CN102732262A - Liquid crystal aligning agent - Google Patents
Liquid crystal aligning agent Download PDFInfo
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- CN102732262A CN102732262A CN201110150807XA CN201110150807A CN102732262A CN 102732262 A CN102732262 A CN 102732262A CN 201110150807X A CN201110150807X A CN 201110150807XA CN 201110150807 A CN201110150807 A CN 201110150807A CN 102732262 A CN102732262 A CN 102732262A
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- 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 51
- 150000007530 organic bases Chemical class 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 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
- 125000003368 amide group Chemical group 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 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 claims description 3
- 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
- 125000003118 aryl 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
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims 6
- 229920000642 polymer Polymers 0.000 abstract description 8
- -1 diamine compound Chemical class 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 18
- 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
- 238000000034 method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000035515 penetration Effects 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 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
- 229910052757 nitrogen Inorganic materials 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002360 preparation 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 239000004642 Polyimide 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
- 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
- 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
- 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 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
- 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
- 238000007740 vapor deposition Methods 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
- 238000005160 1H NMR spectroscopy Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 0 CN(**)*N(*)*c1c(*)c(*)c(*)c(*)c1* Chemical compound CN(**)*N(*)*c1c(*)c(*)c(*)c(*)c1* 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 150000001412 amines Chemical group 0.000 description 1
- 239000003054 catalyst Substances 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
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- 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
- 238000004090 dissolution Methods 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
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-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
- 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
- 238000005259 measurement Methods 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 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
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- 238000010020 roller printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 LCD alignment agent, relate in particular to a kind of LCD alignment agent that comprises polyimide-polyamic acid and have the polyamic acid of side chain diamines with side chain diamines.
Background technology
The indicating meter of liquid-crystal display (liquid crystal display) for utilizing liquid crystal photoelectricity to change, attracting advantage such as it has, and volume is little, in light weight, low power consumption and display quality are good, so become the flat-panel screens main flow in recent years.
The requirement that the development of liquid-crystal display promotes along with the expansion of picture dimension, high saturation, high-contrast and speed of response to color; By twisted nematic (twisted nematic; TN) liquid-crystal display, STN Super TN (super twisted nematic; STN) liquid-crystal display so far develops into thin film transistor (thin filmed transistor, TFT type liquid-crystal display TFT) all is housed in each picture element.Continue in recent years the type of drive of TFT type liquid-crystal display is improved.For example improving aspect the visual angle, developing vertical orientation (vertical alignment, VA) mode or copline conversion (in-plane switching, IPS) mode.In addition, optical compensation curved (optically compensated bend, the OCB) mode of the speed of response that can improve corresponding animation have also been developed.
In liquid-crystal display, be typically twisted nematic (TN) field effect mode liquid-crystal display, its use has positive dielectric undirectional 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 vertical each other, and via the arrangement mode of control electric field may command 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 preparing methods at present.First method is by the steam deposition inorganic substance to be processed mineral membrane.For example, the silicon-dioxide vapor deposition that tilts is formed film in substrate, and liquid crystal molecule in the vapor deposition direction by orientation.Yet,, more do not have an industrial efficiency though above-mentioned method can obtain uniform orientation.Second method then is that organic membrane is coated on the substrate surface, utilize the soft cloth of cotton, nylon or polyester to rub then and the surface of organic membrane be directed so that liquid crystal molecule at frictional direction by orientation.Because this method is simpler and easy and obtain even orientation quite easily, therefore is widely used in technical scale.The polymkeric substance that can form organic film for example is Z 150PH (polyvinylalcohol; PVA), T 46155 (polyethylene oxide; PEO), polymeric amide (polyamide; PA) or polyimide, wherein polyimide is owing to have character such as chemicalstability and thermostability, so the most often is utilized as alignment film material.
Yet; When liquid-crystal display was applied voltage, the ionic electric charge that is produced can be adsorbed by liquid crystal orienting film, even and after removing the voltage that is applied; Also be difficult to make ionic electric charge to break away from, thereby cause picture to produce the problem of image retention from liquid crystal orienting film.Therefore, the exploitation of alignment film material is primary problem to improve image retention problem all in the recent period.
Summary of the invention
The present invention provides a kind of LCD alignment agent, can obtain to have stable tilt angle character, adherence is splendid and can improves the LCD assembly of ghost problem.
The present invention proposes a kind of LCD alignment agent, comprises polymkeric substance (A) and polymkeric substance (B).Polymkeric substance (A) is by the polyimide-polyamic acid with side chain diamines shown in the following formula (1).Polymkeric substance (B) is by the polyamic acid that also has the side chain diamines shown in the following formula (2).Polymkeric substance (A) for example is 5/95 to 95/5 with the weight ratio (A)/(B) of polymkeric substance (B).
Formula (1)
Formula (2)
In formula (1) and the formula (2), T
1, T
2And T
3Be expressed as the monomeric quadrivalent organic radical of tetracarboxylic dianhydride respectively, 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 the formula (4), D
3In at least one part be divalent organic base by diamine compound shown in the formula (4), and D
1, D
2And D
3In rest part be the divalent organic base of diamine compound,
Formula (3)
Formula (4)
In the formula (3), R
1, R
2, R
3, R
5And R
6Individual tables is shown hydrogen or carbon number is the alkyl of 1-5, R respectively
4The expression carbon number is alkyl, the CO of 4-20
2R
22, CONR
22Or (CH
2)
pCF
3, p is the integer of 1-5, R
22The expression carbon number is the alkyl of 4-20, in the formula (4), and R
7-R
11In to appoint the two be the one-level amido, all the other independently are Wasserstoffatoms 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
2The divalence that is expressed as singly-bound or is selected from the group that is made up of ether, ester, ketone, acid amides and secondary amine combines 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 any monovalent organic radical, any monovalent organic radical that contains the aromatic series skeleton of carbon number 6-51 or any monovalent organic radical of heterocycle skeleton of ester ring type skeleton of alkyl, the carbon number 3-40 of carbon number 1-20.
Said according to the embodiment of the invention, D in the LCD alignment agent of the present invention
1, D
2And D
3In, have by formula (3) or the part above-mentioned D except that being selected from by the divalent organic base of diamine compound shown in the formula (4)
1, D
2And D
3In the also optional free style of rest part (5) to the group that formula (12) is formed,
Formula (5) formula (6) formula (7)
Formula (8) formula (9)
Formula (10)
Formula (11) formula (12)
R wherein
13Be 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
14Be halogen atom or unit price organic radical; R
15Alicyclic divalent organic base for carbon number 4-40; R
16The long-chain fat family divalent organic base of, divalence aromatic series alicyclic or carbon number 1-8 for divalence; X and Y be respectively be selected from by-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-divalent radical of the group that CONH-formed; Z is for being selected from by-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 formed.
Said according to the embodiment of the invention, in the polymkeric substance (A) by the content of the divalent organic base of diamine compound shown in the 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.
Said according to the embodiment of the invention, in the polymkeric substance (B) by the content of the divalent organic base of diamine compound shown in the formula (3), with all divalent organic base D of polymkeric substance (B)
3Total amount is counted 0.1 molar percentage to 50 molar percentage.
Said according to the embodiment of the invention, in the polymkeric substance (A) by the content of the divalent organic base of diamine compound shown in the 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.
Said according to the embodiment of the invention, in the polymkeric substance (B) by the content of the divalent organic base of diamine compound shown in the 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; Owing to comprise suc as formula the polyimide-polyamic acid shown in (1) and suc as formula the polyamic acid shown in (2) in the LCD alignment agent of the present invention with side chain diamines with side chain diamines; Therefore can have the effect of stable tilt angle with the formed liquid crystal orienting film of this LCD alignment agent; And make the adherence raising of liquid crystal orienting film also can improve the ghost problem, and then reach the purpose of promoting LCD assembly usefulness.
For letting the above-mentioned feature and advantage of the present invention can be more obviously understandable, hereinafter is special lifts embodiment, and conjunction with figs. elaborates as follows.
Embodiment
LCD alignment 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 the following formula (1).Polymkeric substance (B) is by the polyamic acid that also has side chain two amine structures shown in the following formula (2).
Formula (1)
Formula (1)
Formula (2)
In formula (1) and the formula (2), T
1, T
2And T
3Be expressed as the quaternary organic radical respectively, 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 the formula (4), D
3In at least one part be divalent organic base by diamine compound shown in the formula (4), and D
1, D
2And D
3In rest part be the divalent organic base of diamine compound.
Formula (3)
In the formula (3), R
1, R
2, R
3, R
5And R
6Individual tables is shown hydrogen or carbon number is the alkyl of 1-5, R respectively
4The expression carbon number is alkyl, the CO of 4-20
2R
22, CONR
22Or (CH
2)
pCF
3, p is the integer of 1-5, R
22The expression carbon number is the alkyl of 4-20.
Formula (4)
In the formula (4), R
7-R
11In to appoint the two be the one-level amido, all the other independently are Wasserstoffatoms 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
2The divalence that is expressed as singly-bound or is selected from the group that is made up of ether, ester, ketone, acid amides and secondary amine combines 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 any monovalent organic radical, any monovalent organic radical that contains the aromatic series skeleton of carbon number 6-51 or any monovalent organic radical of heterocycle skeleton of ester ring type skeleton of alkyl, the carbon number 3-40 of carbon number 1-20.
Polymkeric substance (A) for example is 5/95 to 95/5 with the weight ratio (A)/(B) of polymkeric substance (B).
In addition, D in the LCD alignment agent of the present invention
1, D
2And D
3In, have by formula (3) or the part above-mentioned D except that being selected from by the divalent organic base of diamine compound shown in the formula (4)
1, D
2And D
3In the also optional free style of rest part (5) to the group that formula (12) is formed,
Formula (5) formula (6) formula (7)
Formula (8) formula (9)
Formula (10)
Formula (11) formula (12)
R wherein
13Be 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
14Be halogen atom or unit price organic radical; R
15Alicyclic divalent organic base for carbon number 4-40; R
16The long-chain fat family divalent organic base of, divalence aromatic series alicyclic or carbon number 1-8 for divalence; X and Y be respectively be selected from by-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-divalent radical of the group that CONH-formed; Z is for being selected from by-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 formed.
The preparation method of institute's synthetic polymkeric substance of the present invention (A) carries out polyreaction by tetracarboxylic dianhydride and diamine compound in organic solvent; And carry out the part ring-closure reaction by dehydration reaction, can obtain the polyimide-polyamic acid product of tool side chain diamines.
Tetracarboxylic dianhydride in order to synthetic polymer (A) can be selected from the compound shown in table one.Diamine compound in order to synthetic polymer (A) can be selected from having by formula (3) and by the diamine compound shown in the formula (4) shown in table two; Also optional not having shown in the table three freely by formula (3) and by the diamine compound shown in the formula (4).At least one selects the compound shown in the Free Surface two in order to the diamine compound of synthetic polymer (A).
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 the 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 the table three, also can be for this reason the mixture of a little isomers.The present invention is not exceeded with above-mentioned example, and employed tetracarboxylic dianhydride and diamine compound can also be the compound beyond the above-claimed cpd.
Special one carry be, desire to make LCD assembly to have high voltage retention, can have by NO.1-2,1-3,1-4,1-5,1-6 etc. in the table one and select wherein a kind of reaching in the compound of alicyclic ring framework at least.
In addition; The tilt angle of the liquid crystal in the LCD alignment agent of the present invention can be adjusted by the side chain size that changes on polyimide-polyamic acid; For example undertaken by the size that changes the side chain radical on the diamine compound, therefore can be by selecting wherein a kind of suitable tilt angle to be provided in the represented diamine compound of NO.2-1 to 2-3 in the table two at least.In addition, also can be by selecting wherein a kind of good LCD alignment agent of adherence characteristic that obtains in the represented diamine compound of NO.2-4 to 2-7 in the table two at least.
The preparation method of institute's synthetic polymkeric substance 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 the compound shown in table one.Diamine compound in order to synthetic polymer (B) can be selected from having by formula (3) and by the diamine compound shown in the formula (4) shown in table two; Also optional not having shown in the table three freely by formula (3) and by the diamine compound shown in the formula (4).At least one selects the represented compound of Free Surface two NO.2-4 to 2-7 in order to the diamine compound of synthetic polymer (B).
In addition, the tetracarboxylic dianhydride in order to synthetic polymer (B) of the present invention can be the isomer of the compound shown in the 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 the table three, also can be for this reason the mixture of a little isomers.The present invention is not exceeded with above-mentioned example, and employed tetracarboxylic dianhydride and diamine compound can also be the compound beyond the above-claimed cpd.
The orientation effect that has the tilt angle effect of stabilizer pole and make the LCD assembly stabilizer pole by the divalent organic base shown in the formula (3).Content by the divalent organic base of diamine compound shown in the formula (3) in the 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 the formula (3) in the 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 has the tilt angle effect of stabilizer pole and make the LCD assembly stabilizer pole by the divalent organic base shown in the formula (4).Content by the divalent organic base of diamine compound shown in the formula (4) in the 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 the formula (4) in the 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 tetracarboxylic dianhydride of building-up reactions who is used in polymkeric substance of the present invention (A) is to the ratio of diamine compound; With tetracarboxylic dianhydride's anhydride group content is that the amido content of 1 equivalent and diamine compound is that 0.5 equivalent to 2 equivalent is preferable, and the amido content of diamine compound is that 0.7 equivalent to 1.5 equivalent is better.
Polymkeric substance (A) synthetic all in organic solvent reaction accomplish, and employed organic solvent branch be paired in polyimide-polyamic acid solubleness preferable with for polyimide-relatively poor organic solvent of polyamic acid solubleness.For the preferable organic solvent of polyimide-polyamic acid solubleness for example is N-N-methyl-2-2-pyrrolidone N-, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, DMSO 99.8MIN., 4-methyl urea, hexamethylphosphoramide, gamma-butyrolactone, pyridine etc., and above solvent can use in two or more mixing.
The solvent relatively poor for polyimide-polyamic acid solubleness can also mix use for polyimide-preferable organic solvent of polyamic acid solubleness with above-mentioned, being restricted to polyimide-polyamic acid and can not being separated of its use.The relatively poor solvent of solubleness comprises methyl alcohol, ethanol, Virahol, propyl carbinol, hexalin, terepthaloyl moietie, 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, ETHYLE ACETATE, THF, methylene dichloride, trichloromethane, 1,2-ethylene dichloride, benzene,toluene,xylene, normal hexane, normal heptane, octane etc.
Forming polymkeric substance (A) needs to react through dehydration closed-loop.Dehydration closed-loop reaction can or be added dewatering agent and catalyzer carries out by the direct heating dehydration closed-loop.
(1) direct heating dehydration closed-loop:
Temperature of reaction between 50 ℃ to 300 ℃, is good with 100 ℃ to 250 ℃ for example.When temperature of reaction was lower than 50 ℃, the dehydration closed-loop reaction then can not carried out.
(2) add dewatering agent and catalyzer:
Temperature of reaction between-20 ℃ to 150 ℃, is good with 0 ℃ to 120 ℃ for example.Dewatering agent can use acid anhydrides, for example diacetyl oxide, propionic anhydride, trifluoroacetic anhydride etc.The consumption of dewatering agent is looked required closed loop rate and is decided, and it is good using 0.01 mole to 20 moles dewatering agent with the reproducing unit of per 1 mole of polyimide-polyamic acid.Catalyzer can use tertiary amine, for example triethylamine, pyridine, lutidine etc.Catalyst consumption is used 0.01 mole to 10 moles for good with per 1 mole of dewatering agent consumption.
The purifying mode of polymkeric substance (A) is earlier the reaction solvent of polyimide-polyamic acid to be poured in the relatively poor solvent of a large amount of solubleness and obtained throw out.Then, under decompression, carry out drying, can obtain polyimide-polyamic acid.Afterwards, polyimide-polyamic acid is dissolved in the organic solvent, and precipitates with the relatively poor solvent of solubleness.This step can be carried out one or many and come purifying polyimide-polyamic acid.At last, carry out the polyimide-polyamic acid after the above-mentioned steps with the preferable dissolution with solvents of solubleness and obtain the polymkeric substance (A) of purifying.
Viscosity (the η of LCD alignment agent of the present invention
Ln) can obtain by formula (I).
The solids content that LCD alignment agent of the present invention is selected according to viscosity and volatility is preferable with 1 weight percent to 10 weight percent.
Film forming on the substrate is coated in LCD alignment agent of the present invention, promptly formed liquid crystal orienting film.When the solids content of LCD alignment agent was lower than 1 weight percent, it is too thin that the alignment film thickness that is coated with becomes, thereby reduced LCD alignment property; When the solids content of LCD alignment agent is higher than 10 weight percents, then can influence coating quality.
In addition, the temperature for preparing LCD alignment agent of the present invention is preferable with 0 ℃ to 150 ℃, and is better with 20 ℃ to 50 ℃.
The organic solvent of LCD alignment agent of the present invention comprises N-N-methyl-2-2-pyrrolidone N-, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, DMSO 99.8MIN., gamma-butyrolactone, butyrolactam, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-propyl ether, ethylene glycol monobutyl ether etc., and above-mentioned solvent can use in two or more mixing.In addition, all can use as long as beyond above-mentioned solvent, can dissolve the organic solvent of polyimide-polyamic acid.
LCD alignment 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, the 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 are stretched the ethyl triamine, N-trimethoxy-silylpropyl three is stretched ethyl triamine, two (the oxygen base is stretched the ethyl)-3-aminocarbonyl propyl Trimethoxy silanes of N-, two (the oxygen base is stretched the ethyl)-3-aminocarbonyl propyl triethyl silicanes of N-etc.Above-mentioned organosilicon (oxygen) hydride compounds does not influence in the LCD alignment agent under the condition of the desired characteristic of liquid crystal orienting film at its content, can improve the adherence (adhesion) of liquid crystal orienting film to substrate surface.If the content of organosilicon (oxygen) hydride compounds in the LCD alignment agent is too much, then formed liquid crystal orienting film is easy to generate the bad phenomenon of orientation; If the content of organosilicon (oxygen) hydride compounds in the LCD alignment agent is very few, then formed liquid crystal orienting film possibly produce friction bad (rubbing mura) and the too much phenomenon of break flour (particle).Therefore; In the LCD alignment agent of the present invention if contain organosilicon (oxygen) hydride compounds; The concentration of organosilicon (oxygen) hydride compounds is good with respect to the polymer weight in the LCD alignment agent with 0.01 weight percent to 5 weight percent, serves as special good with 0.1 weight percent to 3 weight percent.
In addition, LCD alignment agent of the present invention also can contain epoxy compounds, for example ethylene glycol diglycidylether, 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-four Racemic glycidols-2,4-hexane diol, N, N; N ', N '-four glycidyl group--benzene YLENE, 1, the two (N of 3-; N-2-glycidyl aminomethyl) hexanaphthene, N, N, N '; N '-four glycidyl group-4,4 '-two 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 influence in the LCD alignment agent under the condition of the desired characteristic of liquid crystal orienting film at its content, can improve the adherence of liquid crystal orienting film to substrate surface.If the content of the epoxy compounds in the LCD alignment agent is too much, then formed liquid crystal orienting film is easy to generate the bad phenomenon of orientation; If the content of the epoxy compounds in the LCD alignment agent is very few, then formed liquid crystal orienting film possibly produce the bad and too much phenomenon of break flour of friction.Therefore, if contain epoxy compounds, the concentration of epoxy compounds is good with respect to the gross weight of LCD alignment agent with 0.01 weight percent to 3 weight percent in the LCD alignment agent of the present invention, serves as special good with 0.1 weight percent to 2 weight percent.
Below explanation utilizes the made display panels of LCD alignment agent of the present invention, and above-mentioned display panels can make by following step.
(1) LCD alignment agent of the present invention is put on the glass substrate by roller coating method, method of spin coating or printing coating method.This glass substrate has patterned nesa coating.After the coating of liquid crystalline orientation agent, carry out heated baking, to remove the organic solvent in the LCD alignment 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 is the best with 100 ℃ to 240 ℃ between 80 ℃ to 300 ℃.Formed film thickness is the best with 0.005 micron to 0.5 micron.
(2) formed film is carried out rubbing by the cylinder that is wound with nylon or cotton fiber cloth, so that liquid crystal molecule has regiospecific.
(3) coating frame glue on substrate with above-mentioned liquid crystal orienting film; And on the substrate of the above-mentioned liquid crystal orienting film of another tool, spray separation material; Then two substrates are made up with frictional direction mode orthogonal or parallel to each other each other; And in the gap of two substrates, inject liquid crystal and 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 the crystallization rotational method.
(2) the tilt angle degree of variation measures
Measure nine points in the liquid crystal cell face, the difference of peak and minimum value is assessed as degree of variation, the more little expression stability of tilt angle degree of variation is good more.
(3) voltage retention
Under 90 ℃ envrionment temperature, the direct current of 3V is put on LCD assembly 60Hz, the wide 60 μ sec of pulse are to measure the voltage retention in the LCD assembly.
(4) ghost phenomena is judged
Under energize, measure the penetration and the voltage change of LCD assembly specific position.Then, above-mentioned LCD assembly is carried out the charging two hours of direct current 30V, discharge for some time then.Afterwards in the measurement of same position being carried out penetration and voltage variety.Voltage with penetration 50% is benchmark, measures under votage reference variable quantity before and after the penetration, and divided by the script penetration, representes with per-cent, and variable quantity＜5% is judged to be excellently before and after the penetration, and＞5% is judged to be, and it is poor to be judged to be greater than 10%.
(5) cyclisation rate (imidization ratio)
Polymkeric substance or LCD alignment agent are carried out drying under reduced pressure under room temperature, then dried solid is dissolved in the deuterated DMSO 99.8MIN., use TMS material as a reference, by
1H-NMR measures, and (II) obtains the imidization ratio from formula.
Imidization ratio (%)=(1-A
1/ A
2* α) * 100 (II)
A
1: from the proton deutero-spike area (10ppm) of NH group
A
2: from other proton deutero-spike area
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
The LCD alignment agent is coated on the ito substrate, and ito substrate after 1 hour, is carried out hundred lattice tests (cross cut method) with the 3M adhesive tape with 100 ℃ of poach.
The compound method of synthetic polymer A1-A7, B1-B6 and a1, b1-b3 below is described.
In regular turn diamine compound and tetracarboxylic dianhydride are made an addition to (ratio is shown in table four, table five) in the N-N-methyl-2-2-pyrrolidone N-; Preparation solid composition is the solution of 25 weight percents; And under 50 ℃ to 60 ℃ temperature, reacted 4 hours to 5 hours, can obtain polyamic acid.Add pyridine and acetic anhydride (its consumption must be looked the interpolation of polyimide ratio) in the polyamic acid of gained, under 100 ℃ to 110 ℃, dewater/ring-closure reaction 3 to 4 hours.Use methyl alcohol to precipitate resulting solution, and carry out purifying with methyl alcohol.At last; Collect and with drying under reduced pressure; To obtain having limiting inherent viscosity (intrinsic viscosity) and polymer A 1-A7, B1-B6, a1 and the b1-b3 of imidization ratio shown in table four, table five, wherein a1 and b1-b3 do not contain and have by formula (3) and by the diamine compound shown in the formula (4).
Table four
Table five
| Synthetic 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 (A) of fixed proportion is dissolved in the mixed solvent of gamma-butyrolactone and N-N-methyl-2-2-pyrrolidone N-with solid polymer (B), and preparation solid composition is the solution of 6 weight percents, and filters with the strainer of 1 micron of diameter.Collected filtrating is LCD alignment agent of the present invention.
By the roller printing press LCD alignment agent of the present invention being put on the glass substrate, and be that 200 ℃ hot-plate carried out drying 20 minutes with temperature, is 0.08 micron film to form thickness.With this film with roller rotating speed 1000 (rev/min), platform translational speed 60 (mm/second), the amount of being pressed into (penetration depth) carry out rubbing for 0.4 micron.
Coating frame glue on substrate, and on another substrate, spray separation material.Then, two substrates are made up with the mutually perpendicular mode of frictional direction each other, and in the gap of two substrates, inject liquid crystal (ZLI-4792) and sealing injection hole, to form LCD assembly.
The LCD assembly of gained is carried out the assessment of tilt angle, voltage retention, ghost characteristic and adherence.Assessment result is shown in table six.
Table six
In sum; Owing to comprise suc as formula the polyimide-polyamic acid shown in (1) and suc as formula the polyamic acid shown in (2) in the LCD alignment agent of the present invention with side chain diamines with side chain diamines; Therefore can have the effect of stable tilt angle with the formed liquid crystal orienting film of this LCD alignment agent; And make and can also improve the adherence and the raising of brush film property of liquid crystal orienting film the ghost problem, and then reach the purpose of promoting LCD assembly usefulness.
Though the present invention discloses as above with embodiment, so it is not in order to limiting the present invention, any under those of ordinary skill in the technical field, when can doing a little change and retouching, and do not break away from the spirit and scope of the present invention.
Claims (6)
1. LCD alignment agent is characterized in that comprising:
One polymkeric substance (A) is by the polyimide-polyamic acid with side chain diamines shown in the formula (1); And
One polymkeric substance (B) is by the polyamic acid with side chain diamines shown in the formula (2), and wherein this polymkeric substance (A) is 5/95 to 95/5 with the weight ratio (A)/(B) of this polymkeric substance (B),
Formula (1)
Formula (2)
In formula (1) and formula (2), T
1, T
2And T
3Be respectively the quaternary organic radical; N/ (m+n)≤0.5; D
1, D
2And D
3Be divalent organic base, and D
1Or D
2In at least a portion select free style (3) or by the divalent organic base of diamine monomer shown in the formula (4), D
3Middle at least a portion is the divalent organic base by diamine monomer shown in the formula (4),
Formula (3)
In the formula (3), R
1, R
2, R
3, R
5And R
6Individual tables is shown hydrogen or carbon number is the alkyl of 1-5 respectively; R
4The expression carbon number is alkyl, the CO of 4-20
2R
22, CONR
22Or (CH
2)
pCF
3, wherein p is the integer of 1-5, R
22The expression carbon number is the alkyl of 4-20,
Formula (4)
In the formula (4), R
7-R
11In to appoint the two be the one-level amido, all the other independently are Wasserstoffatoms 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
2The divalence that is expressed as singly-bound or is selected from the group that is made up of ether, ester, ketone, acid amides and secondary amine combines 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 any monovalent organic radical, any monovalent organic radical that contains the aromatic series skeleton of carbon number 6-51 or any monovalent organic radical of heterocycle skeleton of ester ring type skeleton of alkyl, the carbon number 3-40 of carbon number 1-20.
2. LCD alignment agent according to claim 1 is characterized in that said D
1, D
2And D
3In rest part for selecting free style (5) to the group that formula (12) is formed,
Formula (5) formula (6) formula (7)
Formula (8) formula (9)
Formula (10)
Formula (11) formula (12)
R wherein
13Be 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
14Be halogen atom or unit price organic radical; R
15Alicyclic divalent organic base for carbon number 4-40; R
16The long-chain fat family divalent organic base of, divalence aromatic series alicyclic or carbon number 1-8 for divalence; X and Y be respectively be selected from by-O-,-NH-,-S-,-CO-,-COO-,-OCO-,-NHCO-,-divalent radical of the group that CONH-formed; Z is for being selected from by-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 formed.
3. LCD alignment 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 the 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. LCD alignment 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 the 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. LCD alignment 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 the 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. LCD alignment 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 the formula (4), with all divalent organic base D of this polymkeric substance (B)
3Total amount is counted 5 molar percentage to 100 molar percentages.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100112994A TWI452088B (en) | 2011-04-14 | 2011-04-14 | Liquid crystal aligning agent |
| TW100112994 | 2011-04-14 |
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| Publication Number | Publication Date |
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| CN102732262A true CN102732262A (en) | 2012-10-17 |
| CN102732262B CN102732262B (en) | 2014-07-23 |
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| CN201110150807.XA Active CN102732262B (en) | 2011-04-14 | 2011-06-07 | Liquid crystal aligning agent |
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| Country | Link |
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| JP (1) | JP5429236B2 (en) |
| CN (1) | CN102732262B (en) |
| TW (1) | TWI452088B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098496A (en) * | 2013-04-12 | 2014-10-15 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacturing method thereof |
| CN104230973A (en) * | 2013-06-13 | 2014-12-24 | 达兴材料股份有限公司 | Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN105492496A (en) * | 2013-06-27 | 2016-04-13 | 宇部兴产株式会社 | Polyimide precursor and polyimide |
| CN110832392A (en) * | 2017-06-08 | 2020-02-21 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20180373099A1 (en) | 2016-11-28 | 2018-12-27 | Lg Chem, Ltd. | Liquid crystal alignment film, method for preparing the same and liquid crystal display device using the same |
| 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 |
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| 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 |
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| 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
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| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098496A (en) * | 2013-04-12 | 2014-10-15 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacturing method thereof |
| CN104098496B (en) * | 2013-04-12 | 2017-05-24 | 达兴材料股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element and manufacturing method thereof |
| CN104230973A (en) * | 2013-06-13 | 2014-12-24 | 达兴材料股份有限公司 | Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN105492496A (en) * | 2013-06-27 | 2016-04-13 | 宇部兴产株式会社 | Polyimide precursor and polyimide |
| CN110832392A (en) * | 2017-06-08 | 2020-02-21 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102732262B (en) | 2014-07-23 |
| JP5429236B2 (en) | 2014-02-26 |
| TWI452088B (en) | 2014-09-11 |
| JP2012226293A (en) | 2012-11-15 |
| TW201241088A (en) | 2012-10-16 |
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