TWI814748B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal alignment film - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal alignment film Download PDFInfo
- Publication number
- TWI814748B TWI814748B TW107137393A TW107137393A TWI814748B TW I814748 B TWI814748 B TW I814748B TW 107137393 A TW107137393 A TW 107137393A TW 107137393 A TW107137393 A TW 107137393A TW I814748 B TWI814748 B TW I814748B
- Authority
- TW
- Taiwan
- Prior art keywords
- liquid crystal
- group
- solvent
- crystal alignment
- mass
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 229
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002904 solvent Substances 0.000 claims abstract description 114
- 229920000642 polymer Polymers 0.000 claims abstract description 81
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 238000009835 boiling Methods 0.000 claims abstract description 7
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 55
- 239000011248 coating agent Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 36
- 229920000193 polymethacrylate Polymers 0.000 claims description 32
- 239000004952 Polyamide Substances 0.000 claims description 31
- 229920002647 polyamide Polymers 0.000 claims description 31
- 150000002148 esters Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 16
- 229920001721 polyimide Polymers 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical group C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002170 ethers Chemical class 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 150000001298 alcohols Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical group C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 claims description 5
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical group C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 2
- 229920000573 polyethylene Polymers 0.000 claims 2
- CAWGQUPKYLTTNX-UHFFFAOYSA-N 3,4,5,6-tetrahydro-2,7-benzodioxecine-1,8-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=CC=C12 CAWGQUPKYLTTNX-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 162
- 230000015572 biosynthetic process Effects 0.000 description 52
- 238000003786 synthesis reaction Methods 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000000243 solution Substances 0.000 description 39
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 21
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 21
- 125000003700 epoxy group Chemical group 0.000 description 21
- 239000003960 organic solvent Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 18
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 17
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 15
- 125000004093 cyano group Chemical group *C#N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 229920000106 Liquid crystal polymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000013557 residual solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000004962 Polyamide-imide Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920002312 polyamide-imide Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004988 Nematic liquid crystal Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Chemical group 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- LIYRYVJXMPWPAS-UHFFFAOYSA-N 1-methoxy-2-propoxypropane Chemical compound CCCOC(C)COC LIYRYVJXMPWPAS-UHFFFAOYSA-N 0.000 description 3
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 3
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 3
- MAMMVUWCKMOLSG-UHFFFAOYSA-N Cyclohexyl propionate Chemical compound CCC(=O)OC1CCCCC1 MAMMVUWCKMOLSG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229930016911 cinnamic acid Natural products 0.000 description 3
- 235000013985 cinnamic acid Nutrition 0.000 description 3
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YHRPNAWFNBZECU-UHFFFAOYSA-N 1-(3-chloroprop-1-enyl)-4-methoxybenzene Chemical compound COC1=CC=C(C=CCCl)C=C1 YHRPNAWFNBZECU-UHFFFAOYSA-N 0.000 description 2
- HGERSUQOJQWENV-UHFFFAOYSA-N 1-pentan-2-yloxypropan-2-ol Chemical compound CCCC(C)OCC(C)O HGERSUQOJQWENV-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- STXQJDVOMPXMMW-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)butane Chemical compound CCCCOC(C)COC STXQJDVOMPXMMW-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LVIJLEREXMVRAN-UHFFFAOYSA-N 1-bromo-4-cyclohexylbenzene Chemical compound C1=CC(Br)=CC=C1C1CCCCC1 LVIJLEREXMVRAN-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HIEDKZRCABGKJQ-UHFFFAOYSA-N 2,2-bis[2-(4-aminophenyl)ethyl]hexanedioic acid Chemical compound NC1=CC=C(C=C1)CCC(C(=O)O)(CCCC(=O)O)CCC1=CC=C(C=C1)N HIEDKZRCABGKJQ-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- FMDOSJHQLARFRC-UHFFFAOYSA-N 2-(4-iodophenyl)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound C1=CC(OC)=CC=C1C=C(C(O)=O)C1=CC=C(I)C=C1 FMDOSJHQLARFRC-UHFFFAOYSA-N 0.000 description 1
- YWKZUQJJQZPGAN-UHFFFAOYSA-N 2-(diethylamino)-n-methyl-n-(2-phenoxyethyl)acetamide;hydrochloride Chemical compound Cl.CCN(CC)CC(=O)N(C)CCOC1=CC=CC=C1 YWKZUQJJQZPGAN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- UWVHSIFAVYOQGB-UHFFFAOYSA-N 2-[[4-[1-[4-[(2-aminophenyl)methyl]phenyl]-4-butylcyclohexyl]phenyl]methyl]aniline Chemical compound C1CC(CCCC)CCC1(C=1C=CC(CC=2C(=CC=CC=2)N)=CC=1)C(C=C1)=CC=C1CC1=CC=CC=C1N UWVHSIFAVYOQGB-UHFFFAOYSA-N 0.000 description 1
- NVIYKYLBDDQYRZ-UHFFFAOYSA-N 2-butoxy-n-propan-2-ylpropanamide Chemical compound CCCCOC(C)C(=O)NC(C)C NVIYKYLBDDQYRZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- ZKCCKKDTLQTPKF-UHFFFAOYSA-N 2-ethoxy-1-methoxypropane Chemical compound CCOC(C)COC ZKCCKKDTLQTPKF-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- SSONCJTVDRSLNK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;hydrochloride Chemical compound Cl.CC(=C)C(O)=O SSONCJTVDRSLNK-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- ZADOWCXTUZWAKL-UHFFFAOYSA-N 3-(3-trimethoxysilylpropyl)oxolane-2,5-dione Chemical compound CO[Si](OC)(OC)CCCC1CC(=O)OC1=O ZADOWCXTUZWAKL-UHFFFAOYSA-N 0.000 description 1
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 1
- AXTQPVLFIFFQJW-UHFFFAOYSA-N 3-(methoxymethoxy)propanoic acid Chemical compound COCOCCC(O)=O AXTQPVLFIFFQJW-UHFFFAOYSA-N 0.000 description 1
- OOUIOHASXNAAAE-UHFFFAOYSA-N 3-[4-(6-hydroxyhexoxy)phenyl]prop-2-enoic acid Chemical compound OCCCCCCOC1=CC=C(C=CC(O)=O)C=C1 OOUIOHASXNAAAE-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 1
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical compound COCCC(O)=O YSIKHBWUBSFBRZ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- IZKVWDRZXYYFBO-UHFFFAOYSA-N 3-octadecoxybenzene-1,2-diamine Chemical compound C(CCCCCCCCCCCCCCCCC)OC=1C(=C(C=CC=1)N)N IZKVWDRZXYYFBO-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- FBRZXUWXLQSJKY-UHFFFAOYSA-N 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10-tetrone Chemical compound C1C2C3C(=O)OC(=O)C3C1C(=O)OC2=O FBRZXUWXLQSJKY-UHFFFAOYSA-N 0.000 description 1
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- YXKKMVGGPRVHIL-UHFFFAOYSA-N 4-(4-pentylcyclohexyl)benzoic acid Chemical compound C1CC(CCCCC)CCC1C1=CC=C(C(O)=O)C=C1 YXKKMVGGPRVHIL-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- WHZSPVMVRRNYSW-UHFFFAOYSA-N 4-[4-(6-bromohexoxy)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(OCCCCCCBr)C=C1 WHZSPVMVRRNYSW-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- SLHXQWDUYXSTPA-UHFFFAOYSA-N 4-[5-(4-aminophenoxy)pentoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCOC1=CC=C(N)C=C1 SLHXQWDUYXSTPA-UHFFFAOYSA-N 0.000 description 1
- WQYIKPNLSQLBPT-UHFFFAOYSA-N 4-[[(4-aminophenyl)methylamino]methyl]aniline Chemical compound C1=CC(N)=CC=C1CNCC1=CC=C(N)C=C1 WQYIKPNLSQLBPT-UHFFFAOYSA-N 0.000 description 1
- FMJSGXHHTKBGAU-WURCCDHZSA-N 4-[[(8s,9s,10r,13r,14s,17r)-6-(4-aminophenoxy)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]aniline Chemical compound C([C@H]1[C@@H]2CC[C@@H]([C@]2(CC[C@@H]1[C@@]1(C)CCC(CC11)OC=2C=CC(N)=CC=2)C)[C@H](C)CCCC(C)C)C1OC1=CC=C(N)C=C1 FMJSGXHHTKBGAU-WURCCDHZSA-N 0.000 description 1
- QPDNZLWPWXPPIO-UHFFFAOYSA-N 4-n-[4-[4-(4-aminoanilino)phenyl]phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(C=2C=CC(NC=3C=CC(N)=CC=3)=CC=2)C=C1 QPDNZLWPWXPPIO-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 1
- ITCGQBAPLXQYCA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-8-methyl-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C2=CC(C)=CC=C2C1C1CC(=O)OC1=O ITCGQBAPLXQYCA-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GAYWTJPBIQKDRC-UHFFFAOYSA-N 8-trimethoxysilyloctyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCOC(=O)C(C)=C GAYWTJPBIQKDRC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- VZHUBBUZNIULNM-UHFFFAOYSA-N Cyclohexyl butanoate Chemical compound CCCC(=O)OC1CCCCC1 VZHUBBUZNIULNM-UHFFFAOYSA-N 0.000 description 1
- YLCHTSSXNSNXSW-UHFFFAOYSA-N Cyclohexyl pentanoate Chemical compound CCCCC(=O)OC1CCCCC1 YLCHTSSXNSNXSW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 244000126211 Hericium coralloides Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GJPBUXDZJAJIMN-UHFFFAOYSA-N OCCCCCCOC#CC1=CC=CC=C1 Chemical compound OCCCCCCOC#CC1=CC=CC=C1 GJPBUXDZJAJIMN-UHFFFAOYSA-N 0.000 description 1
- ORJATBLBHVAMGX-UHFFFAOYSA-N OCCCCCCOC1=CC(=C(C=C1)O)I Chemical compound OCCCCCCOC1=CC(=C(C=C1)O)I ORJATBLBHVAMGX-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- PWKVNRUSXHSJMJ-VLAKUBLNSA-N [(8s,9s,10r,13r,14s,17r)-6-(4-aminobenzoyl)oxy-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl] 4-aminobenzoate Chemical compound C([C@H]1[C@@H]2CC[C@@H]([C@]2(CC[C@@H]1[C@@]1(C)CCC(CC11)OC(=O)C=2C=CC(N)=CC=2)C)[C@H](C)CCCC(C)C)C1OC(=O)C1=CC=C(N)C=C1 PWKVNRUSXHSJMJ-VLAKUBLNSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- JQICEOPIRHDDER-UHFFFAOYSA-N acetic acid;2-(2-methoxyethoxy)ethanol Chemical compound CC(O)=O.COCCOCCO JQICEOPIRHDDER-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 229940064734 aminobenzoate Drugs 0.000 description 1
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- GMBHLHMRHUMBHU-UHFFFAOYSA-N butan-2-one;hydrochloride Chemical compound Cl.CCC(C)=O GMBHLHMRHUMBHU-UHFFFAOYSA-N 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001788 chalcone derivatives Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- VFTGLSWXJMRZNB-UHFFFAOYSA-N isoamyl isobutyrate Chemical compound CC(C)CCOC(=O)C(C)C VFTGLSWXJMRZNB-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical group CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- WRYWBRATLBWSSG-UHFFFAOYSA-N naphthalene-1,2,4-tricarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 WRYWBRATLBWSSG-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- XSIGLRIVXRKQRA-UHFFFAOYSA-N triethoxysilylmethanethiol Chemical compound CCO[Si](CS)(OCC)OCC XSIGLRIVXRKQRA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
液晶配向劑含有聚合體成分及溶劑成分。溶劑成分中,相對於溶劑成分的總量而包含1質量%~70質量%的(A)溶劑、以及相對於溶劑成分的總量而包含0質量%~40質量%的(B)溶劑。(A)溶劑為選自由3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丁基乙酸酯、式(1)所表示的化合物及式(2)所表示的化合物所組成的群組中的至少一種化合物。(B)溶劑為1氣壓下的沸點為200℃以上且與所述(A)溶劑不同的化合物。 The liquid crystal alignment agent contains polymer components and solvent components. The solvent component contains 1 to 70 mass % of the (A) solvent based on the total amount of the solvent components, and 0 to 40 mass % of the (B) solvent based on the total amount of the solvent components. (A) The solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, a compound represented by formula (1), and formula (2) ) at least one compound in the group consisting of compounds represented by. The solvent (B) is a compound that has a boiling point at 1 atmosphere of 200° C. or higher and is different from the solvent (A).
(R1為碳數1~4的烷基。R2為碳數1~4的烷基,R3為氫原子或碳數1~4的烷基。N為0或1) (R 1 is an alkyl group with 1 to 4 carbon atoms. R 2 is an alkyl group with 1 to 4 carbon atoms. R 3 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. N is 0 or 1)
Description
本申請案基於2017年12月14日提出申請的日本專利申請編號2017-240060號,將其記載內容引用於此。 This application is based on Japanese Patent Application No. 2017-240060 filed on December 14, 2017, and the contents are incorporated herein by reference.
本發明是有關於一種液晶配向劑、液晶配向膜及液晶元件。 The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal element.
液晶元件用於以電視機或個人電腦、行動電話等顯示裝置、或相位差膜等光學補償膜、調光膜等為代表的各種用途中。 該些液晶元件具備具有使液晶分子於一定方向上配向的功能的液晶配向膜。通常,液晶配向膜是藉由如下方式而形成:將聚合體成分溶解於有機溶媒中而成的液晶配向劑塗佈於玻璃製或樹脂製的基材上並進行加熱。作為液晶配向劑的聚合體成分,就機械強度或液晶配向性、與液晶的親和性優異而言,廣泛使用聚醯胺酸或可溶性聚醯亞胺(例如參照專利文獻1、專利文獻2)。 Liquid crystal elements are used in various applications including display devices such as televisions, personal computers, and mobile phones, optical compensation films such as retardation films, and light-adjusting films. These liquid crystal elements include a liquid crystal alignment film that has the function of aligning liquid crystal molecules in a certain direction. Generally, a liquid crystal alignment film is formed by coating a liquid crystal alignment agent in which a polymer component is dissolved in an organic solvent on a glass or resin base material and heating the liquid crystal alignment film. As the polymer component of the liquid crystal alignment agent, polyamide or soluble polyimide is widely used because of its excellent mechanical strength, liquid crystal alignment, and affinity with liquid crystal (see, for example, Patent Document 1 and Patent Document 2).
[現有技術文獻] [Prior art documents]
[專利文獻] [Patent Document]
[專利文獻1]日本專利特開2017-198975號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-198975
[專利文獻2]日本專利特開2016-206645號公報 [Patent Document 2] Japanese Patent Application Publication No. 2016-206645
於將液晶配向劑塗佈於基材上時發生收縮、或液晶配向劑並不均勻而由此於配向膜表面產生塗佈不均(面內不均)的情況下,擔心導致製品良率下降、或所獲得的液晶元件的液晶配向性不充分。所述塗佈不均例如在為了提高液晶配向膜對液晶的配向性、或提高液晶配向膜與基材的密接性而使液晶配向膜的膜厚較厚(例如為0.3μm以上)的情況下容易產生。即,若加厚液晶配向膜的膜厚,則於膜形成時的加熱步驟中無法充分去除溶劑,容易因配向膜中的殘存溶劑的影響而於配向膜表面產生塗佈不均。該情況下,擔心所獲得的液晶元件的液晶配向性不充分。 If the liquid crystal alignment agent shrinks when it is coated on the substrate, or if the liquid crystal alignment agent is not uniform and thus causes uneven coating (in-plane unevenness) on the surface of the alignment film, there is a concern that the product yield will decrease. , or the liquid crystal alignment property of the obtained liquid crystal element is insufficient. The coating unevenness occurs, for example, when the film thickness of the liquid crystal alignment film is thicker (for example, 0.3 μm or more) in order to improve the alignment of the liquid crystal alignment film to the liquid crystal or to improve the adhesion between the liquid crystal alignment film and the substrate. Easy to produce. That is, if the film thickness of the liquid crystal alignment film is increased, the solvent cannot be sufficiently removed in the heating step during film formation, and uneven coating on the surface of the alignment film is likely to occur due to the influence of the residual solvent in the alignment film. In this case, there is a concern that the liquid crystal alignment properties of the obtained liquid crystal element are insufficient.
另外,例如於輥對輥方式中,有時於液晶元件的製造過程中,以輥狀層疊形成有配向膜的基材來進行暫時保管。若配向膜中殘存的溶劑量多,則容易發生配向膜中的聚合體成分或殘存溶劑移至基材側的背移。另外,於發生向基材側的背移的情況下,擔心液晶配向膜容易自基材剝離,或所獲得的液晶元件的液晶配向性惡化。 In addition, for example, in the roll-to-roll method, a base material on which an alignment film is laminated in a roll shape may be temporarily stored during the manufacturing process of a liquid crystal element. If there is a large amount of solvent remaining in the alignment film, back-migration of the polymer component or the remaining solvent in the alignment film to the substrate side is likely to occur. In addition, when the back shift to the base material side occurs, the liquid crystal alignment film may be easily peeled off from the base material, or the liquid crystal alignment properties of the obtained liquid crystal element may be deteriorated.
本揭示是鑒於所述課題而成,其目的之一在於提供一種對基材的塗佈性良好且可充分減少配向膜中的殘存溶劑的液晶配向劑。 The present disclosure is made in view of the above problems, and one of its purposes is to provide a liquid crystal alignment agent that has good coating properties on a substrate and can sufficiently reduce the residual solvent in the alignment film.
本發明者為解決所述課題進行努力研究,發現藉由含有沸點較低的特定溶劑作為液晶配向劑的溶劑成分而能夠解決所述課題。具體而言,本揭示為解決所述課題而採用了以下手段。 The inventors of the present invention have conducted diligent research to solve the above problems and found that the above problems can be solved by containing a specific solvent with a low boiling point as a solvent component of the liquid crystal alignment agent. Specifically, this disclosure adopts the following means to solve the above-mentioned problems.
<1>一種液晶配向劑,其含有聚合體成分及溶劑成分,所述溶劑成分中,相對於所述溶劑成分的總量而包含1質量%~70質量%的下述(A)溶劑、以及相對於所述溶劑成分的總量而包含0質量%~40質量%的下述(B)溶劑。 <1> A liquid crystal alignment agent containing a polymer component and a solvent component, wherein the solvent component contains 1 to 70 mass % of the following (A) solvent relative to the total amount of the solvent component, and The following (B) solvent is contained in 0 mass % to 40 mass % with respect to the total amount of the solvent component.
(A)溶劑為選自由3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丁基乙酸酯、下述式(1)所表示的化合物及下述式(2)所表示的化合物所組成的群組中的至少一種化合物。 (A) The solvent is a compound selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, the following formula (1), and the following at least one compound in the group consisting of compounds represented by formula (2).
(B)溶劑為1氣壓下的沸點為200℃以上且與所述(A)溶劑不同的化合物。 The solvent (B) is a compound that has a boiling point at 1 atmosphere of 200° C. or higher and is different from the solvent (A).
(式(1)中,R1為碳數1~4的烷基) (In formula (1), R 1 is an alkyl group having 1 to 4 carbon atoms)
(式(2)中,R2為碳數1~4的烷基,R3為碳數1~4的烷基。n為0或1)。 (In formula (2), R 2 is an alkyl group having 1 to 4 carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms. n is 0 or 1).
<2>一種液晶配向膜,其是使用所述<1>的液晶配向劑而 形成。 <2>A liquid crystal alignment film produced by using the liquid crystal alignment agent of <1> form.
<3>一種液晶元件,其包括所述<2>的液晶配向膜。 <3> A liquid crystal element including the liquid crystal alignment film of <2>.
<4>一種液晶配向膜的製造方法,其將所述<1>的液晶配向劑塗佈於基材上,於150℃以下進行加熱而形成塗膜。 <4> A method for manufacturing a liquid crystal alignment film, which includes coating the liquid crystal alignment agent of <1> on a substrate and heating it at 150° C. or lower to form a coating film.
本揭示的液晶配向劑對基材的塗佈性良好,而且於配向膜形成時的加熱時可將液晶配向劑中的溶劑充分去除,可充分減少配向膜中的殘存溶劑。藉此,可抑制製品良率的下降,另外可獲得高品質的液晶元件。 The liquid crystal alignment agent of the present disclosure has good coating properties on the substrate, and can fully remove the solvent in the liquid crystal alignment agent during heating during the formation of the alignment film, thereby fully reducing the residual solvent in the alignment film. Thereby, a decrease in product yield can be suppressed, and a high-quality liquid crystal element can be obtained.
以下,對本揭示的液晶配向劑中所含的各成分、以及視需要而任意調配的其他成分進行說明。本揭示的液晶配向劑含有聚合體成分及溶劑成分。該液晶配向劑為聚合體成分溶解於溶劑成分中而成的液狀的聚合體組成物。 Each component contained in the liquid crystal alignment agent of the present disclosure and other components optionally blended as necessary will be described below. The liquid crystal alignment agent of the present disclosure contains polymer components and solvent components. The liquid crystal alignment agent is a liquid polymer composition in which a polymer component is dissolved in a solvent component.
《聚合體成分》 "Polymer Composition"
關於液晶配向劑中所含有的聚合體成分,其主骨架並無特別限定,例如可列舉:聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚有機矽氧烷、聚酯、聚醯胺、聚醯胺醯亞胺、聚苯并噁唑前驅物、聚苯并噁唑、纖維素衍生物、聚縮醛、苯乙烯-馬來醯亞胺系共聚物、聚(甲基)丙烯酸酯等主骨架。再者,(甲基)丙烯酸酯是指包含丙烯酸酯及甲基丙烯酸酯。就充分確保液晶元件的性能等觀點而言,所述中,作為聚合體成分,較佳為選自由聚醯胺酸、聚醯亞胺、 聚醯胺酸酯、聚醯胺醯亞胺、聚(甲基)丙烯酸酯及聚有機矽氧烷所組成的群組中的至少一種聚合體(以下亦稱為「(P)聚合體」),就可使膜形成時的加熱更低溫的方面而言,更佳為選自由聚(甲基)丙烯酸酯及聚有機矽氧烷所組成的群組中的至少一種。 Regarding the polymer component contained in the liquid crystal alignment agent, the main skeleton is not particularly limited. Examples thereof include: polyamide, polyamide ester, polyimide, polyorganosiloxane, polyester, polyamide Amide, polyamide imine, polybenzoxazole precursor, polybenzoxazole, cellulose derivatives, polyacetal, styrene-maleimide copolymer, poly(methyl) Main skeleton such as acrylate. In addition, (meth)acrylate means including acrylate and methacrylate. From the viewpoint of ensuring sufficient performance of the liquid crystal element, the polymer component is preferably selected from the group consisting of polyamide acid, polyimide, At least one polymer from the group consisting of polyamide ester, polyamide imide, poly(meth)acrylate and polyorganosiloxane (hereinafter also referred to as "(P) polymer") , in terms of enabling lower heating temperatures during film formation, it is more preferred to be at least one selected from the group consisting of poly(meth)acrylate and polyorganosiloxane.
(含感光性基的聚合物) (Polymer containing photosensitive groups)
作為(P)聚合體,可將液晶配向劑中含有的聚合體中的一部分或全部設為具有感光性結構的聚合體(以下亦稱為「含感光性基的聚合物」)。作為感光性結構,只要為感應光而引起反應的結構或官能基即可,可列舉光配向性基及聚合性基。 As the (P) polymer, some or all of the polymers contained in the liquid crystal alignment agent may be polymers having a photosensitive structure (hereinafter also referred to as "photosensitive group-containing polymers"). The photosensitive structure may be any structure or functional group that reacts by sensing light, and examples thereof include photoalignment groups and polymerizable groups.
於(P)聚合體具有光配向性基的情況下,能夠藉由光配向法來對使用液晶配向劑所製作的塗膜賦予液晶配向性。藉此,就可獲得應用光配向法所帶來的效果的方面而言較佳,所述效果具體而言為抑制因產生塵埃或靜電等而產生顯示不良或良率降低的效果、可對基板上所形成的有機薄膜均勻地賦予液晶配向能力的效果。另外,於(P)聚合體具有聚合性基的情況下,就可提高液晶配向膜對基板的密接性、可進一步抑制應用輥對輥方式製造液晶元件時良率的降低的方面而言較佳。 When the (P) polymer has a photo-alignment group, liquid crystal alignment can be imparted to a coating film produced using a liquid crystal alignment agent by a photo-alignment method. This is preferable in that the effects brought about by the application of the photoalignment method can be obtained. Specifically, the effect is the effect of suppressing display defects or yield reduction due to the generation of dust, static electricity, etc., and can cause damage to the substrate. The organic thin film formed on the liquid crystal evenly imparts the effect of alignment ability to the liquid crystal. In addition, when the polymer (P) has a polymerizable group, it is preferable in terms of improving the adhesion of the liquid crystal alignment film to the substrate and further suppressing the decrease in yield when the roll-to-roll method is used to manufacture the liquid crystal element. .
光配向性基是藉由光照射所引起的光異構化反應、光二聚化反應、光分解反應、光弗里斯重排反應等而對膜賦予各向異性的官能基。作為其具體例,可列舉:含有偶氮苯或其衍生物作為基本骨架的偶氮苯結構、含有肉桂酸或其衍生物作為基本骨架的肉桂酸結構、含有查爾酮或其衍生物作為基本骨架的查爾酮結 構、含有二苯甲酮或其衍生物作為基本骨架的二苯甲酮結構、含有香豆素或其衍生物作為基本骨架的香豆素衍生物、含有二苯乙烯或其衍生物作為基本骨架的二苯乙烯結構、包含二苯基乙炔或其衍生物作為基本骨架的二苯基乙炔結構、包含苯甲酸苯酯或其衍生物作為基本骨架的苯甲酸苯酯結構、含有環丁烷或其衍生物作為基本骨架的環丁烷結構等。該些中,就對光的反應性高的方面而言,(P)聚合體所具有的光配向性基特佳為具有肉桂酸結構的基。 The photoalignment group is a functional group that imparts anisotropy to the film through photoisomerization reaction, photodimerization reaction, photodecomposition reaction, photo-Friis rearrangement reaction, etc. caused by light irradiation. Specific examples thereof include: an azobenzene structure containing azobenzene or a derivative thereof as a basic skeleton; a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton; and a structure containing chalcone or a derivative thereof as a basic skeleton. Skeleton of Chalcone Knot Structure, benzophenone structure containing benzophenone or its derivatives as the basic skeleton, coumarin derivatives containing coumarin or its derivatives as the basic skeleton, containing stilbene or its derivatives as the basic skeleton The stilbene structure, the diphenylacetylene structure containing diphenylacetylene or its derivatives as the basic skeleton, the phenyl benzoate structure containing phenyl benzoate or its derivatives as the basic skeleton, the phenyl benzoate structure containing cyclobutane or its derivatives Derivatives have a cyclobutane structure as the basic skeleton, etc. Among these, the photo-alignment group contained in the polymer (P) is particularly preferably a group having a cinnamic acid structure in view of high reactivity to light.
作為具有肉桂酸結構的基,具體而言較佳為具有下述式(4)所表示的部分結構。 As a group having a cinnamic acid structure, it is specifically preferred to have a partial structure represented by the following formula (4).
(式(4)中,R31及R32分別獨立地為氫原子、鹵素原子、碳數1~3的烷基、碳數1~3的烷氧基或氰基。R33為鹵素原子、碳數1~3的烷基、碳數1~3的烷氧基或氰基。a1為0~4的整數。其中,在a1為2以上的情況下,多個R33可相同亦可不同。「*」表示鍵結鍵) (In formula (4), R 31 and R 32 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R 33 is a halogen atom, An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. a1 is an integer from 0 to 4. When a1 is 2 or more, a plurality of R 33 may be the same or different. . "*" indicates bonding key)
作為所述式(4)所表示的基,可列舉:將肉桂酸所具有的羧基的氫原子去除而獲得的一價基、或於該一價基所具有的苯環中導入取代基而成的基(以下亦將該些稱為「順肉桂酸酯 基」)、或肉桂酸所具有的羧基經酯化且於苯環上鍵結有二價有機基而成的一價基、或者於該一價基所具有的苯環上導入有取代基的基(以下亦將該些稱為「逆肉桂酸酯基」)等。順肉桂酸酯基例如由下述式(cn-1)所表示。逆肉桂酸酯基例如由下述式(cn-2)所表示。 Examples of the group represented by the formula (4) include a monovalent group obtained by removing the hydrogen atom of the carboxyl group of cinnamic acid, or a monovalent group obtained by introducing a substituent into the benzene ring of the monovalent group. (hereinafter also referred to as "ciscinnamate") group"), or a monovalent group in which the carboxyl group of cinnamic acid is esterified and a divalent organic group is bonded to the benzene ring, or a substituent is introduced into the benzene ring of the monovalent group. groups (hereinafter these are also referred to as "reverse cinnamate groups"), etc. The ciscinnamate group is represented by the following formula (cn-1), for example. The reverse cinnamate group is represented by the following formula (cn-2), for example.
(式(cn-1)中,R34為氫原子、鹵素原子、碳數1~3的烷基、碳數1~3的烷氧基或氰基。R35為伸苯基、伸聯苯基、聯伸三苯基或伸環己基、或者伸苯基、伸聯苯基、聯伸三苯基或伸環己基所具有的氫原子的至少一部分經鹵素原子、氰基、碳數1~10的烷基、碳數1~10的烷氧基及碳數1~10的烷氧基中的任一者取代而成的基。A11為單鍵、氧原子、硫原子、碳數1~3的烷二基、-CH=CH-、-NH-、*2-COO-、*2-OCO-、*2-NH-CO-、*2-CO-NH-、*2-CH2-O-或*2-O-CH2-(「*2」表示與R35的鍵結鍵)。b1為0或1。「*」表示鍵結鍵。 (In formula (cn-1), R 34 is a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, or a cyano group. R 35 is a phenyl group or a biphenyl group. group, biphenylene group or cyclohexylene group, or at least a part of the hydrogen atoms of the phenyl group, biphenylene group, biphenylene group or cyclohexylene group is passed through a halogen atom, a cyano group, a carbon number of 1 to 10 A group substituted by any one of an alkyl group, an alkoxy group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. A 11 is a single bond, an oxygen atom, a sulfur atom, or an alkoxy group having 1 to 3 carbon atoms. Alkanediyl, -CH=CH-, -NH-, * 2 -COO-, * 2 -OCO-, * 2 -NH-CO-, * 2 -CO-NH-, * 2 -CH 2 -O - or * 2 -O-CH 2 - ("* 2 " represents the bond with R 35 ). b1 is 0 or 1. "*" represents the bond.
式(cn-2)中,R36為碳數1~3的烷基。A12為氧原子、*2-COO-、*2-OCO-、*2-NH-CO-或*2-CO-NH-(「*2」表示與R37的鍵結鍵)。R37為碳數1~6的烷二基。c1為0或1。「*」表示鍵結鍵。 In formula (cn-2), R 36 is an alkyl group having 1 to 3 carbon atoms. A 12 is an oxygen atom, * 2 -COO-, * 2 -OCO-, * 2 -NH-CO- or * 2 -CO-NH- ("* 2 " represents a bond with R 37 ). R 37 is an alkanediyl group having 1 to 6 carbon atoms. c1 is 0 or 1. "*" indicates a bonded key.
R31、R32、R33及a1與所述式(4)為相同含義) R 31 , R 32 , R 33 and a1 have the same meaning as the formula (4))
作為聚合性基,較佳為感應光而引起交聯反應的官能基,例如可列舉:(甲基)丙烯醯基、乙烯基(包含乙烯基苯基及乙烯基氧基(CH2=CH-O-)等含乙烯基結構的基)、亞乙烯基、馬來醯亞胺基、烯丙基、乙炔基、烯丙氧基、環氧基等。該些中,就對光的反應性高的方面而言,較佳為(甲基)丙烯醯基或乙烯基。再者,(甲基)丙烯醯基為包含丙烯醯基及甲基丙烯醯基的含義,環氧基為包含氧雜環丙基及氧雜環丁基的含義。 The polymerizable group is preferably a functional group that induces a crosslinking reaction in response to light. Examples thereof include: (meth)acrylyl group, vinyl group (including vinylphenyl group and vinyloxy group (CH 2 =CH- O-) and other vinyl-containing groups), vinylene, maleimide, allyl, ethynyl, allyloxy, epoxy, etc. Among these, a (meth)acryl group or a vinyl group is preferable in terms of high reactivity to light. In addition, the (meth)acrylyl group has a meaning including an acrylyl group and a methacrylyl group, and the epoxy group has a meaning including an oxetanyl group and an oxetanyl group.
該些中,(P)聚合體具有的感光性結構較佳為選自由肉桂酸結構、偶氮苯結構、查爾酮結構、二苯乙烯結構、二苯基乙炔結構、(甲基)丙烯醯基、乙烯基及苯甲酸苯酯結構所組成的群組中的至少一種,特佳為肉桂酸結構或(甲基)丙烯醯基。於(P)聚合體具有感光性結構的情況下,相對於構成(P)聚合體的單量體單元的總量,感光性結構的含有比例較佳為10莫耳%以上,更佳為20莫耳%以上。 Among these, the (P) polymer preferably has a photosensitive structure selected from a cinnamic acid structure, an azobenzene structure, a chalcone structure, a stilbene structure, a diphenylacetylene structure, and (meth)acrylamide. At least one of the group consisting of a vinyl group, a vinyl group and a phenyl benzoate structure, particularly preferably a cinnamic acid structure or a (meth)acrylyl group. When the polymer (P) has a photosensitive structure, the content ratio of the photosensitive structure relative to the total amount of monomer units constituting the polymer (P) is preferably 10 mol% or more, more preferably 20 More than mol%.
於使用具有光配向性基的聚合體作為(P)聚合體的情況下,可將液晶配向劑的聚合體成分的全部設為具有光配向性基的聚合體,亦可將其一部分設為具有光配向性基的聚合體。於將聚合體成分的一部分設為具有光配向性基的聚合體的情況下,該聚合體的使用比例相對於液晶配向劑的製備中使用的聚合體成分的總量而言,較佳為設為1質量%~80質量%,更佳為設為2質量%~70質量%。 When using a polymer having a photo-alignment group as the (P) polymer, all of the polymer components of the liquid crystal alignment agent may be a polymer having a photo-alignment group, or a part thereof may be a polymer having a photo-alignment group. Polymer of photoalignment groups. When a part of the polymer component is a polymer having a photo-alignment group, the usage ratio of the polymer is preferably set to It is 1 mass % - 80 mass %, and it is more preferable that it is 2 mass % - 70 mass %.
另外,於使用具有聚合性基的聚合體作為(P)聚合體的情況 下,該聚合體的使用比例相對於液晶配向劑的製備中使用的聚合體成分的總量而言,較佳為設為1質量%~80質量%,更佳為設為2質量%~70質量%。再者,含感光性基的聚合物可單獨使用一種,亦可混合使用兩種以上。 In addition, when using a polymer having a polymerizable group as the (P) polymer Below, the usage ratio of the polymer relative to the total amount of polymer components used in the preparation of the liquid crystal alignment agent is preferably set to 1 mass % to 80 mass %, and more preferably set to 2 mass % to 70 mass %. Mass %. In addition, one type of photosensitive group-containing polymer may be used alone, or two or more types may be mixed and used.
(液晶性聚合物) (liquid crystalline polymer)
作為(P)聚合體,可將液晶配向劑中含有的聚合體中的一部分或全部設為在側鏈具有於規定的溫度範圍顯現液晶性的部分結構(以下亦稱為「液晶性結構」)的聚合體(以下亦稱為「液晶性聚合物」)。藉由使液晶配向劑中含有液晶性聚合物,就可進一步提高液晶元件的初期的電壓保持率的方面而言較佳。 As the (P) polymer, some or all of the polymers contained in the liquid crystal alignment agent may have a partial structure in the side chain that exhibits liquid crystallinity in a predetermined temperature range (hereinafter also referred to as "liquid crystalline structure") polymer (hereinafter also referred to as "liquid crystalline polymer"). By containing a liquid crystalline polymer in a liquid crystal alignment agent, it is preferable in terms of further improving the initial voltage retention rate of the liquid crystal element.
作為液晶性結構,可列舉具有剛直部位(液晶原結構)的結構,作為其具體例,可列舉具有下述式(5)所表示的基的結構等。 Examples of the liquid crystal structure include a structure having a rigid portion (mesogen structure). Specific examples thereof include a structure having a group represented by the following formula (5), and the like.
(式(5)中,Ar1及Ar2分別獨立地為經取代或未經取代的伸苯基、或者經取代或未經取代的伸環己基,X21為單鍵、-CO-、-COO-、-C=C-、-C≡C-、-N=N-或-CONR41-(R41為氫原子或一價有機基)。r為1~3的整數。當r為2或3時,Ar2、X21各自獨立地具有所述定義。「*」表示鍵結鍵) (In formula (5), Ar 1 and Ar 2 are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexylene group, and X 21 is a single bond, -CO-, - COO-, -C=C-, -C≡C-, -N=N- or -CONR 41 -(R 41 is a hydrogen atom or a monovalent organic group). r is an integer from 1 to 3. When r is 2 or 3, Ar 2 and X 21 independently have the above definitions. "*" indicates a bond)
所述式(5)中,X21較佳為單鍵或-COO-。作為R41的一價有機基,例如可列舉碳數1~6的烷基、保護基等。作為保護 基的具體例,例如可列舉:第三丁氧基羰基、苄氧基羰基、1,1-二甲基-2-鹵乙基氧基羰基、烯丙基氧基羰基等,較佳為第三丁氧基羰基。Ar1及Ar2的環部分的取代基較佳為碳數1~5的烷基或鹵素原子,更佳為甲基或氟原子。 In the formula (5), X 21 is preferably a single bond or -COO-. Examples of the monovalent organic group of R 41 include an alkyl group having 1 to 6 carbon atoms, a protecting group, and the like. Specific examples of the protecting group include: tert-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, allyloxycarbonyl group, etc., and preferred ones are It is the third butoxycarbonyl group. The substituent of the ring part of Ar 1 and Ar 2 is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom, more preferably a methyl group or a fluorine atom.
作為所述式(5)所表示的部分結構的較佳具體例,例如可列舉:4,4'-伸聯苯基、4,4'-雙伸環己基、對伸聯三苯基、及下述式(5-1)~式(5-4)分別所表示的基、以及於該些基的環部分具有甲基或氟原子的基等。再者,所述式(5)及下述式(5-1)~式(5-4)中的「*」亦可鍵結於氫原子上。 Preferable specific examples of the partial structure represented by the formula (5) include: 4,4'-biphenyl group, 4,4'-biscyclohexyl group, p-triphenyl group, and Groups represented by the following formulas (5-1) to (5-4) respectively, and groups having a methyl group or a fluorine atom in the ring part of these groups, etc. Furthermore, "*" in the formula (5) and the following formulas (5-1) to (5-4) may also be bonded to a hydrogen atom.
(式中,「*」表示鍵結鍵) (In the formula, "*" means bonded key)
於(P)聚合體為液晶性聚合物的情況下,作為該液晶性聚合物,可較佳地使用在側鏈具有感光性基的聚合體。具體而言,液晶性聚合物較佳為在側鏈具有由下述式(F-1)~式(F-7)分別所表示的基。 When the polymer (P) is a liquid crystal polymer, a polymer having a photosensitive group in a side chain can be suitably used as the liquid crystal polymer. Specifically, the liquid crystalline polymer preferably has a group represented by the following formula (F-1) to formula (F-7) in a side chain.
(式(F-1)~式(F-7)中,A1及B1及D1分別獨立地為單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-或-NH-CO-。B2為單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-或伸苯基。Y1為苯環、萘環、聯苯環、呋喃環、吡咯環、或具有碳數5~8的環狀烴基的一價環狀基,鍵結於環的至少一個氫原子可經鹵素原子、硝基、氰基、-C=C(CN)2、-C=CH-CN、碳數1~3的烷基、或碳數1~3的烷氧基取代。Y2為苯環、萘環、聯苯環、呋喃環、吡咯環、或具有碳數5~8的環狀烴基的二價環狀基,鍵結於環的至少一個氫原子可經鹵素原子、硝基、氰基、-C=C(CN)2、-C=CH-CN、碳數1~3的烷基、或碳數1~3的烷氧基取代。Y3為具有苯環、萘環或聯苯環的一價環狀基,鍵結於環的至少一個氫原子可經鹵素原子、硝基、氰基、-C=C(CN)2、-C=CH-CN、碳數1~3的烷基、或 碳數1~3的烷氧基取代。X1為單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-或伸苯基。R11為氫原子或碳數1~6的烷基。R12為氫原子、鹵素原子、硝基、氰基、-C=C(CN)2、-C=CH-CN、碳數1~6的烷基、或碳數1~6的烷氧基。R13為氫原子或碳數1~3的烷基。k為1~12的整數,m及j分別獨立地為1~3的整數,g為1~12的整數。再者,鍵結於式(F-6)中的苯環的至少一個氫原子可經鹵素原子、硝基、氰基、-C=C(CN)2、-C=CH-CN、碳數1~3的烷基、或碳數1~3的烷氧基取代。「*1」表示鍵結於主鏈的鍵結鍵) (In formula (F-1) ~ formula (F-7), A 1 , B 1 and D 1 are independently single bonds, -O-, -CH 2 -, -COO-, -OCO-, -CONH - or -NH-CO-. B 2 is a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C- or phenyl group. Y 1 is a benzene ring, Naphthalene ring, biphenyl ring, furan ring, pyrrole ring, or a monovalent cyclic group having a cyclic hydrocarbon group with 5 to 8 carbon atoms. At least one hydrogen atom bonded to the ring can be via a halogen atom, nitro group, or cyano group. , -C=C(CN) 2 , -C=CH-CN, alkyl group with 1 to 3 carbon atoms, or alkoxy group with 1 to 3 carbon atoms substituted. Y 2 is benzene ring, naphthalene ring, biphenyl ring , furan ring, pyrrole ring, or a divalent cyclic group having a cyclic hydrocarbon group with 5 to 8 carbon atoms. At least one hydrogen atom bonded to the ring can be via a halogen atom, nitro group, cyano group, -C=C( CN) 2 , -C=CH-CN, alkyl group with 1 to 3 carbon atoms, or alkoxy group with 1 to 3 carbon atoms substituted. Y 3 is a monovalent ring with a benzene ring, naphthalene ring or biphenyl ring group, at least one hydrogen atom bonded to the ring can be via a halogen atom, nitro group, cyano group, -C=C(CN) 2 , -C=CH-CN, an alkyl group with 1 to 3 carbon atoms, or an alkyl group with a carbon number of 1 to 3. 1~3 alkoxy substitution. X 1 is a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C- or phenyl group. R 11 is a hydrogen atom Or an alkyl group with 1 to 6 carbon atoms. R 12 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, -C=C(CN) 2 , -C=CH-CN, an alkyl group with 1 to 6 carbon atoms, Or an alkoxy group with 1 to 6 carbon atoms. R 13 is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms. k is an integer from 1 to 12, m and j are each independently an integer from 1 to 3, and g is 1 An integer of ~12. Furthermore, at least one hydrogen atom bonded to the benzene ring in formula (F-6) can be passed through a halogen atom, nitro group, cyano group, -C=C(CN) 2 , -C=CH -CN, alkyl group with 1 to 3 carbon atoms, or alkoxy group with 1 to 3 carbon atoms substituted. "*1" indicates a bond bonded to the main chain)
於(P)聚合體的一部分或全部為液晶性聚合物的情況下,該液晶性聚合物較佳為選自由聚(甲基)丙烯酸酯、聚醯胺酸、聚醯亞胺及聚醯胺酸酯所組成的群組中的至少一種,特佳為聚(甲基)丙烯酸酯。於使用液晶性聚合物作為(P)聚合體的情況下,該液晶性聚合物的使用比例可以於液晶配向劑的製備中使用的聚合體成分的總量中為100質量%以下的範圍而適當設定。再者,作為液晶性聚合物,可單獨使用一種,亦可將兩種以上混合使用。 When part or all of the polymer (P) is a liquid crystal polymer, the liquid crystal polymer is preferably selected from the group consisting of poly(meth)acrylate, polyamide, polyimide, and polyamide. At least one member from the group consisting of acid esters, preferably poly(meth)acrylate. When a liquid crystalline polymer is used as the (P) polymer, the usage ratio of the liquid crystalline polymer may be appropriately in the range of 100% by mass or less of the total amount of polymer components used in the preparation of the liquid crystal alignment agent. settings. In addition, as the liquid crystal polymer, one type may be used alone, or two or more types may be mixed and used.
(聚合體的合成) (synthesis of polymers)
(P)聚合體可藉由根據其主骨架適當組合有機化學的通用方法而獲得。以下,分別對聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚醯胺醯亞胺、聚(甲基)丙烯酸酯及聚有機矽氧烷進行說明。 (P) The polymer can be obtained by appropriately combining general methods of organic chemistry according to its main skeleton. Hereinafter, polyamide acid, polyamide imide, polyamide ester, polyamide imide, poly(meth)acrylate, and polyorganosiloxane will be described respectively.
[聚醯胺酸] [Polyamide]
聚醯胺酸可藉由使四羧酸二酐與二胺化合物反應而獲得。 Polyamic acid can be obtained by reacting tetracarboxylic dianhydride and a diamine compound.
(四羧酸二酐) (tetracarboxylic dianhydride)
作為聚醯胺酸的合成中使用的四羧酸二酐,例如可列舉脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作為該些的具體例,脂肪族四羧酸二酐例如可列舉1,2,3,4-丁烷四羧酸二酐等;脂環式四羧酸二酐例如可列舉:1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫呋喃-3-基)-8-甲基-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺環-3'-(四氫呋喃-2',5'-二酮)、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、4,9-二氧雜三環[5.3.1.02,6]十一烷-3,5,8,10-四酮、環戊烷四羧酸二酐、環己烷四羧酸二酐等;芳香族四羧酸二酐例如可列舉均苯四甲酸二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、乙二醇雙偏苯三甲酸酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、4,4'-羧基二鄰苯二甲酸酐等,除此以外,亦可使用日本專利特開2010-97188號公報中記載的四羧酸二酐。再者,所述四羧酸二酐可單獨使用一種或者組合使用兩種以上。 Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and the like. Specific examples of these include, for example, aliphatic tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc.; examples of alicyclic tetracarboxylic dianhydride include: 1,2, 3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3- Oxabicyclo[3.2.1]octane-2,4-dione-6-spirocyclo-3'-(tetrahydrofuran-2',5'-dione), 2,4,6,8-tetracarboxybicyclo [3.3.0]Octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 2,6 ]Undecane-3,5,8,10-tetraone , cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; examples of aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) Diphthalic anhydride, ethylene glycol bis-trimellitic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carboxydiphthalic anhydride, etc. In addition, the tetracarboxylic dianhydride described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used. In addition, the tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.
(二胺化合物) (diamine compound)
作為聚醯胺酸的合成中使用的二胺化合物,例如可列舉:脂肪族二胺、脂環式二胺、芳香族二胺、二胺基有機矽氧烷等。作為該些二胺的具體例,脂肪族二胺例如可列舉:間苯二甲胺、1,3-
丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等;脂環式二胺例如可列舉:1,4-二胺基環己烷、4,4'-亞甲基雙(環己基胺)等;芳香族二胺例如可列舉:十二烷氧基二胺基苯、十八烷氧基二胺基苯、膽甾烷氧基二胺基苯、二胺基苯甲酸膽甾烷基酯、二胺基苯甲酸膽甾烯基酯、3,6-雙(4-胺基苯甲醯基氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、3,5-二胺基苯甲酸=5ξ-膽甾烷-3-基、下述式(E-1)
(式(E-1)中,XI及XII分別獨立地為單鍵、-O-、*-COO-或*-OCO-(其中「*」表示與XI的鍵結鍵),RI為碳數1~3的烷二基,RII為單鍵或碳數1~3的烷二基,a為0或1,b為0~2的整數,c為1~20的整數,d為0或1。其中,a及b不會同時成為0) (In formula (E-1), X I and X II are independently single bonds, -O-, *-COO- or *-OCO- (where "*" represents the bond with X I ), R I is an alkanediyl group with 1 to 3 carbon atoms, R II is a single bond or an alkanediyl group with 1 to 3 carbon atoms, a is 0 or 1, b is an integer from 0 to 2, and c is an integer from 1 to 20. d is 0 or 1. Among them, a and b will not become 0 at the same time)
所表示的化合物、具有肉桂酸結構的二胺、具有液晶性結構的二胺等含配向性基的二胺;對苯二胺、4,4'-二胺基二苯基甲烷、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-二胺基偶氮苯、1,5-雙(4-胺基苯氧基)戊烷、雙[2-(4-胺基苯基)乙基]己二酸、N,N-雙(4-胺基苯基)甲基胺、2,6-二胺基吡啶、1,4-雙(4-胺基苯基)-哌嗪、N,N'-雙(4-胺基苯基)-聯苯胺、2,2'- 二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4'-(伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4,4'-雙(4-胺基苯氧基)聯苯;二胺基有機矽氧烷例如可列舉1,3-雙(3-胺基丙基)-四甲基二矽氧烷等,除此以外,亦可使用日本專利特開2010-97188號公報中記載的二胺。 The represented compounds, diamines having a cinnamic acid structure, diamines having a liquid crystal structure and other diamines containing an alignment group; p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-amine phenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, bis[2-(4- Aminophenyl)ethyl]adipic acid, N,N-bis(4-aminophenyl)methylamine, 2,6-diaminopyridine, 1,4-bis(4-aminophenyl) )-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl Ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylene) Diisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl; diaminoorganosiloxane For example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane can be used. In addition, the diamine described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used.
(聚醯胺酸的合成) (Synthesis of polyamide)
聚醯胺酸可藉由使如所述般的四羧酸二酐與二胺化合物視需要與分子量調整劑一併進行反應而獲得。被供於聚醯胺酸的合成反應的四羧酸二酐與二胺化合物的使用比例較佳為相對於二胺化合物的胺基1當量而四羧酸二酐的酸酐基成為0.2當量~2當量的比例。作為分子量調整劑,例如可列舉:馬來酸酐、鄰苯二甲酸酐、衣康酸酐等酸單酐;苯胺、環己基胺、正丁基胺等單胺化合物;異氰酸苯酯、異氰酸萘酯等單異氰酸酯化合物等。相對於所使用的四羧酸二酐及二胺化合物的合計100質量份,分子量調整劑的使用比例較佳為設為20質量份以下。 Polyamic acid can be obtained by reacting the above-described tetracarboxylic dianhydride and a diamine compound together with a molecular weight adjuster if necessary. The usage ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amine group of the diamine compound. Equivalent ratio. Examples of the molecular weight adjuster include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, isocyanate Naphthyl acid naphthyl ester and other monoisocyanate compounds, etc. The usage ratio of the molecular weight regulator is preferably 20 parts by mass or less relative to 100 parts by mass in total of the tetracarboxylic dianhydride and the diamine compound used.
聚醯胺酸的合成反應較佳為於有機溶媒中進行。此時的反應溫度較佳為-20℃~150℃,反應時間較佳為0.1小時~24小時。 The synthesis reaction of polyamide is preferably carried out in an organic solvent. At this time, the reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours.
作為反應中使用的有機溶媒,例如可列舉:非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。特佳的有機溶媒較佳為使用選自由N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、 N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺、間甲酚、二甲酚及鹵化酚所組成的群組中的一種以上作為溶媒,或者使用該些中的一種以上與其他有機溶媒(例如,丁基賽珞蘇、二乙二醇二乙醚等)的混合物。有機溶媒的使用量(a)較佳為設為使四羧酸二酐及二胺的合計量(b)相對於反應溶液的總量(a+b)而成為0.1質量%~50質量%的量。 Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Particularly preferred organic solvents are those selected from the group consisting of N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, A group consisting of N,N-dimethylformamide, dimethyltrisoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamine, m-cresol, xylenol and halogenated phenols One or more of the group can be used as a solvent, or a mixture of one or more of these and other organic solvents (for example, butyl cellulose, diethylene glycol diethyl ether, etc.) can be used. The usage amount (a) of the organic solvent is preferably set so that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 mass % to 50 mass % with respect to the total amount of the reaction solution (a + b). quantity.
以所述方式可獲得將聚醯胺酸溶解而成的反應溶液。該反應溶液可直接供於液晶配向劑的製備,亦可將反應溶液中所含的聚醯胺酸分離之後供於液晶配向劑的製備。 In this manner, a reaction solution in which polyamide acid is dissolved can be obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.
[聚醯胺酸酯] [Polyamide]
於(P)聚合體為聚醯胺酸酯的情況下,該聚醯胺酸酯例如可藉由如下方法而獲得:[I]使藉由所述合成反應而獲得的聚醯胺酸與酯化劑進行反應的方法;[II]使四羧酸二酯與二胺化合物進行反應的方法;[III]使四羧酸二酯二鹵化物與二胺化合物進行反應的方法等。液晶配向劑中含有的聚醯胺酸酯可僅具有醯胺酸酯結構,亦可為醯胺酸結構與醯胺酸酯結構併存的部分酯化物。再者,將聚醯胺酸酯溶解而成的反應溶液可直接供於液晶配向劑的製備,亦可將反應溶液中所含的聚醯胺酸酯分離之後供於液晶配向劑的製備。 When the polymer (P) is a polyamic acid ester, the polyamic acid ester can be obtained, for example, by the following method: [I] Let the polyamic acid obtained by the synthesis reaction and the ester [II] A method of reacting a tetracarboxylic acid diester with a diamine compound; [III] A method of reacting a tetracarboxylic acid diester dihalide with a diamine compound, etc. The polyamic acid ester contained in the liquid crystal alignment agent may only have a amino acid ester structure, or may be a partial esterification product in which the amino acid structure and the amino acid ester structure coexist. Furthermore, the reaction solution obtained by dissolving the polyamic acid ester can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.
[聚醯亞胺] [Polyimide]
於(P)聚合體為聚醯亞胺的情況下,該聚醯亞胺例如可藉由將如上所述般合成的聚醯胺酸脫水閉環並加以醯亞胺化而獲得。 聚醯亞胺可為將作為其前驅物的聚醯胺酸所具有的醯胺酸結構的全部進行脫水閉環而成的完全醯亞胺化物,亦可為僅將醯胺酸結構的一部分脫水閉環且醯胺酸結構與醯亞胺環結構併存的部分醯亞胺化物。反應中所使用的聚醯亞胺較佳為其醯亞胺化率為20%~99%,更佳為30%~90%。該醯亞胺化率以百分率表示相對於聚醯亞胺的醯胺酸結構的數量與醯亞胺環結構的數量的合計而言醯亞胺環結構的數量所佔的比例。此處,醯亞胺環的一部分亦可為異醯亞胺環。 When the polymer (P) is a polyimide, the polyimide can be obtained by, for example, dehydrating, ring-closing, and imidizing the polyamide acid synthesized as described above. The polyamide imide may be a complete amide imide obtained by dehydration and ring-closure of all the amide acid structures of the polyamide acid as its precursor, or it may be a dehydration and ring-closure of only a part of the amide acid structure. It is a partial amide imide compound in which the amide acid structure and the amide imine ring structure coexist. The polyimide used in the reaction preferably has an imidization rate of 20% to 99%, more preferably 30% to 90%. The acyl imidization rate represents the ratio of the number of amide imine ring structures to the total number of amide acid structures and the number of amide imine ring structures of the polyamide imide as a percentage. Here, part of the imine ring may be an isoimine ring.
聚醯胺酸的脫水閉環較佳為藉由如下方法進行:將聚醯胺酸溶解於有機溶媒中,於該溶液中添加脫水劑及脫水閉環觸媒並視需要進行加熱。該方法中,作為脫水劑,例如可使用乙酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的使用量較佳為相對於聚醯胺酸的醯胺酸結構的1莫耳而設為0.01莫耳~20莫耳。作為脫水閉環觸媒,例如可使用吡啶、三甲吡啶、二甲吡啶、三乙胺等三級胺。脫水閉環觸媒的使用量較佳為相對於所使用的脫水劑1莫耳而設為0.01莫耳~10莫耳。作為脫水閉環反應中所使用的有機溶媒,可列舉作為於聚醯胺酸的合成中所使用者而例示的有機溶媒。脫水閉環反應的反應溫度較佳為0℃~180℃。反應時間較佳為1.0小時~120小時。如此而獲得含有聚醯亞胺的反應溶液。該反應溶液可直接供於液晶配向劑的製備,亦可將聚醯亞胺分離之後供於液晶配向劑的製備。聚醯亞胺亦可藉由聚醯胺酸酯的醯亞胺化而獲得。 The dehydration and ring-closing of polyamide is preferably carried out by the following method: dissolving the polyamide in an organic solvent, adding a dehydrating agent and a dehydration and ring-closing catalyst to the solution, and heating if necessary. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The usage amount of the dehydrating agent is preferably 0.01 mole to 20 mole with respect to 1 mole of the amide acid structure of the polyamide acid. As the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, methylpyridine, dipyridine, and triethylamine can be used. The usage amount of the dehydration closed-loop catalyst is preferably 0.01 mole to 10 mole relative to 1 mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include those exemplified as those used in the synthesis of polyamide. The reaction temperature of the dehydration loop-closure reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hours to 120 hours. In this way, a reaction solution containing polyimide is obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or can be used for the preparation of the liquid crystal alignment agent after the polyimide is separated. Polyimides can also be obtained by imidization of polyamide esters.
以所述方式獲得的聚醯胺酸、聚醯胺酸酯及聚醯亞胺較佳為當將其製成濃度為10質量%的溶液時,具有10mPa.s~800mPa.s的溶液黏度者,更佳為具有15mPa.s~500mPa.s的溶液黏度者。再者,聚醯胺酸、聚醯胺酸酯及聚醯亞胺的溶液黏度(mPa.s)為對於使用該些聚合體的良溶媒(例如,γ-丁內酯、N-甲基-2-吡咯啶酮等)所製備的濃度10質量%的聚合體溶液,使用E型旋轉黏度計於25℃下測定的值。 The polyamic acid, polyamic acid ester and polyimide obtained in the above manner preferably have a concentration of 10 mPa when made into a solution with a concentration of 10 mass%. s~800mPa. The solution viscosity of s is preferably 15mPa. s~500mPa. The solution viscosity of s. Furthermore, the solution viscosity (mPa.s) of polyamic acid, polyamic acid ester and polyimide is a good solvent for using these polymers (for example, γ-butyrolactone, N-methyl- 2-pyrrolidinone, etc.), measured at 25°C using an E-type rotational viscometer.
聚醯胺酸、聚醯胺酸酯及聚醯亞胺的藉由凝膠滲透層析法(Gel Penetration Chromatography,GPC)而測定的聚苯乙烯換算的重量平均分子量(Mw)較佳為1,000~500,000,更佳為2,000~300,000。另外,由Mw與藉由GPC而測定的聚苯乙烯換算的數量平均分子量(Mn)的比所表示的分子量分佈(Mw/Mn)較佳為15以下,更佳為10以下。藉由處於此種分子量範圍,可確保液晶顯示元件的良好的配向性及穩定性。 The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000~ 500,000, preferably 2,000~300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-reduced number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.
[聚醯胺醯亞胺] [Polyamideimide]
聚醯胺醯亞胺例如可藉由以下方法獲得:使三羧酸與二異氰酸酯化合物進行縮合反應的方法;或使三羧酸與二胺化合物反應而於分子中導入醯亞胺鍵,繼而使二異氰酸酯化合物與其反應而醯胺化的方法。 Polyamide imine can be obtained, for example, by a method of condensing a tricarboxylic acid and a diisocyanate compound; or by reacting a tricarboxylic acid with a diamine compound to introduce an imine bond into the molecule, and then A method in which a diisocyanate compound reacts with it to undergo chelation.
作為聚醯胺醯亞胺的合成中使用的三羧酸,例如可列舉偏苯三甲酸酐、丁烷-1,2,4-三羧酸、萘-1,2,4-三羧酸等。作為二異氰酸酯化合物,例如可列舉:二苯基甲烷-4,4'-二異氰酸酯、二苯 基醚-4,4'-二異氰酸酯、甲伸苯基二異氰酸酯、二甲苯二異氰酸酯等。作為二胺化合物,可列舉聚醯胺酸的合成中例示的二胺化合物等。 Examples of the tricarboxylic acid used in the synthesis of polyamide imide include trimellitic anhydride, butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, and the like. Examples of the diisocyanate compound include diphenylmethane-4,4'-diisocyanate, diphenyl Ether-4,4'-diisocyanate, tolylene diisocyanate, xylene diisocyanate, etc. Examples of the diamine compound include diamine compounds exemplified in the synthesis of polyamic acid.
所述反應較佳為於有機溶媒中進行。於聚醯胺醯亞胺的合成時,較佳為將單體的使用比例設為異氰酸酯基或胺基相對於羧基及酸酐基的合計1莫耳而言的數成為0.85莫耳~1.05莫耳的量。聚醯胺醯亞胺的合成反應較佳為於有機溶媒中進行。此時的反應溫度較佳為-20℃~150℃,反應時間較佳為0.1小時~24小時。作為反應中使用的有機溶媒,可列舉作為聚醯胺酸的合成中使用者而例示的有機溶媒。關於所獲得的聚醯胺醯亞胺,藉由GPC而測定的聚苯乙烯換算的重量平均分子量(Mw)較佳為5,000~100,000,更佳為7,000~80,000。 The reaction is preferably carried out in an organic solvent. In the synthesis of the polyamide imide, it is preferable to set the usage ratio of the monomers so that the number of the isocyanate group or the amine group relative to 1 mol in total of the carboxyl group and the acid anhydride group is 0.85 mol to 1.05 mol. amount. The synthesis reaction of polyamide imine is preferably carried out in an organic solvent. At this time, the reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include organic solvents exemplified as those used in the synthesis of polyamide. The polystyrene-reduced weight average molecular weight (Mw) measured by GPC of the obtained polyamide imide is preferably 5,000 to 100,000, more preferably 7,000 to 80,000.
[聚有機矽氧烷] [Polyorganosiloxane]
聚有機矽氧烷例如可藉由對水解性的矽烷化合物進行水解縮合而獲得。作為聚有機矽氧烷的合成中使用的矽烷化合物,例如可列舉:四甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲基二乙氧基矽烷等烷氧基矽烷化合物;3-巰基丙基三乙氧基矽烷、巰基甲基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-(3-環己基胺基)丙基三甲氧基矽烷等含氮.硫的烷氧基矽烷化合物;3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷等含環氧基的矽烷 化合物;3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、乙烯基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷等含不飽和鍵的烷氧基矽烷化合物;三甲氧基矽烷基丙基丁二酸酐等。水解性矽烷化合物可單獨使用該些中的一種或者組合使用兩種以上。再者,「(甲基)丙烯醯氧基」為包含「丙烯醯氧基」及「甲基丙烯醯氧基」的含義。 Polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Examples of the silane compound used in the synthesis of polyorganosiloxane include tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyl Alkoxysilane compounds such as diethoxysilane; 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(3-cyclohexyl Amino)propyltrimethoxysilane and other nitrogen- and sulfur-containing alkoxysilane compounds; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Silanes containing epoxy groups such as glycidoxypropylmethyldimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane Compound; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyl Alkoxysilane compounds containing unsaturated bonds such as methyl diethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, etc.; trimethoxysilylpropylsuccinic anhydride, etc. As a hydrolyzable silane compound, one type of these may be used alone or two or more types may be used in combination. In addition, "(meth)acryloxy group" has a meaning including "acryloxy group" and "methacryloxy group".
所述水解.縮合反應藉由使如上所述的矽烷化合物的一種或兩種以上與水,較佳為於適當的觸媒以及有機溶媒的存在下反應而進行。當進行反應時,相對於矽烷化合物(合計量)1莫耳,水的使用比例較佳為1莫耳~30莫耳。作為所使用的觸媒,例如可列舉:酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物等。觸媒的使用量根據觸媒的種類、溫度等反應條件等不同,應適當設定,例如相對於矽烷化合物的合計量,較佳為0.01倍莫耳~3倍莫耳。作為所使用的有機溶媒,例如可列舉烴、酮、酯、醚、醇等,該些中,較佳為使用非水溶性或難水溶性的有機溶媒。相對於反應中使用的矽烷化合物的合計100質量份,有機溶媒的使用比例較佳為10質量份~10,000質量份。 The hydrolysis. The condensation reaction is performed by reacting one or more of the silane compounds described above with water, preferably in the presence of an appropriate catalyst and organic solvent. When the reaction is carried out, the usage ratio of water is preferably 1 mole to 30 moles relative to 1 mole of silane compound (total amount). Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. The amount of catalyst used should be appropriately set depending on the type of catalyst, temperature and other reaction conditions. For example, it is preferably 0.01 times molar to 3 times molar relative to the total amount of silane compounds. Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, alcohols, and the like. Among these, it is preferable to use water-insoluble or poorly water-soluble organic solvents. The usage ratio of the organic solvent is preferably 10 to 10,000 parts by mass relative to 100 parts by mass of the total silane compound used in the reaction.
所述水解.縮合反應例如較佳為藉由油浴等進行加熱來實施。此時,加熱溫度較佳為設為130℃以下,加熱時間較佳為設為0.5小時~12小時。於反應結束後,在視需要利用乾燥劑對自反應液分取的有機溶媒層進行乾燥後去除溶媒,藉此可獲得作為 目標的聚有機矽氧烷。再者,聚有機矽氧烷的合成方法並不限定於所述水解.縮合反應,例如,可藉由使水解性矽烷化合物於草酸以及醇的存在下反應的方法等而進行。 The hydrolysis. The condensation reaction is preferably carried out by heating in an oil bath or the like. At this time, the heating temperature is preferably 130°C or lower, and the heating time is preferably 0.5 to 12 hours. After the reaction is completed, if necessary, use a desiccant to dry the organic solvent layer separated from the reaction solution and then remove the solvent, thereby obtaining the product as Targeted polyorganosiloxanes. Furthermore, the synthesis method of polyorganosiloxane is not limited to the above-mentioned hydrolysis. The condensation reaction can be performed, for example, by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.
亦可將聚有機矽氧烷設為在側鏈具有感光性結構或液晶性結構的聚有機矽氧烷。合成該聚有機矽氧烷的方法並無特別限定,可列舉:於原料的至少一部分使用含環氧基的矽烷化合物,合成在側鏈具有環氧基的聚有機矽氧烷(以下亦稱為「含環氧基的聚有機矽氧烷」),繼而使含環氧基的聚有機矽氧烷與具有感光性結構或液晶性結構的羧酸反應的方法等。該方法簡便,而且就可提高感光性結構及液晶性結構的導入率的方面而言較佳。除此以外,亦可藉由單體中包含具有感光性結構或液晶性結構的水解性矽烷化合物的反應而合成在側鏈具有感光性結構或液晶性結構的聚有機矽氧烷。對於聚有機矽氧烷,藉由GPC而測定的聚苯乙烯換算的重量平均分子量(Mw)較佳為處於100~50,000的範圍,更佳為處於200~10,000的範圍。 The polyorganosiloxane may be a polyorganosiloxane having a photosensitive structure or a liquid crystal structure in a side chain. The method of synthesizing the polyorganosiloxane is not particularly limited, and examples include using an epoxy group-containing silane compound as at least a part of the raw material to synthesize a polyorganosiloxane having an epoxy group in the side chain (hereinafter also referred to as "Epoxy group-containing polyorganosiloxane"), and then a method of reacting an epoxy group-containing polyorganosiloxane with a carboxylic acid having a photosensitive structure or a liquid crystal structure, etc. This method is simple and preferable in that it can improve the introduction rate of the photosensitive structure and the liquid crystal structure. In addition, a polyorganosiloxane having a photosensitive structure or a liquid crystal structure in the side chain can also be synthesized by reaction of a monomer containing a hydrolyzable silane compound having a photosensitive structure or a liquid crystal structure. For polyorganosiloxane, the polystyrene-reduced weight average molecular weight (Mw) measured by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 10,000.
[聚(甲基)丙烯酸酯] [Poly(meth)acrylate]
聚(甲基)丙烯酸酯可藉由將包含(甲基)丙烯酸系化合物的單體聚合而獲得。作為(甲基)丙烯酸系化合物,例如可列舉:(甲基)丙烯酸、丙烯酸α-乙酯、馬來酸、富馬酸、苯甲酸乙烯酯等不飽和羧酸;(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸三甲氧基矽烷基丙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸縮水甘油酯、(甲 基)丙烯酸3,4-環氧基環己基甲酯、(甲基)丙烯酸3,4-環氧基丁酯、丙烯酸4-羥基丁基縮水甘油醚等不飽和羧酸酯;馬來酸酐等不飽和多元羧酸酐等。再者,聚合時,作為(甲基)丙烯酸系化合物,可單獨使用一種或者組合使用兩種以上。 Poly(meth)acrylate can be obtained by polymerizing a monomer containing a (meth)acrylic compound. Examples of (meth)acrylic compounds include: (meth)acrylic acid, unsaturated carboxylic acids such as α-ethyl acrylate, maleic acid, fumaric acid, and vinyl benzoate; (meth)acrylic acid alkyl groups Ester, cycloalkyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, glycidyl (meth)acrylate, (meth)acrylate (basic) unsaturated carboxylic acid esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxybutyl (meth)acrylate, 4-hydroxybutyl glycidyl acrylate; maleic anhydride, etc. Unsaturated polycarboxylic acid anhydrides, etc. In addition, during polymerization, as the (meth)acrylic compound, one type may be used alone or two or more types may be used in combination.
於聚(甲基)丙烯酸酯的合成時,亦可使用(甲基)丙烯酸系化合物以外的單體。作為該單體,例如可列舉:苯乙烯、甲基苯乙烯、二乙烯基苯等芳香族乙烯基化合物;1,3-丁二烯、2-甲基-1,3-丁二烯等共軛二烯化合物;N-甲基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺等含馬來醯亞胺基的化合物等。該些單體可單獨使用一種或者組合使用兩種以上。 In the synthesis of poly(meth)acrylate, monomers other than (meth)acrylic compounds may be used. Examples of the monomer include aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene; and co-monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene. Conjugated diene compounds; compounds containing maleimide groups such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. These monomers can be used individually by 1 type or in combination of 2 or more types.
相對於聚合中使用的單體的合計量,(甲基)丙烯酸系化合物以外的單體的使用比例較佳為設為50莫耳%以下,更佳為設為40莫耳%以下,進而佳為設為30莫耳%以下。 The usage ratio of monomers other than the (meth)acrylic compound is preferably 50 mol% or less, more preferably 40 mol% or less, based on the total amount of monomers used in the polymerization, and still more preferably It is set to 30 mol% or less.
聚(甲基)丙烯酸酯可藉由於聚合起始劑的存在下對所述單體進行聚合而獲得。作為所使用的聚合起始劑,例如較佳為2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物。相對於反應中所使用的總單體100質量份,聚合起始劑的使用比例較佳為設為0.01質量份~30質量份。 Poly(meth)acrylate can be obtained by polymerizing the monomer in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2 '-Azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds. The usage ratio of the polymerization initiator is preferably set to 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomers used in the reaction.
所述聚合反應較佳為於有機溶媒中進行。作為反應中所使用的有機溶媒,例如可列舉:醇、醚、酮、醯胺、酯、烴化合物等,較佳為二乙二醇乙基甲基醚、丙二醇單甲醚乙酸酯等。反 應溫度較佳為設為30℃~120℃,反應時間較佳為設為1小時~36小時。有機溶媒的使用量(a)較佳為設為反應中使用的單體的合計量(b)相對於反應溶液的總體量(a+b)而成為0.1質量%~60質量%的量。 The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like. Preferred examples are diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, and the like. opposite The reaction temperature is preferably set to 30°C to 120°C, and the reaction time is preferably set to 1 hour to 36 hours. The usage amount (a) of the organic solvent is preferably 0.1 mass % to 60 mass % of the total amount (b) of the monomers used in the reaction relative to the total amount (a + b) of the reaction solution.
於將聚(甲基)丙烯酸酯設為含感光性基的聚合物或液晶性聚合物的情況下,其合成方法並無特別限定,例如可列舉:(I)藉由於單體中包含具有感光性結構或液晶性結構的水解性矽烷化合物的聚合而進行合成的方法;(II)於原料的至少一部分中使用含環氧基的化合物而合成在側鏈具有環氧基的聚合體,繼而與具有感光性結構或液晶性結構的羧酸反應的方法等。藉由GPC對聚(甲基)丙烯酸酯測定而得的聚苯乙烯換算的重量平均分子量(Mw)較佳為250~500,000,更佳為500~100,000,進而佳為1,000~50,000。 When the poly(meth)acrylate is a photosensitive group-containing polymer or a liquid crystal polymer, the synthesis method is not particularly limited, and examples include: (I) By including a photosensitive group in the monomer A method of synthesizing by polymerizing a hydrolyzable silane compound with a natural structure or a liquid crystal structure; (II) using an epoxy group-containing compound in at least part of the raw materials to synthesize a polymer having an epoxy group in the side chain, and then Methods for reacting carboxylic acids with photosensitive structures or liquid crystal structures, etc. The polystyrene-reduced weight average molecular weight (Mw) measured by GPC on the poly(meth)acrylate is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.
《溶劑成分》 "Solvent Composition"
本揭示的液晶配向劑含有(A)溶劑作為溶劑成分的至少一部分,所述(A)溶劑為選自由3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丁基乙酸酯、所述式(1)所表示的化合物及所述式(2)所表示的化合物所組成的群組中的至少一種。 The liquid crystal alignment agent of the present disclosure contains (A) solvent as at least part of the solvent component, and the (A) solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and 3-methoxypropionate. At least one of the group consisting of oxybutyl acetate, the compound represented by the formula (1) and the compound represented by the formula (2).
[(A)溶劑] [(A)Solvent]
所述式(1)及式(2)中,R1、R2及R3的烷基可為直鏈狀亦可為分支狀,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等。該些中,R1較佳為碳數為3或4,更 佳為正丙基或正丁基。R2較佳為碳數為1或2。R3較佳為甲基。所述式(2)的n為0或1,較佳為0。 In the formula (1) and formula (2), the alkyl groups of R 1 , R 2 and R 3 may be linear or branched. Examples include: methyl, ethyl, n-propyl, iso- Propyl, n-butyl, isobutyl, tert-butyl, etc. Among these, R 1 preferably has 3 or 4 carbon atoms, more preferably n-propyl or n-butyl. R 2 preferably has 1 or 2 carbon atoms. R 3 is preferably methyl. n in the formula (2) is 0 or 1, preferably 0.
作為所述式(1)所表示的化合物的具體例,例如可列舉:丙二醇甲基乙基醚、丙二醇二甲醚、丙二醇甲基正丙醚、丙二醇甲基正丁醚等。較佳為丙二醇甲基正丙醚或丙二醇甲基正丁醚。再者,作為所述式(1)所表示的化合物,可單獨使用一種,亦可組合使用兩種以上。 Specific examples of the compound represented by the formula (1) include propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol methyl n-propyl ether, propylene glycol methyl n-butyl ether, and the like. Preferred is propylene glycol methyl n-propyl ether or propylene glycol methyl n-butyl ether. In addition, as the compound represented by the said formula (1), one type may be used individually, or two or more types may be used in combination.
作為所述式(2)所表示的化合物的具體例,例如可列舉:乙酸環己酯、丙酸環己酯、丁酸環己酯、戊酸環己酯等。較佳為乙酸環己酯或丙酸環己酯。再者,作為所述式(2)所表示的化合物,可單獨使用一種,亦可組合使用兩種以上。 Specific examples of the compound represented by the formula (2) include, for example, cyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, and cyclohexyl valerate. Preferred is cyclohexyl acetate or cyclohexyl propionate. In addition, as the compound represented by the said formula (2), one type may be used individually, or two or more types may be used in combination.
[(B)溶劑] [(B)Solvent]
就於加厚液晶配向膜的膜厚的情況下亦可充分抑制塗佈不均的產生的方面而言,溶劑成分較佳為與(A)溶劑一併而更包含1氣壓下的沸點為200℃以上且與(A)溶劑不同的(B)溶劑。 In order to fully suppress the occurrence of coating unevenness even when the thickness of the liquid crystal alignment film is increased, the solvent component preferably has a boiling point of 200 at 1 atmosphere together with the solvent (A). (B) solvent that is above ℃ and different from (A) solvent.
(B)溶劑較佳為選自由非質子性極性溶媒及酚類所組成的群組中的至少一種,更佳為非質子性極性溶媒。具體而言,特佳為選自由N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、1,3-二甲基-2-咪唑啶酮、γ-丁內酯及下述式(3)所表示的化合物所組成的群組中的至少一種。 (B) The solvent is preferably at least one selected from the group consisting of aprotic polar solvents and phenols, and is more preferably an aprotic polar solvent. Specifically, those selected from the group consisting of N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone are particularly preferred. and at least one member from the group consisting of compounds represented by the following formula (3).
[化9]
(式(3)中,R4及R5分別獨立地為氫原子、或者可具有醚鍵的碳數1~6的一價烴基,R4與R5亦可鍵結而形成環結構;R6為碳數1~4的烷基)。 (In formula (3), R 4 and R 5 are each independently a hydrogen atom, or a monovalent hydrocarbon group with 1 to 6 carbon atoms that may have an ether bond, and R 4 and R 5 may also be bonded to form a ring structure; R 6 is an alkyl group with 1 to 4 carbon atoms).
(式(3)所表示的化合物) (Compound represented by formula (3))
所述式(3)中,作為R4及R5的碳數1~6的一價烴基,例如可列舉:碳數1~6的鏈狀烴基、碳數3~6的脂環式烴基、碳數5或6的芳香族烴基等。另外,作為具有醚鍵的一價基,例如可列舉碳數2~6的烷氧基烷基等。作為R4、R5相互鍵結而與R4及R5所鍵結的氮原子一併形成的環,例如可列舉吡啶環、哌啶環等含氮雜環。該些含氮雜環中亦可鍵結有甲基等一價的鏈狀烴基。 In the formula (3), examples of monovalent hydrocarbon groups having 1 to 6 carbon atoms in R 4 and R 5 include chain hydrocarbon groups having 1 to 6 carbon atoms, alicyclic hydrocarbon groups having 3 to 6 carbon atoms, Aromatic hydrocarbon group having 5 or 6 carbon atoms, etc. Examples of the monovalent group having an ether bond include an alkoxyalkyl group having 2 to 6 carbon atoms. Examples of the ring in which R 4 and R 5 are bonded to each other and form together with the nitrogen atom to which R 4 and R 5 are bonded include nitrogen-containing heterocyclic rings such as a pyridine ring and a piperidine ring. These nitrogen-containing heterocycles may also be bonded with monovalent chain hydrocarbon groups such as methyl groups.
R4及R5較佳為氫原子或碳數1~6的烷基,更佳為氫原子或碳數1~3的烷基,進而佳為氫原子或甲基。R6的碳數1~4的烷基可為直鏈狀亦可為分支狀。R6較佳為甲基或乙基。 R 4 and R 5 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or a methyl group. The alkyl group having 1 to 4 carbon atoms in R 6 may be linear or branched. R 6 is preferably methyl or ethyl.
作為所述式(3)所表示的化合物的具體例,例如可列舉:3-丁氧基-N,N-二甲基丙醯胺(3-butoxy-N,N-dimethyl propanamide)、3-甲氧基-N,N-二甲基丙醯胺、3-己氧基-N,N-二甲基丙醯胺、異丙氧基-N-異丙基-丙醯胺(isopropoxy-N-isopropyl-propionamide)、正丁氧基-N-異丙基-丙醯胺等。所述式(3)所表示的化合物可單獨使用一種或者組合使用兩種以上。 Specific examples of the compound represented by the formula (3) include: 3-butoxy-N,N-dimethyl propanamide (3-butoxy-N,N-dimethyl propanamide), 3- Methoxy-N,N-dimethylpropylamide, 3-hexyloxy-N,N-dimethylpropylamide, isopropoxy-N-isopropyl-propylamide (isopropoxy-N -isopropyl-propionamide), n-butoxy-N-isopropyl-propionamide, etc. The compound represented by the said formula (3) can be used individually by 1 type, or in combination of 2 or more types.
[(C)溶劑] [(C)Solvent]
溶劑成分亦可更包含(A)溶劑及(B)溶劑以外的溶劑(以下亦稱為「(C)溶劑」)。作為(C)溶劑,若為與(A)溶劑及(B)溶劑不同的溶劑,只要不妨礙本揭示的效果則並無特別限定。(C)溶劑較佳為選自由醇類、酮類、酯類、醚類、鹵化烴類及烴類所組成的群組中的至少一種。作為該些的具體例,醇類例如可列舉:甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、1,4-丁二醇、三乙二醇、二丙酮醇等;酮類例如可列舉:丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮等;酯類例如可列舉:乳酸乙酯、乳酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二酸二乙酯、丙二酸二乙酯、丙酸異戊酯、異丁酸異戊酯等;醚類例如可列舉:二乙醚、乙二醇甲醚、乙二醇乙醚、乙二醇正丙醚、乙二醇異丙醚、乙二醇單丁醚(丁基賽珞蘇)、乙二醇二甲醚、乙二醇乙醚乙酸酯、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚(propylene glycol monomethyl ether,PGME)、丙二醇單甲醚乙酸酯(propylene glycol methyl ether acetate,PGMEA)、四氫呋喃、二異戊醚等;鹵化烴類例如可列舉:二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯等; 烴類例如可列舉:己烷、庚烷、辛烷、環戊烷、環己烷、苯、甲苯、二甲苯等。再者,作為(C)溶劑,可單獨使用一種或者組合使用兩種以上。 The solvent component may further include solvents other than (A) solvent and (B) solvent (hereinafter also referred to as "(C) solvent"). The solvent (C) is not particularly limited as long as it is a solvent different from the solvent (A) and the solvent (B) as long as the effect of the present disclosure is not hindered. (C) The solvent is preferably at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, etc.; ketones Examples of esters include: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.; examples of esters include: ethyl lactate, butyl lactate, methyl acetate, and ethyl acetate. , butyl acetate, methyl methoxypropionate, ethoxyethyl propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, etc.; ethers Examples of the class include: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosu), ethylene glycol di Methyl ether, glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid Ester, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), tetrahydrofuran, diisoamyl ether, etc.; Examples of halogenated hydrocarbons include: methylene chloride, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, etc.; Examples of hydrocarbons include hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, and the like. In addition, as the (C) solvent, one type can be used alone or two or more types can be used in combination.
作為(C)溶劑,就可較佳實現塗佈不均的抑制的方面而言,該些中較佳為選自由酮類、酯類、醚類及烴類所組成的群組中的至少一種。就能夠藉由低溫煅燒來形成液晶配向膜,能夠應用於膜基材的方面而言,所述中,較佳為1氣壓下的沸點為180℃以下的低沸點溶劑。具體而言,較佳為選自由丙二醇單甲醚、丙二醇單甲醚乙酸酯、甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸丁酯、環己酮、環戊烷及環戊酮所組成的群組中的一種。 (C) The solvent is preferably at least one selected from the group consisting of ketones, esters, ethers, and hydrocarbons in terms of preferably suppressing coating unevenness. . Among them, a low-boiling point solvent having a boiling point of 180° C. or less under 1 atmosphere is preferred in terms of being able to form a liquid crystal alignment film by low-temperature calcination and being applicable to film base materials. Specifically, it is preferably selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, cyclohexanone, and cyclopentane. and cyclopentanone.
溶劑成分中,相對於液晶配向劑中所含有的溶劑成分的總量,(A)溶劑的含有比例為1質量%~70質量%。若小於1質量%,則改善液晶配向劑的塗佈性的效果及減少配向膜中殘存的溶劑的效果小,另一方面,若多於70質量%,則聚合體的溶解性降低,配向膜的塗佈不均的抑制效果小。(A)溶劑的含有比例較佳為3質量%~65質量%,進而佳為5質量%~60質量%。 Among the solvent components, the content ratio of the (A) solvent is 1 mass% to 70 mass% relative to the total amount of solvent components contained in the liquid crystal alignment agent. If it is less than 1 mass %, the effect of improving the coating properties of the liquid crystal alignment agent and reducing the residual solvent in the alignment film is small. On the other hand, if it is more than 70 mass %, the solubility of the polymer decreases and the alignment film The effect of inhibiting coating unevenness is small. The content ratio of (A) the solvent is preferably 3% by mass to 65% by mass, and more preferably 5% by mass to 60% by mass.
相對於液晶配向劑中所含有的溶劑成分的總量,(B)溶劑的含有比例為0質量%~40質量%。若(B)溶劑的含有比例多於40質量%,則配向膜中的溶劑的殘存量過多,就容易產生背移的方面而言欠佳。再者,所謂「包含0質量%的(B)溶劑」是指液晶配向劑中不含(B)溶劑。就厚膜的情況下亦可獲得更不易產生塗佈不均的液晶配向膜的方面而言,較佳為與(A)溶劑一併而 於液晶配向劑中含有較少量的(B)溶劑。具體而言,就可進一步提高抑制塗佈不均的效果的方面而言,相對於液晶配向劑中所含有的溶劑成分的總量,較佳為將(B)溶劑的含有比例設為0.1質量%~40質量%,更佳為設為0.5質量%~40質量%,進而佳為設為1質量%~35質量%,特佳為設為1質量%~20質量%。 Relative to the total amount of solvent components contained in the liquid crystal alignment agent, the content ratio of the (B) solvent is 0 mass% to 40 mass%. If the content ratio of the (B) solvent is more than 40% by mass, the remaining amount of the solvent in the alignment film will be too large, which is undesirable in that backshift is likely to occur. Furthermore, the so-called "containing 0 mass % of (B) solvent" means that the liquid crystal alignment agent does not contain (B) solvent. In order to obtain a liquid crystal alignment film that is less likely to cause uneven coating even when the film is thick, it is preferable to use it together with the solvent (A). The liquid crystal alignment agent contains a relatively small amount of (B) solvent. Specifically, in order to further enhance the effect of suppressing uneven coating, it is preferable to set the content ratio of the solvent (B) to 0.1 mass with respect to the total amount of solvent components contained in the liquid crystal alignment agent. % to 40 mass %, more preferably 0.5 mass % to 40 mass %, further preferably 1 mass % to 35 mass %, particularly preferably 1 mass % to 20 mass %.
相對於液晶配向劑中所含有的溶劑成分的總量,(C)溶劑的含有比例較佳為設為5質量%~98質量%,更佳為設為10質量%~95質量%,進而佳為設為20質量%~90質量%。就於低溫下(例如150℃以下)進行膜形成時的加熱的情況下亦可充分減少液晶配向膜中的殘存溶劑的量的方面而言,相對於液晶配向劑中所含有的溶劑成分的總量,較佳為將(C)溶劑的含有比例設為40質量%以上,更佳為設為50質量%以上。該情況下,藉由將聚合體成分設為選自由聚(甲基)丙烯酸酯及聚有機矽氧烷所組成的群組中的至少一種,可使聚合體對溶劑的溶解性更良好,就可充分抑制塗佈不均的方面而言較佳。液晶配向劑較佳為溶劑成分為包含(A)溶劑與(B)溶劑的混合溶媒,特佳為包含(A)溶劑與(B)溶劑及(C)溶劑的混合溶媒。 Relative to the total amount of solvent components contained in the liquid crystal alignment agent, the content ratio of the (C) solvent is preferably 5 mass% to 98 mass%, more preferably 10 mass% to 95 mass%, and still more preferably It is set to 20 mass% to 90 mass%. In order to sufficiently reduce the amount of residual solvent in the liquid crystal alignment film even when heating during film formation is performed at low temperature (for example, 150° C. or less), relative to the total amount of solvent components contained in the liquid crystal alignment agent, The content of the solvent (C) is preferably 40% by mass or more, more preferably 50% by mass or more. In this case, by using the polymer component as at least one selected from the group consisting of poly(meth)acrylate and polyorganosiloxane, the solubility of the polymer in the solvent can be improved, and thus It is preferable in that it can sufficiently suppress uneven coating. The liquid crystal alignment agent preferably has a solvent component that is a mixed solvent containing (A) solvent and (B) solvent, and particularly preferably a mixed solvent containing (A) solvent, (B) solvent, and (C) solvent.
<<其他成分>> <<Other ingredients>>
液晶配向劑含有聚合體成分及溶劑成分,視需要亦可含有其他成分。作為該其他成分,例如可列舉:含環氧基的化合物、官能性矽烷化合物、抗氧化劑、金屬螫合化合物、硬化觸媒、硬化促進劑、界面活性劑、填充劑、分散劑、光增感劑等。其他成分 的調配比例可於不損及本發明的效果的範圍內,根據各化合物而適當選擇。 The liquid crystal alignment agent contains polymer components and solvent components, and may also contain other components if necessary. Examples of the other components include epoxy group-containing compounds, functional silane compounds, antioxidants, metal chelating compounds, curing catalysts, curing accelerators, surfactants, fillers, dispersants, and photosensitizers. Agents, etc. other ingredients The compounding ratio can be appropriately selected according to each compound within the range that does not impair the effect of the present invention.
液晶配向劑中的固體成分濃度(液晶配向劑的溶媒以外的成分的合計質量於液晶配向劑的總質量中所佔的比例)可考慮黏性、揮發性等而適當選擇,較佳為1質量%~10質量%的範圍。於固體成分濃度小於1質量%的情況下,塗膜的膜厚過小而難以獲得良好的液晶配向膜。另一方面,於固體成分濃度超過10質量%的情況下,塗膜的膜厚過大而難以獲得良好的液晶配向膜,而且液晶配向劑的黏性增大而有塗佈性降低的傾向。 The solid component concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected considering viscosity, volatility, etc., and is preferably 1 mass %~10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases and the coatability tends to decrease.
《液晶元件》 "Liquid Crystal Component"
本揭示的液晶元件具備使用以上所說明的液晶配向劑而形成的液晶配向膜。液晶元件可有效地應用於各種用途,例如可用作鐘錶、可攜式遊戲機、文字處理器、筆記型個人電腦、汽車導航系統、攝錄像機、個人數位助理(Personal Digital Assistant,PDA)、數位相機、行動電話、智慧型電話、各種監視器、液晶電視機、資訊顯示器等各種顯示裝置、或調光膜、相位差膜等。於用作液晶顯示元件的情況下,液晶的動作模式並無特別限定,例如可應用於扭轉向列(Twisted Nematic,TN)型、超扭轉向列(Super Twisted Nematic,STN)型、垂直配向型(包含垂直配向-多域垂直配向(Vertical Alignment-Multi-domain Vertical Alignment,VA-MVA)型、垂直配向-圖案垂直配向(Vertical Alignment-Patterned Vertical Alignment,VA-PVA)型等)、共面切 換(In-Plane Switching,IPS)型、邊緣場切換(Fringe Field Switching,FFS)型、光學補償彎曲(Optically Compensated Bend,OCB)型等各種模式中。 The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. Liquid crystal elements can be effectively used in various applications, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital Various display devices such as cameras, mobile phones, smart phones, various monitors, LCD TVs, and information displays, or dimming films, phase difference films, etc. When used as a liquid crystal display element, the operation mode of the liquid crystal is not particularly limited. For example, it can be applied to twisted nematic (TN) type, super twisted nematic (Super Twisted Nematic, STN) type, and vertical alignment type. (Including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar cutting In-Plane Switching (IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Bend (OCB) type and other modes.
液晶元件例如可藉由以下步驟來製造。此處,列舉製造相位差膜及液晶顯示元件的情況為一例來進行說明。 A liquid crystal element can be manufactured by the following steps, for example. Here, a case of manufacturing a retardation film and a liquid crystal display element will be described as an example.
[步驟1:塗膜的形成] [Step 1: Formation of coating film]
首先,將液晶配向劑塗佈於基材上,繼而,視需要對塗佈面進行加熱,藉此於基材上形成塗膜。作為基材,可較佳地使用透明基材。具體而言,例如可列舉:浮法玻璃、鈉鈣玻璃等玻璃基板;醯化纖維素(三乙醯纖維素(triacetyl cellulose,TAC)等纖維素乙酸酯等)、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碸、聚醚碸、聚醯胺、聚醯亞胺、聚(甲基)丙烯酸酯、聚甲基丙烯酸甲酯、聚碳酸酯、環狀聚烯烴等樹脂膜等。特別是本揭示的液晶配向劑可作為用於對樹脂膜進行塗佈的液晶配向劑而較佳地應用。再者,為了使基材表面與液晶配向膜的密接性良好,亦可對塗佈液晶配向劑的基材實施鹼化處理等現有公知的前處理。 First, the liquid crystal alignment agent is coated on the substrate, and then, if necessary, the coated surface is heated to form a coating film on the substrate. As the base material, a transparent base material can be preferably used. Specific examples include: glass substrates such as float glass and soda-lime glass; cellulose acetates such as cellulose (triacetyl cellulose (TAC), etc.); polyethylene terephthalate Diester, polyethylene naphthalate, polybutylene terephthalate, polyester, polyether ester, polyamide, polyimide, poly(meth)acrylate, polymethylmethacrylate , polycarbonate, cyclic polyolefin and other resin films, etc. In particular, the liquid crystal alignment agent of the present disclosure can be preferably used as a liquid crystal alignment agent for coating a resin film. Furthermore, in order to ensure good adhesion between the surface of the substrate and the liquid crystal alignment film, the substrate coated with the liquid crystal alignment agent may also be subjected to conventionally known pretreatments such as alkalinization treatment.
於液晶顯示元件的情況下,一對基材中的至少一者使用於基材的單面設置有透明導電膜的基材。作為透明導電膜,可設為包含氧化錫(SnO2)的奈塞(NESA)膜(美國PPG公司註冊商標)、包含氧化銦-氧化錫(In2O3-SnO2)的氧化銦錫(Indium tin oxide,ITO)膜等。於製造TN型、STN型或垂直配向型的液晶顯 示元件的情況下,使用兩塊設置有經圖案化的透明導電膜的基板。於製造IPS型或FFS型的橫電場式的液晶顯示元件的情況下,使用設置有包含經圖案化為梳齒狀的透明導電膜或金屬膜的電極的基板及未設置電極的相向基板。作為金屬膜,例如可使用包含鉻等金屬的膜。 In the case of a liquid crystal display element, at least one of a pair of base materials is a base material in which a transparent conductive film is provided on one side of the base material. Examples of the transparent conductive film include NESA (registered trademark of PPG Corporation, USA) containing tin oxide (SnO 2 ), indium tin oxide (In 2 O 3 -SnO 2 ) containing Indium tin oxide, ITO) film, etc. When manufacturing a TN type, STN type or vertical alignment type liquid crystal display element, two substrates provided with patterned transparent conductive films are used. When manufacturing an IPS type or FFS type transverse electric field type liquid crystal display element, a substrate provided with an electrode including a transparent conductive film or a metal film patterned in a comb-tooth shape and a counter substrate provided with no electrode are used. As the metal film, for example, a film containing metal such as chromium can be used.
液晶配向劑對基材的塗佈可根據基材的種類而採用適當的塗佈方法。作為具體例,可列舉:輥塗佈機法、旋轉器法、噴墨印刷法、平板印刷法、柔版印刷法、棒塗機法、擠出模法、直接凹版印刷塗布機法、腔室刮刀塗佈機法、平板凹版塗佈機法、含浸塗佈機法、MB塗佈機法等。塗佈液晶配向劑後,較佳為對塗佈面進行加熱(烘烤)。此時的加熱溫度是根據基材來設定,於將基材設為樹脂膜的情況下,較佳為150℃以下,更佳為40℃~150℃,進而佳為80℃~140℃。加熱時間較佳為0.1分鐘~15分鐘,更佳為1分鐘~10分鐘。塗佈面的加熱亦可設為利用預烘烤及後烘烤的多次加熱處理。如此在基材上形成作為液晶配向膜的塗膜。 The liquid crystal alignment agent can be coated on the substrate using an appropriate coating method according to the type of the substrate. Specific examples include: roll coater method, rotator method, inkjet printing method, offset printing method, flexographic printing method, rod coater method, extrusion die method, direct gravure coating method, chamber Blade coater method, plate gravure coater method, dip coater method, MB coater method, etc. After coating the liquid crystal alignment agent, it is preferred to heat (bake) the coating surface. The heating temperature at this time is set according to the base material. When the base material is a resin film, it is preferably 150°C or lower, more preferably 40°C to 150°C, and even more preferably 80°C to 140°C. The heating time is preferably 0.1 minute to 15 minutes, more preferably 1 minute to 10 minutes. Heating of the coated surface can also be set as multiple heat treatments using pre-baking and post-baking. In this way, a coating film serving as a liquid crystal alignment film is formed on the base material.
基材上所形成的塗膜的膜厚較佳為1nm~1μm,更佳為5nm~0.5μm。此處,當於基材上形成液晶配向膜時,為了提高液晶配向膜對液晶的配向性、或提高液晶配向膜與基材(特別是樹脂膜基材)的密接性,有時會使液晶配向膜的膜厚較厚(例如0.2μm或0.3μm以上)。另一方面,若使液晶配向膜的膜厚厚,則配向膜中容易殘存溶劑,藉由該殘存溶劑的影響,有時會於配向膜表面產生塗佈不均,或者於將形成有液晶配向膜的基材層疊 時發生配向膜中的聚合體成分或殘存溶劑移至基材側的背移。該情況下,所獲得的顯示元件的液晶的配向性容易降低、或製品良率容易降低。作為用以減少配向膜中的殘存溶劑的手段之一,考慮提高膜形成時的加熱溫度,但若需要在高溫下加熱,則樹脂膜作為基材的應用受到限制。就該方面而言,於使液晶配向膜的膜厚厚至0.3μm以上的情況下,本揭示的液晶配向劑亦可抑制產生所述不良,作為用於樹脂膜的液晶配向劑而言較佳。 The film thickness of the coating film formed on the substrate is preferably 1 nm to 1 μm, more preferably 5 nm to 0.5 μm. Here, when forming a liquid crystal alignment film on a base material, in order to improve the alignment of the liquid crystal alignment film to the liquid crystal or to improve the adhesion between the liquid crystal alignment film and the base material (especially the resin film base material), the liquid crystal alignment film may be The alignment film has a relatively thick film thickness (for example, 0.2 μm or 0.3 μm or more). On the other hand, if the thickness of the liquid crystal alignment film is increased, a solvent is likely to remain in the alignment film. Due to the influence of the remaining solvent, uneven coating may occur on the surface of the alignment film, or a liquid crystal alignment film may be formed. Membrane substrate lamination When the polymer component or residual solvent in the alignment film moves to the substrate side, back migration occurs. In this case, the alignment property of the liquid crystal of the obtained display element is likely to decrease, or the product yield is likely to decrease. As one of the means to reduce the residual solvent in the alignment film, it is considered to increase the heating temperature during film formation. However, if heating at high temperature is required, the application of the resin film as a base material is limited. In this regard, when the film thickness of the liquid crystal alignment film is made to be 0.3 μm or more, the liquid crystal alignment agent of the present disclosure can suppress the occurrence of the above-mentioned defects, and is preferred as a liquid crystal alignment agent used for resin films. .
[步驟2:配向處理] [Step 2: Alignment Processing]
繼而,實施對所述步驟1中形成的塗膜賦予液晶配向能力的處理(配向處理)。藉此,對塗膜賦予液晶分子的配向能力而成為液晶配向膜。作為配向處理,可列舉:利用捲繞著包含例如尼龍(nylon)、人造絲(rayon)、棉(cotton)等纖維的布的輥對塗膜朝一定方向進行摩擦,藉此而對塗膜賦予液晶配向能力的摩擦處理;對塗佈有液晶配向劑的基板面進行光照射而對塗膜賦予液晶配向能力的光配向處理等。就可抑制因產生塵埃或靜電等而產生顯示不良或良率降低的方面、可對基板上所形成的有機薄膜均勻地賦予液晶配向能力的方面而言,可較佳地應用光配向處理。再者,於製造垂直配向型的液晶顯示元件的情況下,可將所述步驟1中形成的塗膜直接用作液晶配向膜,但亦可對該塗膜實施配向處理。 Next, a process (alignment process) for imparting liquid crystal alignment capability to the coating film formed in step 1 is performed. Thereby, the alignment ability of liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include rubbing the coating film in a certain direction with a roller wound with a cloth containing fibers such as nylon, rayon, cotton, etc., thereby imparting the coating film with Rubbing treatment for liquid crystal alignment ability; photo-alignment treatment for irradiating the substrate surface coated with liquid crystal alignment agent with light to impart liquid crystal alignment ability to the coating film, etc. The photo-alignment treatment can be preferably applied in terms of suppressing display defects or yield reduction due to generation of dust, static electricity, etc., and in terms of uniformly imparting liquid crystal alignment ability to the organic thin film formed on the substrate. Furthermore, when manufacturing a vertical alignment type liquid crystal display element, the coating film formed in step 1 can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to alignment treatment.
於光配向處理中,作為所照射的光,例如可列舉包含150nm~800nm的波長的光的紫外線、可見光線等。該些中,較佳為 包含300nm~400nm的波長的光的紫外線。照射光可為偏光,亦可為非偏光。作為偏光,較佳為使用包含直線偏光的光。於所使用的光為偏光的情況下,光的照射可自垂直於基板面的方向進行,亦可自傾斜方向進行,或者可將該些組合來進行。於照射非偏光的情況下,需要自相對於基板面傾斜的方向進行照射。 In the photo-alignment treatment, examples of the light to be irradiated include ultraviolet rays and visible rays containing light with a wavelength of 150 nm to 800 nm. Among these, the better one is Ultraviolet light containing light with a wavelength of 300nm~400nm. The irradiation light can be polarized light or non-polarized light. As the polarized light, it is preferable to use light containing linearly polarized light. When the light used is polarized light, the light can be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating non-polarized light, it is necessary to irradiate from a direction inclined with respect to the substrate surface.
作為所使用的光源,例如可列舉:低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、水銀-氙燈(Hg-Xe燈)等。偏光可藉由將所述光源與例如濾光器、繞射光柵等併用的方法等而獲得。光的照射量較佳為設為0.1mJ/cm2~1,000mJ/cm2,更佳為設為1mJ/cm2~500mJ/cm2。 Examples of the light source used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). Polarized light can be obtained by using the light source in combination with, for example, a filter, a diffraction grating, or the like. The amount of light irradiation is preferably 0.1mJ/cm 2 ~1,000mJ/cm 2 , more preferably 1mJ/cm 2 ~500mJ/cm 2 .
[步驟3-1:光學各向異性膜的形成] [Step 3-1: Formation of optically anisotropic film]
於作為液晶元件而製造相位差膜的情況下,繼而,於光照射後的塗膜(液晶配向膜)上塗佈聚合性液晶來進行硬化。藉此,於液晶配向膜的表面上形成作為具有光學補償功能的有機薄膜的光學各向異性膜。此處所使用的聚合性液晶為藉由加熱及光照射中的至少任一種處理而進行聚合的液晶化合物。作為聚合性液晶所具有的聚合性基,例如可列舉:(甲基)丙烯醯基、乙烯基、乙烯基苯基、烯丙基等,較佳為(甲基)丙烯醯基。 When producing a retardation film as a liquid crystal element, polymerizable liquid crystal is applied to the coating film (liquid crystal alignment film) after light irradiation and cured. Thereby, an optically anisotropic film as an organic thin film with an optical compensation function is formed on the surface of the liquid crystal alignment film. The polymerizable liquid crystal used here is a liquid crystal compound polymerized by at least any one of heating and light irradiation. Examples of the polymerizable group possessed by the polymerizable liquid crystal include (meth)acrylyl group, vinyl group, vinylphenyl group, allyl group, etc., and a (meth)acrylyl group is preferred.
作為聚合性液晶,可使用現有公知者,具體而言,例如可列舉非專利文獻1(「UV可硬化液晶及其應用」、液晶、第3卷第1號(1999年)、第34~42頁))中記載的向列液晶。另外,亦可為膽固醇液晶、盤狀液晶、添加有手性劑的扭轉向列配向型液 晶等。聚合性液晶可為多個液晶化合物的混合物,亦可為進而含有公知的聚合起始劑或適當的溶媒、聚合性單體、界面活性劑等的組成物。於所形成的液晶配向膜上塗佈聚合性液晶時,例如可採用棒塗佈機法、輥塗佈機法、旋轉器法、印刷法、噴墨法等適當的塗佈方法。 As the polymerizable liquid crystal, conventionally known ones can be used. Specific examples include Non-Patent Document 1 ("UV Curable Liquid Crystal and Its Application", Liquid Crystal, Vol. 3, No. 1 (1999), Nos. 34 to 42 Nematic liquid crystals described on page)). In addition, cholesteric liquid crystals, discotic liquid crystals, and twisted nematic liquid crystals added with chiral agents can also be used. Jing et al. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds, or may be a composition further containing a known polymerization initiator, an appropriate solvent, a polymerizable monomer, a surfactant, and the like. When the polymerizable liquid crystal is coated on the formed liquid crystal alignment film, an appropriate coating method such as a rod coater method, a roll coater method, a rotator method, a printing method, an inkjet method, etc. can be used.
繼而,對以所述方式所形成的聚合性液晶的塗膜實施選自加熱及光照射中的一種以上的處理,藉此而將該塗膜硬化,形成液晶層(光學各向異性膜)。就獲得良好的配向而言,較佳為重疊進行該些處理。塗膜的加熱溫度可根據所使用的聚合性液晶的種類而適當選擇。例如,於使用默克(Merck)公司製造的RMS03-013C的情況下,較佳為於40℃~80℃的範圍的溫度下進行加熱。加熱時間較佳為0.5分鐘~5分鐘。作為對塗膜的照射光,可較佳地使用具有200nm~500nm的範圍的波長的非偏光的紫外線。作為光的照射量,較佳為設為50mJ/cm2~10,000mJ/cm2,更佳為設為100mJ/cm2~5,000mJ/cm2。再者,對塗膜的偏光放射線的照射可自規定的偏光方向僅進行一次,亦可對塗膜照射多次偏光方向(入射方向)不同的放射線。 Next, the coating film of polymerizable liquid crystal formed in the above manner is subjected to one or more treatments selected from heating and light irradiation, thereby curing the coating film to form a liquid crystal layer (optically anisotropic film). In terms of obtaining good alignment, it is preferable to overlap these processes. The heating temperature of the coating film can be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40°C to 80°C. The preferred heating time is 0.5 minutes to 5 minutes. As the irradiation light for the coating film, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light irradiation is preferably 50mJ/cm 2 to 10,000mJ/cm 2 , and more preferably 100mJ/cm 2 to 5,000mJ/cm 2 . Furthermore, the coating film may be irradiated with polarized radiation only once in a predetermined polarization direction, or the coating film may be irradiated multiple times with radiation having different polarization directions (incident directions).
作為所形成的光學各向異性膜的厚度,可根據所期望的光學特性而適當設定。例如,作為相位差膜,於製造波長540nm的可見光下的1/2波長板的情況下,選擇作為相位差膜的光學各向異性膜的相位差成為240nm~300nm的厚度,若為1/4波長板,則選擇相位差成為120nm~150nm般的厚度。可獲得目標相位差 的光學各向異性膜的厚度視所使用的聚合性液晶的光學特性而不同。例如於使用默克製造的RMS03-013C的情況下,用於製造1/4波長板的厚度為0.6μm~1.5μm的範圍。 The thickness of the optically anisotropic film to be formed can be appropriately set depending on the desired optical properties. For example, when manufacturing a 1/2 wavelength plate under visible light with a wavelength of 540 nm as a retardation film, the phase difference of the optically anisotropic film selected as the retardation film is such that the thickness is 240 nm to 300 nm. If it is 1/4 For the wavelength plate, select a phase difference with a thickness of 120nm~150nm. The target phase difference can be obtained The thickness of the optically anisotropic film varies depending on the optical properties of the polymeric liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness used to manufacture the 1/4-wavelength plate is in the range of 0.6 μm to 1.5 μm.
作為生產相位差膜的方法,就工業上可簡便地規模生產而言,有時採用輥對輥方式。該方法中,進行連續實施以下處理的步驟,並將經過該些步驟後的膜再次以捲繞體的形式回收,所述處理為:自長條狀的樹脂膜為卷狀的捲繞體卷出樹脂膜,於該卷出的膜上形成液晶配向膜的處理;於液晶配向膜上塗佈聚合性液晶並進行硬化的處理;以及視需要將保護膜積層的處理。另外,於輥對輥方式中,有時在自形成液晶配向膜的步驟轉而進行塗佈聚合性液晶及硬化的步驟的期間,將帶配向膜的樹脂膜暫時捲繞,其後,進行下一步驟(聚合性液晶的塗佈及硬化)。此時,若存在液晶配向膜中的殘存溶劑或聚合體成分向基材側移動的背移,或即便不存在背移,配向膜中的溶劑去除亦不充分,則於為了進行聚合性液晶的塗佈及硬化處理而將膜卷出時,容易產生液晶配向膜自基材剝離的膜剝離。關於該方面,根據本揭示的液晶配向劑,可減少配向膜中殘存的溶劑量,藉此可不易產生向基材的背移,就該方面而言較佳。 As a method for producing a retardation film, a roll-to-roll method may be used in order to enable industrial scale production easily. In this method, the following steps of processing a long resin film into a roll are performed continuously, and the film after these steps is recovered in the form of a roll again. A process of unwinding a resin film and forming a liquid crystal alignment film on the rolled-out film; a process of applying polymerizable liquid crystal on the liquid crystal alignment film and curing it; and a process of laminating a protective film if necessary. In addition, in the roll-to-roll method, when the step of forming the liquid crystal alignment film is transferred to the steps of applying polymerizable liquid crystal and curing, the resin film with the alignment film may be temporarily wound, and then the following steps may be performed. One step (coating and hardening of polymeric liquid crystal). At this time, if there is back migration of the residual solvent or polymer component in the liquid crystal alignment film to the substrate side, or even if there is no back migration, the removal of the solvent in the alignment film is insufficient, it will be difficult to process the polymerizable liquid crystal. When the film is rolled out after coating and curing treatment, film peeling in which the liquid crystal alignment film is peeled off from the base material is likely to occur. In this regard, the liquid crystal alignment agent of the present disclosure can reduce the amount of solvent remaining in the alignment film, thereby making back migration to the substrate less likely to occur, which is preferable in this regard.
[步驟3-2:液晶單元的構築] [Step 3-2: Construction of liquid crystal cell]
於作為液晶元件而製造液晶顯示元件的情況下,準備如所述般形成有液晶配向膜的兩塊基材,於相向配置的兩塊基材間配置液晶,藉此製造液晶單元。具體而言,可列舉:藉由密封劑將一 對基材的周邊部貼合,並將液晶注入填充於藉由基材表面及密封劑所劃分的單元間隙內,然後將注入孔密封的方法;將密封劑塗佈於其中一個基材的液晶配向膜側的周邊部,進而於液晶配向膜面上的規定幾處滴加液晶後,以使液晶配向膜相向的方式將另一個基材貼合,並且將液晶擴散於基板的整個面上,其後使密封劑硬化的方法(液晶滴注(one drop filling,ODF)方式)等。作為密封劑,例如可列舉含有硬化劑及作為間隔物(spacer)的氧化鋁球的環氧樹脂等。液晶可列舉向列液晶及層列液晶,其中較佳為向列液晶。另外,亦可於液晶中添加膽甾醇型液晶(cholesteric liquid crystal)、手性劑、鐵電性液晶(ferroelectric liquid crystal)等來使用。 When manufacturing a liquid crystal display element as a liquid crystal element, two substrates on which a liquid crystal alignment film is formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other to manufacture a liquid crystal cell. Specifically, it can be enumerated: sealing a A method of laminating the peripheral portion of the substrate, injecting liquid crystal into the cell gap divided by the substrate surface and the sealant, and then sealing the injection hole; applying the sealant to the liquid crystal of one of the substrates After adding liquid crystal dropwise to the peripheral portion on the alignment film side and at predetermined places on the surface of the liquid crystal alignment film, another substrate is bonded so that the liquid crystal alignment films face each other, and the liquid crystal is spread over the entire surface of the substrate. A method of subsequently hardening the sealant (liquid crystal drop filling (ODF) method), etc. Examples of the sealant include epoxy resin containing a hardener and alumina balls as spacers. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferred. In addition, cholesteric liquid crystal, chiral agent, ferroelectric liquid crystal, etc. can also be added to the liquid crystal for use.
接下來,視需要在液晶單元的外側表面貼合偏光板,藉此而獲得液晶顯示元件。作為偏光板,可列舉以乙酸纖維素保護膜將一邊使聚乙烯醇延伸配向一邊使其吸收碘而成的被稱為「H膜」的偏光膜夾持所得的偏光板、或包含H膜本身的偏光板。 Next, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell, thereby obtaining a liquid crystal display element. Examples of the polarizing plate include those in which a polarizing film called an "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between a cellulose acetate protective film and the H film itself. polarizing plate.
[實施例] [Example]
以下,藉由實施例來對本發明進一步進行具體說明,但本發明並不該些實施例的任何限制。 Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited in any way by these examples.
以下的例子中,藉由以下方法測定聚合體的重量平均分子量Mw、數量平均分子量Mn及環氧當量、以及聚合體溶液的溶液黏度。以下的實施例中使用的原料化合物及聚合體的必要量藉由視需要重覆進行下述的合成例中所示的合成規模下的合成而確 保。 In the following examples, the weight average molecular weight Mw, number average molecular weight Mn and epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following methods. The necessary amounts of raw material compounds and polymers used in the following examples were determined by repeating the synthesis at the synthesis scale shown in the following synthesis examples as necessary. Save.
[聚合體的重量平均分子量Mw及數量平均分子量Mn] [Weight average molecular weight Mw and number average molecular weight Mn of the polymer]
Mw及Mn是藉由以下的條件下的GPC進行測定而得的聚苯乙烯換算值。 Mw and Mn are polystyrene-converted values measured by GPC under the following conditions.
管柱:東曹(股)製造、TSKgelGRCXLII Pipe string: Tosoh Co., Ltd. manufacturing, TSKgelGRCXLII
溶劑:四氫呋喃 Solvent: Tetrahydrofuran
溫度:40℃ Temperature: 40℃
壓力:68kgf/cm2 Pressure: 68kgf/ cm2
[環氧當量] [Epoxy equivalent]
環氧當量是藉由日本工業標準(Japanese Industrial Standards,JIS)C 2105中記載的鹽酸-甲基乙基酮法進行測定。 The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105.
[聚合體溶液的溶液黏度] [Solution viscosity of polymer solution]
聚合體溶液的溶液黏度(mPa.s)使用E型旋轉黏度計於25℃下進行測定。 The solution viscosity (mPa.s) of the polymer solution was measured using an E-type rotational viscometer at 25°C.
<聚合體及化合物的合成> <Synthesis of polymers and compounds>
[合成例1-1:含環氧基的聚有機矽氧烷(EPS-1)的合成] [Synthesis Example 1-1: Synthesis of epoxy group-containing polyorganosiloxane (EPS-1)]
於具備攪拌機、溫度計、滴加漏斗及回流冷卻管的反應容器中裝入丙二醇單甲醚乙酸酯100g、去離子水100g、三乙胺10.0g、2-(3,4-環氧基環己基)乙基三甲氧基矽烷68.1g、甲基丙烯醯氧基辛基三甲氧基矽烷31.9g、季戊四醇四[3-(3,5-第三丁基-4-羥基苯基)丙酸酯]0.074g,於室溫下加以混合。繼而,於60℃下回流6小時來進行反應。於反應結束後,取出有機層,藉由0.2質量%硝 酸銨水溶液進行清洗至清洗後的水成為中性為止後,於減壓下蒸餾去除溶媒及水,藉此,以黏稠的透明液體形式獲得含環氧基的聚有機矽氧烷(EPS-1)。對該含環氧基的聚矽氧烷進行1H-核磁共振(nuclear magnefic resonance,NMR)方析,結果確認到於化學偏移(δ)=3.2ppm附近可獲得基於氧雜環丙基的波峰,反應過程中不會引起環氧基的副反應。該含環氧基的聚有機矽氧烷的重量平均分子量Mw為2,200,環氧當量為186g/莫耳。 Put 100g of propylene glycol monomethyl ether acetate, 100g of deionized water, 10.0g of triethylamine, and 2-(3,4-epoxy ring) into a reaction vessel equipped with a mixer, a thermometer, a dropping funnel, and a reflux cooling tube. Hexyl)ethyltrimethoxysilane 68.1g, methacryloxyoctyltrimethoxysilane 31.9g, pentaerythritol tetrakis[3-(3,5-tert-butyl-4-hydroxyphenyl)propionate ]0.074g, mix at room temperature. Then, the reaction was carried out by refluxing at 60° C. for 6 hours. After the reaction is completed, the organic layer is taken out, washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water becomes neutral, and then the solvent and water are distilled under reduced pressure to obtain a viscous transparent liquid. Epoxy-containing polyorganosiloxane (EPS-1). The epoxy group-containing polysiloxane was subjected to 1 H-nuclear magnetic resonance (NMR) analysis, and it was confirmed that an oxanyl group-based polysiloxane can be obtained at a chemical offset (δ) of around 3.2 ppm. Wave peak, no side reactions of epoxy groups will be caused during the reaction. The weight average molecular weight Mw of the epoxy group-containing polyorganosiloxane is 2,200, and the epoxy equivalent weight is 186 g/mol.
[合成例1-2:聚有機矽氧烷(PS-1)的合成] [Synthesis Example 1-2: Synthesis of polyorganosiloxane (PS-1)]
於100mL的三口燒瓶中裝入合成例1-1中所得的含環氧基的聚有機矽氧烷(EPS-1)10.1g、4-(4-正戊基環己基)苯甲酸1.3g、丙二醇單甲醚乙酸酯17g、及四丁基溴化銨0.3g,於90℃下攪拌12小時。反應結束後,對於反應溶液,利用0.75當量(質量)的環己烷加以稀釋,並進行5次水洗。將該溶液濃縮,並利用丙二醇單甲醚乙酸酯(PGMEA)加以稀釋,反覆進行2次該操作,獲得包含具有垂直配向性基的聚有機矽氧烷(PS-1)的溶液。該聚有機矽氧烷(PS-1)的重量平均分子量Mw為8,000。 A 100 mL three-necked flask was charged with 10.1 g of the epoxy group-containing polyorganosiloxane (EPS-1) obtained in Synthesis Example 1-1, 1.3 g of 4-(4-n-pentylcyclohexyl)benzoic acid, 17 g of propylene glycol monomethyl ether acetate and 0.3 g of tetrabutylammonium bromide were stirred at 90° C. for 12 hours. After the reaction was completed, the reaction solution was diluted with 0.75 equivalents (mass) of cyclohexane and washed with water five times. The solution was concentrated and diluted with propylene glycol monomethyl ether acetate (PGMEA). This operation was repeated twice to obtain a solution containing polyorganosiloxane (PS-1) having vertical alignment groups. The weight average molecular weight Mw of the polyorganosiloxane (PS-1) is 8,000.
[合成例2-A:肉桂酸衍生物(mc-1)的合成] [Synthesis Example 2-A: Synthesis of cinnamic acid derivative (mc-1)]
於具備冷卻管的500mL的三口燒瓶中加入1-溴-4-環己基苯19.2g、乙酸鈀0.18g、三(2-甲苯基)膦0.98g、三基胺32.4g及二甲基乙醯胺135mL加以混合。繼而,利用注射器將丙烯酸7g加入混合溶液中進行攪拌。進而一邊於120℃下將該混合溶液加熱3小時,一邊進行攪拌。利用薄層層析儀(TLC)確認反應的結束後, 將反應溶液冷卻至室溫。將沈澱物過濾分離後,將濾液注入1N鹽酸水溶液300mL中,並回收沈澱物。利用乙酸乙酯與己烷的1:1(質量比)溶液對該些沈澱物進行再結晶,藉此而獲得10.2g的由下述式(mc-1)所表示的肉桂酸衍生物。 Add 19.2g of 1-bromo-4-cyclohexylbenzene, 0.18g of palladium acetate, 0.98g of tris(2-tolyl)phosphine, 32.4g of triylamine and dimethylacetyl into a 500mL three-necked flask equipped with a cooling tube. Add 135 mL of amine and mix. Next, 7 g of acrylic acid was added to the mixed solution using a syringe and stirred. Furthermore, the mixed solution was stirred while heating it at 120°C for 3 hours. After confirming the completion of the reaction using thin layer chromatography (TLC), The reaction solution was cooled to room temperature. After filtering and separating the precipitate, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution, and the precipitate was recovered. These precipitates were recrystallized from a 1:1 (mass ratio) solution of ethyl acetate and hexane, thereby obtaining 10.2 g of a cinnamic acid derivative represented by the following formula (mc-1).
[合成例2-1:含環氧基的聚有機矽氧烷(EPS-2)的合成] [Synthesis Example 2-1: Synthesis of epoxy group-containing polyorganosiloxane (EPS-2)]
於具備攪拌機、溫度計、滴加漏斗及回流冷卻管的反應容器中裝入2-(3,4-環氧基環己基)乙基三甲氧基矽烷100.0g、甲基異丁基酮500g及三乙胺10.0g,於室溫下加以混合。繼而,自滴加漏斗花費30分鐘滴加去離子水100g後,於回流下加以混合,並且於80℃下使其反應6小時。於反應結束後,取出有機層,藉由0.2重量%硝酸銨水溶液進行清洗至清洗後的水成為中性為止後,於減壓下蒸餾去除溶媒及水,藉此,以黏稠的透明液體形式獲得含環氧基的聚有機矽氧烷(EPS-1)。 Put 100.0g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500g of methyl isobutyl ketone and trimethoxysilane into a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux cooling tube. 10.0g of ethylamine, mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, mixed under reflux, and reacted at 80° C. for 6 hours. After the reaction is completed, the organic layer is taken out, washed with 0.2% by weight ammonium nitrate aqueous solution until the washed water becomes neutral, and then the solvent and water are distilled under reduced pressure to obtain a viscous transparent liquid. Epoxy-containing polyorganosiloxane (EPS-1).
對該含環氧基的聚矽氧烷進行1H-NMR分析,結果確認到於化學偏移(δ)=3.2ppm附近可獲得基於氧雜環丙基的波峰,反應過程中不會引起環氧基的副反應。該含環氧基的聚有機矽氧烷的重量平均分子量Mw為2,200,環氧當量為186g/莫耳。 The 1 H-NMR analysis of the epoxy group-containing polysiloxane confirmed that an oxetanyl-based peak was obtained near the chemical shift (δ) = 3.2 ppm, and no cyclopropyl groups were caused during the reaction. Oxygen side reactions. The weight average molecular weight Mw of the epoxy group-containing polyorganosiloxane is 2,200, and the epoxy equivalent weight is 186 g/mol.
[合成例2-2:含光配向性基的聚有機矽氧烷(PS-2)的合成] [Synthesis Example 2-2: Synthesis of photoalignment group-containing polyorganosiloxane (PS-2)]
於100mL的三口燒瓶中裝入合成例2-1中所得的含環氧基的聚有機矽氧烷(EPS-2)10.1g、含丙烯酸基的羧酸(東亞合成股份有限公司,商品名「亞羅尼斯(Aronix)M-5300」、丙烯酸ω-羧基聚己內酯(聚合度n≒2))0.5g、乙酸丁酯20g、合成例2-A中獲得的肉桂酸衍生物(mc-1)1.5g、及四丁基溴化銨0.3g,於90℃下攪拌12小時。於反應結束後,利用與反應溶液等量(質量)的丙二醇單甲醚乙酸酯加以稀釋,並進行3次水洗。將該溶液濃縮,並利用丙二醇單甲醚乙酸酯加以稀釋,反覆進行2次該操作,最終獲得包含具有光配向性基的聚有機矽氧烷(PS-2)的溶液。該聚有機矽氧烷(PS-2)的重量平均分子量Mw為9,000。 A 100 mL three-necked flask was charged with 10.1 g of the epoxy group-containing polyorganosiloxane (EPS-2) obtained in Synthesis Example 2-1 and an acrylic acid group-containing carboxylic acid (Toagosei Co., Ltd., trade name " Aronix M-5300", ω-carboxypolycaprolactone acrylate (degree of polymerization n≒2)) 0.5 g, butyl acetate 20 g, cinnamic acid derivative (mc- 1) 1.5g, and 0.3g of tetrabutylammonium bromide, stir at 90°C for 12 hours. After the reaction is completed, the reaction solution is diluted with the same amount (mass) of propylene glycol monomethyl ether acetate, and washed with water three times. The solution was concentrated and diluted with propylene glycol monomethyl ether acetate. This operation was repeated twice, and finally a solution containing polyorganosiloxane (PS-2) having a photoalignment group was obtained. The weight average molecular weight Mw of the polyorganosiloxane (PS-2) is 9,000.
[合成例3-1:含環氧基的聚甲基丙烯酸酯(AP-1)的合成] [Synthesis Example 3-1: Synthesis of epoxy group-containing polymethacrylate (AP-1)]
於具備冷卻管及攪拌機的燒瓶中裝入作為聚合起始劑的2,2'-偶氮雙(異丁腈)1質量份、及作為溶媒的丙二醇單甲醚乙酸酯180質量份。於其中加入甲基丙烯酸3,4-環氧基環己基甲酯50質量份、及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯50質量份,對燒瓶內進行氮氣置換後,緩慢地開始攪拌。使溶液溫度上升至80℃,並維持該溫度5小時,藉此而獲得含有32.9質量%的具有環氧基的聚甲基丙烯酸酯的聚合體溶液。所獲得的含環氧基的聚甲基丙烯酸酯的數量平均分子量Mn為16,000。 A flask equipped with a cooling tube and a stirrer was charged with 1 part by mass of 2,2'-azobis(isobutyronitrile) as a polymerization initiator and 180 parts by mass of propylene glycol monomethyl ether acetate as a solvent. 50 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate and 50 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate were added to the flask. After nitrogen replacement, stirring was slowly started. The solution temperature was raised to 80° C. and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing 32.9 mass % of polymethacrylate having an epoxy group. The number average molecular weight Mn of the obtained epoxy group-containing polymethacrylate was 16,000.
[合成例4-1:含光配向性基的聚醯胺酸(PAA-1)的合成] [Synthesis Example 4-1: Synthesis of photoalignment group-containing polyamide (PAA-1)]
將作為四羧酸二酐的2,3,5-三羧基環戊基乙酸二酐2.24g(0.01莫耳)、以及作為二胺的由下述式(8)所表示的化合物2.54g(0.01莫耳)溶解於N-甲基-2-吡咯啶酮(N-methyl-2-pyrrolidone,NMP)27.1g中,於40℃下使其反應3小時,藉此而獲得含有15質量%的聚醯胺酸(PAA-1)的溶液31.8g。該聚醯胺酸溶液的溶液黏度為68mPa.s。 2.24 g (0.01 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride as tetracarboxylic dianhydride and 2.54 g (0.01 mol) of a compound represented by the following formula (8) as a diamine Mol) was dissolved in 27.1 g of N-methyl-2-pyrrolidone (NMP) and reacted at 40°C for 3 hours to obtain a poly(P) containing 15% by mass. 31.8g of solution of hydroxyamide (PAA-1). The solution viscosity of the polyamide solution is 68mPa. s.
[合成例5-A:甲基丙烯酸酯(9)的合成] [Synthesis Example 5-A: Synthesis of methacrylate (9)]
將4,4'-聯苯基二醇與1,6-二溴己烷於鹼條件下加熱,藉此而合成4'-(6-溴己基氧基)聯苯基-4-醇。使甲基丙烯酸鋰與該產物反應,獲得2-(4'-羥基聯苯基-4-基氧基)己基氧基甲基丙烯酸酯。繼而,於鹼性條件下加入4-甲氧基肉桂醯氯,合成由下述式(9)所表示的化合物(甲基丙烯酸酯(9))。 4'-(6-bromohexyloxy)biphenyl-4-ol is synthesized by heating 4,4'-biphenyldiol and 1,6-dibromohexane under alkaline conditions. Lithium methacrylate is reacted with this product to obtain 2-(4'-hydroxybiphenyl-4-yloxy)hexyloxy methacrylate. Next, 4-methoxycinnamyl chloride was added under basic conditions to synthesize a compound (methacrylate (9)) represented by the following formula (9).
[合成例5-B:甲基丙烯酸酯(10)的合成] [Synthesis Example 5-B: Synthesis of methacrylate (10)]
將4-羥基肉桂酸與1-羥基-6-己醇於鹼條件下加熱,藉此而合成4-(6-羥基己基氧基)肉桂酸。使甲基丙烯醯氯與該產物於鹼性條件下反應,獲得由下述式(10)所表示的化合物(甲基丙烯酸酯(10))。 4-(6-hydroxyhexyloxy)cinnamic acid is synthesized by heating 4-hydroxycinnamic acid and 1-hydroxy-6-hexanol under alkaline conditions. Methacrylate chloride and this product are reacted under basic conditions to obtain a compound (methacrylate (10)) represented by the following formula (10).
[合成例5-C:甲基丙烯酸酯(11)的合成] [Synthesis Example 5-C: Synthesis of Methacrylate (11)]
將4-碘酚與6-氯-1-己醇於鹼條件下加熱,藉此而合成4-(6-羥基己基氧基)碘酚。使2-甲基-3-丁炔-2-醇與該產物反應後,於鹼條件下進行加熱,藉此而獲得4-(6-羥基己基氧基)乙炔基苯(將其設為化合物A)。另外,於另一路徑,使4-甲氧基肉桂醯氯與4-碘酚反應,合成4-碘苯基-3-(4-甲氧基苯基)丙烯酸酯(將其設為化合物B)。接下來,使化合物A與化合物B於鹼性條件下反應,藉此而獲得由下述式(12)所表示的化合物(甲基丙烯酸酯(11))。 4-(6-hydroxyhexyloxy)iodophenol is synthesized by heating 4-iodophenol and 6-chloro-1-hexanol under alkaline conditions. After reacting 2-methyl-3-butyn-2-ol with the product, the product is heated under alkaline conditions to obtain 4-(6-hydroxyhexyloxy)ethynylbenzene (referred to as compound A). In addition, in another route, 4-methoxycinnamyl chloride and 4-iodophenol were reacted to synthesize 4-iodophenyl-3-(4-methoxyphenyl)acrylate (referred to as compound B ). Next, compound A and compound B are reacted under basic conditions to obtain a compound (methacrylate (11)) represented by the following formula (12).
[合成例5-1:具有液晶性的聚甲基丙烯酸酯(LCP-1)的合成] [Synthesis Example 5-1: Synthesis of liquid crystalline polymethacrylate (LCP-1)]
將甲基丙烯酸酯(9)溶解於四氫呋喃中,添加作為反應起始劑的偶氮雙異丁腈(AIBN)來進行聚合,藉此而獲得聚合物溶液。將該聚合物溶液滴加至二乙醚(5000ml)中,將所獲得的沈澱物過濾。利用二乙醚來清洗該沈澱物,並於40℃的烘箱中減壓乾燥,以粉末形式獲得具有液晶性的聚甲基丙烯酸酯(LCP-1)。所獲得的聚甲基丙烯酸酯(LCP-1)的數量平均分子量為46,000,重量平 均分子量為119,600。該聚甲基丙烯酸酯(LCP-1)於116℃~315℃的溫度範圍內顯示出液晶性。 Methacrylate (9) is dissolved in tetrahydrofuran, and azobisisobutyronitrile (AIBN) is added as a reaction initiator to polymerize, thereby obtaining a polymer solution. This polymer solution was added dropwise to diethyl ether (5000 ml), and the obtained precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40° C. to obtain liquid crystalline polymethacrylate (LCP-1) in powder form. The obtained polymethacrylate (LCP-1) had a number average molecular weight of 46,000 and a weight average of The average molecular weight is 119,600. This polymethacrylate (LCP-1) exhibits liquid crystallinity in the temperature range of 116°C to 315°C.
[合成例5-2:具有液晶性的聚甲基丙烯酸酯(LCP-2)的合成] [Synthesis Example 5-2: Synthesis of liquid crystalline polymethacrylate (LCP-2)]
使用甲基丙烯酸酯(10)來代替甲基丙烯酸酯(9),除該方面以外,進行與合成例5-1同樣的操作,藉此而獲得聚甲基丙烯酸酯(LCP-2)。所獲得的聚甲基丙烯酸酯(LCP-2)的數量平均分子量為46,000,重量平均分子量為119,600。該聚甲基丙烯酸酯(LCP-2)於135℃~187℃的溫度範圍內顯示出液晶性。 Polymethacrylate (LCP-2) was obtained by performing the same operation as Synthesis Example 5-1 except that methacrylate (10) was used instead of methacrylate (9). The obtained polymethacrylate (LCP-2) had a number average molecular weight of 46,000 and a weight average molecular weight of 119,600. This polymethacrylate (LCP-2) exhibits liquid crystallinity in the temperature range of 135°C to 187°C.
[合成例5-3:具有液晶性的聚甲基丙烯酸酯(LCP-3)的合成] [Synthesis Example 5-3: Synthesis of liquid crystalline polymethacrylate (LCP-3)]
使用甲基丙烯酸酯(11)來代替甲基丙烯酸酯(9),除該方面以外,進行與合成例5-1同樣的操作,藉此而獲得聚甲基丙烯酸酯(LCP-3)。所獲得的聚甲基丙烯酸酯(LCP-3)的數量平均分子量為46,000,重量平均分子量為119,600。該聚甲基丙烯酸酯(LCP-3)於66℃~320℃的溫度範圍內顯示出液晶性。 Polymethacrylate (LCP-3) was obtained by performing the same operation as Synthesis Example 5-1 except that methacrylate (11) was used instead of methacrylate (9). The obtained polymethacrylate (LCP-3) had a number average molecular weight of 46,000 and a weight average molecular weight of 119,600. This polymethacrylate (LCP-3) exhibits liquid crystallinity in the temperature range of 66°C to 320°C.
<液晶配向膜的製作及評價> <Production and Evaluation of Liquid Crystal Alignment Film>
[實施例1] [Example 1]
1.液晶配向劑的製備 1. Preparation of liquid crystal alignment agent
於含有聚甲基丙烯酸酯(AP-1)作為聚合體成分的溶液中,以聚甲基丙烯酸酯(AP-1):聚有機矽氧烷(PS-1)=95:5(質量比)的方式加入聚有機矽氧烷(PS-1),進而加入作為溶劑的3- 甲氧基丙酸甲酯(MMP)、丙二醇單甲醚乙酸酯(PGMEA)、及丙二醇單甲醚(PGME)並充分攪拌,製成溶劑組成為MMP:PGMEA:PGME=10:40:50(質量比)、固體成分濃度為4.0質量%的溶液。使用孔徑為1μm的過濾器將該溶液過濾,藉此製備液晶配向劑(AL-1)。 In a solution containing polymethacrylate (AP-1) as a polymer component, polymethacrylate (AP-1): polyorganosiloxane (PS-1) = 95:5 (mass ratio) Add polyorganosiloxane (PS-1), and then add 3- Methoxymethoxypropionate (MMP), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME) and stir thoroughly to make a solvent composition of MMP: PGMEA: PGME=10:40:50 (mass ratio), a solution with a solid content concentration of 4.0 mass%. The solution was filtered using a filter with a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-1).
2.塗佈性的評價 2. Evaluation of coating properties
作為評價用樣品,利用棒塗機將所述1.中製備的液晶配向劑(AL-1)塗佈於PET膜上,於120℃下乾燥2分鐘而形成液晶配向膜。於顯微鏡下觀察該液晶配向膜的表面的不均,藉此來評價液晶配向劑的塗佈性(塗佈不均)。作為評價用樣品,製作乾燥後的液晶配向膜的膜厚為0.1μm、0.3μm的兩種。再者,膜厚越厚,越容易於液晶配向膜的表面產生不均。評價時,將塗膜表面完全未觀察到不均的情況評價為「非常良好(◎)」,將塗膜表面觀察到極少不均的情況評價為「良好(○)」,將塗佈表面觀察到稍許不均的情況評價為「可(△)」,將塗膜表面觀察到許多不均的情況評價為「不良(×)」。結果,該實施例中,膜厚0.1μm的情況下為「非常良好」的評價,膜厚0.3μm的情況下為「良好」的評價。 As a sample for evaluation, the liquid crystal alignment agent (AL-1) prepared in the above 1. was coated on the PET film using a bar coater, and dried at 120° C. for 2 minutes to form a liquid crystal alignment film. The unevenness on the surface of the liquid crystal alignment film was observed under a microscope to evaluate the coating properties (uneven coating) of the liquid crystal alignment agent. As evaluation samples, two types of liquid crystal alignment films having a film thickness of 0.1 μm and 0.3 μm after drying were prepared. Furthermore, the thicker the film thickness, the easier it is for unevenness to occur on the surface of the liquid crystal alignment film. During the evaluation, the case where no unevenness was observed on the coating film surface was evaluated as "very good (◎)", the case where very little unevenness was observed on the coating film surface was evaluated as "good (○)", and the coating surface was evaluated as "very good (◎)". When a slight unevenness is observed, it is evaluated as "acceptable (△)", and when a lot of unevenness is observed on the coating film surface, it is evaluated as "poor (×)". As a result, in this Example, the evaluation of "very good" was made when the film thickness was 0.1 micrometer, and the evaluation was "good" when the film thickness was 0.3 micrometer.
3.向基材的背移性的評價 3. Evaluation of back migration to the base material
作為評價用樣品,利用棒塗機將所述1.中製備的液晶配向劑(AL-1)塗佈於PET膜上,於120℃下乾燥2分鐘而形成膜厚0.1μm的液晶配向膜。繼而,於液晶配向膜面(A)上層疊PET膜(B), 於80℃下保持施加有負荷40g/cm2的狀態30分鐘後,維持層疊狀態而冷卻至室溫。其後,將PET膜(B)自液晶配向膜面(A)剝離,目視觀察PET膜(B)中液晶配向膜的聚合體成分及殘留溶劑是否發生背移。再者,於液晶配向膜的聚合體成分及殘留溶劑背移至PET膜(B)的情況下,以白濁的形式觀察到背移的部分。評價時,將PET膜(B)中完全未觀察到背移的情況評價為「非常良好(◎)」,將觀察到極少背移的情況評價為「良好(○)」,將觀察到稍許背移的情況評價為「可(△)」,將整體觀察到背移的情況評價為「不良(×)」。另外,將負荷自40g/cm2變更為80g/cm2,除此以外,以與所述相同的方式進行評價。結果,該實施例中,將負荷設為40g/cm2的情況及設為80g/cm2的情況的兩者均為「非常良好」的評價。 As a sample for evaluation, the liquid crystal alignment agent (AL-1) prepared in the above 1. was coated on a PET film using a bar coater, and dried at 120° C. for 2 minutes to form a liquid crystal alignment film with a film thickness of 0.1 μm. Next, the PET film (B) was laminated on the liquid crystal alignment film surface (A), and the state where a load of 40 g/cm 2 was applied was maintained at 80° C. for 30 minutes. The layer was then cooled to room temperature while maintaining the stacked state. Thereafter, the PET film (B) was peeled off from the liquid crystal alignment film surface (A), and it was visually observed whether the polymer components and residual solvent of the liquid crystal alignment film in the PET film (B) were back-migrated. Furthermore, when the polymer component and residual solvent of the liquid crystal alignment film back-migrated to the PET film (B), the back-migrated portion was observed in the form of white turbidity. During the evaluation, the case where no back shift was observed in the PET film (B) was evaluated as "very good (◎)", the case where very little back shift was observed was evaluated as "good (○)", and the case where a slight back shift was observed was evaluated as "very good (◎)". The case where the back shift was observed was evaluated as "acceptable (△)", and the case where back shift was observed overall was evaluated as "poor (×)". In addition, evaluation was performed in the same manner as described above, except that the load was changed from 40 g/cm 2 to 80 g/cm 2 . As a result, in this Example, both the case where the load was set to 40 g/cm 2 and the case where the load was set to 80 g/cm 2 were evaluated as "very good".
[參考例1、實施例3~實施例23及比較例1~比較例4] [Reference Example 1, Example 3 to Example 23 and Comparative Example 1 to Comparative Example 4]
將液晶配向劑的調配組成如下述表1及表2所記載般變更,除此以外,進行與實施例1同樣的操作,分別製備液晶配向劑(AL-2)~液晶配向劑(AL-23)、液晶配向劑(BL-1)~液晶配向劑(BL-4)。另外,分別使用液晶配向劑(AL-2)~液晶配向劑(AL-23)、液晶配向劑(BL-1)~液晶配向劑(BL-4)來代替液晶配向劑(AL-1),除此以外,以與實施例1相同的方式進行各種評價。將該些結果示於下述表3中。 The compounding composition of the liquid crystal alignment agent was changed as described in Table 1 and Table 2 below. Except for this, the same operation as in Example 1 was performed to prepare liquid crystal alignment agent (AL-2) ~ liquid crystal alignment agent (AL-23) respectively. ), liquid crystal alignment agent (BL-1) ~ liquid crystal alignment agent (BL-4). In addition, liquid crystal alignment agent (AL-2) ~ liquid crystal alignment agent (AL-23), liquid crystal alignment agent (BL-1) ~ liquid crystal alignment agent (BL-4) are used respectively to replace the liquid crystal alignment agent (AL-1). Other than that, various evaluations were performed in the same manner as in Example 1. These results are shown in Table 3 below.
[表1]
表1及表2中,聚合體一欄括弧內的數值表示各聚合體相對於液晶配向劑的製備中使用的聚合體成分的合計100質量份的調配比例(質量份)。溶劑一欄的數值表示各溶劑相對於液晶配向劑的製備中使用的溶劑成分的合計100質量份的調配比例(質量份)。「-」是指並未使用該化合物。化合物的略號如以下所述。 In Tables 1 and 2, the numerical values in parentheses in the polymer column represent the blending ratio (parts by mass) of each polymer relative to a total of 100 parts by mass of the polymer components used in the preparation of the liquid crystal alignment agent. The numerical value in the solvent column represents the compounding ratio (parts by mass) of each solvent relative to a total of 100 parts by mass of the solvent components used in the preparation of the liquid crystal alignment agent. "-" means that the compound was not used. The abbreviations of the compounds are as follows.
<溶劑> <Solvent>
MMP:3-甲氧基丙酸甲酯 MMP: methyl 3-methoxypropionate
EEP:3-乙氧基丙酸乙酯 EEP: ethyl 3-ethoxypropionate
MBA:3-甲氧基丁基乙酸酯 MBA: 3-methoxybutylacetate
PGMPE:丙二醇甲基丙基醚 PGMPE: propylene glycol methyl propyl ether
PGMBE:丙二醇甲基丁基醚 PGMBE: propylene glycol methyl butyl ether
CA:乙酸環己酯 CA: cyclohexyl acetate
CP:丙酸環己酯 CP: cyclohexyl propionate
NMP:N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone
GBL:γ-丁內酯 GBL: gamma-butyrolactone
NEP:N-乙基-2-吡咯啶酮 NEP: N-ethyl-2-pyrrolidinone
DMI:1,3-二甲基-2-咪唑啶酮 DMI: 1,3-dimethyl-2-imidazolidinone
PGMEA:丙二醇單甲醚乙酸酯 PGMEA: propylene glycol monomethyl ether acetate
PGME:丙二醇單甲醚 PGME: propylene glycol monomethyl ether
DEDG:二乙二醇二乙醚 DEDG: Diethylene glycol diethyl ether
BC:丁基賽珞蘇 BC: Dinkycellosu
[表3]
如根據表3可知般,使用包含(A)溶劑的液晶配向劑的實施例1、參考例1及實施例3~實施例23的塗佈性及背移性為「非常良好」、「良好」或「可」的評價,取得兩者的平衡。另外,藉由併用(B)溶劑,將液晶配向膜的膜厚設為0.3μm時的塗佈性進一步改善。另一方面,不含溶劑(A)的比較例的比較例 1~比較例3中,若將膜厚設為0.3μm,則塗佈性為「不良」的評價。另外,比較例3、比較例4中背移性為「不良」的評價。 As can be seen from Table 3, the coating properties and back transfer properties of Example 1, Reference Example 1, and Examples 3 to 23 using the liquid crystal alignment agent containing (A) solvent were "very good" and "good" or "yes" evaluation to achieve a balance between the two. In addition, by using the solvent (B) in combination, the coatability when the film thickness of the liquid crystal alignment film is set to 0.3 μm is further improved. On the other hand, comparative examples that do not contain the solvent (A) In Comparative Examples 1 to 3, when the film thickness was 0.3 μm, the coating properties were evaluated as "poor". In addition, in Comparative Examples 3 and 4, the back migration properties were evaluated as "poor".
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-240060 | 2017-12-14 | ||
JP2017240060 | 2017-12-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201927865A TW201927865A (en) | 2019-07-16 |
TWI814748B true TWI814748B (en) | 2023-09-11 |
Family
ID=66820188
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW107137393A TWI814748B (en) | 2017-12-14 | 2018-10-23 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal alignment film |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6891975B2 (en) |
CN (1) | CN111212878B (en) |
TW (1) | TWI814748B (en) |
WO (1) | WO2019116702A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115521446B (en) * | 2022-09-19 | 2023-07-18 | 广东省科学院生物与医学工程研究所 | Azobenzene liquid crystal polymer and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1073825A (en) * | 1996-09-02 | 1998-03-17 | Japan Synthetic Rubber Co Ltd | Liquid crystal orienting agent |
TW201546182A (en) * | 2014-02-19 | 2015-12-16 | Rolic Ag | Liquid crystal alignment composition, liquid crystal alignment film and liquid crystal display element |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3177872B2 (en) * | 1995-03-27 | 2001-06-18 | ジェイエスアール株式会社 | Liquid crystal alignment agent |
JP3603472B2 (en) * | 1996-05-14 | 2004-12-22 | Jsr株式会社 | Liquid crystal alignment agent and liquid crystal display device |
JP4433175B2 (en) * | 2004-07-01 | 2010-03-17 | Jsr株式会社 | Liquid crystal alignment agent for inkjet coating |
JP5273357B2 (en) * | 2007-07-06 | 2013-08-28 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP2009251094A (en) * | 2008-04-02 | 2009-10-29 | Konica Minolta Opto Inc | Retardation film, polarizing plate and liquid crystal display device |
JP5532195B2 (en) * | 2008-06-10 | 2014-06-25 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5671797B2 (en) * | 2009-01-29 | 2015-02-18 | Jnc株式会社 | Alignment agent and liquid crystalline polyimide used therefor |
JP6179076B2 (en) * | 2011-10-13 | 2017-08-16 | Jsr株式会社 | Liquid crystal alignment agent |
JP6146135B2 (en) * | 2012-08-30 | 2017-06-14 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display element |
KR102538726B1 (en) * | 2017-04-25 | 2023-05-31 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
-
2018
- 2018-10-11 WO PCT/JP2018/037876 patent/WO2019116702A1/en active Application Filing
- 2018-10-11 JP JP2019558932A patent/JP6891975B2/en active Active
- 2018-10-11 CN CN201880066614.6A patent/CN111212878B/en active Active
- 2018-10-23 TW TW107137393A patent/TWI814748B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1073825A (en) * | 1996-09-02 | 1998-03-17 | Japan Synthetic Rubber Co Ltd | Liquid crystal orienting agent |
TW201546182A (en) * | 2014-02-19 | 2015-12-16 | Rolic Ag | Liquid crystal alignment composition, liquid crystal alignment film and liquid crystal display element |
Also Published As
Publication number | Publication date |
---|---|
WO2019116702A1 (en) | 2019-06-20 |
JP6891975B2 (en) | 2021-06-18 |
JPWO2019116702A1 (en) | 2020-08-27 |
CN111212878B (en) | 2022-06-14 |
TW201927865A (en) | 2019-07-16 |
CN111212878A (en) | 2020-05-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6686298B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device | |
JP6911885B2 (en) | Manufacturing method of liquid crystal alignment film and manufacturing method of liquid crystal element | |
KR102236019B1 (en) | Liquid crystal aligning agent, liquid crystal alignment film and manufacturing method therefor, liquid crystal device, and polymer | |
TWI691526B (en) | Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film, liquid crystal display element, polymer, diamine compound and carboxylic acid | |
JP2017138575A (en) | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and diamine | |
JP2016029465A (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film, and manufacturing method of phase difference film | |
JP5158314B2 (en) | Liquid crystal aligning agent and liquid crystal display element | |
TWI815876B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal element | |
TWI791817B (en) | Liquid crystal alignment agent and manufacturing method thereof, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element | |
TWI814748B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal alignment film | |
JPWO2020148953A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element | |
JP2017040721A (en) | Liquid crystal aligning agent, liquid crystal alignment film, production method of liquid crystal alignment film, liquid crystal display element, polymer and compound | |
CN106947498B (en) | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, and method for producing liquid crystal alignment film and liquid crystal element | |
TWI683845B (en) | Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal display element, and phase difference film and manufacturing method thereof | |
KR102404078B1 (en) | A liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and the manufacturing method of a liquid crystal element | |
TWI791838B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and method for manufacturing liquid crystal element | |
TWI850211B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element | |
JP2023170991A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element | |
JP2023107736A (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and method for producing liquid crystal element | |
CN115449376A (en) | Liquid crystal aligning agent and application thereof, polyamic acid ester, polyimide, diamine and tetracarboxylic dianhydride manufacturing method | |
TW201938770A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element |