CN102732262B - Liquid crystal aligning agent - Google Patents
Liquid crystal aligning agent Download PDFInfo
- Publication number
- CN102732262B CN102732262B CN201110150807.XA CN201110150807A CN102732262B CN 102732262 B CN102732262 B CN 102732262B CN 201110150807 A CN201110150807 A CN 201110150807A CN 102732262 B CN102732262 B CN 102732262B
- Authority
- CN
- China
- Prior art keywords
- formula
- polymkeric substance
- organic base
- carbon number
- divalent organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 45
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 34
- 150000004985 diamines Chemical class 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims description 52
- 239000013078 crystal Substances 0.000 claims description 46
- 150000007530 organic bases Chemical class 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 8
- -1 polyoxyethylene Polymers 0.000 description 44
- 239000010408 film Substances 0.000 description 31
- 239000000758 substrate Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 229920001059 synthetic polymer Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000035515 penetration Effects 0.000 description 7
- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KOUONPVXNPOEHQ-UHFFFAOYSA-N 2-[dimethoxy(propyl)silyl]oxyacetamide Chemical compound CCC[Si](OC)(OC)OCC(N)=O KOUONPVXNPOEHQ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- NSSIZMPQSZKECB-UHFFFAOYSA-N (diethoxyamino)oxyethane Chemical compound CCON(OCC)OCC NSSIZMPQSZKECB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- HTLMNYSFRMFQEV-UHFFFAOYSA-N C(C)OC(=O)NC(=O)CCC[Si](OC)(OC)OC Chemical compound C(C)OC(=O)NC(=O)CCC[Si](OC)(OC)OC HTLMNYSFRMFQEV-UHFFFAOYSA-N 0.000 description 1
- HJIYHOVBJRVELV-UHFFFAOYSA-N C(C)OCC(=S)OCCO Chemical compound C(C)OCC(=S)OCCO HJIYHOVBJRVELV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IQSBKDJPSOMMRZ-UHFFFAOYSA-N ethenyl(methyl)silane Chemical compound C[SiH2]C=C IQSBKDJPSOMMRZ-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000010020 roller printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
The invention discloses a liquid crystal alignment agent. The liquid crystal aligning agent comprises a polymer and a polymer (B). The polymer (a) is a polyimide-polyamic acid having a side chain diamine, and the polymer (B) is a polyamic acid having a side chain diamine. The liquid crystal alignment agent has the characteristics of stable pretilt angle property, excellent adherence and improvement of the problem of residual images.
Description
Technical field
The present invention relates to a kind of crystal aligning agent, relate in particular to a kind of crystal aligning agent that there is the polyimide-polyamic acid of side chain diamines and there is the polyamic acid of side chain diamines that comprises.
Background technology
The indicating meter of liquid-crystal display (liquid crystal display) for utilizing liquid crystal photoelectricity to change, the attracting advantage such as it has, and volume is little, lightweight, low power consumption and display quality are good, so become in recent years flat-panel screens main flow.
The development of liquid-crystal display is along with the expansion of picture dimension, the requirement that the high saturation of color, high-contrast and speed of response are promoted, by twisted nematic (twisted nematic, TN) liquid-crystal display, STN Super TN (super twisted nematic, STN) liquid-crystal display, so far develop into the TFT type liquid-crystal display that thin film transistor (thin filmed transistor, TFT) is all housed in each picture element.Continue in recent years the type of drive of TFT type liquid-crystal display to improve.For example improving aspect visual angle, developing vertical orientation (vertical alignment, VA) mode or copline conversion (in-plane switching, IPS) mode.In addition also developed, optical compensation curved (optically compensated bend, the OCB) mode of the speed of response that can improve corresponding animation.
In liquid-crystal display, be typically twisted nematic (TN) field effect mode liquid-crystal display, its use has positive dielectric anisotropy nematic liquid crystal.Generally speaking, liquid crystal molecule is inserted between a pair of substrate that contains electrode, and the alignment direction of these two substrates is mutually vertical, and via control electric field, can control the arrangement mode of liquid crystal molecule.With regard to the liquid-crystal display of this type, it is considerable making the long axis direction of liquid crystal molecule and orientation that substrate surface can have even angle of inclination.Make Liquid Crystal Molecules Alignment become the material of even tilt angle (pre-tilt angle) orientation to be commonly referred to as alignment film (alignment film).
Industry member has two kinds of typical alignment film preparation methods at present.First method is, by steam deposition, inorganic substance are made to mineral membrane.For example, the silicon-dioxide evaporation that tilts is formed to film in substrate, and liquid crystal molecule in evaporation direction by orientation.Yet, although above-mentioned method can obtain uniform orientation, more do not have an industrial efficiency.Second method is that organic membrane is coated on substrate surface, then utilizes the soft cloth of cotton, nylon or polyester rubbed and the surface of organic membrane is directed so that liquid crystal molecule at frictional direction by orientation.Because this method is simpler and easy and quite easily obtain even orientation, be therefore widely used in technical scale.The polymkeric substance that can form organic film is for example polyvinyl alcohol (polyvinylalcohol, PVA), polyoxyethylene (polyethylene oxide, PEO), polymeric amide (polyamide, PA) or polyimide, wherein polyimide, owing to having the character such as chemical stability and thermostability, is therefore the most often utilized as alignment film material.
Yet, when liquid-crystal display is applied to voltage, the ionic electric charge producing can be adsorbed by liquid crystal orienting film, even and after removing the voltage applying, also be difficult to make ionic electric charge to depart from from liquid crystal orienting film, thereby cause picture to produce the problem of image retention.Therefore, the in the recent period exploitation of alignment film material all be take and is improved image retention problem as primary problem.
Summary of the invention
The invention provides a kind of crystal aligning agent, can obtain and there is stable tilt angle character, adherence is splendid and can improves the LCD assembly of ghost problem.
The present invention proposes a kind of crystal aligning agent, comprises polymkeric substance (A) and polymkeric substance (B).Polymkeric substance (A) is by the polyimide-polyamic acid with side chain diamines shown in following formula (1).Polymkeric substance (B) is by the polyamic acid also with side chain diamines shown in following formula (2).The weight ratio (A) of polymkeric substance (A) and polymkeric substance (B)/(B) is for example 5/95 to 95/5.
Formula (1)
Formula (2)
In formula (1) and formula (2), T
1, T
2and T
3be expressed as the quadrivalent organic radical of tetracarboxylic dianhydride's monomer, m+n=1, n≤0.5, D
1or D
2in at least one part for selecting free style (3) or by the divalent organic base of diamine compound shown in formula (4), D
3in at least one part be the divalent organic base by diamine compound shown in formula (4), and D
1, D
2and D
3in the rest part divalent organic base that is diamine compound,
Formula (3)
Formula (4)
In formula (3), R
1, R
2, R
3, R
5and R
6independently be expressed as respectively the alkyl that hydrogen or carbon number are 1-5, R
4represent alkyl, CO that carbon number is 4-20
2r
22, CONR
22or (CH
2)
pcF
3, the integer that p is 1-5, R
22represent the alkyl that carbon number is 4-20, in formula (4), R
7-R
11in to appoint the two be one-level amido, all the other are independently hydrogen atom or one-level amido any monovalent organic radical in addition separately, R
7-R
11separately can be identical also can be different, X
1and X
2be expressed as singly-bound or select the divalence of the group that free ether, ester, ketone, acid amides and secondary amine form in conjunction with base, X
1and X
2separately can be identical also can be different, X
3and X
4be expressed as the straight chain shape alkylidene group of carbon number 1-3, X
3and X
4separately can be identical also can be different, R
12be expressed as the alkyl of carbon number 1-20, any monovalent organic radical of the ester ring type skeleton of carbon number 3-40, carbon number 6-51 containing any monovalent organic radical of aromatic series skeleton or any monovalent organic radical of heterocycle skeleton.
Described in the embodiment of the present invention, D in crystal aligning agent of the present invention
1, D
2and D
3in, except being selected from, there is by formula (3) or the part by the divalent organic base of diamine compound shown in formula (4) above-mentioned D
1, D
2and D
3in rest part also optional free style (5) to the group that formula (12) forms,
Formula (5) formula (6) formula (7)
Formula (8) formula (9)
Formula (10)
Formula (11) formula (12)
R wherein
13for the alicyclic unit price organic radical of carbon number 4-40 or the long-chain fat family unit price organic radical of carbon number 8-20; R
14for halogen atom or unit price organic radical; R
15alicyclic divalent organic base for carbon number 4-40; R
16for divalence is alicyclic, the long-chain fat family divalent organic base of divalence aromatic series or carbon number 1-8; X and Y are respectively the divalent radical of the group that choosing freedom-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-form; Z is choosing freedom-CF
3,-CN, COCH
3,-COOH ,-NO
2, SOCH
3,-SO
2cH
3,-OCF
3,-F and-the unit price organic radical of the group that Cl forms.
Described in the embodiment of the present invention, in polymkeric substance (A) by the content of the divalent organic base of diamine compound shown in formula (3), with all divalent organic base D of polymkeric substance (A)
1and D
2total amount is counted 0.1 molar percentage to 50 molar percentage.
Described in the embodiment of the present invention, in polymkeric substance (B) by the content of the divalent organic base of diamine compound shown in formula (3), with all divalent organic base D of polymkeric substance (B)
3total amount is counted 0.1 molar percentage to 50 molar percentage.
Described in the embodiment of the present invention, in polymkeric substance (A) by the content of the divalent organic base of diamine compound shown in formula (4), with all divalent organic base D of polymkeric substance (A)
1and D
2total amount is counted 5 molar percentage to 50 molar percentages.
Described in the embodiment of the present invention, in polymkeric substance (B) by the content of the divalent organic base of diamine compound shown in formula (4), with all divalent organic base D of polymkeric substance (B)
3total amount is counted 5 molar percentage to 100 molar percentages.
Based on above-mentioned, because crystal aligning agent of the present invention comprises suc as formula the polyimide-polyamic acid with side chain diamines shown in (1) and suc as formula the polyamic acid with side chain diamines shown in (2), therefore with the formed liquid crystal orienting film of this crystal aligning agent, can there is the effect of stable tilt angle, and make the adherence of liquid crystal orienting film improve and can improve ghost problem, and then reach the object of promoting LCD assembly usefulness.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below, and coordinate accompanying drawing to be described in detail below.
Embodiment
Crystal aligning agent of the present invention comprises polymkeric substance (A) and polymkeric substance (B).Polymkeric substance (A) is by the polyimide-polyamic acid with side chain diamines shown in following formula (1).Polymkeric substance (B) is by the polyamic acid also with side chain two amine structures shown in following formula (2).
Formula (1)
Formula (1)
Formula (2)
In formula (1) and formula (2), T
1, T
2and T
3be expressed as the organic radical of tetravalence, m+n=1, n≤0.5, D
1or D
2in at least one part for selecting free style (3) or by the divalent organic base of diamine compound shown in formula (4), D
3in at least one part be the divalent organic base by diamine compound shown in formula (4), and D
1, D
2and D
3in the rest part divalent organic base that is diamine compound.
Formula (3)
In formula (3), R
1, R
2, R
3, R
5and R
6independently be expressed as respectively the alkyl that hydrogen or carbon number are 1-5, R
4represent alkyl, CO that carbon number is 4-20
2r
22, CONR
22or (CH
2)
pcF
3, the integer that p is 1-5, R
22represent the alkyl that carbon number is 4-20.
Formula (4)
In formula (4), R
7-R
11in to appoint the two be one-level amido, all the other are independently hydrogen atom or one-level amido any monovalent organic radical in addition separately, R
7-R
11separately can be identical also can be different, X
1and X
2be expressed as singly-bound or select the divalence of the group that free ether, ester, ketone, acid amides and secondary amine form in conjunction with base, X
1and X
2separately can be identical also can be different, X
3and X
4be expressed as the straight chain shape alkylidene group of carbon number 1-3, X
3and X
4separately can be identical also can be different, R
12be expressed as the alkyl of carbon number 1-20, any monovalent organic radical of the ester ring type skeleton of carbon number 3-40, carbon number 6-51 containing any monovalent organic radical of aromatic series skeleton or any monovalent organic radical of heterocycle skeleton.
The weight ratio (A) of polymkeric substance (A) and polymkeric substance (B)/(B) is for example 5/95 to 95/5.
In addition D in crystal aligning agent of the present invention,
1, D
2and D
3in, except being selected from, there is by formula (3) or the part by the divalent organic base of diamine compound shown in formula (4) above-mentioned D
1, D
2and D
3in rest part also optional free style (5) to the group that formula (12) forms,
Formula (5) formula (6) formula (7)
Formula (8) formula (9)
Formula (10)
Formula (11) formula (12)
R wherein
13for the alicyclic unit price organic radical of carbon number 4-40 or the long-chain fat family unit price organic radical of carbon number 8-20; R
14for halogen atom or unit price organic radical; R
15alicyclic divalent organic base for carbon number 4-40; R
16for divalence is alicyclic, the long-chain fat family divalent organic base of divalence aromatic series or carbon number 1-8; X and Y are respectively the divalent radical of the group that choosing freedom-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-form; Z is choosing freedom-CF
3,-CN, COCH
3,-COOH ,-NO
2, SOCH
3,-SO
2cH
3,-OCF
3,-F and-the unit price organic radical of the group that Cl forms.
The preparation method of the polymkeric substance of synthesized of the present invention (A) carries out polyreaction by tetracarboxylic dianhydride and diamine compound in organic solvent, and carry out part ring-closure reaction by dehydration reaction, can obtain polyimide-polyamic acid product of tool side chain diamines.
Tetracarboxylic dianhydride in order to synthetic polymer (A) can be selected from compound as shown in Table 1.In order to the diamine compound of synthetic polymer (A), can be selected from having by formula (3) and by the diamine compound shown in formula (4) as shown in Table 2; Also optional from not having by formula (3) and by the diamine compound shown in formula (4) as shown in Table 3.In order to the diamine compound of synthetic polymer (A), at least one selects the compound shown in Free Surface two.
Table one
Table two
Table three
In addition, the tetracarboxylic dianhydride in order to synthetic polymer (A) of the present invention can be the isomer of the compound shown in above-mentioned table one, also can be for this reason the mixture of a little isomers.Diamine compound in order to synthetic polymer (A) of the present invention can be the isomer of the compound shown in above-mentioned table two or table three, also can be for this reason the mixture of a little isomers.The present invention is not limited with above-mentioned example, and the tetracarboxylic dianhydride who uses and diamine compound can also be the compound beyond above-claimed cpd.
Special one carries, and wants to make LCD assembly to have high voltage retention, can be had and in the compound of alicyclic ring framework, at least be selected wherein a kind of reaching by NO.1-2,1-3,1-4,1-5,1-6 etc. in table one.
In addition, the tilt angle of the liquid crystal in crystal aligning agent of the present invention can be adjusted by the side chain size changing on polyimide-polyamic acid, for example by the size that changes the side chain radical on diamine compound, undertaken, therefore can in the represented diamine compound of NO.2-1 to 2-3 in table two, at least select wherein a kind ofly can provide suitable tilt angle.In addition, also can in the represented diamine compound of NO.2-4 to 2-7 in table two, at least select wherein a kind of good crystal aligning agent of adherence characteristic that obtains.
The preparation method of the polymkeric substance of synthesized of the present invention (B) carries out polyreaction by tetracarboxylic dianhydride and diamine compound in organic solvent, to obtain the polyamic acid product of tool side chain diamines.
Tetracarboxylic dianhydride in order to synthetic polymer (B) can be selected from compound as shown in Table 1.In order to the diamine compound of synthetic polymer (B), can be selected from having by formula (3) and by the diamine compound shown in formula (4) as shown in Table 2; Also optional from not having by formula (3) and by the diamine compound shown in formula (4) as shown in Table 3.In order to the diamine compound of synthetic polymer (B), at least one selects the represented compound of Free Surface two NO.2-4 to 2-7.
In addition, the tetracarboxylic dianhydride in order to synthetic polymer (B) of the present invention can be the isomer of the compound shown in above-mentioned table one, also can be for this reason the mixture of a little isomers.Diamine compound in order to synthetic polymer (B) of the present invention can be the isomer of the compound shown in above-mentioned table two or table three, also can be for this reason the mixture of a little isomers.The present invention is not limited with above-mentioned example, and the tetracarboxylic dianhydride who uses and diamine compound can also be the compound beyond above-claimed cpd.
The orientation effect that there is the tilt angle effect of stabilizer pole and make LCD assembly stabilizer pole by the divalent organic base shown in formula (3).Content by the divalent organic base of diamine compound shown in formula (3) in polymkeric substance (A) is preferably with all divalent organic base D of polymkeric substance (A)
1and D
2total amount is counted 0.1 molar percentage to 50 molar percentage.Content by the divalent organic base of diamine compound shown in formula (3) in polymkeric substance (B) is preferably with all divalent organic base D of polymkeric substance (B)
3total amount is counted 0.1 molar percentage to 50 molar percentage
The orientation effect that there is the tilt angle effect of stabilizer pole and make LCD assembly stabilizer pole by the divalent organic base shown in formula (4).Content by the divalent organic base of diamine compound shown in formula (4) in polymkeric substance (A) is preferably with all divalent organic base D of polymkeric substance (A)
1and D
2total amount is counted 5 molar percentage to 50 molar percentages.Content by the divalent organic base of diamine compound shown in formula (4) in polymkeric substance (B) is preferably with all divalent organic base D of polymkeric substance (B)
3total amount is counted 5 molar percentage to 100 molar percentages.
The ratio of the tetracarboxylic dianhydride of building-up reactions who is used in polymkeric substance of the present invention (A) to diamine compound, the amido content that tetracarboxylic dianhydride's the anhydride group content of take is 1 equivalent and diamine compound is better as 0.5 equivalent to 2 equivalent, and the amido content of diamine compound is that 0.7 equivalent to 1.5 equivalent is better.
The synthetic of polymkeric substance (A) all react in organic solvent, and the organic solvent using divides, to be paired in polyimide-polyamic acid solubleness better and for the poor organic solvent of polyimide-polyamic acid solubleness.For polyimide-polyamic acid solubleness preferably organic solvent be for example METHYLPYRROLIDONE, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), 4-methyl urea, hexamethylphosphoramide, gamma-butyrolactone, pyridine etc., and above solvent can be used in two or more mixing.
For the poor solvent of polyimide-polyamic acid solubleness can also with above-mentioned for polyimide-polyamic acid solubleness preferably organic solvent mix use, being restricted to polyimide-polyamic acid and can not being separated of its use.The poor solvent of solubleness comprises methyl alcohol, ethanol, Virahol, propyl carbinol, hexalin, ethylene glycol, Ethylene Glycol Methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, Anaesthetie Ether, acetone, methyl ethyl ketone, pimelinketone, methyl acetate, ethyl acetate, tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1,2-ethylene dichloride, benzene,toluene,xylene, normal hexane, normal heptane, octane etc.
Forming polymkeric substance (A) need react through dehydration closed-loop.Dehydration closed-loop reaction can or be added dewatering agent and catalyzer carries out by direct heating dehydration closed-loop.
(1) direct heating dehydration closed-loop:
Temperature of reaction for example, between 50 ℃ to 300 ℃, be take 100 ℃ to 250 ℃ as good.When temperature of reaction is during lower than 50 ℃, dehydration closed-loop reaction can not carried out.
(2) add dewatering agent and catalyzer:
Temperature of reaction for example, between-20 ℃ to 150 ℃, be take 0 ℃ to 120 ℃ as good.Dewatering agent can be used acid anhydrides, such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride etc.The consumption of dewatering agent is depending on required closed loop rate, take every 1 mole of polyimide-polyamic acid reproducing unit and use the dewatering agent of 0.01 mole to 20 moles as good.Catalyzer can be used tertiary amine, such as triethylamine, pyridine, lutidine etc.The consumption of catalyzer be take every 1 mole of dewatering agent consumption and is used 0.01 mole to 10 moles as good.
The purifying mode of polymkeric substance (A) is first the reaction solvent of polyimide-polyamic acid poured in the poor solvent of a large amount of solubleness and be precipitated thing.Then, under decompression, be dried, can obtain polyimide-polyamic acid.Afterwards, polyimide-polyamic acid is dissolved in organic solvent, and precipitates with the poor solvent of solubleness.This step can be carried out one or many and be carried out purifying polyimide-polyamic acid.Finally, with solubleness preferably dissolution with solvents carry out the polyimide-polyamic acid after above-mentioned steps and obtain the polymkeric substance (A) of purifying.
Viscosity (the η of crystal aligning agent of the present invention
ln) can be obtained by formula (I).
The solids content that crystal aligning agent of the present invention is selected according to viscosity and volatility is better with 1 weight percent to 10 weight percent.
Crystal aligning agent of the present invention is coated to film forming on substrate, form liquid crystal orienting film.When the solids content of crystal aligning agent is during lower than 1 weight percent, it is too thin that the alignment film thickness being coated with becomes, thereby reduced LCD alignment; When the solids content of crystal aligning agent is during higher than 10 weight percent, can affect coating quality.
In addition, the temperature of preparing crystal aligning agent of the present invention is better with 0 ℃ to 150 ℃, better with 20 ℃ to 50 ℃.
The organic solvent of crystal aligning agent of the present invention comprises METHYLPYRROLIDONE, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), gamma-butyrolactone, butyrolactam, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol monobutyl ether etc., and above-mentioned solvent can be used in two or more mixing.In addition, as long as can dissolve the organic solvent of polyimide-polyamic acid beyond above-mentioned solvent, all can use.
Crystal aligning agent of the present invention also can contain organosilicon (oxygen) hydride compounds, for example aminocarbonyl propyl Trimethoxy silane, aminocarbonyl propyl triethyl silicane, vinyl methyl-monosilane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-(2-amido ethyl)-3-aminocarbonyl propyl Trimethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-aminocarbonyl propyl Trimethoxy silane, N-ethoxycarbonyl-3-aminocarbonyl propyl triethoxy amine silane, N-triethoxysilylpropyltetrasulfide three is stretched ethyl triamine, N-trimethoxy-silylpropyl three is stretched ethyl triamine, two (oxygen base is stretched the ethyl)-3-aminocarbonyl propyl Trimethoxy silanes of N-, two (oxygen base is stretched the ethyl)-3-aminocarbonyl propyl triethyl silicanes of N-etc.Above-mentioned organosilicon (oxygen) hydride compounds does not affect under the condition of the desired characteristic of liquid crystal orienting film at its content in crystal aligning agent, can improve liquid crystal orienting film to the adherence of substrate surface (adhesion).If the content of the organosilicon in crystal aligning agent (oxygen) hydride compounds is too much, formed liquid crystal orienting film easily produces the bad phenomenon of orientation; If the content of the organosilicon in crystal aligning agent (oxygen) hydride compounds is very few, formed liquid crystal orienting film may produce the too much phenomenon of friction bad (rubbing mura) and break flour (particle).Therefore, if contain organosilicon (oxygen) hydride compounds in crystal aligning agent of the present invention, the polymer weight of the relative concentration of organosilicon (oxygen) hydride compounds in crystal aligning agent be take 0.01 weight percent to 5 weight percent as good, take 0.1 weight percent to 3 weight percent as special good.
In addition, crystal aligning agent of the present invention also can contain epoxy compounds, ethylene glycol diglycidylether for example, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexane diol diglycidylether, glycerin diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, 1, 3, 5, 6-tetra-Racemic glycidol-2, 4-hexane diol, N, N, N ', N '-four glycidyl group-m-benzene dimethylbenzene, 1, two (the N of 3-, N-2-glycidyl aminomethyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-bis-amido ditans, 3-(N-allyl group-N-glycidyl) aminocarbonyl propyl Trimethoxy silane, 3-(N, N-diglycidyl) aminocarbonyl propyl Trimethoxy silane.Above-mentioned epoxy compounds does not affect under the condition of the desired characteristic of liquid crystal orienting film at its content in crystal aligning agent, can improve the adherence of liquid crystal orienting film to substrate surface.If the content of the epoxy compounds in crystal aligning agent is too much, formed liquid crystal orienting film easily produces the bad phenomenon of orientation; If the content of the epoxy compounds in crystal aligning agent is very few, formed liquid crystal orienting film may produce the phenomenon that friction is bad and break flour is too much.Therefore, if contain epoxy compounds in crystal aligning agent of the present invention, the relative concentration of epoxy compounds be take 0.01 weight percent to 3 weight percent as good in the gross weight of crystal aligning agent, take 0.1 weight percent to 2 weight percent as special good.
Below explanation utilizes the made display panels of crystal aligning agent of the present invention, and above-mentioned display panels can make by following step.
(1) crystal aligning agent of the present invention is put on glass substrate by roller coating method, method of spin coating or printing coating method.This glass substrate has patterned nesa coating.After coating of liquid crystalline orientation agent, carry out heated baking, removing the organic solvent in crystal aligning agent and to promote the polyamic acid of not cyclisation to dewater/ring-closure reaction and form Kapton.The temperature of above-mentioned heated baking, between 80 ℃ to 300 ℃, be take 100 ℃ to 240 ℃ as best.Formed film thickness be take 0.005 micron to 0.5 micron as best.
(2) formed film is carried out to rubbing by the cylinder that is wound with nylon or cotton fiber cloth, so that liquid crystal molecule has regiospecific.
(3) on the substrate with above-mentioned liquid crystal orienting film, be coated with frame glue, and spray separation material on the substrate of the above-mentioned liquid crystal orienting film of another tool, then two substrates are combined in frictional direction mode orthogonal or parallel to each other each other, and in the gap of two substrates, inject liquid crystal sealing injection hole, can form display panels.
For LCD assembly, generally can utilize following characteristic as evaluation index:
(1) tilt angle
The display panels that injects liquid crystal is measured by crystallization rotational method.
(2) tilt angle degree of variation measures
Measure nine points in liquid crystal cell face, the difference of maximum value and minimum value is assessed as degree of variation, the less expression stability of tilt angle degree of variation is better.
(3) voltage retention
Under the envrionment temperature of 90 ℃, the direct current of 3V is put on to LCD assembly 60Hz, the wide 60 μ sec of pulse, to measure the voltage retention in LCD assembly.
(4) ghost phenomena is judged
Prior to energising, depress, measure penetration and the voltage change of LCD assembly specific position.Then, above-mentioned LCD assembly is carried out to the charging two hours of direct current 30V, then discharge for some time.Same position is being carried out to the measurement of penetration and voltage variety afterwards.The voltage of penetration 50% of take is benchmark, measurement is penetration front and back variable quantity under votage reference, and divided by script penetration, with per-cent, represent, before and after penetration, variable quantity < 5% is judged to be excellent, during > 5% is judged to be, be greater than 10% be judged to be poor.
(5) cyclisation rate (imidization ratio)
Polymkeric substance or crystal aligning agent are carried out to drying under reduced pressure under room temperature, then by dried dissolution of solid in the dimethyl sulfoxide (DMSO) through deuterate, use tetramethylsilane as with reference to material, by
1h-NMR measures, and from formula (II), obtains imidization ratio.
Imidization ratio (%)=(1-A
1/ A
2* α) * 100 (II)
A
1: from the derivative spike area (10ppm) of the proton of NH group
A
2: from the derivative spike area of other proton
α: other proton is with respect to the quantity ratio of a proton of the middle NH group of polybenzazole precursor thing (polyamic acid)
(6) adherence
Crystal aligning agent is coated on ito substrate, and ito substrate after 1 hour, is carried out to hundred lattice tests (cross cut method) with 3M adhesive tape with 100 ℃ of poach.
The synthetic method of synthetic polymer A1-A7, B1-B6 and a1, b1-b3 is below described.
Sequentially diamine compound and tetracarboxylic dianhydride are made an addition to (ratio is as shown in table four, table five) in METHYLPYRROLIDONE, prepare the solution that solid composition is 25 weight percents, and at the temperature of 50 ℃ to 60 ℃, react 4 hours to 5 hours, can obtain polyamic acid.Add pyridine and acetic anhydride in the polyamic acid of gained (its consumption must be looked polyimide ratio and add), at 100 ℃ to 110 ℃, dewater/ring-closure reaction is 3 to 4 hours.Use methyl alcohol to precipitate resulting solution, and carry out purifying with methyl alcohol.Finally, collect and with drying under reduced pressure, to obtain having limiting inherent viscosity (intrinsic viscosity) as shown in table four, table five and polymer A 1-A7, B1-B6, a1 and the b1-b3 of imidization ratio, wherein a1 and b1-b3 are containing having by formula (3) and by the diamine compound shown in formula (4).
Table four
Table five
| Synthesis example | Diamine compound (mmole number) | Dicarboxylic anhydride (mmole number) | Limiting inherent viscosity (dl/g) | Polymkeric substance |
| 9 | 2-4(100) | 1-2(100) | 0.75 | B1 |
| 10 | 2-4(50)3-3(50) | 1-2(50)、1-5(50) | 0.80 | B2 |
| 11 | 2-4(50)3-2(50) | 1-2(50)、1-5(50) | 0.79 | B3 |
| 12 | 2-4(50)3-5(50) | 1-2(70)、1-5(50) | 0.81 | B4 |
| 13 | 2-4(100) | 1-3(100) | 0.65 | B5 |
| 14 | 2-4(100) | 1-1(100) | 0.52 | B6 |
| 15 | 3-5(100) | 1-2(50)、1-5(50) | 0.89 | b1 |
| 16 | 3-2(50)3-3(50) | 1-2(50)、1-5(50) | 0.78 | b2 |
| 17 | 3-2(100) | 1-2(50)、1-5(50) | 0.86 | b3 |
Embodiment and reference examples experimental technique
The solid polymer of fixed proportion (A) and solid polymer (B) are dissolved in the mixed solvent of gamma-butyrolactone and METHYLPYRROLIDONE, prepare the solution that solid composition is 6 weight percents, and filter with the strainer of 1 micron of diameter.Collected filtrate is crystal aligning agent of the present invention.
By roller printing press, crystal aligning agent of the present invention is put on glass substrate, and take the hot-plate that temperature is 200 ℃ and be dried 20 minutes, take and form the film that thickness is 0.08 micron.By this film with roller rotating speed 1000 (rev/min), 0.4 micron of platform movement speed 60 (mm/second), the amount of being pressed into (penetration depth) carries out rubbing.
On substrate, be coated with frame glue, and spray separation material on another substrate.Then, two substrates are combined in the mutually perpendicular mode of frictional direction each other, and in the gap of two substrates, inject liquid crystal (ZLI-4792) sealing injection hole, to form LCD assembly.
The LCD assembly of gained is carried out to the assessment of tilt angle, voltage retention, ghost characteristic and adherence.Assessment result as shown in Table 6.
Table six
In sum, because crystal aligning agent of the present invention comprises suc as formula the polyimide-polyamic acid with side chain diamines shown in (1) and suc as formula the polyamic acid with side chain diamines shown in (2), therefore with the formed liquid crystal orienting film of this crystal aligning agent, can there is the effect of stable tilt angle, and the adherence of liquid crystal orienting film and brush film are improved, can also improve ghost problem, and then reach the object of promoting LCD assembly usefulness.
Although the present invention discloses as above with embodiment, so it is not in order to limit the present invention, and the those of ordinary skill in any affiliated technical field, when doing a little change and retouching, and does not depart from the spirit and scope of the present invention.
Claims (6)
1. a crystal aligning agent, is characterized in that comprising:
One polymkeric substance (A) is by the polyimide-polyamic acid with side chain diamines shown in formula (1); And
One polymkeric substance (B), is by the polyamic acid with side chain diamines shown in formula (2), and wherein the weight ratio (A) of this polymkeric substance (A) and this polymkeric substance (B)/(B) is 5/95 to 95/5,
In formula (1) and formula (2), T
1, T
2and T
3be respectively the organic radical of tetravalence; N/ (m+n)≤0.5; D
1, D
2and D
3for divalent organic base, and D
1or D
2middle at least a portion is selected free style (3) or by the divalent organic base of diamine monomer shown in formula (4), D
3middle at least a portion is the divalent organic base by diamine monomer shown in formula (4),
In formula (3), R
1, R
2, R
3, R
5and R
6independently be expressed as respectively hydrogen or carbon number and be 1-5 alkyl; R4 represents that carbon number is 4-20 alkyl, CO
2r
22, CONHR
22or (CH
2)
pcF
3, the integer that wherein p is 1-5, R
22represent the alkyl that carbon number is 4-20,
In formula (4), R
7-R
11in to appoint the two be one-level amido, all the other are independently hydrogen atom or one-level amido any monovalent organic radical in addition separately, R
7-R
11separately can be identical also can be different; X
1and X
2be expressed as singly-bound or select the divalence of the group that free ether, ester, ketone, acid amides and secondary amine form in conjunction with base, X
1and X
2separately can be identical also can be different; X
3and X
4be expressed as the straight chain shape alkylidene group of carbon number 1-3, X
3and X
4separately can be identical also can be different; R
12be expressed as the alkyl of carbon number 1-20, any monovalent organic radical of the ester ring type skeleton of carbon number 3-40, carbon number 6-51 containing any monovalent organic radical of aromatic series skeleton or any monovalent organic radical of heterocycle skeleton.
2. crystal aligning agent according to claim 1, is characterized in that described D
1, D
2and D
3in rest part for to select free style (5) to the group that formula (12) forms,
R wherein
13for the alicyclic unit price organic radical of carbon number 4-40 or the long-chain fat family unit price organic radical of carbon number 8-20; R
14for halogen atom or unit price organic radical; R
15alicyclic divalent organic base for carbon number 4-40; R
16for divalence is alicyclic, the long-chain fat family divalent organic base of divalence aromatic series or carbon number 1-8; X and Y are respectively the divalent radical of the group that choosing freedom-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-form; Z is choosing freedom-CF
3,-CN, COCH
3,-COOH ,-NO
2, SOCH
3,-SO
2cH
3,-OCF
3,-F and-the unit price organic radical of the group that Cl forms.
3. crystal aligning agent according to claim 1, is characterized in that in this polymkeric substance (A) content by the divalent organic base of diamine monomer shown in formula (3), with all divalent organic base D of this polymkeric substance (A)
1and D
2total amount is counted 0.1 molar percentage to 50 molar percentage.
4. crystal aligning agent according to claim 1, is characterized in that in this polymkeric substance (B) content by the divalent organic base of diamine monomer shown in formula (3), with all divalent organic base D of this polymkeric substance (B)
3total amount is counted 0.1 molar percentage to 50 molar percentage.
5. crystal aligning agent according to claim 1, is characterized in that in this polymkeric substance (A) content by the divalent organic base of diamine monomer shown in formula (4), with all divalent organic base D of this polymkeric substance (A)
1and D
2total amount is counted 5 molar percentage to 50 molar percentages.
6. crystal aligning agent according to claim 1, is characterized in that in this polymkeric substance (B) content by the divalent organic base of diamine monomer shown in formula (4), with all divalent organic base D of this polymkeric substance (B)
3total amount is counted 5 molar percentage to 100 molar percentages.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100112994 | 2011-04-14 | ||
| TW100112994A TWI452088B (en) | 2011-04-14 | 2011-04-14 | Liquid crystal aligning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102732262A CN102732262A (en) | 2012-10-17 |
| CN102732262B true CN102732262B (en) | 2014-07-23 |
Family
ID=46988573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110150807.XA Active CN102732262B (en) | 2011-04-14 | 2011-06-07 | Liquid crystal aligning agent |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5429236B2 (en) |
| CN (1) | CN102732262B (en) |
| TW (1) | TWI452088B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI480264B (en) * | 2013-04-12 | 2015-04-11 | Daxin Materials Corp | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element and method of manufacturing the same |
| TWI468415B (en) * | 2013-06-13 | 2015-01-11 | Daxin Materials Corp | Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| JP6350526B2 (en) * | 2013-06-27 | 2018-07-04 | 宇部興産株式会社 | Polyimide precursor and polyimide |
| TWI549992B (en) * | 2015-09-14 | 2016-09-21 | 達興材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display |
| KR101879834B1 (en) * | 2015-11-11 | 2018-07-18 | 주식회사 엘지화학 | Prapapation method of liquid crystal alignment film, liquid crystal alignment film using the same and liquid crystal display device |
| KR101856725B1 (en) | 2016-05-13 | 2018-05-10 | 주식회사 엘지화학 | Composition for photoinduced liquid crystal alignment, prapapation method of liquid crystal alignment film, liquid crystal alignment film using the same and liquid crystal display device |
| CN108885375B (en) | 2016-11-28 | 2021-05-18 | 株式会社Lg化学 | Liquid crystal alignment film, method for preparing the same, and liquid crystal display device using the same |
| TW201920628A (en) * | 2017-06-08 | 2019-06-01 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| KR102030079B1 (en) | 2017-06-30 | 2019-10-08 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| KR102065718B1 (en) | 2017-10-17 | 2020-02-11 | 주식회사 엘지화학 | Liquid crystal alignment film and liquid crystal display using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011010619A1 (en) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent |
| KR20110030297A (en) * | 2009-09-16 | 2011-03-23 | 제이에스알 가부시끼가이샤 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and compound and polymers contained therein |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI367233B (en) * | 2008-02-01 | 2012-07-01 | Liquid crystal alignment solution | |
| TWI393732B (en) * | 2009-03-31 | 2013-04-21 | Daxin Materials Corp | Liquid crystal alignment solution |
| JP5712524B2 (en) * | 2009-10-28 | 2015-05-07 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5751403B2 (en) * | 2010-06-08 | 2015-07-22 | Jsr株式会社 | Liquid crystal alignment agent |
-
2011
- 2011-04-14 TW TW100112994A patent/TWI452088B/en active
- 2011-06-07 CN CN201110150807.XA patent/CN102732262B/en active Active
- 2011-07-14 JP JP2011155947A patent/JP5429236B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011010619A1 (en) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | Diamine compound, polyamic acid, polyimide, and liquid crystal aligning agent |
| KR20110030297A (en) * | 2009-09-16 | 2011-03-23 | 제이에스알 가부시끼가이샤 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and compound and polymers contained therein |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201241088A (en) | 2012-10-16 |
| JP2012226293A (en) | 2012-11-15 |
| CN102732262A (en) | 2012-10-17 |
| JP5429236B2 (en) | 2014-02-26 |
| TWI452088B (en) | 2014-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102732262B (en) | Liquid crystal aligning agent | |
| JP5643985B2 (en) | Diamine, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element | |
| CN104673328B (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element | |
| TWI675067B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer, diamine, and tetracarboxylic dianhydride | |
| CN104927880B (en) | Compound, polymer, aligning agent for liquid crystal, liquid crystal orientation film and display element | |
| TWI658065B (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP2011209505A (en) | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element | |
| CN102382661B (en) | Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal orientation display element, polyamic acid and polyimide | |
| TW201726810A (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal elements, polymers, and diamines consisting of polyamic acid, polyamic acid ester and polyimide and other partial structure | |
| CN103805213A (en) | Liquid crystal aligning agent, liquid crystal alignment film and method for producing the same, and liquid crystal display device | |
| CN104098496B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacturing method thereof | |
| CN101885967A (en) | Liquid crystal alignment liquid | |
| CN103074075B (en) | Liquid crystal aligning agent | |
| CN101556405B (en) | Liquid crystal alignment liquid | |
| JP2021038260A (en) | Novel diamine | |
| TWI786195B (en) | Liquid crystal alignment agent, method for manufacturing liquid crystal element, liquid crystal alignment film, and liquid crystal element | |
| CN102558096B (en) | Aromatic diamine compound, polyamic acid and polyimide prepared from aromatic diamine compound, and liquid crystal aligning agent | |
| CN101498867A (en) | Liquid crystal oriented agent, liquid crystal oriented film and liquid crystal indicator element | |
| CN104513669B (en) | Crystal aligning agent, liquid crystal orienting film and liquid crystal display cells | |
| JP2017097024A (en) | Liquid crystal aligning agent, liquid crystal alignment film and production method of the same, liquid crystal element, polymer and compound | |
| TW201607990A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP5865423B2 (en) | Diamine compound, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element | |
| JP5894566B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same | |
| CN104448298B (en) | Polymer, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display module | |
| JP5673869B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |