KR101647537B1 - Silicon liquid crystal orientation agent, liquid crystal oriented film, and liquid crystal display element - Google Patents
Silicon liquid crystal orientation agent, liquid crystal oriented film, and liquid crystal display element Download PDFInfo
- Publication number
- KR101647537B1 KR101647537B1 KR1020117028568A KR20117028568A KR101647537B1 KR 101647537 B1 KR101647537 B1 KR 101647537B1 KR 1020117028568 A KR1020117028568 A KR 1020117028568A KR 20117028568 A KR20117028568 A KR 20117028568A KR 101647537 B1 KR101647537 B1 KR 101647537B1
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- KR
- South Korea
- Prior art keywords
- liquid crystal
- group
- alkoxysilane
- formula
- carbon atoms
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 177
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 4
- 229910052710 silicon Inorganic materials 0.000 title description 3
- 239000010703 silicon Substances 0.000 title description 3
- -1 polysiloxane Polymers 0.000 claims abstract description 60
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 125000005641 methacryl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 35
- 210000002858 crystal cell Anatomy 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 claims description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 239000000243 solution Substances 0.000 description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 25
- 230000004044 response Effects 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 235000006408 oxalic acid Nutrition 0.000 description 10
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 8
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MLNCEQPFSFGNIW-UHFFFAOYSA-N heptadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCCC[Si](OC)(OC)OC MLNCEQPFSFGNIW-UHFFFAOYSA-N 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- LIJFLHYUSJKHKV-UHFFFAOYSA-N trimethoxy(undecyl)silane Chemical compound CCCCCCCCCCC[Si](OC)(OC)OC LIJFLHYUSJKHKV-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- GPAAEXYTRXIWHR-UHFFFAOYSA-N (1-methylpiperidin-1-ium-1-yl)methanesulfonate Chemical compound [O-]S(=O)(=O)C[N+]1(C)CCCCC1 GPAAEXYTRXIWHR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- LJWBIAMZBJWAOW-UHFFFAOYSA-N benzhydryloxysilane Chemical compound C=1C=CC=CC=1C(O[SiH3])C1=CC=CC=C1 LJWBIAMZBJWAOW-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 2
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- 230000001771 impaired effect Effects 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- PPUHSHGIVZSPFO-UHFFFAOYSA-N trimethoxy(nonadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC PPUHSHGIVZSPFO-UHFFFAOYSA-N 0.000 description 2
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- 0 *1c2ccc(cccc3)c3c2-c2c1ccc1c2CCC=C1 Chemical compound *1c2ccc(cccc3)c3c2-c2c1ccc1c2CCC=C1 0.000 description 1
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- GLISOBUNKGBQCL-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(C)CCCN GLISOBUNKGBQCL-UHFFFAOYSA-N 0.000 description 1
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
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- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 description 1
- VBSUMMHIJNZMRM-UHFFFAOYSA-N triethoxy(2-phenylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=CC=C1 VBSUMMHIJNZMRM-UHFFFAOYSA-N 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZJEYUFMTCHLQQI-UHFFFAOYSA-N triethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OCC)(OCC)OCC)=CC=CC2=C1 ZJEYUFMTCHLQQI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- BBWMWJONYVGXGQ-UHFFFAOYSA-N triethoxy(undecyl)silane Chemical compound CCCCCCCCCCC[Si](OCC)(OCC)OCC BBWMWJONYVGXGQ-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZSOVVFMGSCDMIF-UHFFFAOYSA-N trimethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)=CC=CC2=C1 ZSOVVFMGSCDMIF-UHFFFAOYSA-N 0.000 description 1
- RKFOUDRIIBYXLR-UHFFFAOYSA-N trimethoxy-(1,1,2,3,3-pentafluoro-3-phenylpropyl)silane Chemical compound FC(C([Si](OC)(OC)OC)(F)F)C(C1=CC=CC=C1)(F)F RKFOUDRIIBYXLR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Liquid Crystal (AREA)
Abstract
액정 중의 중합성 화합물이 첨가되는 경우도, 무첨가인 경우도, 응답 속도를 향상시켜 양호한 배향 상태가 얻어지는 액정 표시 소자용 액정 배향막을 얻기 위한 액정 배향제를 제공한다.
식 (1) 및 식 (2) 로 나타내는 알콕시실란을 함유하는 알콕시실란을 중축합하여 얻어지는 폴리실록산을 함유하는 액정 배향제
R1Si(OR2)3 (1)
(R1 은 불소 원자로 치환되어 있어도 되는, 탄소 원자수 8 ∼ 30 의 탄화수소기이고, R2 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다)
R3Si(OR4)3 (2)
(R3 은 아크릴기 또는 메타크릴기로 치환된 알킬기, R4 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다) Provided is a liquid crystal aligning agent for obtaining a liquid crystal alignment film for a liquid crystal display element in which a polymerizable compound in a liquid crystal is added or a liquid crystal alignment film in which a good alignment state can be obtained even when no addition is made.
A liquid crystal aligning agent containing a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1) and the formula (2)
R 1 Si (OR 2 ) 3 (1)
(Wherein R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and R 2 is an alkyl group having 1 to 5 carbon atoms)
R 3 Si (OR 4 ) 3 (2)
(R 3 is an alkyl group substituted with an acrylic group or a methacryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms)
Description
본 발명은 알콕시실란을 중축합하여 얻어지는 폴리실록산을 함유하는 액정 배향제, 및 상기 액정 배향제로부터 얻어지는 액정 배향막, 그리고 그 액정 배향막을 갖는 액정 표시 소자에 관한 것이다. The present invention relates to a liquid crystal aligning agent containing a polysiloxane obtained by polycondensation of an alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film.
최근, 액정 표시 소자의 표시 방식 중에서도, 수직 (VA) 방식의 액정 표시 소자는, 대화면의 액정 텔레비전이나 고정세한 모바일 용도 (디지털 카메라나 휴대 전화의 표시부) 등, 널리 이용되고 있다. VA 방식에는, 액정이 넘어질 방향을 제어하기 위한 돌기를 TFT 기판이나 컬러 필터 기판에 형성하는 MVA 방식 (Multi Vertical Alignment) 이나, 기판의 ITO 전극에 슬릿을 형성하여 전계에 의해 액정이 넘어질 방향을 제어하는 PVA (Paterned Vertical Alignment) 방식이 알려져 있다. Recently, among the display methods of liquid crystal display devices, vertical (VA) type liquid crystal display devices have been widely used, such as large-screen liquid crystal televisions and fixed-size mobile applications (display portions of digital cameras and cellular phones). The VA system includes a MVA system (Multi Vertical Alignment) in which a projection for controlling the direction in which the liquid crystal falls is formed on a TFT substrate or a color filter substrate, a slit is formed in the ITO electrode of the substrate, A PVA (Pater- ned Vertical Alignment) method is known.
다른 VA 배향 방식으로서 PSA (Polymer susutained Alignment) 방식이 있다. VA 방식 중에서도, PSA 방식은 최근 주목받고 있는 기술이다. 이 방식은 액정 중에 광 중합성 화합물을 첨가하고, 액정 패널 제작 후에 전계를 인가하여 액정이 넘어진 상태에서 UV 를 액정 패널에 조사한다. 이로써, 중합성 화합물이 광 중합함으로써 액정의 배향 방향이 고정화되어, 프레틸트가 생겨 응답 속도가 향상된다. VA 방식에는, 액정 패널을 구성하는 편측의 전극에 슬릿을 제작하고, 대향측의 전극 패턴에는 MVA 와 같은 돌기나 PVA 와 같은 슬릿을 형성하지 않은 구조에서도 동작 가능하고, 제조의 간략화나 우수한 패널 투과율이 얻어지는 것을 특징으로 하고 있다 (특허문헌 1 참조).Another VA orientation method is the PSA (Polymer Suscepted Alignment) method. Among the VA methods, the PSA method is a technology that has recently attracted attention. In this method, a photopolymerizable compound is added to the liquid crystal, and after the liquid crystal panel is manufactured, an electric field is applied to irradiate the liquid crystal panel with UV in a state where the liquid crystal falls. As a result, the alignment direction of the liquid crystal is fixed by photopolymerization of the polymerizable compound, and the response speed is improved by forming the pretilt. In the VA system, it is possible to manufacture a slit on one side of the liquid crystal panel and operate on a structure in which a slit such as MVA or a slit such as PVA is not formed on the electrode pattern on the opposite side. (See Patent Document 1).
한편, 종래부터 이용되고 있는 폴리이미드 등의 유기계 액정 배향막 재료와 함께, 무기계 액정 배향막 재료도 알려져 있다. 예를 들어, 도포형 무기계 배향막의 재료로서 테트라알콕시실란과 트리알콕시실란과 알코올 및 옥살산의 반응 생성물을 함유하는 액정 배향제 조성물을 사용하고, 액정 표시 소자의 전극 기판 상에서 수직 배향성, 내열성 및 균일성이 우수한 액정 배향막을 형성하는 것이 보고되어 있다 (특허문헌 2 참조).On the other hand, an inorganic liquid crystal alignment film material is known along with an organic liquid crystal alignment film material such as polyimide which has been conventionally used. For example, a liquid crystal aligning composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, and alcohol and oxalic acid as a material of the coating type inorganic alignment film is used, and a liquid crystal display device having a liquid crystal display device having a vertical alignment property, heat resistance and uniformity It has been reported that this excellent liquid crystal alignment film is formed (see Patent Document 2).
또, 테트라알콕시실란, 특정 트리알콕시실란 및 물과의 반응 생성물과 특정 글리콜에테르계 용매를 함유하는 액정 배향제 조성물을 사용함으로써, 표시 불량을 방지하고, 장시간 구동 후에도 잔상 특성이 양호한, 액정을 배향시키는 능력을 저하시키지 않고, 또한 광 및 열에 대한 전압 유지율의 저하가 적은 액정 배향막을 형성하는 것이 보고되어 있다 (특허문헌 3 참조).In addition, by using a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, a specific trialkoxysilane and water and a specific glycol ether solvent, it is possible to prevent display defects and improve the afterimage characteristic even after long- It is reported that a liquid crystal alignment film with less deterioration of voltage holding ratio with respect to light and heat is formed (see Patent Document 3).
종래, PSA 방식의 액정 표시 소자에 있어서는, 액정에 첨가하는 중합성 화합물의 용해성이 낮고, 첨가량을 늘리면 저온시에 석출된다는 문제가 있다. 한편, 중합성 화합물의 첨가량을 줄이면 양호한 배향 상태를 얻을 수 없게 된다. 또, 액정 중에 잔류하는 미반응의 중합성 화합물은 액정 중의 불순물 (오염) 이 되기 때문에 액정 표시 소자의 신뢰성을 저하시킨다는 문제가 있다. Conventionally, in a liquid crystal display element of the PSA type, the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that precipitation occurs at a low temperature when the addition amount is increased. On the other hand, if the amount of the polymerizable compound to be added is reduced, a good alignment state can not be obtained. In addition, since the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered.
본 발명의 과제는 PSA 방식의 액정 표시 소자에 있어서, 중합성 화합물의 양이 적은 경우에 있어서도, 또한 중합성 화합물을 첨가하지 않는 액정을 사용한 경우에 있어서도, 응답 속도를 향상시켜 양호한 배향 상태를 얻는 것이 가능한, 액정 표시 소자용의 액정 배향제, 그 액정 배향제로부터 얻어지는 액정 배향막, 및 그 액정 배향막을 갖는 액정 표시 소자를 제공하는 것이다. It is an object of the present invention to provide a liquid crystal display element of a PSA type in which even when a small amount of a polymerizable compound is used and a liquid crystal not containing a polymerizable compound is used, A liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
본 발명은 이하를 요지로 한다. The present invention provides the following.
〔1〕식 (1) 로 나타내는 알콕시실란 및 식 (2) 로 나타내는 알콕시실란을 함유하는 알콕시실란을 중축합하여 얻어지는 폴리실록산을 함유하는 액정 배향제. [1] A liquid crystal aligning agent containing a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing an alkoxysilane represented by the formula (2).
R1Si(OR2)3 (1) R 1 Si (OR 2 ) 3 (1)
(R1 은 불소 원자로 치환되어 있어도 되는, 탄소 원자수 8 ∼ 30 의 탄화수소기이고, R2 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다) (Wherein R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and R 2 is an alkyl group having 1 to 5 carbon atoms)
R3Si(OR4)3 (2) R 3 Si (OR 4 ) 3 (2)
(R3 은 아크릴기 또는 메타크릴기로 치환된 알킬기, R4 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다) (R 3 is an alkyl group substituted with an acrylic group or a methacryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms)
〔2〕폴리실록산이 추가로, 하기 식 (3) 으로 나타내는 알콕시실란을 함유하는 알콕시실란을 중축합하여 얻어지는 폴리실록산인 상기〔1〕에 기재된 액정 배향제. [2] The liquid crystal aligning agent according to the above [1], wherein the polysiloxane is further a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (3).
(R5)nSi(OR6)4-n (3)(R 5 ) n Si (OR 6 ) 4-n (3)
(R5 는 수소 원자, 또는 헤테로 원자, 할로겐 원자, 아미노기, 글리시독시기, 메르캅토기, 이소시아네이트기 혹은 우레이도기로 치환되어 있어도 되는, 탄소 원자수 1 ∼ 16 의 탄화수소기이고, R6 은 탄소 원자수 1 ∼ 5 의 알킬기이며, n 은 0 ∼ 3 의 정수를 나타낸다) (R 5 is a hydrogen atom or a hetero atom, a halogen atom, an amino group, a glycidyl sidok group, a mercapto group, carbon atoms, optionally substituted with an isocyanate group or a ureido group 1-16 hydrocarbon group, R 6 is a carbon An alkyl group of 1 to 5 atoms, and n represents an integer of 0 to 3)
〔3〕상기 식 (1) 로 나타내는 알콕시실란이, 식 (1) 에 있어서의 R1 이 탄소 원자수가 8 ∼ 22 의 탄화수소기이고, R2 가 메틸 또는 에틸인 상기〔1〕또는〔2〕에 기재된 액정 배향제.[3] This alkoxysilane represented by the formula (1), formula (1) R 1 is a group of carbon atoms of 8 to 22 hydrocarbon group, R 2 is methyl or ethyl in the [1] or [2] in the Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.
〔4〕상기 식 (2) 로 나타내는 알콕시실란이, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란으로 이루어지는 군에서 선택되는 적어도 1 종인 상기〔1〕∼〔3〕중 어느 하나에 기재된 액정 배향제. [4] The positive photosensitive composition as described in [4], wherein the alkoxysilane represented by the formula (2) is at least one selected from the group consisting of 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, The liquid crystal aligning agent according to any one of [1] to [3], wherein the liquid crystal aligning agent is at least one selected from the group consisting of propyltriethoxysilane.
〔5〕상기 식 (3) 으로 나타내는 알콕시실란의 R5 가, 탄소 원자수 1 ∼ 6 의 탄화수소기인 상기〔2〕∼〔4〕중 어느 하나에 기재된 액정 배향제. [5] The liquid crystal aligning agent according to any one of [2] to [4], wherein R 5 of the alkoxysilane represented by the formula (3) is a hydrocarbon group having 1 to 6 carbon atoms.
〔6〕상기 식 (3) 으로 나타내는 알콕시실란이, 식 (3) 에 있어서의 n 이 0 인 테트라알콕시실란인 상기〔2〕∼〔5〕중 어느 하나에 기재된 액정 배향제. [6] The liquid crystal aligning agent according to any one of [2] to [5], wherein the alkoxysilane represented by the formula (3) is tetraalkoxysilane wherein n in the formula (3) is 0.
〔7〕상기 식 (1) 로 나타내는 알콕시실란이, 전체 알콕시실란 중 0.1 ∼ 30 몰％ 함유되고, 또한 상기 식 (2) 로 나타내는 알콕시실란이 전체 알콕시실란 중 3 ∼ 60 몰％ 함유되는 상기〔1〕∼〔4〕중 어느 하나에 기재된 액정 배향제.[7] The alkoxysilane represented by the above formula (1), wherein the alkoxysilane is contained in the total alkoxysilane in an amount of 0.1 to 30 mol% and the alkoxysilane represented by the formula (2) is contained in the total alkoxysilane in an amount of 3 to 60 mol% 1] to [4].
〔8〕상기 식 (3) 으로 나타내는 알콕시실란이, 전체 알콕시실란 중 10 ∼ 96.9 몰％ 함유되는 상기〔2〕∼〔7〕중 어느 하나에 기재된 액정 배향제. [8] The liquid crystal aligning agent according to any one of [2] to [7], wherein the alkoxysilane represented by the formula (3) is contained in an amount of 10 to 96.9 mol% in the total alkoxysilane.
〔9〕폴리실록산의 함유량이, SiO2 환산 농도로 0.5 ∼ 15 질량％ 함유되는 상기〔1〕∼〔8〕중 어느 하나에 기재된 액정 배향제. [9] The liquid crystal aligning agent according to any one of [1] to [8], wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO 2 .
〔10〕상기〔1〕∼〔9〕중 어느 하나에 기재된 액정 배향제를 기판에 도포하고 소성하여 얻어지는 액정 배향막. [10] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [9] to a substrate and baking.
〔11〕상기〔10〕에 기재된 액정 배향막을 갖는 액정 표시 소자. [11] A liquid crystal display element having the liquid crystal alignment film according to [10] above.
〔12〕상기〔1〕∼〔9〕중 어느 하나에 기재된 액정 배향제를 도포하고, 소성된 2 장의 기판에 의해 액정이 협지 (挾持) 된 액정셀에, 전압을 인가한 상태에서 UV 를 조사한 액정 표시 소자. [12] A liquid crystal aligning agent as described in any one of [1] to [9] above, wherein the liquid crystal cell sandwiched between two fired substrates is irradiated with UV light Liquid crystal display element.
〔13〕상기〔1〕∼〔9〕중 어느 하나에 기재된 액정 배향제를 도포하고, 소성한 2 장의 기판에 의해 액정을 협지하고, 전압을 인가한 상태에서 UV 를 조사하는 액정 표시 소자의 제조 방법.[13] A process for producing a liquid crystal display element in which the liquid crystal aligning agent according to any one of [1] to [9] above is applied, the liquid crystal is sandwiched between two fired substrates, Way.
본 발명의 액정 배향제에 따르면, PSA 방식의 액정 표시 소자에 있어서, 액정에 첨가되는 중합성 화합물의 양이 적은 경우에 있어서도, 또, 중합성 화합물을 첨가하지 않은 액정을 사용한 경우에 있어서도, 응답 속도를 향상시켜 양호한 배향 상태를 얻을 수 있는 액정 표시 소자용의 액정 배향막, 및 그 액정 배향막을 갖는 액정 표시 소자 가 얻어진다. According to the liquid crystal aligning agent of the present invention, even in the case where the amount of the polymerizable compound to be added to the liquid crystal is small in the PSA type liquid crystal display element, or even when a liquid crystal to which no polymerizable compound is added is used, A liquid crystal alignment film for a liquid crystal display element capable of improving the speed and obtaining a good alignment state, and a liquid crystal display element having the liquid crystal alignment film can be obtained.
이하에, 본 발명에 대해 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 식 (1) 로 나타내는 알콕시실란 및 식 (2) 로 나타내는 알콕시실란을 함유하는 알콕시실란을 중축합하여 얻어지는 폴리실록산을 함유하는 액정 배향제이다. The present invention is a liquid crystal aligning agent containing a polysiloxane obtained by polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane containing alkoxysilane represented by formula (2).
R1Si(OR2)3 (1) R 1 Si (OR 2 ) 3 (1)
(R1 은 불소 원자로 치환되어 있어도 되는 탄소 원자수 8 ∼ 30 의 탄화수소기이고, R2 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다). 또한, 본 명세서에 있어서 「치환되어 있어도 되는」이란, 「치환된 또는 치환되어 있지 않은」을 의미한다. (R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and R 2 is an alkyl group having 1 to 5 carbon atoms). In the present specification, the term " optionally substituted " means " substituted or unsubstituted ".
R3Si(OR4)3 (2) R 3 Si (OR 4 ) 3 (2)
(R3 은 아크릴기 또는 메타크릴기로 치환된 알킬기, R4 는 탄소수 1 ∼ 5 의 알킬기를 나타낸다) (R 3 is an alkyl group substituted with an acrylic group or a methacryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms)
［폴리실록산］[Polysiloxane]
식 (1) 로 나타내는 알콕시실란의 R1 (이하, 특정 유기기라고도 한다) 은, 불소로 치환되어 있어도 되는 탄소 원자수가 8 ∼ 30, 바람직하게는 8 ∼ 22, 특히 바람직하게는 10 ∼ 22 인 탄화수소기로서, 액정을 수직으로 배향시키는 효과를 갖는 것이면 특별히 한정되지 않는다. 그들의 예로는, 알킬기, 플루오로알킬기, 알케닐기, 페네틸기, 스티릴알킬기, 나프틸기, 플루오로페닐알킬기 등을 들 수 있다. 이들 중에서도, R1 이 알킬기, 또는 플루오로알킬기인 알콕시실란은 비교적 저렴하고 시판품으로서 입수가 용이하기 때문에 바람직하다. 특히, R1 이 알킬기인 알콕시실란이 바람직하다. 본 발명에 사용하는 폴리실록산은, 이들 특정 유기기를 복수 종 갖고 있어도 된다. The R 1 of the alkoxysilane represented by the formula (1) (hereinafter also referred to as a specific organic group) has 8 to 30 carbon atoms which may be substituted with fluorine, preferably 8 to 22 carbon atoms, particularly preferably 10 to 22 carbon atoms The hydrocarbon group is not particularly limited as long as it has an effect of vertically orienting the liquid crystal. Examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group. Among them, alkoxysilane in which R 1 is an alkyl group or a fluoroalkyl group is preferable because it is comparatively inexpensive and is commercially available and easy to obtain. Especially, alkoxysilane in which R 1 is an alkyl group is preferable. The polysiloxane used in the present invention may have a plurality of these specific organic groups.
식 (1) 로 나타내는 알콕시실란의 R2 는 탄소 원자수 1 ∼ 5, 바람직하게는 1 ∼ 3 의 알킬기이다. 보다 바람직하게는 R2 가 메틸기 또는 에틸기이다. R 2 of the alkoxysilane represented by the formula (1) is an alkyl group of 1 to 5, preferably 1 to 3, carbon atoms. More preferably, R 2 is a methyl group or an ethyl group.
이와 같은 식 (1) 로 나타내는 알콕시실란의 구체예를 들지만, 이것에 한정되는 것은 아니다. Specific examples of the alkoxysilane represented by the formula (1) are shown below, but the present invention is not limited thereto.
예를 들어, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 데실트리메톡시실란, 데실트리에톡시실란, 도데실트리메톡시실란, 도데실트리에톡시실란, 헥사데실트리메톡시실란, 헥사데실트리에톡시실란, 헵타데실트리메톡시실란, 헵타데실트리에톡시실란, 옥타데실트리메톡시실란, 옥타데실트리에톡시실란, 노나데실트리메톡시실란, 노나데실트리에톡시실란, 운데실트리에톡시실란, 운데실트리메톡시실란, 21-도코세닐트리에톡시실란, 트리데카플루오로옥틸트리메톡시실란, 트리데카플루오로옥틸트리에톡시실란, 헵타데카플루오로데실트리메톡시실란, 헵타데카플루오로데실트리에톡시실란, 이소옥틸트리에톡시실란, 페네틸트리에톡시실란, 펜타플루오로페닐프로필트리메톡시실란, (1-나프틸)트리에톡시실란, (1-나프틸)트리메톡시실란 등을 들 수 있다. 그 중에서도, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 데실트리메톡시실란, 데실트리에톡시실란, 도데실트리메톡시실란, 도데실트리에톡시실란, 헥사데실트리메톡시실란, 헥사데실트리에톡시실란, 헵타데실트리메톡시실란, 헵타데실트리에톡시실란, 옥타데실트리메톡시실란, 옥타데실트리에톡시실란, 노나데실트리메톡시실란, 노나데실트리에톡시실란, 운데실트리에톡시실란 또는 운데실트리메톡시실란이 바람직하다. Examples of the silane coupling agent include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexa Heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, But are not limited to, triethoxysilane, undecyltrimethoxysilane, 21-dococenyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane Heptadecafluorodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, (1-naphthyl) triethoxysilane, (1-naphthyl) Trimethoxysilane and the like. The. Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyl Heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, Ethoxysilane or undecyltrimethoxysilane is preferred.
상기 서술한 특정 유기기를 갖는 식 (1) 로 나타내는 알콕시실란은, 폴리실록산을 얻기 위해서 사용하는 전체 알콕시실란 중에 있어서, 양호한 액정 배향성을 얻기 위해 0.1 몰％ 이상이 바람직하다. 보다 바람직하게는 0.5 몰％ 이상이다. 더욱 바람직하게는 1 몰％ 이상이다. 또, 형성되는 액정 배향막의 충분한 경화 특성을 얻기 위해서는 30 몰％ 이하가 바람직하다. 보다 바람직하게는 22 몰％ 이하이다. The alkoxysilane represented by the formula (1) having the specific organic group described above is preferably 0.1 mol% or more in the total alkoxysilane used for obtaining the polysiloxane in order to obtain good liquid crystal alignability. More preferably, it is 0.5 mol% or more. More preferably, it is at least 1 mol%. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, it is preferably 30 mol% or less. More preferably, it is 22 mol% or less.
한편, 식 (2) 로 나타내는 알콕시실란의 R3 (이하, 제 2 특정 유기기라고도 한다) 은 아크릴기 또는 메타크릴기로 치환된 알킬기다. 치환되어 있는 수소 원자는 1 개 이상이며, 바람직하게는 1 개이다. 알킬기의 탄소 원자수는 1 ∼ 30 이 바람직하고, 보다 바람직하게는 1 ∼ 10 이다. 더욱 바람직하게는 1 ∼ 5 이다. 식 (2) 로 나타내는 알콕시실란의 R4 는, 상기한 식 (1) 에 있어서의 R2 의 정의와 동일하고, 또, R4 의 바람직한 기도 R2 의 경우와 동일하다.On the other hand, R 3 of the alkoxysilane represented by the formula (2) (hereinafter also referred to as the second specific organic group) is an alkyl group substituted with an acrylic group or a methacryl group. The number of hydrogen atoms to be substituted is one or more, preferably one. The number of carbon atoms of the alkyl group is preferably from 1 to 30, more preferably from 1 to 10. More preferably 1 to 5 carbon atoms. R 4 of the alkoxysilane represented by the formula (2), as defined in R 2 in the above formula (1), and further, the same as in the case of R 4 Preferred R 2 of prayer.
식 (2) 로 나타내는 알콕시실란의 구체예를 들지만, 이들에 한정되는 것은 아니다. 예를 들어, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 메타크릴옥시메틸트리메톡시실란, 메타크릴옥시메틸트리에톡시실란, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 아크릴옥시에틸트리메톡시실란, 아크릴옥시에틸트리에톡시실란 등을 들 수 있다.Specific examples of the alkoxysilane represented by the formula (2) include, but are not limited to, the following. For example, there may be mentioned 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyl tri Acryloxypropyltrimethoxysilane, methoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, and acryloxyethyltriethoxysilane.
PSA 방식의 중합성 화합물이 적은 경우에도 PSA 방식의 액정 표시 소자의 응답 속도를 향상시키기 위해서는, 제 2 특정 유기기를 갖는 식 (2) 로 나타내는 알콕시실란은, 폴리실록산을 얻기 위해서 사용하는 전체 알콕시실란 중에 있어서, 3 몰％ 이상이 바람직하다. 보다 바람직하게는 5 몰％ 이상이다. 더욱 바람직하게는 10 몰％ 이상이다. 또, 형성되는 액정 배향막을 충분히 경화시키기 위해서는 60 몰％ 이하가 바람직하다. In order to improve the response speed of the liquid crystal display element of the PSA system even in the case where the polymerizable compound of the PSA system is small, the alkoxysilane represented by the formula (2) having the second specific organic group is preferably added to the total alkoxysilane used for obtaining the polysiloxane , And it is preferably 3 mol% or more. More preferably, it is at least 5 mol%. More preferably, it is 10 mol% or more. Further, in order to sufficiently cure the liquid crystal alignment film to be formed, it is preferably 60 mol% or less.
본 발명에서는, 식 (1) 로 나타내는 알콕시실란이, 사용되는 전체 알콕시실란 중 바람직하게는 0.1 ∼ 30 몰％, 특히 바람직하게는 2 ∼ 20 몰％ 함유되고, 또한 식 (2) 로 나타내는 알콕시실란이 사용되는 전체 알콕시실란 중 3 ∼ 60 몰％, 특히 바람직하게는 5 ∼ 30 몰％ 함유되는 것이 바람직하다. In the present invention, the alkoxysilane represented by the formula (1) is contained in an amount of preferably 0.1 to 30 mol%, particularly preferably 2 to 20 mol%, of the total alkoxysilane to be used, and the alkoxysilane represented by the formula (2) Is preferably contained in an amount of 3 to 60 mol%, particularly preferably 5 to 30 mol%, of the total alkoxysilane used.
본 발명에서는, 식 (1) 및 식 (2) 로 나타내는 알콕시실란 이외에, 하기 식 (3) 으로 나타내는 알콕시실란을 사용할 수 있다. 식 (3) 으로 나타내는 알콕시실란은, 폴리실록산에 여러 가지 특성을 부여시키는 것이 가능하기 때문에, 필요 특성에 따라 1 종 또는 복수 종을 선택하여 사용할 수 있다. In the present invention, in addition to the alkoxysilanes represented by the formulas (1) and (2), an alkoxysilane represented by the following formula (3) can be used. Since the alkoxysilane represented by the formula (3) can impart various properties to the polysiloxane, one or more kinds of alkoxysilanes can be selected depending on the required characteristics.
(R5)nSi(OR6)4-n (3) (R 5 ) n Si (OR 6 ) 4-n (3)
식 중, R5 는 수소 원자, 또는 헤테로 원자, 할로겐 원자, 아미노기, 글리시독시기, 메르캅토기, 이소시아네이트기 혹은 우레이도기로 치환되어 있어도 되는, 탄소 원자수 1 ∼ 6 의 탄화수소기이고, R6 은 탄소 원자수 1 ∼ 5, 바람직하게는 1 ∼ 3 의 알킬기이며, n 은 0 ∼ 3, 바람직하게는 0 ∼ 2 의 정수를 나타낸다.Wherein R 5 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or an ureido group, and R 6 Is an alkyl group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.
식 (3) 으로 나타내는 알콕시실란의 R5 는 수소 원자, 또는 탄소 원자수가 1 ∼ 6 인 유기기 (이하, 제 3 유기기라고도 한다) 이다. 제 3 유기기의 예로는, 지방족 탄화수소；지방족 고리, 방향족 고리 및 헤테로 고리와 같은 고리 구조；불포화 결합；및 산소 원자, 질소 원자, 황 원자 등의 헤테로 원자 등을 함유하고 있어도 되고, 분기 구조를 갖고 있어도 되는, 탄소 원자수가 1 ∼ 16, 보다 바람직하게는 1 ∼ 12, 특히 바람직하게는 1 ∼ 6 인 탄화수소이다. 이 탄화수소는 할로겐 원자, 아미노기, 글리시독시기, 메르캅토기, 이소시아네이트기, 우레이도기 등으로 치환되어 있어도 된다. R 5 of the alkoxysilane represented by formula (3) is a hydrogen atom or an organic group having 1 to 6 carbon atoms (hereinafter, also referred to as a third organic group). Examples of the third organic group include an aliphatic hydrocarbon, a cyclic structure such as an aliphatic ring, an aromatic ring and a heterocyclic ring, an unsaturated bond, and a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom, Hydrocarbon having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The hydrocarbon may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, an ureido group, or the like.
이와 같은 식 (3) 으로 나타내는 알콕시실란의 구체예를 들지만, 이것에 한정되는 것은 아니다. Specific examples of the alkoxysilane represented by the formula (3) are shown below, but the invention is not limited thereto.
식 (3) 의 알콕시실란에 있어서, R5 가 수소 원자인 경우의 알콕시실란의 구체예로는, 트리메톡시실란, 트리에톡시실란, 트리프로폭시실란, 트리부톡시실란 등을 들 수 있다. Specific examples of the alkoxysilane in the case where R 5 is a hydrogen atom in the alkoxysilane of the formula (3) include trimethoxysilane, triethoxysilane, tripropoxysilane and tributoxysilane .
또, 식 (3) 의 알콕시실란에 있어서, R5 가 제 3 유기기인 경우의 알콕시실란의 구체예로는, 메틸트리메톡시실란, 메틸트리에톡시실란, 에틸트리메톡시실란, 에틸트리에톡시실란, 프로필트리메톡시실란, 프로필트리에톡시실란, 메틸트리프로폭시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, N-2(아미노에틸)3-아미노프로필트리에톡시실란, N-2(아미노에틸)3-아미노프로필트리메톡시실란, 3-(2-아미노에틸아미노프로필)트리메톡시실란, 3-(2-아미노에틸아미노프로필)트리에톡시실란, 2-아미노에틸아미노메틸트리메톡시실란, 2-(2-아미노에틸티오에틸)트리에톡시실란, 3-메르캅토프로필트리에톡시실란, 메르캅토메틸트리메톡시실란, 3-이소시아네이트프로필트리에톡시실란, 트리플루오로프로필트리메톡시실란, 클로로프로필트리에톡시실란, 브로모프로필트리에톡시실란, 3-메르캅토프로필트리메톡시실란, 디메틸디에톡시실란, 디메틸디메톡시실란, 디에틸디에톡시실란, 디에틸디메톡시실란, 디페닐디메톡시실란, 디페닐디에톡시실란, 3-아미노프로필메틸디에톡시실란, 3-아미노프로필디메틸에톡시실란, 트리메틸에톡시실란, 트리메틸메톡시실란, γ-우레이도프로필트리에톡시실란, γ-우레이도프로필트리메톡시실란 및 γ-우레이도프로필트리프로폭시실란 등을 들 수 있다.Specific examples of the alkoxysilane in the case where R 5 is a tertiary organic group in the alkoxysilane of the formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, Triethoxysilane, triethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) , 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, 3-isocyanatepropyltri Ethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, But are not limited to, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, trimethylsilane, diphenylmethoxy silane, diphenylmethoxy silane, diphenyl dimethoxy silane, diphenyl dimethoxy silane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane,? - ureidopropyltriethoxysilane,? -Ureidopropyltrimethoxy silane,? -Ureidopropyltrimethoxysilane, Silane and? -Ureidopropyltripropoxysilane, and the like.
본 발명에 사용하는 폴리실록산은 기판과의 밀착성, 액정 분자와의 친화성 개선 등을 목적으로 하여, 본 발명의 효과를 저해하지 않는 한에 있어서, 상기한 식 (3) 으로 나타내는 알콕시실란을 1 종 또는 복수 종 갖고 있어도 된다. The polysiloxane used in the present invention is a polysiloxane used for the purpose of improving adhesiveness to a substrate and improving affinity with liquid crystal molecules, and it is preferable that the alkoxysilane represented by the formula (3) Or may have a plurality of species.
식 (3) 으로 나타내는 알콕시실란에 있어서, n 이 0 인 알콕시실란은, 테트라알콕시실란이다. 테트라알콕시실란은, 식 (1) 및 식 (2) 로 나타내는 알콕시실란과 용이하게 축합되기 때문에, 본 발명의 폴리실록산을 얻기 위해서 바람직하다.In the alkoxysilane represented by the formula (3), the alkoxysilane wherein n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention since it is easily condensed with the alkoxysilane represented by the formula (1) and the formula (2).
이와 같은 식 (3) 에 있어서 n 이 0 인 알콕시실란으로는, 테트라메톡시실란, 테트라에톡시실란, 테트라프로폭시실란 또는 테트라부톡시실란이 보다 바람직하고, 특히 테트라메톡시실란 또는 테트라에톡시실란이 바람직하다. The alkoxysilane in which n is 0 in the formula (3) is preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane, more preferably tetramethoxysilane or tetraethoxy Silane is preferred.
식 (3) 으로 나타내는 알콕시실란을 병용하는 경우, 식 (3) 으로 나타내는 알콕시실란의 사용량은, 폴리실록산을 얻기 위해서 사용하는 전체 알콕시실란 중에 있어서, 10 ∼ 96.9 몰％ 인 것이 바람직하다. 보다 바람직하게는 35 ∼ 99.8 몰％ 이다. When the alkoxysilane represented by the formula (3) is used in combination, the amount of the alkoxysilane represented by the formula (3) is preferably 10 to 96.9 mol% in the total alkoxysilane used for obtaining the polysiloxane. And more preferably 35 to 99.8 mol%.
［폴리실록산의 제조 방법］[Production method of polysiloxane]
본 발명에 사용하는 폴리실록산을 얻는 방법은 특별히 한정되지 않는다. 본 발명에 있어서는, 상기한 식 (1) 및 식 (2) 를 필수 성분으로 하는 알콕시실란을 유기 용매 중에서 축합시켜 얻어진다. 통상적으로, 폴리실록산은 이와 같은 알콕시실란을 중축합하여, 유기 용매에 균일하게 용해시킨 용액으로서 얻어진다.The method for obtaining the polysiloxane used in the present invention is not particularly limited. In the present invention, it is obtained by condensing an alkoxysilane containing the above-mentioned formulas (1) and (2) as essential components in an organic solvent. Generally, polysiloxane is obtained as a solution in which such alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.
상기 알콕시실란을 중축합하는 방법으로서, 예를 들어, 알콕시실란을 알코올 또는 글리콜 등의 용매 중에서 가수분해·축합하는 방법을 들 수 있다. 그 때, 가수분해·축합 반응은 부분 가수분해 및 완전 가수분해 중 어느 것이어도 된다. 완전 가수분해의 경우에는, 이론상, 알콕시실란 중의 전체 알콕시기의 0.5 배몰의 물을 첨가하면 되는데, 통상적으로는 0.5 배몰보다 과잉량의 물을 첨가하는 것이 바람직하다. As a method for polycondensing the alkoxysilane, for example, a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or a glycol may be mentioned. At this time, the hydrolysis-condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, in theory, 0.5-fold molar excess of the total alkoxy groups in the alkoxysilane may be added, and it is usually preferred to add an excess of water in excess of 0.5-molar mol.
상기 반응에 사용하는 물의 양은, 원하는 바에 따라 적절히 선택할 수 있는데, 통상적으로 알콕시실란 중의 전체 알콕시기의 0.5 ∼ 2.5 배몰인 것이 바람직하다. The amount of water used in the reaction may be appropriately selected according to the desired amount, and is preferably 0.5 to 2.5 times of the total alkoxy group in the alkoxysilane.
또, 본 발명에 있어서는, 통상적으로 가수분해·축합 반응을 촉진시킬 목적으로, 염산, 황산, 질산, 아세트산, 포름산, 옥살산, 말레산, 푸마르산 등의 산；암모니아, 메틸아민, 에틸아민, 에탄올아민, 트리에틸아민 등의 알칼리；염산, 황산, 질산 등의 금속염； 등의 촉매를 사용하는 것이 바람직하다. 또, 알콕시실란이 용해된 용액을 가열함으로써, 추가로 가수분해·축합 반응을 촉진시킬 수도 있다. 그 때, 가열 온도 및 가열 시간은 원하는 바에 따라 적절히 선택할 수 있다. 예를 들어, 50 ℃ 에서 24 시간 가열·교반하거나 환류하에서 1 시간 가열·교반하는 등의 방법을 들 수 있다. In the present invention, for the purpose of accelerating the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; ammonia, methylamine, ethylamine, , Triethylamine and the like, and metal salts such as hydrochloric acid, sulfuric acid and nitric acid. The hydrolysis / condensation reaction may be further promoted by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours or heating and stirring for 1 hour under reflux.
또, 다른 방법으로서, 예를 들어, 알콕시실란, 용매 및 옥살산의 혼합물을 가열하여 중축합하는 방법을 들 수 있다. 구체적으로는, 미리 알코올에 옥살산을 첨가하여 옥살산의 알코올 용액으로 한 후, 그 용액을 가열한 상태에서, 알콕시실란을 혼합하는 방법이다. 그 때, 사용하는 옥살산의 양은, 알콕시실란이 갖는 전체 알콕시기의 1 몰에 대해 0.2 ∼ 2 몰로 하는 것이 바람직하다. 이 방법에 있어서의 가열은, 액온 50 ∼ 180 ℃ 에서 실시할 수 있다. 바람직하게는, 액의 증발, 휘산 등이 일어나지 않게, 환류하에서 수십 분 내지 수십 시간 가열하는 방법이다. As another method, for example, a method of polycondensing a mixture of alkoxysilane, a solvent and oxalic acid by heating may be mentioned. Specifically, oxalic acid is added to the alcohol in advance to prepare an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while heating the solution. At this time, the amount of oxalic acid to be used is preferably 0.2 to 2 mol per 1 mol of the total alkoxy group of the alkoxysilane. The heating in this method can be carried out at a liquid temperature of 50 to 180 ° C. Preferably, the solution is heated for several tens of minutes to several tens of hours under reflux so that evaporation of the liquid, vaporization and the like do not occur.
폴리실록산을 얻을 때에, 알콕시실란을 복수 종 사용하는 경우에는, 알콕시실란을 미리 혼합해도 되고, 복수 종의 알콕시실란을 순차 혼합해도 된다. When a plurality of alkoxysilanes are used in obtaining the polysiloxane, the alkoxysilane may be mixed in advance, or a plurality of alkoxysilanes may be sequentially mixed.
알콕시실란을 중축합할 때에 사용되는 용매 (이하, 중합 용매라고도 한다) 는, 알콕시실란을 용해하는 것이면 특별히 한정되지 않는다. 또, 알콕시실란이 용해되지 않는 경우에도, 알콕시실란의 중축합 반응의 진행과 함께 용해되는 것이면 된다. 일반적으로는, 알콕시실란의 중축합 반응에 의해 알코올이 생성되기 때문에, 알코올류, 글리콜류, 글리콜에테르류, 또는 알코올류와 상용성이 양호한 유기 용매가 사용된다. The solvent used for polycondensing the alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. In addition, even when the alkoxysilane is not dissolved, it may be any one that dissolves along with the progress of the polycondensation reaction of the alkoxysilane. Generally, an organic solvent having good compatibility with alcohols, glycols, glycol ethers, or alcohols is used because alcohol is produced by the polycondensation reaction of alkoxysilane.
이와 같은 중합 용매의 구체예로는, 메탄올, 에탄올, 프로판올, 부탄올, 디아세톤알코올 등의 알코올류：에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 헥실렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 2,3-부탄디올, 1,2-펜탄디올, 1,3-펜탄디올, 1,4-펜탄디올, 1,5-펜탄디올, 2,4-펜탄디올, 2,3-펜탄디올, 1,6-헥산디올 등의 글리콜류：에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜디프로필에테르, 에틸렌글리콜디부틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노프로필에테르, 디에틸렌글리콜모노부틸에테르, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜디프로필에테르, 디에틸렌글리콜디부틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노프로필에테르, 프로필렌글리콜모노부틸에테르, 프로필렌글리콜디메틸에테르, 프로필렌글리콜디에틸에테르, 프로필렌글리콜디프로필에테르, 프로필렌글리콜디부틸에테르 등의 글리콜에테르류, N-메틸-2-피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, γ-부티로락톤, 디메틸술폭사이드, 테트라메틸우레아, 헥사메틸포스포트리아미드, m-크레졸 등을 들 수 있다. Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, Glycols such as pentanediol, 2,4-pentanediol, 2,3-pentanediol and 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, di Diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, and the like; glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Dimethylacetamide,? -Butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and m-cresol.
본 발명에 있어서는, 상기 중합 용매를 복수 종 혼합하여 사용해도 된다.In the present invention, a plurality of the polymerization solvents may be mixed and used.
상기 방법에서 얻어진 폴리실록산의 중합 용액 (이하, 중합 용액이라고도 한다) 은, 원료로서 주입한 전체 알콕시실란의 규소 원자를 SiO2 로 환산한 농도 (이하, SiO2 환산 농도라고 한다) 를 바람직하게는 20 질량％ 이하, 나아가서는 5 ∼ 15 질량％ 로 하는 것이 보다 바람직하다. 이 농도 범위에 있어서 임의의 농도를 선택함으로써, 겔의 생성을 억제하여 균질한 용액을 얻을 수 있다. The polymerization solution of the polysiloxane (hereinafter also referred to as a polymerization solution) obtained by the above method is a solution in which silicon atoms of the entire alkoxysilane injected as a raw material are converted into SiO 2 (hereinafter referred to as SiO 2 -converted concentration) By mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration in this concentration range, it is possible to obtain a homogeneous solution by suppressing gel formation.
［폴리실록산의 용액］ [Solution of polysiloxane]
본 발명에 있어서는, 상기 방법에서 얻어진 중합 용액을 그대로 폴리실록산의 용액이라고 해도 되고, 필요에 따라, 상기 방법에서 얻어진 용액을 농축하거나 용매를 첨가하여 희석하거나 또는 다른 용매로 치환하여, 폴리실록산의 용액이라고 해도 된다. In the present invention, the polymerized solution obtained by the above method may be directly referred to as a polysiloxane solution. If necessary, the solution obtained by the above method may be concentrated or a solvent may be added to dilute or replace with another solvent to obtain a polysiloxane solution do.
그 때, 사용하는 용매 (이하, 첨가 용매라고도 한다) 는, 중합 용매와 동일해도 되고, 다른 용매이어도 된다. 이 첨가 용매는, 폴리실록산이 균일하게 용해되고 있는 한 특별히 한정되지 않고, 1 종이어도 복수 종이어도 임의로 선택하여 사용할 수 있다. At this time, the solvent to be used (hereinafter also referred to as an addition solvent) may be the same as or different from the polymerization solvent. This additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one or more kinds of additives can be arbitrarily selected and used.
이와 같은 첨가 용매의 구체예로는, 상기한 중합 용매의 예로서 든 용매 이외에, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류；아세트산메틸, 아세트산에틸, 락트산에틸 등의 에스테르류를 들 수 있다. Specific examples of such an addition solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and ethyl lactate, have.
이들의 용매는, 액정 배향제의 점도의 조정, 또는 스핀 코트, 플렉소 인쇄, 잉크젯 등에 의해 액정 배향제를 기판 상에 도포할 때의 도포성을 향상할 수 있다.These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, inkjet or the like.
［그 밖의 성분］[Other components]
본 발명의 액정 배향제에 있어서는, 본 발명의 효과를 저해하지 않는 한에 있어서, 폴리실록산 이외의 그 밖의 성분, 예를 들어, 무기 미립자, 메탈록산 올리고머, 메탈록산 폴리머, 레벨링제, 또한 계면활성제 등의 성분이 함유되어 있어도 된다. In the liquid crystal aligning agent of the present invention, other components other than the polysiloxane such as an inorganic fine particle, a metal oxal oligomer, a metal acid polymer, a leveling agent, a surfactant, and the like may be used as long as the effect of the present invention is not impaired May be contained.
무기 미립자로는, 실리카 미립자, 알루미나 미립자, 티타니아 미립자, 또는 불화마그네슘 미립자 등의 미립자가 바람직하고, 특히 콜로이드 용액 상태인 것이 바람직하다. 이 콜로이드 용액은, 무기 미립자를 분산매에 분산시킨 것이어도 되고, 시판품의 콜로이드 용액이어도 된다. 본 발명에 있어서는, 무기 미립자를 함유시킴으로써, 형성되는 경화 피막의 표면 형상 및 그 밖의 기능을 부여하는 것이 가능해진다. 무기 미립자로는, 그 평균 입자경이 0.001 ∼ 0.2 ㎛ 인 것이 바람직하고, 더욱 바람직하게는 0.001 ∼ 0.1 ㎛ 이다. 무기 미립자의 평균 입자경이 0.2 ㎛ 를 초과하는 경우에는, 조제되는 도포액을 사용하여 형성되는 경화 피막의 투명성이 저하되는 경우가 있다. As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and in particular, they are preferably in a colloidal solution state. The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a colloidal solution of a commercial product. In the present invention, by containing the inorganic fine particles, the surface shape and other functions of the formed cured coating can be imparted. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 탆, more preferably 0.001 to 0.1 탆. When the average particle size of the inorganic fine particles exceeds 0.2 탆, the transparency of the cured coating formed using the coating liquid to be prepared may be lowered.
무기 미립자의 분산매로는, 물 및 유기 용제를 들 수 있다. 콜로이드 용액으로는, 피막 형성용 도포액의 안정성 관점에서, pH 또는 pKa 가 1 ∼ 10 으로 조정되어 있는 것이 바람직하다. 보다 바람직하게는 2 ∼ 7 이다. Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. As the colloidal solution, it is preferable that the pH or the pKa is adjusted to 1 to 10 from the viewpoint of the stability of the film-forming coating liquid. And more preferably 2 to 7.
콜로이드 용액의 분산매에 사용하는 유기 용제로는, 메탄올, 프로판올, 부탄올, 에틸렌글리콜, 프로필렌글리콜, 부탄디올, 펜탄디올, 헥실렌글리콜, 디에틸렌글리콜, 디프로필렌글리콜, 에틸렌글리콜모노프로필에테르 등의 알코올류；메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류；톨루엔, 자일렌 등의 방향족 탄화수소류；디메틸포름아미드, 디메틸아세트아미드, N-메틸피롤리돈 등의 아미드류；아세트산에틸, 아세트산부틸, γ-부티로락톤 등의 에스테르류；테트라하이드로푸란, 1,4-디옥산 등의 에테르류를 들 수 있다. 이들 중에서, 알코올류 또는 케톤류가 바람직하다. 이들 유기 용제는, 단독으로 또는 2 종 이상을 혼합하여 분산매로서 사용할 수 있다. Examples of the organic solvent for use in the dispersion medium of the colloid solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexyleneglycol, diethylene glycol, dipropylene glycol and ethylene glycol monopropyl ether Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethyl acetate, butyl acetate, Ethers such as tetrahydrofuran and 1,4-dioxane, and the like. Of these, alcohols or ketones are preferred. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.
메탈록산 올리고머, 메탈록산 폴리머로는, 규소, 티탄, 알루미늄, 탄탈, 안티몬, 비스무트, 주석, 인듐, 아연 등의 단독 또는 복합 산화물 전구체가 사용된다. 메탈록산 올리고머, 메탈록산 폴리머로는, 시판품이어도 되고, 금속 알콕사이드, 질산염, 염산염, 카르복실산염 등의 모노머로부터 가수분해 등의 통상적인 방법에 의해 얻어진 것이어도 된다. As the metal oxalic oligomer and the metal oxalic polymer, a single or complex oxide precursor such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium and zinc is used. The metal roxanic acid oligomer and the metallonic acid polymer may be commercially available products or may be obtained by a conventional method such as hydrolysis from monomers such as metal alkoxide, nitrate, hydrochloride, and carboxylate.
시판품인 메탈록산 올리고머, 메탈록산 폴리머의 구체예로는, 코루코트사 제조의, 메틸실리케이트 51, 메틸실리케이트 53A, 에틸실리케이트 40, 에틸실리케이트 48, EMS-485, SS-101 등의 실록산 올리고머 또는 실록산 폴리머, 칸토 화학사 제조의 티타늄-n-부톡사이드 테트라머 등의 티타녹산 올리고머를 들 수 있다. 이들은 단독 또는 2 종 이상 혼합하여 사용해도 된다. Specific examples of the commercially available metal oligomer and metal acid polymer include siloxane oligomers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485 and SS-101, Polymer, and titanoxane oligomer such as titanium-n-butoxide tetramer manufactured by Kanto Chemical. These may be used alone or in combination of two or more.
또, 레벨링제 및 계면활성제 등은, 공지된 것을 사용할 수 있고, 특히 시판품은 입수가 용이해서 바람직하다. As the leveling agent and the surfactant, known ones can be used, and commercial products are particularly preferable since they are readily available.
또, 폴리실록산에, 상기한 그 밖의 성분을 혼합하는 방법은, 폴리실록산과 동시이어도 되고, 이후이어도 되며, 특별히 한정되지 않는다. The method of mixing the above other components with the polysiloxane may be carried out simultaneously with the polysiloxane, and thereafter, and there is no particular limitation.
［액정 배향제］ [Liquid crystal aligning agent]
본 발명의 액정 배향제는 용매 중에, 상기 서술한 폴리실록산을 용해시키고, 필요에 따라 그 밖의 성분을 용해 또는 분산시켜 함유한다. 용매로는, 상기 서술한 폴리실록산의 중합 용매 및 첨가 용매로 이루어지는 군에서 선택되는 용매가 사용된다. 액정 배향제에 있어서의 폴리실록산의 함유량은, SiO2 환산 농도가 바람직하게는 0.5 ∼ 15 질량％, 보다 바람직하게는 1 ∼ 6 질량％ 이다. 이와 같은 SiO2 환산 농도의 범위이면, 1 회의 도포로 원하는 막두께를 용이하게 얻을 수 있어, 충분한 용액의 포트 라이프가 용이하게 얻어진다. The liquid crystal aligning agent of the present invention contains the above-mentioned polysiloxane in a solvent and, if necessary, dissolves or disperses other components. As the solvent, a solvent selected from the group consisting of a polymerization solvent of the above-mentioned polysiloxane and an addition solvent is used. The content of the polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO 2 . With such a SiO 2 -converted concentration range, a desired film thickness can be easily obtained by one application, and a sufficient pot life of the solution can be easily obtained.
본 발명의 액정 배향제를 조제하는 방법은 특별히 한정되지 않는다. 본 발명에 사용하는 폴리실록산, 필요에 따라 첨가되는 그 밖의 성분이 균일하게 혼합된 상태이면 된다. 통상적으로 폴리실록산은, 용매 중에서 중축합되기 때문에, 폴리실록산의 용액을 그대로 사용하거나, 폴리실록산의 용액에 필요에 따라 그 밖의 성분을 첨가하는 것이 간편하다. 또한, 폴리실록산의 중합 용액을 그대로 사용하는 방법이 가장 간편하다. The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention and other components to be added as required may be uniformly mixed. Since the polysiloxane is usually polycondensed in a solvent, it is convenient to use a solution of the polysiloxane as it is or to add other components to the polysiloxane solution as needed. The most convenient method is to use the polymerization solution of polysiloxane as it is.
또, 액정 배향제 중에 있어서의 폴리실록산의 함유량을 조정할 때에는, 상기 서술한 폴리실록산의 중합 용매 및 첨가 용매로 이루어지는 군에서 선택되는 용매를 사용할 수 있다. When adjusting the content of the polysiloxane in the liquid crystal aligning agent, a solvent selected from the group consisting of a polymerization solvent of the above-mentioned polysiloxane and an additive solvent may be used.
［액정 배향막］[Liquid Crystal Alignment Layer]
본 발명의 액정 배향막은 상기 액정 배향제를 사용하여 얻어진다. 예를 들어, 본 발명의 액정 배향제를 기판에 도포한 후, 건조·소성을 실시함으로써 얻어지는 경화막을, 그대로 액정 배향막으로서 사용할 수도 있다. 또, 이 경화막을 러빙하거나 편광 또는 특정 파장의 광 등을 조사하거나 이온 빔 등의 처리를 하거나 PSA 용 배향막으로서 액정 충전 후의 액정 표시 소자에 전압을 인가한 상태에서 UV 를 조사할 수도 있다. 특히, PSA 용 배향막으로서 사용하는 것이 유용하다.The liquid crystal alignment film of the present invention is obtained using the liquid crystal aligning agent. For example, a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, followed by drying and firing, may be used as the liquid crystal alignment film as it is. It is also possible to rub the cured film, to irradiate polarized light, light of a specific wavelength, or the like, or to irradiate UV with the PSA orientation film applied with a voltage to the liquid crystal display element after liquid crystal filling. In particular, it is useful to use it as an alignment film for PSA.
액정 배향제를 도포하는 기판으로는, 투명성이 높은 기판이면 특별히 한정되지 않지만, 기판 상에 액정을 구동하기 위한 투명 전극이 형성된 기판이 바람직하다. The substrate to which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate having high transparency, but a substrate on which a transparent electrode for driving the liquid crystal is formed is preferable.
구체예를 들면, 유리판, 폴리카보네이트, 폴리(메트)아크릴레이트, 폴리에테르술폰, 폴리알릴레이트, 폴리우레탄, 폴리술폰, 폴리에테르, 폴리에테르케톤, 트리메틸펜텐, 폴리올레핀, 폴리에틸렌테레프탈레이트, (메트)아크릴로니트릴, 트리아세틸셀룰로오스, 디아세틸셀룰로오스, 아세테이트부틸레이트셀룰로오스 등의 플라스틱판 등에 투명 전극이 형성된 기판을 들 수 있다. Specific examples thereof include glass plates, polycarbonates, poly (meth) acrylates, polyethersulfones, polyallylates, polyurethanes, polysulfones, polyethers, polyether ketones, trimethylpentens, polyolefins, polyethylene terephthalates, A substrate on which a transparent electrode is formed on a plastic plate such as acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butyrate cellulose.
액정 배향제의 도포 방법으로는, 스핀 코트법, 인쇄법, 잉크젯법, 스프레이법, 롤 코트법 등을 들 수 있는데, 생산성면에서 공업적으로는 전사 인쇄법이 널리 사용되고 있고, 본 발명에서도 바람직하게 사용된다. Examples of the application method of the liquid crystal aligning agent include a spin coating method, a printing method, an ink jet method, a spraying method and a roll coating method. From the viewpoint of productivity, the transfer printing method is widely used industrially, Lt; / RTI >
액정 배향제를 도포한 후의 건조 공정은 반드시 필요하지 않지만, 도포 후부터 소성까지의 시간이 기판마다 일정하지 않은 경우, 또는 도포 후 즉시 소성되지 않는 경우에는, 건조 공정을 포함하는 것이 바람직하다. 이 건조는 기판의 반송 등에 의해 도포막 형상이 변형되지 않는 정도로 용매가 제거되어 있으면 되고, 그 건조 수단에 대해서는 특별히 한정되지 않는다. 예를 들어, 온도 40 ℃ ∼ 150 ℃, 바람직하게는 60 ℃ ∼ 100 ℃ 의 핫 플레이트 상에서, 0.5 ∼ 30 분, 바람직하게는 1 ∼ 5 분 건조시키는 방법을 들 수 있다. The drying step after the application of the liquid crystal aligning agent is not necessarily required. However, when the time from the application to the baking is not constant for each substrate or when the baking is not performed immediately after the application, it is preferable to include a drying step. The drying is not particularly limited as long as the solvent is removed to the extent that the shape of the coated film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes.
상기 방법에 의해 액정 배향제를 도포하여 형성되는 도포막은, 소성하여 경화막으로 할 수 있다. 그 때, 소성 온도는 100 ℃ ∼ 350 ℃ 의 임의의 온도에서 실시할 수 있지만, 바람직하게는 140 ℃ ∼ 300 ℃ 이고, 보다 바람직하게는 150 ℃ ∼ 230 ℃, 더욱 바람직하게는 160 ℃ ∼ 220 ℃ 이다. 소성 시간은 5 분 ∼ 240 분의 임의의 시간에서 소성을 실시할 수 있다. 바람직하게는 10 ∼ 90 분이고, 보다 바람직하게는 20 ∼ 90 분이다. 가열은 통상적으로 공지된 방법, 예를 들어, 핫 플레이트, 열풍 순환 오븐, IR 오븐, 벨트로 등을 사용할 수 있다.The coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a cured film. In this case, the firing temperature may be any temperature of 100 ° C to 350 ° C, preferably 140 ° C to 300 ° C, more preferably 150 ° C to 230 ° C, and more preferably 160 ° C to 220 ° C to be. The firing time can be fired at any time between 5 minutes and 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating can be carried out by a commonly known method, for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace or the like.
액정 배향막 중의 폴리실록산은 소성 공정에 있어서 중축합이 진행된다. 그러나, 본 발명에 있어서는, 본 발명의 효과를 저해하지 않는 한 완전하게 중축합시킬 필요는 없다. 단, 액정셀 제조 행정에서 필요한, 시일제 경화 등의 열처리 온도보다 10 ℃ 이상 높은 온도에서 소성하는 것이 바람직하다. Polysiloxane in the liquid crystal alignment film progresses in polycondensation in the firing step. However, in the present invention, it is not necessary to completely polycondensate the polycarbonate resin as long as the effect of the present invention is not impaired. However, it is preferable to carry out the firing at a temperature higher by at least 10 캜 than the heat treatment temperature such as seal hardening required in the liquid crystal cell production process.
이 경화막의 두께는 필요에 따라 선택할 수 있는데, 바람직하게는 5 ㎚ 이상, 보다 바람직하게는 10 ㎚ 이상인 경우, 액정 표시 소자의 신뢰성이 양호하게 얻어지기 때문에 바람직하다. 또, 경화막의 두께가 바람직하게는 300 ㎚ 이하, 보다 바람직하게는 150 ㎚ 이하인 경우에는, 액정 표시 소자의 소비 전력이 극단적으로 커지지 않기 때문에 바람직하다. The thickness of the cured film can be selected as required, preferably 5 nm or more, and more preferably 10 nm or more, because the reliability of the liquid crystal display element can be satisfactorily obtained. When the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely increased, which is preferable.
＜액정 표시 소자＞ <Liquid crystal display element>
본 발명의 액정 표시 소자는, 상기 방법에 의해 기판에 액정 배향막을 형성한 후, 공지된 방법에 의해 액정셀을 제작하여 얻을 수 있다. 액정셀 제작의 일례를 들면, 액정 배향막이 형성된 1 쌍의 기판을, 스페이서를 사이에 두고, 시일제로 고정시켜, 액정을 주입하여 밀봉하는 방법이 일반적이다. 그 때, 사용하는 스페이서의 크기는 1 ∼ 30 ㎛ 이지만, 바람직하게는 2 ∼ 10 ㎛ 이다. The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method, and then manufacturing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is fixed by a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed. At this time, the size of the spacer used is 1 to 30 mu m, preferably 2 to 10 mu m.
액정을 주입하는 방법은 특별히 제한되지 않고, 제작한 액정셀 내를 감압으로 한 후, 액정을 주입하는 진공법, 액정을 적하한 후에 밀봉을 실시하는 적하법 등을 들 수 있다. The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which the inside of the produced liquid crystal cell is reduced in pressure, a liquid crystal is injected, and a dropping method in which liquid crystal is dripped and sealed.
PSA 방식의 액정 표시 소자에서는, 사용되는 액정으로서 광 중합성 화합물을 소량 (전형적으로는 0.2 ∼ 1 중량％) 첨가한 액정을 사용한다. 이 액정이 도입된 액정셀의, 양측 기판의 전극 사이에 전압을 인가한 상태에서 UV 조사함으로써, 중합성 화합물이 그 자리에서 중합되어 가교됨으로써, 액정 디스플레이의 응답 속도가 빨라진다. 여기서, 인가하는 전압은 5 ∼ 30 Vp-p 이지만, 바람직하게는, 5 ∼ 20 Vp-p 이다. 조사하는 UV 조사량은 1 ∼ 60 J 이지만, 바람직하게는 40 J 이하이며, UV 조사량이 적은 편이 액정 디스플레이를 구성하는 부재의 파괴로 이루어지는 신뢰성 저하를 억제할 수 있고, 또한 UV 조사 시간을 줄임으로써 제조상의 택트가 높아지기 때문에 바람직하다. In the PSA type liquid crystal display device, a liquid crystal in which a small amount (typically 0.2 to 1% by weight) of a photopolymerizable compound is added is used as a liquid crystal used. By UV irradiation in the state of applying voltage between the electrodes of the liquid crystal cell into which the liquid crystal is introduced, the polymerizable compound is polymerized and cross-linked in situ, whereby the response speed of the liquid crystal display is increased. Here, the applied voltage is 5 to 30 Vp-p, but preferably 5 to 20 Vp-p. The amount of UV irradiation to be irradiated is 1 to 60 J, preferably 40 J or less. The smaller amount of UV irradiation can suppress the reliability degradation due to the breakage of the members constituting the liquid crystal display. Further, by reducing the UV irradiation time, The tact of the tungsten carbide increases.
액정 표시 소자에 사용하는 기판으로는, 투명성이 높은 기판이면 특별히 한정되지 않지만, 통상적으로는, 기판 상에 액정을 구동하기 위한 투명 전극이 형성된 기판이다. 구체예는［액정 배향막］으로 기재한 기판과 동일하다. PSA 방식의 액정셀에 사용할 수 있는 기판에는, 표준적인 PVA 나 MVA 와 같은 전극 패턴이나 돌기 패턴에서도 사용할 수 있다. 그러나, PSA 방식의 액정 디스플레이에는, 편측 기판에 1 ∼ 10 ㎛ 의 라인/슬릿 전극 패턴을 형성하고, 대향 기판에는 슬릿 패턴이나 돌기 패턴을 형성하지 않은 구조에 있어서도 동작 가능하고, 이 구조의 액정 디스플레이에 의해, 제조시의 프로세스를 간략화할 수 있어 높은 투과율을 얻을 수 있다. The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, but usually it is a substrate on which a transparent electrode for driving the liquid crystal is formed. A specific example is the same as the substrate described as [liquid crystal alignment film]. A substrate that can be used for a PSA type liquid crystal cell can be used for an electrode pattern such as standard PVA or MVA or a projection pattern. However, in the PSA type liquid crystal display, it is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 mu m is formed on a unilateral substrate and a slit pattern or a projection pattern is not formed on the counter substrate, The process at the time of production can be simplified, and a high transmittance can be obtained.
또, TFT 형의 소자와 같은 고기능 소자에 있어서는, 액정 구동을 위한 전극과 기판 사이에 트랜지스터와 같은 소자가 형성된 것이 사용된다. In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.
투과형 액정 표시 소자의 경우에는, 상기와 같은 기판을 사용하는 것이 일반적이지만, 반사형 액정 표시 소자에서는, 편측의 기판에만이라면 실리콘 웨이퍼 등의 불투명한 기판도 사용할 수 있다. 그 때, 기판에 형성된 전극에는, 광을 반사하는 알루미늄과 같은 재료를 사용할 수도 있다. In the case of a transmissive liquid crystal display device, it is common to use such a substrate as described above. However, in a reflection type liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only on one substrate. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
실시예Example
이하 본 발명의 실시예에 의해 추가로 구체적으로 설명하지만, 이들에 한정하여 해석되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not construed as being limited thereto.
본 실시예에서 사용한 화합물에 있어서의 약어는 이하와 같다. The abbreviations of the compounds used in this embodiment are as follows.
TEOS：테트라에톡시실란 TEOS: tetraethoxysilane
C18：옥타데실트리에톡시실란C18: octadecyltriethoxysilane
ACPS：3-아크릴옥시프로필트리메톡시실란ACPS: 3-acryloxypropyltrimethoxysilane
HG：2-메틸-2,4-펜탄디올 (별명：헥실렌글리콜) HG: 2-methyl-2,4-pentanediol (also known as hexylene glycol)
BCS：2-부톡시에탄올BCS: 2-butoxyethanol
UPS：3-우레이도프로필트리에톡시실란 UPS: 3-ureidopropyltriethoxysilane
MPMS：3-메타크릴옥시프로필트리메톡시실란MPMS: 3-methacryloxypropyltrimethoxysilane
＜실시 합성예 1＞ ≪ Synthesis Example 1 &
온도계, 환류관을 구비한 200 ㎖ (리터) 의 4 구 반응 플라스크 중에서, HG 를 22.5 g, BCS 를 7.5 g, TEOS 를 28.3 g, C18 을 1.7 g, 및 ACPS 를 14.1 g 혼합하여, 알콕시실란 모노머의 용액을 조제하였다. 이 용액에, 미리 HG 를 11.2 g, BCS 를 3.7 g, 물을 10.8 g 및 촉매로서 옥살산 0.2 g 을 혼합시킨 용액을, 실온하에서 30 분에 걸쳐 적하하였다. 이 용액을 30 분간 교반하고 나서 1 시간 환류시킨 후에 방랭하여 SiO2 환산 농도가 12 중량％ 인 폴리실록산 용액을 얻었다.22.5 g of HG, 7.5 g of BCS, 28.3 g of TEOS, 1.7 g of C18, and 14.1 g of ACPS were mixed in a 200 ml (liter) four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Was prepared. To this solution, a solution prepared by previously mixing 11.2 g of HG, 3.7 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature. This solution was stirred for 30 minutes, refluxed for 1 hour, and then cooled to obtain a polysiloxane solution having a SiO 2 concentration of 12 wt%.
얻어진 폴리실록산 용액 10.0 g 에 BCS 20.0 g 을 혼합하여, SiO2 환산 농도가 4 중량％ 인 액정 배향제 (K1) 을 얻었다. Mixing the resulting polysiloxane solution, 10.0 g to 20.0 g to BCS, SiO 2 in terms of a concentration of 4% by weight to obtain a liquid crystal aligning agent (K1).
＜실시 합성예 2＞ ≪ Synthesis Example 2 &
온도계, 환류관을 구비한 200 ㎖ 의 4 구 반응 플라스크 중에서, HG 를 21.1 g, BCS 를 7.0 g, TEOS 를 19.2 g, C18 을 1.7 g, 및 ACPS 를 23.4 g 혼합하여, 알콕시실란 모노머의 용액을 조제하였다. 이 용액에, 미리 HG 를 10.5 g, BCS 를 3.5 g, 물을 10.8 g 및 촉매로서 옥살산 0.9 g 을 혼합시킨 용액을, 실온하에서 30 분에 걸쳐 적하하였다. A solution of alkoxysilane monomer was prepared by mixing 21.1 g of HG, 7.0 g of BCS, 19.2 g of TEOS, 1.7 g of C18 and 23.4 g of ACPS in a 200 ml four-neck reaction flask equipped with a thermometer and reflux tube Lt; / RTI > A solution prepared by previously mixing 10.5 g of HG, 3.5 g of BCS, 10.8 g of water and 0.9 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature.
이 용액을 30 분간 교반하고 나서 1 시간 환류시킨 후, 미리 UPS 함유량 92 질량％ 의 메탄올 용액을 1.2 g, HG 를 0.5 g 및 BCS 를 0.2 g 의 혼합액을 첨가하였다. 추가로 30 분간 환류시키고 나서 방랭하여 SiO2 환산 농도가 12 중량％ 인 폴리실록산 용액을 얻었다. This solution was stirred for 30 minutes and then refluxed for 1 hour. Thereafter, a mixed solution of 1.2 g of a methanol solution having a UPS content of 92 mass%, 0.5 g of HG and 0.2 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO 2 -conversion concentration of 12% by weight.
얻어진 폴리실록산 용액 10.0 g 에 BCS 20.0 g 을 혼합하여, SiO2 환산 농도가 4 중량％ 인 액정 배향제 (K2) 를 얻었다. Mixing the resulting polysiloxane solution BCS 20.0 g to 10.0 g and, SiO 2 in terms of a concentration of 4% by weight to obtain a liquid crystal aligning agent (K2).
＜실시 합성예 3＞ ≪ Synthesis Example 3 &
온도계, 환류관을 구비한 200 ㎖ 의 4 구 반응 플라스크 중에서, HG 를 20.2 g, BCS 를 6.7 g, TEOS 를 27.9 g, C18 을 1.7 g, 및 MPMS 를 17.4 g 혼합하여, 알콕시실란 모노머의 용액을 조제하였다. 이 용액에, 미리 HG 를 10.0 g, BCS 를 3.4 g, 물을 10.8 g 및 촉매로서 옥살산 0.9 g 을 혼합시킨 용액을, 실온하에서 30 분에 걸쳐 적하하였다. 20.2 g of HG, 6.7 g of BCS, 27.9 g of TEOS, 1.7 g of C18 and 17.4 g of MPMS were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to give a solution of the alkoxysilane monomer Lt; / RTI > A solution prepared by previously mixing 10.0 g of HG, 3.4 g of BCS, 10.8 g of water and 0.9 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature.
이 용액을 30 분간 교반하고 나서 1 시간 환류시킨 후, 미리 UPS 함유량 92 질량％ 의 메탄올 용액 0.6 g, HG 0.3 g 및 BCS 0.1 g 의 혼합액을 첨가하였다. 추가로 30 분간 환류시키고 나서 방랭하여 SiO2 환산 농도가 12 중량％ 인 폴리실록산 용액을 얻었다. This solution was stirred for 30 minutes and then refluxed for 1 hour. Thereafter, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO 2 -conversion concentration of 12% by weight.
얻어진 폴리실록산 용액 10.0 g 에 BCS 20.0 g 을 혼합하여, SiO2 환산 농도가 4 중량％ 인 액정 배향제 (K3) 을 얻었다. Mixing the resulting polysiloxane solution, 10.0 g to 20.0 g to BCS, SiO 2 in terms of a concentration of 4% by weight to obtain a liquid crystal aligning agent (K3).
＜비교 합성예 1＞ <Comparative Synthesis Example 1>
온도계, 환류관을 구비한 200 ㎖ 의 4 구 반응 플라스크 중에서, HG 를 23.3 g, BCS 를 7.7 g, TEOS 를 40.8 g, C18 을 1.7 g 혼합하여, 알콕시실란 모노머의 용액을 조제하였다. 이 용액에, 미리 HG 를 11.6 g, BCS 를 3.9 g, 물을 10.8 g 및 촉매로서 옥살산 0.2 g 을 혼합시킨 용액을, 실온하에서 30 분에 걸쳐 적하하였다. 23.3 g of HG, 7.7 g of BCS, 40.8 g of TEOS and 1.7 g of C18 were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.6 g of HG, 3.9 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature.
이 용액을 30 분간 교반하고 나서 1 시간 환류시킨 후에 방랭하여 SiO2 환산 고형분 농도가 12 중량％ 인 폴리실록산 용액을 얻었다. This solution was stirred for 30 minutes, refluxed for 1 hour and then cooled to obtain a polysiloxane solution having a solid content of 12% by weight in terms of SiO 2 .
얻어진 폴리실록산 용액 10.0 g 에 BCS 20.0 g 을 혼합하여, SiO2 환산 농도가 4 중량％ 인 액정 배향제 (L1) 을 얻었다. 10.0 g of the obtained polysiloxane solution was mixed with 20.0 g of BCS to obtain a liquid crystal aligning agent (L1) having a SiO 2 concentration of 4% by weight.
＜실시예 1＞ ≪ Example 1 >
합성예 1 에서 얻어진 액정 배향 처리제［K1］을, 화소 사이즈가 100 ㎛ × 300 ㎛ 이고, 라인/스페이스가 각각 5 ㎛ 인 ITO 전극 패턴이 형성되어 있는 ITO 전극 기판의 ITO 면에 스핀 코트하였다. 80 ℃ 의 핫 플레이트에서 5 분간 건조시킨 후, 180 ℃ 의 열풍 순환식 오븐에서 30 분간 소성을 실시하여, 막두께 100 ㎚ 인 액정 배향막을 형성하였다. The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having the pixel size of 100 mu m x 300 mu m and the line / space of 5 mu m each was formed. Dried on a hot plate at 80 DEG C for 5 minutes, and then fired in a hot air circulating oven at 180 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
합성예 1 에서 얻어진 액정 배향 처리제［K1］을, 전극 패턴이 형성되어 있지 않은 ITO 면에 스핀 코트하고, 80 ℃ 의 핫 플레이트에서 5 분간 건조시킨 후, 180 ℃ 의 열풍 순환식 오븐에서 30 분간 소성을 실시하여, 막두께 100 ㎚ 인 액정 배향막을 형성하였다. 이들 2 장의 기판을 준비하여, 일방의 기판의 액정 배향막면 상에 6 ㎛ 의 비즈 스페이서를 산포한 후, 그 위에서부터 시일제를 인쇄하였다. 타방의 기판을 액정 배향막면을 내측으로 하여, 접착시킨 후, 시일제를 경화시켜 빈 셀을 제작하였다. 액정 MLC-6608 (메르크사 제조 상품명) 에 대해 식 (S-1) 로 나타내는 중합성 화합물을 0.2 중량％ 첨가한 액정을 제작하고, 빈 셀에 감압 주입법에 의해, 상기 액정을 주입한 액정셀을 제작하였다. The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on an ITO surface on which no electrode pattern was formed and dried on a hot plate at 80 DEG C for 5 minutes and then baked in a hot air circulating oven at 180 DEG C for 30 minutes To form a liquid crystal alignment film having a thickness of 100 nm. These two substrates were prepared, a bead spacer of 6 mu m was dispersed on the liquid crystal alignment film surface of one of the substrates, and a sealant was printed thereon from above. The other substrate was adhered with the liquid crystal alignment film surface facing inward, and then the sealant was cured to prepare empty cells. A liquid crystal in which 0.2% by weight of a polymerizable compound represented by the formula (S-1) was added to liquid crystal MLC-6608 (trade name, manufactured by Merck) was prepared and a liquid crystal cell into which the liquid crystal was injected Respectively.
[화학식 1][Chemical Formula 1]
이들 액정셀의 응답 속도 특성을 후술하는 방법에 의해 측정하였다. 그 후, 이 액정셀에 20 Vp-p 의 전압을 인가한 상태에서, 이 액정셀의 외측으로부터 UV 를 20 J 조사하였다. 그 후, 다시 응답 속도 특성을 측정하여, UV 조사 전후에서의 응답 속도 (단위 ms：millisecond) 를 비교하였다. 그 결과를 표 1 에 나타냈다. The response speed characteristics of these liquid crystal cells were measured by a method described later. Thereafter, in a state in which a voltage of 20 Vp-p was applied to the liquid crystal cell, 20 J of UV was irradiated from the outside of the liquid crystal cell. Then, the response speed characteristics were measured again, and the response speed (unit: ms) before and after UV irradiation was compared. The results are shown in Table 1.
＜실시예 2＞ ≪ Example 2 >
액정 MLC-6608 에 첨가하는 중합성 화합물을 0.05 중량％ 로 변경한 것 이외에는 실시예 1 과 동일하게 하여 응답 속도를 측정하였다. 결과를 표 1 에 나타냈다. The response speed was measured in the same manner as in Example 1 except that the amount of the polymerizable compound added to the liquid crystal MLC-6608 was changed to 0.05% by weight. The results are shown in Table 1.
＜실시예 3＞ ≪ Example 3 >
액정 MLC-6608 에 첨가하는 중합성 화합물을 0.02 중량％ 로 변경한 것 이외에는 실시예 1 과 동일하게 하여 응답 속도를 측정하였다. 결과를 표 1 에 나타냈다. The response speed was measured in the same manner as in Example 1 except that the amount of the polymerizable compound added to the liquid crystal MLC-6608 was changed to 0.02% by weight. The results are shown in Table 1.
＜실시예 4＞ <Example 4>
액정 MLC-6608 에 중합성 화합물을 첨가하지 않은 것 이외에는 실시예 1 과 동일하게 하여 응답 속도를 측정하였다. 결과를 표 1 에 나타냈다. The response speed was measured in the same manner as in Example 1 except that the polymerizable compound was not added to the liquid crystal MLC-6608. The results are shown in Table 1.
＜실시예 5＞ ≪ Example 5 >
액정 배향 처리제［K1］을 실시 합성예 2 에서 얻어진 액정 배향 처리제［K2］로 변경한 것 이외에는, 실시예 4 와 동일하게 하여 액정셀을 제작하고, 응답 속도를 측정하였다. 그 결과를 표 1 에 나타냈다. A liquid crystal cell was prepared in the same manner as in Example 4 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K2] obtained in Synthesis Example 2, and the response speed was measured. The results are shown in Table 1.
＜실시예 6＞ ≪ Example 6 >
액정 배향 처리제［K1］을 실시 합성예 3 에서 얻어진 액정 배향 처리제［K3］으로 변경한 것 이외에는, 실시예 4 와 동일하게 하여 액정셀을 제작하고, 응답 속도를 측정하였다. 그 결과를 표 1 에 나타냈다. A liquid crystal cell was prepared in the same manner as in Example 4 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K3] obtained in Synthesis Example 3, and the response speed was measured. The results are shown in Table 1.
＜비교예 1 ∼ 비교예 4＞ ≪ Comparative Examples 1 to 4 >
액정 배향 처리제［K1］을 비교 합성예 1 에서 얻어진 액정 배향 처리제［L1］로 변경한 것 이외에는, 실시예 1 ∼ 실시예 4 와 동일하게 하여 액정셀을 제작하고, 응답 속도를 측정하였다. 그 결과를 표 1 에 나타냈다. A liquid crystal cell was prepared in the same manner as in Examples 1 to 4 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [L1] obtained in Comparative Synthesis Example 1, and the response speed was measured. The results are shown in Table 1.
［응답 속도 특성］ [Response speed characteristics]
전압을 인가하지 않은 액정셀에, 전압 ±4 V, 주파수 1 ㎑ 의 구형파를 인가했을 때의, 액정 패널의 휘도의 시간 변화를 오실로스코프에 넣었다. 전압을 인가하고 있지 않을 때의 휘도를 0 ％, ±4 V 의 전압을 인가하여, 포화된 휘도의 값을 100 ％ 로 하여 휘도가 10 ％ 에서 90 ％ 까지 변화하는 시간을 상승의 응답 속도로 하였다. A time change of the luminance of the liquid crystal panel when a square wave of voltage ± 4 V and a frequency of 1 kHz was applied to a liquid crystal cell to which no voltage was applied was inputted to the oscilloscope. A voltage of 0% and a voltage of +4 V was applied to the luminance when no voltage was applied, and the time when the luminance varied from 10% to 90% with the value of the saturated luminance as 100% was set as the rising response speed .
[표 1] [Table 1]
표 1 로부터 알 수 있는 바와 같이, 실시예의 액정셀에서는, 중합성 화합물을 0.05 중량％ 로 줄였을 경우에도, UV 조사 후의 응답 속도가 중합성 화합물 0.2 중량％ 일 때와 동일한 정도까지 향상되었다. 또한 중합성 화합물을 0.02 중량％ 로 했을 경우에도, 응답 속도는 향상되었다. 또한, 중합성 화합물을 첨가하지 않은 액정을 사용했을 경우에도, 응답 속도가 향상되었다. 실시예 5, 6 에서는, 중합성 화합물을 첨가하지 않은 액정에서 응답 속도가 크게 향상되었다. 한편, 비교예에서는 중합성 화합물을 줄인 경우나 첨가하지 않은 액정의 경우에는 응답 속도는 향상되지 않았다. As can be seen from Table 1, in the liquid crystal cell of the examples, even when the polymerizable compound was reduced to 0.05 wt%, the response speed after UV irradiation was improved to the same degree as when the polymerizable compound was 0.2 wt%. Also, when the amount of the polymerizable compound was 0.02 wt%, the response speed was improved. Furthermore, even when a liquid crystal to which no polymerizable compound was added was used, the response speed was improved. In Examples 5 and 6, the response speed was greatly improved in the liquid crystal to which the polymerizable compound was not added. On the other hand, in the comparative example, the response speed was not improved when the polymerizable compound was reduced or when the liquid crystal was not added.
산업상 이용가능성Industrial availability
본 발명의 액정 배향제를 사용하여 제작한 액정 표시 소자는, PSA 방식의 배향 방식에 있어서, 중합성 화합물을 줄인 경우에 있어서도, 응답 속도를 향상시켜 양호한 배향 상태를 얻을 수 있고, 또한 중합성 화합물을 첨가하지 않은 액정을 사용한 경우에 있어서도, PSA 방식과 동등한 특성을 얻을 수 있는 액정 표시 소자를 제공할 수 있다. 이 결과, PSA 방식의 TFT 액정 표시 소자, TN 액정 표시 소자, VA 액정 표시 소자 등에 유용하다. The liquid crystal display device manufactured by using the liquid crystal aligning agent of the present invention can improve the response speed and can obtain a favorable alignment state even when the polymerizable compound is reduced in the PSA system alignment method, It is possible to provide a liquid crystal display element capable of obtaining characteristics equivalent to those of the PSA system. As a result, it is useful for a TFT liquid crystal display element of a PSA system, a TN liquid crystal display element, a VA liquid crystal display element, and the like.
또한, 2009년 5월 1일에 출원된 일본 특허 출원 2009-112197호 및 2009년 10월 29일에 출원된 일본 특허 출원 2009-249301호의 명세서, 특허 청구의 범위, 및 요약서의 전체 내용을 여기에 인용하고, 본 발명 명세서의 개시로서 도입하는 것이다.The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-112197 filed on May 1, 2009 and Japanese Patent Application No. 2009-249301 filed on October 29, 2009 are hereby incorporated by reference herein Quot ;, the disclosure of which is incorporated herein by reference.
Claims (13)
R1Si(OR2)3 (1)
(R1 은 불소 원자로 치환되어 있어도 되는, 탄소 원자수 8 ∼ 30 의 탄화수소기이고, R2 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다)
R3Si(OR4)3 (2)
(R3 은 아크릴기 또는 메타크릴기로 치환된 알킬기, R4 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다) A liquid crystal aligning agent containing a polysiloxane obtained by polycondensing an alkoxysilane represented by the following formula (1) and an alkoxysilane containing an alkoxysilane represented by the following formula (2) is applied, and the liquid crystal is sandwiched between two fired substrates A liquid crystal display element in which UV light is irradiated to a liquid crystal cell under a voltage applied thereto.
R 1 Si (OR 2 ) 3 (1)
(Wherein R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and R 2 is an alkyl group having 1 to 5 carbon atoms)
R 3 Si (OR 4 ) 3 (2)
(R 3 is an alkyl group substituted with an acrylic group or a methacryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms)
상기 폴리실록산이 추가로, 하기 식 (3) 으로 나타내는 알콕시실란을 함유하는 알콕시실란을 중축합하여 얻어지는 폴리실록산인, 액정 표시 소자.
(R5)nSi(OR6)4-n (3)
(R5 는 수소 원자, 또는 헤테로 원자, 할로겐 원자, 아미노기, 글리시독시기, 메르캅토기, 이소시아네이트기 혹은 우레이도기로 치환되어 있어도 되는, 탄소 원자수 1 ∼ 16 의 탄화수소기이고, R6 은 탄소 원자수 1 ∼ 5 의 알킬기이며, n 은 0 ∼ 3 의 정수를 나타낸다) The method according to claim 1,
Wherein the polysiloxane is further a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (3).
(R 5 ) n Si (OR 6 ) 4-n (3)
(R 5 is a hydrogen atom or a hetero atom, a halogen atom, an amino group, a glycidyl sidok group, a mercapto group, carbon atoms, optionally substituted with an isocyanate group or a ureido group 1-16 hydrocarbon group, R 6 is a carbon An alkyl group of 1 to 5 atoms, and n represents an integer of 0 to 3)
상기 식 (1) 로 나타내는 알콕시실란이, 식 (1) 에 있어서의 R1 이 탄소 원자수가 8 ∼ 22 의 탄화수소기이고, R2 가 메틸 또는 에틸인, 액정 표시 소자.3. The method according to claim 1 or 2,
Alkoxy silane, formula (1) R 1 is a hydrocarbon group of a carbon number of 8 ~ 22, R 2 is methyl or ethyl, a liquid crystal display element according to the represented by the formula (1).
상기 식 (2) 로 나타내는 알콕시실란이, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란으로 이루어지는 군에서 선택되는 적어도 1 종인, 액정 표시 소자.3. The method according to claim 1 or 2,
Wherein the alkoxysilane represented by the formula (2) is at least one selected from the group consisting of 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Wherein the liquid crystal display element is a liquid crystal display element.
상기 식 (3) 으로 나타내는 알콕시실란의 R5 가, 탄소 원자수 1 ∼ 6 의 탄화수소기인, 액정 표시 소자.3. The method of claim 2,
Wherein R 5 of the alkoxysilane represented by the formula (3) is a hydrocarbon group having 1 to 6 carbon atoms.
상기 식 (3) 으로 나타내는 알콕시실란이, 식 (3) 에 있어서의 n 이 0 인 테트라알콕시실란인, 액정 표시 소자.3. The method of claim 2,
Wherein the alkoxysilane represented by the formula (3) is tetraalkoxysilane in which n in the formula (3) is 0.
상기 식 (1) 로 나타내는 알콕시실란이, 전체 알콕시실란 중 0.1 ∼ 30 몰％ 함유되고, 또한 상기 식 (2) 로 나타내는 알콕시실란이 전체 알콕시실란 중 3 ∼ 60 몰％ 함유되는, 액정 표시 소자.3. The method according to claim 1 or 2,
Wherein the alkoxysilane represented by the formula (1) is contained in 0.1 to 30 mol% of the total alkoxysilane and the alkoxysilane represented by the formula (2) is contained in the total alkoxysilane in an amount of 3 to 60 mol%.
상기 식 (3) 으로 나타내는 알콕시실란이, 전체 알콕시실란 중 10 ∼ 96.9 몰％ 함유되는, 액정 표시 소자.3. The method of claim 2,
Wherein the alkoxysilane represented by the formula (3) is contained in an amount of 10 to 96.9 mol% in the total alkoxysilane.
상기 폴리실록산의 함유량이 SiO2 환산 농도로 0.5 ∼ 15 질량％ 함유되는, 액정 표시 소자.3. The method according to claim 1 or 2,
Wherein the polysiloxane content is contained in an amount of 0.5 to 15 mass% in terms of SiO 2 .
R1Si(OR2)3 (1)
(R1 은 불소 원자로 치환되어 있어도 되는, 탄소 원자수 8 ∼ 30 의 탄화수소기이고, R2 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다)
R3Si(OR4)3 (2)
(R3 은 아크릴기 또는 메타크릴기로 치환된 알킬기, R4 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다) A liquid crystal aligning agent containing a polysiloxane obtained by polycondensation of an alkoxysilane represented by the following formula (1) and an alkoxysilane containing an alkoxysilane represented by the following formula (2) is applied and sandwiched between two fired substrates And irradiating UV light while applying a voltage.
R 1 Si (OR 2 ) 3 (1)
(Wherein R 1 is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and R 2 is an alkyl group having 1 to 5 carbon atoms)
R 3 Si (OR 4 ) 3 (2)
(R 3 is an alkyl group substituted with an acrylic group or a methacryl group, and R 4 is an alkyl group having 1 to 5 carbon atoms)
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| JP5966329B2 (en) * | 2011-03-30 | 2016-08-10 | Jsr株式会社 | Manufacturing method of liquid crystal display element |
| KR101883521B1 (en) * | 2011-05-27 | 2018-07-30 | 닛산 가가쿠 고교 가부시키 가이샤 | Silicon-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| KR102082525B1 (en) * | 2011-11-17 | 2020-02-27 | 닛산 가가쿠 가부시키가이샤 | Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| KR102133066B1 (en) * | 2012-07-31 | 2020-07-10 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element and method for manufacturing liquid crystal display element |
| CN104903786B (en) * | 2012-11-06 | 2017-12-08 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells |
| KR102280839B1 (en) * | 2013-10-10 | 2021-07-22 | 닛산 가가쿠 가부시키가이샤 | Composition, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
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| WO2007102513A1 (en) * | 2006-03-07 | 2007-09-13 | Nissan Chemical Industries, Ltd. | Silicon-containing liquid crystal aligning agent, liquid crystal alignment film and their production methods |
| WO2007119805A1 (en) * | 2006-04-13 | 2007-10-25 | Nissan Chemical Industries, Ltd. | Phosphoric ester containing coating fluid and antireflection coatings |
| EP2182407A4 (en) * | 2007-08-21 | 2011-03-23 | Jsr Corp | Liquid crystal aligning agent, method for producing liquid crystal alignment film, and liquid crystal display device |
| JP5311054B2 (en) * | 2009-02-19 | 2013-10-09 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, liquid crystal display element and manufacturing method thereof |
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| WO2008044644A1 (en) * | 2006-10-06 | 2008-04-17 | Nissan Chemical Industries, Ltd. | Silicon-containing liquid crystal aligning agent and liquid crystal alignment film |
| WO2009050869A1 (en) * | 2007-10-15 | 2009-04-23 | Sharp Kabushiki Kaisha | Liquid crystal display device |
Also Published As
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| CN102414605A (en) | 2012-04-11 |
| CN102414605B (en) | 2014-11-12 |
| WO2010126108A1 (en) | 2010-11-04 |
| JPWO2010126108A1 (en) | 2012-11-01 |
| KR20120023726A (en) | 2012-03-13 |
| TW201107375A (en) | 2011-03-01 |
| JP2014219684A (en) | 2014-11-20 |
| TWI483969B (en) | 2015-05-11 |
| JP5605359B2 (en) | 2014-10-15 |
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