of the two substrates are bonded to each other using a sealant; A method of injecting and filling liquid crystal into a cell gap defined by a substrate surface and a sealing agent, and then sealing the injection hole. (2) Applying a sealing agent to a predetermined location on one substrate on which a liquid crystal alignment film is formed Then, after dropping the liquid crystal at predetermined positions on the surface of the liquid crystal alignment film, the other substrate is attached to the liquid crystal alignment film so as to face the liquid crystal alignment film, and the liquid crystal is spread over the entire surface of the substrate (an ODF method). No. It is desirable that the manufactured liquid crystal cell is further heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.
シール剤としては、例えば硬化剤及びスペーサーとしての酸化アルミニウム球を含有するエポキシ樹脂などを用いることができる。液晶としては、ネマチック液晶及びスメクチック液晶を挙げることができ、その中でもネマチック液晶が好ましく、例えばシッフベース系液晶、アゾキシ系液晶、ビフェニル系液晶、フェニルシクロヘキサン系液晶、エステル系液晶、ターフェニル系液晶、ビフェニルシクロヘキサン系液晶、ピリミジン系液晶、ジオキサン系液晶、ビシクロオクタン系液晶、キュバン系液晶などを用いることができる。また、これらの液晶に、例えばコレステリック液晶、カイラル剤、強誘電性液晶などを添加して使用してもよい。 As the sealant, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, a nematic liquid crystal is preferable, for example, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, and biphenyl. A cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like can be used. Further, a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, or the like may be added to these liquid crystals for use.
PSA型液晶表示素子を製造する場合には、液晶と共に光重合性化合物を注入又は滴下する点以外は上記と同様にして液晶セルを構築する。その後、一対の基板の有する導電膜間に、直流又は交流の電圧を印加した状態で液晶セルに光照射する。また、光重合性化合物を含む液晶配向剤を用いて基板上に塗膜を形成した場合、上記と同様にして液晶セルを構築し、その後、一対の基板の有する導電膜間に、直流又は交流の電圧を印加した状態で液晶セルに光照射する工程を経ることにより液晶素子を製造してもよい。 When a PSA-type liquid crystal display element is manufactured, a liquid crystal cell is constructed in the same manner as described above except that a photopolymerizable compound is injected or dropped together with liquid crystal. After that, the liquid crystal cell is irradiated with light while a DC or AC voltage is applied between the conductive films of the pair of substrates. When a coating film is formed on a substrate using a liquid crystal aligning agent containing a photopolymerizable compound, a liquid crystal cell is constructed in the same manner as described above, and then a direct current or an alternating current is applied between the conductive films of the pair of substrates. The liquid crystal element may be manufactured through a step of irradiating the liquid crystal cell with light in a state where the voltage is applied.
そして、液晶セルの外側表面に偏光板を貼り合わせることにより、本発明の液晶表示素子を得ることができる。液晶セルの外表面に貼り合わされる偏光板としては、ポリビニルアルコールを延伸配向させながらヨウ素を吸収させた「H膜」と称される偏光フィルムを酢酸セルロース保護膜で挟んだ偏光板又はH膜そのものからなる偏光板を挙げることができる。 Then, by attaching a polarizing plate to the outer surface of the liquid crystal cell, the liquid crystal display device of the present invention can be obtained. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched by a cellulose acetate protective film or the H film itself. Can be mentioned.
本発明の液晶素子は種々の装置に有効に適用することができ、例えば、時計、携帯型ゲーム、ワープロ、ノート型パソコン、カーナビゲーションシステム、カムコーダー、PDA、デジタルカメラ、携帯電話、スマートフォン、各種モニター、液晶テレビなどの各種表示装置や、調光フィルム等に用いることができる。また、本発明の液晶配向剤を用いて形成された液晶素子は位相差フィルムに適用することもできる。 The liquid crystal element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors. And various display devices such as a liquid crystal television, a light control film, and the like. Further, a liquid crystal element formed using the liquid crystal alignment agent of the present invention can be applied to a retardation film.
以下、本発明を実施例により更に具体的に説明するが、本発明はこれらの実施例に制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
合成例における各重合体溶液の溶液粘度、ポリイミドのイミド化率、重量平均分子量、及びエポキシ当量は以下の方法により測定した。
[重合体溶液の溶液粘度(mPa・s)]所定の溶媒を用い、重合体濃度10重量%に調整した溶液について、E型回転粘度計を用いて25℃で測定した。
[ポリイミドのイミド化率]ポリイミドの溶液を純水に投入し、得られた沈殿を室温で十分に減圧乾燥した後、重水素化ジメチルスルホキシドに溶解し、テトラメチルシランを基準物質として室温で1H−NMRを測定した。得られた1H−NMRスペクトルから、下記数式(1)によりイミド化率[%]を求めた。
イミド化率[%]=(1−A1/A2×α)×100 …(1)
(数式(1)中、A1は化学シフト10ppm付近に現れるNH基のプロトン由来のピーク面積であり、A2はその他のプロトン由来のピーク面積であり、αは重合体の前駆体(ポリアミック酸)におけるNH基のプロトン1個に対するその他のプロトンの個数割合である。)
[重合体の重量平均分子量Mw]以下の条件におけるゲルパーミエーションクロマトグラフィーにより測定したポリスチレン換算値である。
カラム:東ソー(株)製、TSKgelGRCXLII
溶剤:テトラヒドロフラン
温度:40℃
圧力:68kgf/cm2
[エポキシ当量]JIS C 2105に記載の塩酸−メチルエチルケトン法により測定した。
The solution viscosity of each polymer solution, the imidation ratio of polyimide, the weight average molecular weight, and the epoxy equivalent in the synthesis examples were measured by the following methods.
[Solution Viscosity of Polymer Solution (mPa · s)] A solution adjusted to a polymer concentration of 10% by weight using a predetermined solvent was measured at 25 ° C. using an E-type rotational viscometer.
After the solution of the polyimide [imidization of the polyimide] was put into pure water, the resulting precipitate was thoroughly dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, at room temperature with tetramethylsilane as a reference substance 1 1 H-NMR was measured. From the obtained 1 H-NMR spectrum, the imidation ratio [%] was determined by the following equation (1).
Imidation ratio [%] = (1−A 1 / A 2 × α) × 100 (1)
(In the formula (1), A 1 is the peak area derived from the proton of the NH group, which appears near the chemical shift of 10 ppm, A 2 is the peak area derived from the other protons, and α is the precursor of the polymer (polyamic acid ) Is the number ratio of other protons to one proton of the NH group.)
[Weight average molecular weight of polymer Mw] It is a value in terms of polystyrene measured by gel permeation chromatography under the following conditions.
Column: TSKgelGRCXLII, manufactured by Tosoh Corporation
Solvent: tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm 2
[Epoxy equivalent] It was measured by a hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
<重合体の合成>
[合成例1:ポリイミド(PI−1)の合成]
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物(TCA)22.4g(0.1モル)、ジアミンとしてp−フェニレンジアミン(PDA)8.6g(0.08モル)及び3,5−ジアミノ安息香酸コレスタニル(HCDA)10.5g(0.02モル)を、N−メチル−2−ピロリドン(NMP)166gに溶解し、60℃で6時間反応を行い、ポリアミック酸を20重量%含有する溶液を得た。得られたポリアミック酸溶液を少量分取し、NMPを加えてポリアミック酸濃度10重量%の溶液として測定した溶液粘度は90mPa・sであった。
次いで、得られたポリアミック酸溶液に、NMPを追加してポリアミック酸濃度7重量%の溶液とし、ピリジン11.9g及び無水酢酸15.3gを添加して110℃で4時間脱水閉環反応を行った。脱水閉環反応後、系内の溶媒を新たなNMPで溶媒置換(本操作によって脱水閉環反応に使用したピリジン及び無水酢酸を系外に除去した。以下同じ。)することにより、イミド化率約68%のポリイミド(PI−1)を26重量%含有する溶液を得た。得られたポリイミド溶液を少量分取し、NMPを加えてポリイミド濃度10重量%の溶液として測定した溶液粘度は45mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−1)を得た。
<Synthesis of polymer>
[Synthesis Example 1: Synthesis of polyimide (PI-1)]
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic dianhydride and 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ) And 10.5 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) were dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours to obtain polyamic acid. Was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 90 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. . After the dehydration ring-closing reaction, the solvent in the system was solvent-replaced with fresh NMP (the pyridine and acetic anhydride used in the dehydration ring-closing reaction were removed from the system by this operation; the same applies hereinafter), resulting in an imidization ratio of about 68. % Polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 45 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyimide (PI-1).
[合成例2:ポリイミド(PI−2)の合成]
テトラカルボン酸二無水物としてTCA22.5g(0.1モル)、ジアミンとしてPDA7.6g(0.07モル)、HCDA5.2g(0.01モル)及び4,4’−ジアミノジフェニルメタン(DDM)4.0g(0.02モル)、をNMP157gに溶解し、60℃で6時間反応を行い、ポリアミック酸を20重量%含有する溶液を得た。得られたポリアミック酸溶液を少量分取し、NMPを加えてポリアミック酸濃度10重量%の溶液として測定した溶液粘度は110mPa・sであった。
次いで、得られたポリアミック酸溶液に、NMPを追加してポリアミック酸濃度7重量%の溶液とし、ピリジン16.6g及び無水酢酸21.4gを添加して110℃で4時間脱水閉環反応を行った。脱水閉環反応後、系内の溶媒を新たなNMPで溶媒置換することにより、イミド化率約82%のポリイミド(PI−2)を26重量%含有する溶液を得た。得られたポリイミド溶液を少量分取し、NMPを加えてポリイミド濃度10重量%の溶液として測定した溶液粘度は62mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−2)を得た。
[Synthesis Example 2: Synthesis of polyimide (PI-2)]
22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 5.2 g (0.01 mol) of HCDA and 4,4′-diaminodiphenylmethane (DDM) 4 0.0g (0.02 mol) was dissolved in 157g of NMP and reacted at 60 ° C for 6 hours to obtain a solution containing 20% by weight of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 110 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 16.6 g of pyridine and 21.4 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. . After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing 26% by weight of polyimide (PI-2) having an imidization ratio of about 82%. A small amount of the obtained polyimide solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 62 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain polyimide (PI-2).
[合成例3:ポリイミド(PI−3)の合成]
テトラカルボン酸二無水物として2,4,6,8−テトラカルボキシビシクロ[3.3.0]オクタン−2:4,6:8−二無水物(BODA)24.9g(0.10モル)、ジアミンとしてPDA8.6g(0.08モル)及びHCDA10.4g(0.02モル)を、NMP176gに溶解し、60℃で6時間反応を行い、ポリアミック酸を20重量%含有する溶液を得た。得られたポリアミック酸溶液を少量分取し、NMPを加えてポリアミック酸濃度10重量%の溶液として測定した溶液粘度は103mPa・sであった。
次いで、得られたポリアミック酸溶液に、NMPを追加してポリアミック酸濃度7重量%の溶液とし、ピリジン11.9g及び無水酢酸15.3gを添加して110℃で4時間脱水閉環反応を行った。脱水閉環反応後、系内の溶媒を新たなNMPで溶媒置換することにより、イミド化率約71%のポリイミド(PI−3)を26重量%含有する溶液を得た。得られたポリイミド溶液を少量分取し、NMPを加えてポリイミド濃度10重量%の溶液として測定した溶液粘度は57mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−3)を得た。
[Synthesis Example 3: Synthesis of polyimide (PI-3)]
As a tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride (BODA) 24.9 g (0.10 mol) Then, 8.6 g (0.08 mol) of PDA as a diamine and 10.4 g (0.02 mol) of HCDA were dissolved in 176 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. . A small amount of the obtained polyamic acid solution was taken out, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 103 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. . After the dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 26% by weight of polyimide (PI-3) having an imidization ratio of about 71%. A small amount of the obtained polyimide solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 57 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-3).
[合成例4:ポリイミド(PI−4)の合成]
テトラカルボン酸二無水物として、TCA110g(0.50モル)及び1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)ナフト[1,2−c]フラン−1,3−ジオン160g(0.50モル)、ジアミンとして、PDA91g(0.85モル)、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン25g(0.10モル)及び3,6−ビス(4−アミノベンゾイルオキシ)コレスタン25g(0.040モル)、並びにモノアミンとしてアニリン1.4g(0.015モル)を、NMP960gに溶解し、60℃で6時間反応を行うことにより、ポリアミック酸を含有する溶液を得た。得られたポリアミック酸溶液を少量分取し、NMPを加えてポリアミック酸濃度10重量%の溶液として測定した溶液粘度は60mPa・sであった。
次いで、得られたポリアミック酸溶液にNMP2,700gを追加し、ピリジン390g及び無水酢酸410gを添加して110℃で4時間脱水閉環反応を行った。脱水閉環反応後、系内の溶媒を新たなγ−ブチロラクトンで溶媒置換することにより、イミド化率約95%のポリイミド(PI−4)を15重量%含有する溶液約2,500gを得た。この溶液を少量分取し、NMPを加え、ポリイミド濃度10重量%の溶液として測定した溶液粘度は70mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−4)を得た。
[Synthesis Example 4: Synthesis of polyimide (PI-4)]
As tetracarboxylic dianhydride, 110 g (0.50 mol) of TCA and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho 160 g (0.50 mol) of [1,2-c] furan-1,3-dione, 91 g (0.85 mol) of PDA as diamine, 25 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ( 0.10 mol) and 25 g (0.040 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, and 1.4 g (0.015 mol) of aniline as a monoamine were dissolved in 960 g of NMP. By performing the reaction for 6 hours, a solution containing a polyamic acid was obtained. A small amount of the obtained polyamic acid solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-replaced with fresh γ-butyrolactone to obtain about 2,500 g of a solution containing 15% by weight of a polyimide (PI-4) having an imidization ratio of about 95%. A small amount of this solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 70 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a polyimide (PI-4).
[合成例5:ポリイミド(PI−5)の合成]
テトラカルボン酸二無水物としてTCA22.4g(0.1モル)、ジアミンとしてPDA8.6g(0.08モル)、DDM2.0g(0.01モル)及び4,4’−ジアミノ−2,2’−ビス(トリフルオロメチル)ビフェニル3.2g(0.01モル)を、NMP324gに溶解し、60℃で4時間反応を行い、ポリアミック酸を10重量%含有する溶液を得た。
次いで、得られたポリアミック酸溶液に、NMP360gを追加し、ピリジン39.5g及び無水酢酸30.6gを添加して110℃で4時間脱水閉環反応を行った。脱水閉環反応後、系内の溶媒を新たなNMPで溶媒置換し、イミド化率約93%のポリイミド(PI−5)を10重量%含有する溶液を得た。得られたポリイミド溶液を少量分取して測定した溶液粘度は30mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−5)を得た。
[Synthesis Example 5: Synthesis of polyimide (PI-5)]
22.4 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 8.6 g (0.08 mol) of PDA as diamine, 2.0 g (0.01 mol) of DDM, and 4,4′-diamino-2,2 ′ 3.2 g (0.01 mol) of -bis (trifluoromethyl) biphenyl was dissolved in 324 g of NMP and reacted at 60 ° C. for 4 hours to obtain a solution containing 10% by weight of polyamic acid.
Next, 360 g of NMP was added to the obtained polyamic acid solution, 39.5 g of pyridine and 30.6 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with fresh NMP to obtain a solution containing 10% by weight of polyimide (PI-5) having an imidization ratio of about 93%. The solution viscosity measured by dispensing a small amount of the obtained polyimide solution was 30 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-5).
[合成例6:ポリイミド(PI−6)の合成]
使用するジアミンを、3,5−ジアミノ安息香酸(3,5DAB)0.08モル及びコレスタニルオキシ−2,4−ジアミノベンゼン(HCODA)0.02モルに変更した以外は、上記合成例1と同様の方法によりポリアミック酸溶液を得た。得られたポリアミック酸溶液を少量分取し、NMPを加えてポリアミック酸濃度10重量%の溶液として測定した溶液粘度は80mPa・sであった。
次いで、上記合成例1と同様の方法によりイミド化を行い、イミド化率約65%のポリイミド(PI−6)を26重量%含有する溶液を得た。得られたポリイミド溶液を少量分取し、NMPを加えてポリイミド濃度10重量%の溶液として測定した溶液粘度は40mPa・sであった。次いで、反応溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリイミド(PI−6)を得た。
[Synthesis Example 6: Synthesis of polyimide (PI-6)]
Synthesis Example 1 was repeated except that the diamine used was changed to 0.08 mol of 3,5-diaminobenzoic acid (3,5 DAB) and 0.02 mol of cholestanyloxy-2,4-diaminobenzene (HCODA). A polyamic acid solution was obtained in the same manner. A small amount of the obtained polyamic acid solution was taken out, NMP was added thereto, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 80 mPa · s.
Next, imidation was performed in the same manner as in Synthesis Example 1 above, to obtain a solution containing 26% by weight of polyimide (PI-6) having an imidization ratio of about 65%. A small amount of the obtained polyimide solution was fractionated, NMP was added thereto, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 40 mPa · s. Then, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. This precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-6).
[合成例7:ポリアミック酸(PA−1)の合成]
テトラカルボン酸二無水物として1,2,3,4−シクロブタンテトラカルボン酸二無水物(CB)200g(1.0モル)、ジアミンとして2,2’−ジメチル−4,4’−ジアミノビフェニル210g(1.0モル)を、NMP370g及びγ−ブチロラクトン3,300gの混合溶媒に溶解し、40℃で3時間反応を行い、固形分濃度10重量%、溶液粘度160mPa・sのポリアミック酸溶液を得た。次いで、このポリアミック酸溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリアミック酸(PA−1)を得た。
[Synthesis Example 7: Synthesis of polyamic acid (PA-1)]
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride and 210 g of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine (1.0 mol) was dissolved in a mixed solvent of 370 g of NMP and 3,300 g of γ-butyrolactone, and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a solid concentration of 10% by weight and a solution viscosity of 160 mPa · s. Was. Then, the polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyamic acid (PA-1).
[合成例8:ポリアミック酸(PA−2)の合成]
使用するテトラカルボン酸二無水物を、ピロメリット酸二無水物(PMDA)0.9モル及びCB0.1モルとし、ジアミンを、PDA0.2モル及び4,4’−ジアミノジフェニルエーテル(DDE)0.8モルとした以外は上記合成例7と同様の方法により、固形分濃度10重量%、溶液粘度170mPa・sのポリアミック酸溶液を得た。次いで、このポリアミック酸溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリアミック酸(PA−2)を得た。
[Synthesis Example 8: Synthesis of polyamic acid (PA-2)]
The tetracarboxylic dianhydride used is 0.9 mol of pyromellitic dianhydride (PMDA) and 0.1 mol of CB, and the diamine is 0.2 mol of PDA and 0.4 mol of 4,4′-diaminodiphenyl ether (DDE). A polyamic acid solution having a solid content of 10% by weight and a solution viscosity of 170 mPa · s was obtained in the same manner as in Synthesis Example 7 except that the amount was changed to 8 mol. Then, the polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain a polyamic acid (PA-2).
[合成例9:ポリアミック酸(PA−3)の合成]
テトラカルボン酸二無水物としてTCA7.0g(0.031モル)、ジアミンとして下記式(R−1)で表される化合物13g(TCA1モルに対して1モルに相当する。)を、NMP80gに溶解し、60℃で4時間反応を行うことにより、ポリアミック酸(PA−3)を20重量%含有する溶液を得た。このポリアミック酸溶液の溶液粘度は2,000mPa・sであった。なお、下記式(R−1)で表される化合物は、特開2011−100099号公報の記載に従って合成した。次いで、このポリアミック酸溶液を大過剰のメタノール中に注ぎ、反応生成物を沈殿させた。この沈殿物をメタノールで洗浄し、減圧下40℃で15時間乾燥させることにより、ポリアミック酸(PA−3)を得た。
7.0 g (0.031 mol) of TCA as a tetracarboxylic dianhydride and 13 g (corresponding to 1 mol per 1 mol of TCA) of a compound represented by the following formula (R-1) as a diamine are dissolved in 80 g of NMP. Then, the solution was reacted at 60 ° C. for 4 hours to obtain a solution containing 20% by weight of polyamic acid (PA-3). The solution viscosity of this polyamic acid solution was 2,000 mPa · s. In addition, the compound represented by the following formula (R-1) was synthesized according to the description in JP-A-2011-100099. Then, the polyamic acid solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyamic acid (PA-3).
[合成例10:ポリオルガノシロキサン(APS−1)の合成]
撹拌機、温度計、滴下漏斗及び還流冷却管を備えた反応容器に、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン(ECETS)100.0g、メチルイソブチルケトン500g及びトリエチルアミン10.0gを仕込み、室温で混合した。次いで、脱イオン水100gを滴下漏斗より30分かけて滴下した後、還流下で撹拌しつつ、80℃で6時間反応を行った。反応終了後、有機層を取り出し、0.2重量%硝酸アンモニウム水溶液により、洗浄後の水が中性になるまで洗浄した後、減圧下で溶媒及び水を留去することにより、反応性ポリオルガノシロキサン(EPS−1)を粘調な透明液体として得た。この反応性ポリオルガノシロキサン(EPS−1)について、1H−NMR分析を行ったところ、化学シフト(δ)=3.2ppm付近にエポキシ基に基づくピークが理論強度どおりに得られ、反応中にエポキシ基の副反応が起こっていないことが確認された。得られた反応性ポリオルガノシロキサンの重量平均分子量Mwは3,500、エポキシ当量は180g/モルであった。
次いで、200mLの三口フラスコに、反応性ポリオルガノシロキサン(EPS−1)を10.0g、溶媒としてメチルイソブチルケトン30.28g、反応性化合物として4−ドデシルオキシ安息香酸3.98g、及び触媒としてUCAT 18X(商品名、サンアプロ(株)製)0.10gを仕込み、100℃で48時間撹拌下に反応を行った。反応終了後、反応混合物に酢酸エチルを加えて得た溶液を3回水洗し、有機層を硫酸マグネシウムを用いて乾燥した後、溶剤を留去することにより、液晶配向性ポリオルガノシロキサン(APS−1)を9.0g得た。得られた重合体の重量平均分子量Mwは9,900であった。
[Synthesis Example 10: Synthesis of polyorganosiloxane (APS-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added. Charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain a reactive polyorganosiloxane. (EPS-1) was obtained as a viscous transparent liquid. When 1 H-NMR analysis was performed on this reactive polyorganosiloxane (EPS-1), a peak based on an epoxy group was obtained at a chemical shift (δ) of around 3.2 ppm in accordance with the theoretical intensity. It was confirmed that no side reaction of the epoxy group occurred. The obtained reactive polyorganosiloxane had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g / mol.
Next, in a 200 mL three-necked flask, 10.0 g of the reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as the solvent, 3.98 g of 4-dodecyloxybenzoic acid as the reactive compound, and UCAT as the catalyst 0.10 g of 18X (trade name, manufactured by San Apro Co., Ltd.) was charged, and the reaction was carried out at 100 ° C. with stirring for 48 hours. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture was washed three times with water, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain a liquid crystal aligning polyorganosiloxane (APS- 9.0 g of 1) was obtained. The weight average molecular weight Mw of the obtained polymer was 9,900.
[合成例11:ポリオルガノシロキサン(PS1)の合成]
撹拌機、温度計、滴下漏斗及び還流冷却管を備えた反応容器に、p−スチリルトリメトキシシラン31g、テトラヒドロフラン70g、トリエチルアミン33g及び脱イオン水25gを加え、室温で混合した。次いで、還流下で撹拌しつつ、60℃で3時間反応を行った。反応終了後、有機層を取り出し、ジエチレングリコールジエチルエーテル60gを加え、加熱濃縮を行った。固形分濃度が30%になるまで濃縮することで、ポリシロキサン(PS1)のジエチレングリコールジエチルエーテル溶液を得た。
[合成例12,13]
仕込み原料を下記表1に示すとおりとした以外は、合成例11と同様の合成方法で、ポリオルガノシロキサン(PS−2)及び(PS−3)のジエチレングリコールジエチルエーテル溶液を得た。得られたポリオルガノシロキサンの重量平均分子量Mwを下記表1に併せて示した。
[Synthesis Example 11: Synthesis of polyorganosiloxane (PS1)]
To a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 31 g of p-styryltrimethoxysilane, 70 g of tetrahydrofuran, 33 g of triethylamine and 25 g of deionized water were added and mixed at room temperature. Next, the reaction was carried out at 60 ° C. for 3 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, 60 g of diethylene glycol diethyl ether was added, and the mixture was concentrated by heating. By concentrating until the solid concentration became 30%, a diethylene glycol diethyl ether solution of polysiloxane (PS1) was obtained.
[Synthesis Examples 12 and 13]
A diethylene glycol diethyl ether solution of polyorganosiloxanes (PS-2) and (PS-3) was obtained in the same manner as in Synthesis Example 11 except that the charged raw materials were as shown in Table 1 below. The weight average molecular weight Mw of the obtained polyorganosiloxane is also shown in Table 1 below.
なお、表1において、原料シラン化合物の略称は、それぞれ以下の意味である。
STTMS:p−スチリルトリメトキシシラン
ECETMS:2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン
PTMS:フェニルトリメトキシシラン
In Table 1, the abbreviations of the raw material silane compounds have the following meanings.
STTMS: p-styryltrimethoxysilane ECETMS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane PTMS: phenyltrimethoxysilane
[実施例1]
<液晶配向剤の調製>
重合体としてポリイミド(PI−1)を用い、これに溶剤としてリン酸トリメチル(PTM)、N−メチル−2−ピロリドン(NMP)及びブチルセロソルブ(BC)を加え、溶剤組成がPTM:NMP:BC=20:40:40(重量比)、固形分濃度6.5重量%の溶液とした。この溶液を孔径1μmのフィルターを用いて濾過することにより液晶配向剤(S−1)を調製した。なお、液晶配向剤(S−1)は、主に垂直配向型の液晶表示素子の製造用である。
[Example 1]
<Preparation of liquid crystal alignment agent>
Polyimide (PI-1) was used as a polymer, and trimethyl phosphate (PTM), N-methyl-2-pyrrolidone (NMP), and butyl cellosolve (BC) were added as a solvent, and the solvent composition was PTM: NMP: BC = 20:40:40 (weight ratio), and a solution having a solid content of 6.5% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent (S-1). The liquid crystal aligning agent (S-1) is mainly used for manufacturing a vertical alignment type liquid crystal display device.
<印刷版の膨潤特性の評価>
上記液晶配向剤(S−1)を用いて、APR版の膨潤しやすさ(膨潤特性)について評価を行った。APR版は、紫外線照射部分が硬化する液状感光性樹脂によって形成された樹脂版であり、液晶配向膜印刷機の印刷版に一般に使用されている。液晶配向剤とAPR版とを接触させた場合にAPR版が膨潤しにくいということは、印刷時に液晶配向剤がAPR版に浸み込みにくく、印刷性が良好であることを意味する。膨潤特性の評価は、液晶配向剤中にAPR版を1日間浸漬し、浸漬前後でのAPR版の重量変化を測定することにより行った。このとき、APR版の重量の増加率(膨潤率)が4%未満の場合に、APR版が膨潤しにくく良好(○)、増加率が4%以上の場合に、APR版が膨潤しやすく不良(×)と評価した。その結果、この実施例では、膨潤率が3.5%であり、膨潤特性「良好(○)」であった。膨潤率は下記数式(2)を用いて算出した。
膨潤率[%]=(W2−W1/W1)×100 …(2)
(数式(2)中、W1は浸漬前のAPR版の重量であり、W2は浸漬後のAPR版の重量である。)
<Evaluation of swelling characteristics of printing plate>
Using the liquid crystal aligning agent (S-1), the swellability (swelling characteristics) of the APR plate was evaluated. The APR plate is a resin plate formed of a liquid photosensitive resin in which an ultraviolet irradiation part is cured, and is generally used for a printing plate of a liquid crystal alignment film printing machine. The fact that the APR plate is less likely to swell when the liquid crystal aligning agent is brought into contact with the APR plate means that the liquid crystal aligning agent is less likely to penetrate into the APR plate during printing and has good printability. The swelling property was evaluated by immersing the APR plate in a liquid crystal aligning agent for one day and measuring the change in weight of the APR plate before and after immersion. At this time, when the increase rate (swelling rate) of the weight of the APR plate is less than 4%, the APR plate hardly swells and is good (○), and when the increase rate is 4% or more, the APR plate easily swells and is poor. (X) was evaluated. As a result, in this example, the swelling ratio was 3.5%, and the swelling characteristics were “good (○)”. The swelling ratio was calculated using the following equation (2).
Swelling ratio [%] = (W 2 −W 1 / W 1 ) × 100 (2)
(In Equation (2), W 1 is the weight of the APR plate before immersion, W 2 is the weight of APR plate after immersion.)
<印刷性の評価>
上記で調製した液晶配向剤(S−1)につき、基板への印刷を連続して行った場合の印刷性(連続印刷性)について評価した。評価は以下のようにして行った。まず、液晶配向膜印刷機(日本写真印刷機(株)製、オングストローマー形式「S40L−532」)を用いて、アニロックスロールへの液晶配向剤(S−1)の滴下量を往復20滴(約0.2g)の条件にて、ITO膜からなる透明電極付きガラス基板の透明電極面に印刷した。基板への印刷は、1分間隔で新しい基板を用いながら20回実施した。
続いて、液晶配向剤(S−1)を1分間隔でアニロックスロール上にディスペンス(片道)し、その都度、アニロックスロールと印刷版とを接触させる作業(以下、空運転という)を合計10回行った(この間、ガラス基板への印刷は行わない)。なお、この空運転は、液晶配向剤の印刷を意図的に過酷な状況下で実施するようにするために行った操作である。
10回の空運転の後、続いてガラス基板を用いて本印刷を行った。本印刷では、空運転後、基板を30秒間隔で5枚投入し、印刷後のそれぞれの基板を80℃で1分間加熱(プレベーク)して溶媒を除去した後、200℃で10分間加熱(ポストベーク)して、膜厚約80nmの塗膜を形成した。この塗膜を倍率20倍の顕微鏡で観察することにより印刷性(連続印刷性)を評価した。評価は、空運転後の本印刷1回目から重合体の析出が観察されない場合を連続印刷性「良好(○)」、空運転後の本印刷1回目では重合体の析出が観察されるが、本印刷を5回実施する間に重合体の析出が観察されなくなる場合を連続印刷性「可(△)」、本印刷を5回繰り返した後においても重合体の析出が観察される場合を連続印刷性「不良(×)」とした。その結果、この実施例では連続印刷性「良好(○)」であった。なお、印刷性が良好な液晶配向剤では、連続で基板を投入している間に重合体の析出が良化(消失)することが実験により分かっている。また更に、空運転の回数を15回、20回、25回に変更し、それぞれについて上記と同様にして液晶配向剤の印刷性を評価したところ、この実施例では、空運転を15回及び20回としたときには「良好(○)」、25回のときには「可(△)」であった。
<Evaluation of printability>
With respect to the liquid crystal aligning agent (S-1) prepared above, printability (continuous printability) when printing on a substrate was continuously performed was evaluated. The evaluation was performed as follows. First, using a liquid crystal alignment film printing machine (manufactured by Nissha Printing Co., Ltd., Angstromer type “S40L-532”), the amount of the liquid crystal alignment agent (S-1) dropped on the anilox roll was reciprocated by 20 drops. (About 0.2 g), printing was performed on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film. Printing on the substrate was performed 20 times at 1 minute intervals using a new substrate.
Subsequently, the liquid crystal aligning agent (S-1) is dispensed (one way) on the anilox roll at one-minute intervals, and each time the work of bringing the anilox roll into contact with the printing plate (hereinafter, referred to as idle operation) is performed 10 times in total. (Printing on the glass substrate was not performed during this time). The idle operation is an operation performed for intentionally performing printing of the liquid crystal alignment agent under severe conditions.
After ten idle operations, main printing was subsequently performed using a glass substrate. In this printing, after idling, five substrates are inserted at intervals of 30 seconds, each substrate after printing is heated (prebaked) at 80 ° C. for 1 minute to remove the solvent, and then heated at 200 ° C. for 10 minutes ( Post baking) to form a coating film having a thickness of about 80 nm. The printability (continuous printability) was evaluated by observing the coating film with a microscope having a magnification of 20 times. In the evaluation, continuous printability was “good (()” when no polymer precipitation was observed from the first printing after the idling, and polymer deposition was observed at the first printing after the idling. Continuous printability "Possible (△)" when no polymer precipitation is observed during the fifth printing, and continuous polymer printing even after 5 times of the final printing. The printability was evaluated as "poor (x)". As a result, in this example, the continuous printability was “good (○)”. Experiments have shown that a liquid crystal aligning agent having good printability improves (disappears) the precipitation of the polymer while the substrate is continuously charged. Further, the number of idle operations was changed to 15, 20, and 25 times, and the printability of the liquid crystal alignment agent was evaluated in the same manner as described above. In this example, the idle operation was performed 15 times and 20 times. When the number of times was 25, it was "good (O)", and when it was 25 times, it was "OK (△)".
[実施例2〜31及び比較例1〜5]
使用する重合体、並びに溶剤の種類及び組成を、それぞれ下記表2に記載のとおり変更した以外は、上記実施例1と同様の方法により液晶配向剤(S−2)〜(S−31)及び(SR−1)〜(SR−5)をそれぞれ調製した。また、それぞれの液晶配向剤について、上記実施例1と同様にして印刷版の膨潤特性及び印刷性を評価した。それらの結果を下記表2に示した。
[Examples 2 to 31 and Comparative Examples 1 to 5]
Liquid crystal aligning agents (S-2) to (S-31) and liquid crystal aligning agents (S-2) to (S-31) were prepared in the same manner as in Example 1 above, except that the type and composition of the polymer used and the solvent were changed as described in Table 2 below. (SR-1) to (SR-5) were prepared respectively. The swelling characteristics and printability of the printing plate were evaluated for each liquid crystal alignment agent in the same manner as in Example 1 above. The results are shown in Table 2 below.
表2中、重合体成分として2種の重合体を使用したもの(実施例18〜31)については、使用した重合体の全体量100重量部に対する各重合体の使用割合(重量比)を併せて示した。各液晶配向剤のうち、(S−2)〜(S−17)、(SR−1)〜(SR−5)は主に垂直配向型、(S−18)〜(S−23)は主にTN型、(S−24)は主にIPS型の液晶表示素子の製造用であり、(S−29)〜(S−31)は主に光配向法による垂直配向型液晶表示素子の製造用、(S−25)〜(S−28)は主にPSA方式の液晶表示素子の製造用である。表2中、溶剤組成の数値は、液晶配向剤の調製に使用した溶剤の合計量に対する各化合物の配合割合(重量比)を示す(以下の表3〜表5についても同じ)。溶剤組成の記号はそれぞれ以下の意味である。
a:リン酸トリメチル
b:リン酸トリエチル
c:ヘキサメチルリン酸トリアミド
d:N−メチル−2−ピロリドン
e:N−エチル−2−ピロリドン
f:γ−ブチロラクトン
g:γ−バレロラクトン
h:δ−バレロラクトン
i:N,N−ジエチルアセトアミド
j:ブチルセロソルブ
k:ジエチレングリコールジエチルエーテル
l:プロピレングリコールモノメチルエーテルアセテート
In Table 2, with respect to those using two kinds of polymers as the polymer components (Examples 18 to 31), the usage ratio (weight ratio) of each polymer to 100 parts by weight of the total amount of the used polymers is also shown. Shown. Among the liquid crystal alignment agents, (S-2) to (S-17) and (SR-1) to (SR-5) are mainly vertical alignment type, and (S-18) to (S-23) are mainly (S-24) is mainly used for manufacturing an IPS type liquid crystal display device, and (S-29) to (S-31) are mainly used for manufacturing a vertical alignment type liquid crystal display device by a photo-alignment method. (S-25) to (S-28) are mainly for manufacturing a PSA-type liquid crystal display element. In Table 2, the numerical value of the solvent composition indicates the compounding ratio (weight ratio) of each compound to the total amount of the solvent used for preparing the liquid crystal aligning agent (the same applies to Tables 3 to 5 below). The symbols of the solvent compositions have the following meanings.
a: trimethyl phosphate b: triethyl phosphate c: hexamethylphosphate triamide d: N-methyl-2-pyrrolidone e: N-ethyl-2-pyrrolidone f: γ-butyrolactone g: γ-valerolactone h: δ- Valerolactone i: N, N-diethylacetamide j: butyl cellosolve k: diethylene glycol diethyl ether 1: propylene glycol monomethyl ether acetate
[実施例32〜52]
使用する重合体、並びに溶剤の種類及び組成を、それぞれ下記表3に記載のとおり変更した以外は、上記実施例1と同様の方法により液晶配向剤(S−32)〜(S−52)をそれぞれ調製した。また、それぞれの液晶配向剤について、上記実施例1と同様にして印刷版の膨潤特性及び印刷性の評価を行った。それらの結果を下記表3に示す。
[Examples 32-52]
The liquid crystal aligning agents (S-32) to (S-52) were prepared in the same manner as in Example 1 except that the polymer used, and the type and composition of the solvent were changed as described in Table 3 below. Each was prepared. The swelling characteristics and printability of the printing plate were evaluated for each liquid crystal alignment agent in the same manner as in Example 1 above. The results are shown in Table 3 below.
表3中、重合体成分として2種の重合体を使用したもの(実施例40〜43、50〜52)については、使用した重合体の全体量100重量部に対する各重合体の使用割合(重量比)を併せて示した。また、各液晶配向剤のうち、(S−32)〜(S−39)、(S−44)〜(S−49)は主に垂直配向型、(S−40)〜(S−43)、(S−50)〜(S−52)は主にTN型の液晶表示素子の製造用である。表3中、溶剤組成の記号はそれぞれ以下の意味である。d及びjは上記表2と同じである。
m:N,N−ジメチルプロピレン尿素
n:4−ホルミルモルホリン
o:3−メチル−2−オキサゾリドン
p:テトラヒドロ−4H−ピラン−4−オン
r:テトラメチレンスルホキシド
s:3−メチルシクロヘキサノン
t:4−メチルシクロヘキサノン
In Table 3, for those using two kinds of polymers as the polymer components (Examples 40 to 43 and 50 to 52), the usage ratio (weight) of each polymer to 100 parts by weight of the total amount of the used polymers was used. Ratio) are also shown. Among the liquid crystal aligning agents, (S-32) to (S-39) and (S-44) to (S-49) are mainly of vertical alignment type, and (S-40) to (S-43). , (S-50) to (S-52) are mainly for manufacturing a TN type liquid crystal display element. In Table 3, the symbols of the solvent compositions have the following meanings. d and j are the same as in Table 2 above.
m: N, N-dimethylpropylene urea n: 4-formylmorpholine o: 3-methyl-2-oxazolidone p: tetrahydro-4H-pyran-4-one r: tetramethylene sulfoxide s: 3-methylcyclohexanone t: 4- Methylcyclohexanone
[実施例53〜56]
使用する重合体成分、並びに溶剤の種類及び組成を、それぞれ下記表4に記載のとおり変更した以外は、上記実施例1と同様の方法により液晶配向剤(S−53)〜(S−56)をそれぞれ調製した。また、それぞれの液晶配向剤について、上記実施例1と同様にして印刷版の膨潤特性及び印刷性の評価を行った。それらの結果を下記表4に示す。
[Examples 53 to 56]
The liquid crystal aligning agents (S-53) to (S-56) were prepared in the same manner as in Example 1 except that the polymer component used and the type and composition of the solvent were changed as shown in Table 4 below. Was prepared respectively. The swelling characteristics and printability of the printing plate were evaluated for each liquid crystal alignment agent in the same manner as in Example 1 above. The results are shown in Table 4 below.
表4中、重合体成分として2種の重合体を使用したもの(実施例55,56)については、使用した重合体の全体量100重量部に対する各重合体の使用割合(重量比)を併せて示した。また、各液晶配向剤のうち、(S−53)、(S−54)は主に垂直配向型、(S−55)、(S−56)は主にTN型の液晶表示素子の製造用である。表4中、溶剤組成の記号はそれぞれ以下の意味である。d及びjは上記表2と同じである。
q:5−メチル−2−フルアルデヒド
u:N,N−ジメチルラクトアミド(下記式(10−1)で表される化合物)
q: 5-methyl-2-furaldehyde u: N, N-dimethyllactoamide (compound represented by the following formula (10-1))
[実施例57〜60]
使用する重合体、並びに溶剤の種類及び組成を、それぞれ下記表5に記載のとおり変更した以外は、上記実施例1と同様の方法により液晶配向剤(S−57)〜(S−60)をそれぞれ調製した。また、それぞれの液晶配向剤について、上記実施例1と同様にして印刷版の膨潤特性及び印刷性の評価を行った。それらの結果を下記表5に示す。なお、表5中、重合体成分の欄の数値は、使用した重合体の全体量100重量部に対する各重合体の使用割合(重量比)を示す。溶剤組成の記号(d,m,j)は上記表2及び表3と同じである。
The liquid crystal aligning agents (S-57) to (S-60) were prepared in the same manner as in Example 1 except that the type of the polymer used and the type and composition of the solvent were changed as shown in Table 5 below. Each was prepared. The swelling characteristics and printability of the printing plate were evaluated for each liquid crystal alignment agent in the same manner as in Example 1 above. The results are shown in Table 5 below. In Table 5, the numerical value in the column of the polymer component indicates the use ratio (weight ratio) of each polymer to 100 parts by weight of the total amount of the used polymers. The symbols (d, m, j) of the solvent composition are the same as in Tables 2 and 3 above.
上記の結果から、上記特定溶剤を含む液晶配向剤(実施例1〜60)はいずれも印刷版を膨潤させにくく、連続印刷性も良好であることが分かった。これに対し、上記特定溶剤を含まない比較例のものは、膨潤特性及び連続印刷性のいずれかが実施例よりも劣る結果であった。 From the above results, it was found that all of the liquid crystal aligning agents containing the specific solvent (Examples 1 to 60) hardly swell the printing plate and have good continuous printability. On the other hand, in the case of the comparative example containing no specific solvent, either the swelling property or the continuous printability was inferior to those of the example.
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