JPH02124534A - Liquid crystal display element and manufacture thereof - Google Patents
Liquid crystal display element and manufacture thereofInfo
- Publication number
- JPH02124534A JPH02124534A JP27817988A JP27817988A JPH02124534A JP H02124534 A JPH02124534 A JP H02124534A JP 27817988 A JP27817988 A JP 27817988A JP 27817988 A JP27817988 A JP 27817988A JP H02124534 A JPH02124534 A JP H02124534A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- film
- display element
- crystal display
- alignment film
- 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.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000010408 film Substances 0.000 claims abstract description 125
- 239000000758 substrate Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 229920000620 organic polymer Polymers 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 210000002858 crystal cell Anatomy 0.000 claims description 6
- 238000001259 photo etching Methods 0.000 claims description 6
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 22
- 230000005611 electricity Effects 0.000 abstract description 12
- 230000003068 static effect Effects 0.000 abstract description 12
- 229920006254 polymer film Polymers 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 34
- 229920005575 poly(amic acid) Polymers 0.000 description 32
- -1 cinnamoyl groups Chemical group 0.000 description 21
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 15
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 125000006267 biphenyl group Chemical group 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- IBFXOWJTDUNEFS-UHFFFAOYSA-N (1-aminocyclohexa-2,4-dien-1-yl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1(N)C=CC=CC1 IBFXOWJTDUNEFS-UHFFFAOYSA-N 0.000 description 1
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BIAWAXVRXKIUQB-UHFFFAOYSA-N 2-(2-phenylethenyl)pyridine Chemical group C=1C=CC=CC=1C=CC1=CC=CC=N1 BIAWAXVRXKIUQB-UHFFFAOYSA-N 0.000 description 1
- XFOHWECQTFIEIX-UHFFFAOYSA-N 2-nitrofluorene Chemical compound C1=CC=C2C3=CC=C([N+](=O)[O-])C=C3CC2=C1 XFOHWECQTFIEIX-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- LOIBXBUXWRVJCF-UHFFFAOYSA-N 4-(4-aminophenyl)-3-phenylaniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C1=CC=CC=C1 LOIBXBUXWRVJCF-UHFFFAOYSA-N 0.000 description 1
- BVPJPRYNQHAOPQ-UHFFFAOYSA-N 4-nitronaphthalen-1-amine Chemical compound C1=CC=C2C(N)=CC=C([N+]([O-])=O)C2=C1 BVPJPRYNQHAOPQ-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- CUARLQDWYSRQDF-UHFFFAOYSA-N 5-Nitroacenaphthene Chemical compound C1CC2=CC=CC3=C2C1=CC=C3[N+](=O)[O-] CUARLQDWYSRQDF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical group NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SKACCCDFHQZGIA-UHFFFAOYSA-N n-(4-nitronaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C([N+]([O-])=O)C2=C1 SKACCCDFHQZGIA-UHFFFAOYSA-N 0.000 description 1
- XHKYACWISXFMHD-UHFFFAOYSA-N n-[bis(dimethylamino)phosphoryl]-n-methylmethanamine;methylsulfinylmethane Chemical compound CS(C)=O.CN(C)P(=O)(N(C)C)N(C)C XHKYACWISXFMHD-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004986 phenylenediamines Chemical group 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JREWFSHZWRKNBM-UHFFFAOYSA-N pyridine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C(C(O)=O)=C1C(O)=O JREWFSHZWRKNBM-UHFFFAOYSA-N 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分子配向性を有する高分子薄膜からなり、配
向膜のパターン化を必要とする液晶表示素子およびその
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a liquid crystal display element which is made of a thin polymer film having molecular orientation and requires patterning of the orientation film, and a method for manufacturing the same.
従来から、液晶表示素子が各種のデイスプレィに実用化
されている。このような液晶表示素子の良好な表示品質
を得るためには、液晶分子を均一に配向させる必要があ
る。その役割を担うのが、液晶の配向膜である。そのた
め、配向膜に関する多くの開発研究がなされ、作業性、
コストの面から現在では有機系配向膜が主流になってい
る。このような配向膜は、基板上の全面ではなく液晶と
接触する部分にだけコーティングされる。すなわち、基
板の外部端子部、内部接続部およびシール部は配向膜を
除去しなければならない。配向膜の除去方法としては、
一般に、スピンコード等により基板全面に塗布された高
分子膜をプラズマ処理もしくは化学処理等によって部分
的に剥離する工程が用いられているが、上記処理方法は
その作業が極めて煩雑であるという問題を有している。BACKGROUND ART Liquid crystal display elements have been put to practical use in various displays. In order to obtain good display quality of such a liquid crystal display element, it is necessary to uniformly align liquid crystal molecules. The liquid crystal alignment film plays this role. For this reason, much research and development has been conducted on alignment films to improve workability and
Organic alignment films are currently mainstream due to cost considerations. Such an alignment film is coated not on the entire surface of the substrate but only on the portion that comes into contact with the liquid crystal. That is, the alignment film must be removed from the external terminal portions, internal connection portions, and seal portions of the substrate. The method for removing the alignment film is as follows:
Generally, a process is used in which a polymer film coated on the entire surface of a substrate using a spin cord or the like is partially peeled off by plasma treatment or chemical treatment, but the above treatment method has the problem that the work is extremely complicated. have.
このような処理工程を短縮するために、スクリーン印刷
により基板の特定部分にのみ高分子膜を塗布する方法や
、感光性有機高分子を配向膜素材として用いレジストを
用いずにフォトエツチング法によりパターンを形成する
方法（特開昭５７−８１２３４号公報）等が開示されて
いる。通常、有機系高分子配向膜は、上記のようにして
、パターン状に形成された高分子膜の表面を布等でラビ
ング処理して配向性を付与され液晶配向膜として用いら
れている。In order to shorten these processing steps, there are methods of applying a polymer film only to specific parts of the substrate using screen printing, and methods of patterning using a photoetching method using a photosensitive organic polymer as an alignment film material without using a resist. (Japanese Unexamined Patent Publication No. 57-81234) etc. have been disclosed. Usually, an organic polymer alignment film is used as a liquid crystal alignment film by rubbing the surface of the polymer film formed in a pattern with a cloth or the like as described above to impart alignment properties.
しかしながら、上記有機配向膜の場合、量産性の点では
極めて優れているが高分子膜を均一な膜厚で塗布できな
いという問題がある。また、布等で配向膜を擦るラビン
グ処理により静電気が発生し、配向膜表面を汚染する等
の問題も生じている。例えば、ネマチック液晶を用いた
スーパーツイスト液晶素子（ＳＴＮ）（ＳＩＤインター
ナショナルシンポジウム＝１２０〜１２３ページ、（１
９８５））では、配向膜の不均一膜厚に起因するしきい
値電圧（ｖｔｈ）の不均一により表示むらが生じたり、
静電気によるＩＴＯ電極の破壊で非点灯部が発生し易い
状況になる。また、電極間のショート等も発生し易い。However, in the case of the above-mentioned organic alignment film, although it is extremely excellent in terms of mass production, there is a problem that the polymer film cannot be coated with a uniform thickness. In addition, static electricity is generated due to the rubbing process in which the alignment film is rubbed with a cloth or the like, causing problems such as contamination of the surface of the alignment film. For example, a super twisted liquid crystal device (STN) using nematic liquid crystal (SID International Symposium = pages 120-123, (1)
In 985)), display unevenness occurs due to non-uniform threshold voltage (vth) due to non-uniform thickness of the alignment film.
This creates a situation where non-lighting parts are likely to occur due to destruction of the ITO electrode due to static electricity. Furthermore, short circuits between electrodes are likely to occur.
さらに、配向膜表面の汚染は、液晶表示素子のしきい値
電圧の周波数依存性の不均一化を招き、これは表示むら
につながることになる。アクティブマトリックス液晶素
子では、薄膜トランジスタ（ＴＰＴ）あるいはダイオー
ド等のスイッチング素子の損傷、あるいはスイッチング
特性の変化による点灯不良を引き起こす。また、ラビン
グ処理時の荷重を基板全体でコントロールする困難さも
あり、特に大形の液晶素子においてラビング処理に起因
する傷を生じさせてしまう等の問題も有している。Furthermore, contamination on the surface of the alignment film causes non-uniform frequency dependence of the threshold voltage of the liquid crystal display element, which leads to display unevenness. In active matrix liquid crystal devices, lighting failures occur due to damage to switching elements such as thin film transistors (TPTs) or diodes, or changes in switching characteristics. Furthermore, there is also the difficulty of controlling the load during the rubbing process over the entire substrate, and there are also problems such as scratches caused by the rubbing process, especially in large liquid crystal elements.
本発明は、このような事情に鑑みなされたもので、分子
配向にラビング処理を要さず、量産性に冨んだパターン
状の高分子配向膜を備えている液晶表示素子およびそれ
を容易に製造する方法の提供をその目的とする。The present invention was made in view of the above circumstances, and provides a liquid crystal display element equipped with a patterned polymer alignment film that does not require rubbing treatment for molecular alignment and is highly suitable for mass production, and also provides a liquid crystal display element that is easily manufactured. Its purpose is to provide a method for manufacturing.
本発明は、少なくとも一方が透光性の一対の電極基板間
に、少なくとも液晶層および液晶分子配向膜を挟持して
なる液晶表示素子において、上記液晶分子配向膜の膜厚
が０．１μｍ以下であり、上記配向膜は、単層の膜厚が
０．００３μｍ以上の有機高分子の水面展開膜からなり
、かつ上記配向膜がパターン状に形成されている液晶表
示素子を第１の要旨とし、有機高分子溶液を水面上に供
給し、上記溶液を一方向に引いて製膜し、得られた水面
展開膜を電極基板上の所定の部位に密着形成し、さらに
フォトエツチングにより配向膜をパターン状に形成した
上記電極基板を用いて作製した液晶セルに、液晶を封入
する液晶表示素子の製法を第２の要旨とする。The present invention provides a liquid crystal display element in which at least a liquid crystal layer and a liquid crystal molecule alignment film are sandwiched between a pair of electrode substrates, at least one of which is transparent, in which the thickness of the liquid crystal molecule alignment film is 0.1 μm or less. The first aspect is a liquid crystal display element in which the alignment film is made of a water-surface-deployed organic polymer film with a single layer thickness of 0.003 μm or more, and the alignment film is formed in a pattern; An organic polymer solution is supplied onto the water surface, the solution is pulled in one direction to form a film, the resulting water surface spread film is closely formed on a predetermined location on the electrode substrate, and an alignment film is patterned by photo-etching. The second gist is a method for manufacturing a liquid crystal display element in which a liquid crystal is sealed in a liquid crystal cell manufactured using the electrode substrate formed in a shape.
本発明者らは、分子配向にラビング等の処理が不要で、
液晶分子に対する配向機能を示す配向膜を得るための一
連の研究を重ねた。その結果、水面展開製膜法によって
有機高分子の分子鎖を配列させた膜をガラス基板上に形
成させることに成功し、さらにフォトエツチング等によ
りパターンを形成した上記膜によって液晶分子を配向さ
せうろことを見出し本発明に到達した。The present inventors discovered that no treatment such as rubbing is required for molecular orientation;
A series of studies were conducted to obtain an alignment film that exhibits an alignment function for liquid crystal molecules. As a result, they succeeded in forming a film in which organic polymer molecular chains were aligned on a glass substrate using a water surface spreading method, and furthermore, they were able to form scales by aligning liquid crystal molecules using the film, which had been patterned by photo-etching, etc. We have discovered this and arrived at the present invention.
すなわち、本発明者らは、水面展開製膜法よる場合には
、−回の処理で極めて短時間のうちに膜厚が３０〜１０
００人の高分子膜をガラス基板上に形成でき、かつ水面
上に展開される薄膜を一定方向に引き取る操作によって
高分子の分子配列が一定方向に揃った薄膜を作製するこ
とができることを突き止めた。そして、このように形成
した膜は液晶分子に対して配向作用を示すことを見出し
た。このような水面展開製膜法により形成された配向膜
は、ラビング処理が不要なため静電気等が発生せず、電
極やＴＰＴ等を破壊することが全くない。しかも、配向
境界面を汚染することなく、膜厚も均一にすることがで
きるため表示むら等を生じさせることがない。さらに、
配向膜として感光性高分子を用いたときには、フォトエ
ツチングにより、基板上の不要な部分の配向膜の除去が
容易になり、しかも配向膜の絶縁性による点灯不良を生
ずることなく量産性にも優れている。In other words, the present inventors have found that when using the water surface spreading film forming method, the film thickness can be increased from 30 to 10 mm in a very short time in -100 times of processing.
It was discovered that a polymer film of 00 people can be formed on a glass substrate, and that a thin film in which the polymer molecules are aligned in a certain direction can be created by pulling the thin film developed on the water surface in a certain direction. . They also discovered that the film formed in this way exhibits an orienting effect on liquid crystal molecules. The alignment film formed by such a water surface spreading film forming method does not require a rubbing treatment, and therefore does not generate static electricity or the like, and does not destroy electrodes, TPT, etc. at all. Furthermore, since the film thickness can be made uniform without contaminating the alignment boundary surface, display unevenness and the like will not occur. moreover,
When a photosensitive polymer is used as the alignment film, it is easy to remove unnecessary portions of the alignment film on the substrate by photoetching, and it is also excellent in mass production without causing lighting defects due to the insulating properties of the alignment film. ing.
上記水面展開製膜法は、例えば第１図に示すようにして
行われる。すなわち、定量ポンプ（図示せず）でノズル
ｌから有機高分子溶液を水槽２内の水面３上に放出させ
る。これにより、上記有機高分子溶液が水面３上に自発
的に展開して薄膜４が形成される。このような有機高分
子溶液の水面での展開状態を模式的に第２図（Ａ）およ
び第２図（Ｂ）に示す。第２図（Ａ）は水面上での有機
高分子溶液の展開を示す平面模式図であり、第２図（Ｂ
）はその要部の拡大側面図である。第２図において、ａ
は有機高分子溶液部、ｂはゲル状部Ｃは固体の薄膜部で
ある。The above-mentioned water surface development film forming method is carried out, for example, as shown in FIG. That is, the organic polymer solution is discharged onto the water surface 3 in the water tank 2 from the nozzle 1 using a metering pump (not shown). As a result, the organic polymer solution spontaneously spreads on the water surface 3 to form a thin film 4. The state of development of such an organic polymer solution on the water surface is schematically shown in FIGS. 2(A) and 2(B). Figure 2 (A) is a schematic plan view showing the development of an organic polymer solution on the water surface;
) is an enlarged side view of the main part. In Figure 2, a
C is an organic polymer solution part, b is a gel-like part, and C is a solid thin film part.
このように水面３上に生成された薄膜４を第１、第２．
第３０−ル５，６．７により、連続的に移行するフィル
ム状基材８に接触させ付着移行させるか、液晶表示素子
の基板上の所定の部位に接触させ薄膜４を付着移行させ
引き取るということにより行われる。この際、展開する
高分子溶液の自発的な配向挙動を利用するか、もしくは
有機高分子溶液の水面上での自発的展開速度以上の引取
速度で引き取ることによって、薄膜に分子配向性を付与
することができる。上記のような基材上への配向膜の積
層は、水面上の薄膜を直接積層してもよいし、予めセパ
レーターのようなフィルム上に積層したものを透明電極
付ガラス板に転写する方式を用いてもよい。上記基材上
への薄膜の付着（付設）は単層であってもよいし、複層
であってもよい。複層の場合は、先に付設している水分
を完全に乾燥させてからつぎの薄膜を積層するのが好ま
しい。The thin film 4 thus generated on the water surface 3 is spread over the first, second, and so on.
According to Rule 30-5, 6.7, the thin film 4 is brought into contact with the continuously moving film-like substrate 8 to be attached and transferred, or the thin film 4 is brought into contact with a predetermined portion on the substrate of the liquid crystal display element to be attached and transferred. This is done by At this time, molecular orientation is imparted to the thin film by utilizing the spontaneous orientation behavior of the developing polymer solution or by pulling it at a speed higher than the spontaneous expansion speed of the organic polymer solution on the water surface. be able to. The above-mentioned alignment film can be laminated on the substrate by directly laminating a thin film on the water surface, or by a method in which the film is laminated in advance on a film such as a separator and then transferred to a glass plate with transparent electrodes. May be used. The thin film may be attached (attached) onto the base material in a single layer or in multiple layers. In the case of multiple layers, it is preferable to completely dry the attached moisture before laminating the next thin film.
このようにして得られる配向膜は、一定方向に配向する
効果を有し、分子配向に起因する赤外二色比が１．０５
以上の値を示す。The alignment film obtained in this way has the effect of aligning in a certain direction, and has an infrared dichroic ratio of 1.05 due to molecular alignment.
The above values are shown.
上記液晶分子配向膜の赤外二色比は、赤外分光装置ＦＴ
−ＩＲを用い、つぎのようにして求められる。すなわち
、配向薄膜単独か、あるいは赤外的に透明な基材（例え
ばシリコンウェハー）上に配向薄膜を積層した試料を用
い、この試料と赤外線ビームとの間に偏光子を設は透過
法により赤外線吸収スペクトルを測定する。第３図にモ
デル的なスペクトルを示した。図において、曲線Ａが吸
光度Ａｂｓ／／を示し、曲線Ｂが吸光度Ａｂｓ土を示し
ている。このように、赤外の直線偏光軸が薄膜の製膜方
向と平行の場合の吸光度（Ａｂｓ／／）および垂直な場
合の吸光度（Ａｂｓ上）を各々測定し、特定波長におい
て得られる上記吸光度の比（Ａ ｂ ｓ ／／／Ａ ｂ
ｓ上）が赤外二色比となる。The infrared dichroic ratio of the above liquid crystal molecular alignment film was determined using an infrared spectrometer FT.
- It is obtained as follows using IR. That is, using a sample with an oriented thin film alone or with an oriented thin film laminated on an infrared transparent substrate (for example, a silicon wafer), a polarizer is installed between this sample and the infrared beam, and the infrared rays are transmitted using the transmission method. Measure the absorption spectrum. Figure 3 shows a model spectrum. In the figure, curve A shows the absorbance Abs//, and curve B shows the absorbance Abs//. In this way, the absorbance when the infrared linear polarization axis is parallel to the film forming direction of the thin film (Abs//) and the absorbance when it is perpendicular to the film forming direction (Abs) are measured, and the absorbance obtained at a specific wavelength is calculated. Ratio (A b s ///A b
s) is the infrared dichroic ratio.
液晶分子配向膜の赤外二色比は、第４図に示すように、
引取速度により影響を受ける。すなわち、第４図は、引
取速度を変えて作製した配向膜の赤外二色比を、横軸に
引取速度（ｍ／分）、縦軸に赤外二色比（Ａ ｂ ｓ／
／／Ａ ｂ ｓ上）をとり関係を示している。The infrared dichroic ratio of the liquid crystal molecular alignment film is as shown in Figure 4.
Affected by withdrawal speed. That is, FIG. 4 shows the infrared dichroic ratios of alignment films produced by changing the take-up speed, with the take-up speed (m/min) on the horizontal axis and the infrared dichroic ratio (A b s/min) on the vertical axis.
//A b s above) to show the relationship.
本発明の効果を発現できる系は、水面展開製膜法で薄膜
を形成できる全ての系である。特に、感光性高分子を用
いることが好ましい。上記感光性高分子としては、オレ
フィン基、シンナモイル基、スチリルピリジン基、フェ
ニルアミド基、ジアゾ基等の感光性基を有する高分子、
重クロム酸塩化合物、ジアゾ化合物、アジド化合物等の
感光性化合物が混合された有機系高分子、アクリレート
樹脂、エポキシ樹脂、シリコーン樹脂等のＸ線および電
子線感応性高分子等があげられる。Systems that can exhibit the effects of the present invention are all systems that can form a thin film by the water surface spreading film forming method. In particular, it is preferable to use a photosensitive polymer. The photosensitive polymers include polymers having photosensitive groups such as olefin groups, cinnamoyl groups, styrylpyridine groups, phenylamide groups, and diazo groups;
Examples include organic polymers mixed with photosensitive compounds such as dichromate compounds, diazo compounds, and azide compounds, and X-ray and electron beam-sensitive polymers such as acrylate resins, epoxy resins, and silicone resins.
本発明において、液晶配向膜に、特に好適に用いられる
感光性高分子としては、ポリイミド系およびポリイミド
前駆体のポリアミド酸系樹脂があげられる。In the present invention, photosensitive polymers that are particularly suitably used in the liquid crystal alignment film include polyimide-based resins and polyamic acid-based resins that are polyimide precursors.
上記のような感光性ポリイミドおよびポリアミド酸は、
つぎのようにして得られる。すなわち、上記感光性ポリ
イミドおよびポリアミド酸としては、特開昭５５−４６
７１９号公報および特開昭５５−３０２０７号公報に開
示されているように、下記の式（１）で示されるような
構造のテトラカルボン酸二無水物とジアミン化合物また
は二塩基酸ヒドラジドとの反応によって得られる感光性
重合体が用いられる。Photosensitive polyimide and polyamic acid as mentioned above are
It can be obtained as follows. That is, as the photosensitive polyimide and polyamic acid, JP-A-55-46
As disclosed in JP-A No. 719 and JP-A-55-30207, the reaction between a tetracarboxylic dianhydride having a structure represented by the following formula (1) and a diamine compound or a dibasic acid hydrazide A photosensitive polymer obtained by is used.
上記Ｒ１ は、 感光性基であり、 具体的には下記に 示すようなものがある。R1 above teeth, is a photosensitive group, Specifically, below There is something to show.
一（ツーＣＨ＝ＣＨＣ０−０＞
、−（フーＣＯＣ詳Ｃト（）
上記テトラカルボン酸二無水物としては、ピロメリット
酸二無水物、３．３’、４．４’−ベンゾフエノンテ１
−ラカルボン酸二無水物、３．３’．４．４’−ビフェ
ニルテトラカルボン酸二無水物、シクロペンクンテトラ
カルボン酸二無水物、シクロブタンテトラカルボン酸二
無水物、ナフタレンテトラカルボン酸二無水物、ピリジ
ンテトラカルボン酸二無水物、ペリレンテトラカルボン
酸二無水物、４．４′−ジスルホニルシフタル酸二無水
物、ビス〔（ジカルボキシフェノキシ）フェニル〕プロ
バンチトラカルボン酸二無水物、ビス〔（ジカルボキシ
フェノキシ）ジフェニルエーテルテトラカルボン酸二無
水物、ビス〔（ジカルボキシフェノキシ）フェニル〕へ
キサフルオロプロパンテトラカルボン酸二無水物、ブタ
ンテトラカルボン酸二無水物等があげられ、単独でもし
くは併せて用いられる。1(2CH=CHC0-0>, -(Fu COC details Ct()) Examples of the above tetracarboxylic dianhydride include pyromellitic dianhydride, 3.3', 4.4'-benzophenone 1
-Lacarboxylic dianhydride, 3.3'. 4.4'-Biphenyltetracarboxylic dianhydride, cyclopenkune tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride Acid dianhydride, 4,4'-disulfonyl cyphthalic dianhydride, bis[(dicarboxyphenoxy)phenyl]probanthitracarboxylic dianhydride, bis[(dicarboxyphenoxy)diphenyl ether tetracarboxylic dianhydride dianhydride, bis[(dicarboxyphenoxy)phenyl]hexafluoropropane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, etc., which may be used alone or in combination.
上記テトラカルボン酸二無水物と共重合させるジアミン
化合物としては、フェニレンジアミン。The diamine compound to be copolymerized with the above-mentioned tetracarboxylic dianhydride is phenylenediamine.
ジフェニレンジアミン、トリフェニレンジアミン、下記
の式（２）で表される化合物。Diphenylene diamine, triphenylene diamine, a compound represented by the following formula (2).
Ｈｔ Ｎ −’０）−Ｘ−ＣＦＮ Ｈｚ ・・・
（２）下記の式（３）で表される構造を有する化合物２
例えば下記の式（４）で表されるビス（アミノフェノキ
シ）ジフェニル化合物等があげられる。HtN-'0)-X-CFNHz...
(2) Compound 2 having a structure represented by the following formula (3)
For example, there may be mentioned a bis(aminophenoxy)diphenyl compound represented by the following formula (4).
−（）−〇−Ｑ−ｘ−Ｑ−ｏ−Ｏｒ ・・・（３）
Ｈ２Ｎ−ｊクト０ （トＸ（ト０（）Ｎ Ｈｚ ・・
・（４）具体的には、ｐ−フェニレンジアミン、ｍ−フ
ェニレンジアミン、４．４’ −ジアミノターフェニル
、４，４′−ジアミノジフェニルスルホン、３３′−ジ
アミノジフェニルスルホン、４，４′ジアミノジフエニ
ルエーテル、４，４′−ジアミノフェニルベンゾエート
、４．４’ −ジアミノジフェニルメタン、２．２−
（４，４’ −ジアミノジフェニル）プロパン、４．４
′−ビス（ｐ −アミノフェノキシ）ジフェニルスルホ
ン、４，４′−ビス（ｍ−アミノフェノキシ）ジフェニ
ルス）Ｌｉ＊７．４．４’−ビス（ｐ−アミノフェノキ
シ）ジフェニルエーテル、４．４’−ビス（ｐ〜アミノ
フェノキシ）ジフェニルケトン、４．４’ビス（ｐ−ア
ミノフェノキシ）ジフェニルメタン、２．２− （４，
４’−ビス（Ｐ−アミノフェノキシ）ジフェニル〕プロ
パン、２．２−（４，４ビス（ｐ−アミノフェノキシ）
ジフェニル〕へキサフルオロプロパン等があげられる。-()-〇-Q-x-Q-o-Or...(3)
H2N-jkuto0 (toX(to0()N Hz...
・(4) Specifically, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminoterphenyl, 4,4'-diaminodiphenylsulfone, 33'-diaminodiphenylsulfone, 4,4'diaminodiphenyl enyl ether, 4,4'-diaminophenylbenzoate, 4.4'-diaminodiphenylmethane, 2.2-
(4,4'-diaminodiphenyl)propane, 4.4
'-bis(p-aminophenoxy)diphenylsulfone, 4,4'-bis(m-aminophenoxy)diphenyls)Li*7.4.4'-bis(p-aminophenoxy)diphenyl ether, 4.4'- Bis(p-aminophenoxy)diphenylketone, 4.4'bis(p-aminophenoxy)diphenylmethane, 2.2-(4,
4'-bis(P-aminophenoxy)diphenyl]propane, 2,2-(4,4bis(p-aminophenoxy)
Diphenyl]hexafluoropropane, etc.
また、下記の式（５）で表される４、４′−ジアミノ−
３カルバモイルジフエニルエーテル、
また、下記の式（６）〜（８）で表されるジアミノシロ
キサン化合物があげられる。In addition, 4,4'-diamino- represented by the following formula (5)
3-carbamoyl diphenyl ether, and diaminosiloxane compounds represented by the following formulas (6) to (8).
ＣＬ ＣＨ３
また、上記二塩基酸ヒドラジド化合物としては、イソフ
タル酸ジヒドラジド、テレフタル酸ジヒドラジド、４．
４′−ジヒドラジドジフェニルエーテル、４．４’−ジ
ヒドラジドジフェニルスルホン、４，４′−ジヒドラジ
ドジフェニル、４゜４′−ジヒドラジドジフェニルメタ
ン、４．４′ジヒドラジドフエニルベンゾエート、４．
４’ジヒドラジドフエニルスルフイド、３．３’ジヒド
ラジドフエニルスルホン、４．４’ −ビス（ｐ−ヒド
ラジドフェノキシ）ジフェニルスルホン、４．４’−ビ
ス（ｍ−ヒドラジドフェノキシ）ジフェニルスルホン、
４．４′−ビス（ｐ−ヒドラジドフェノキシ）ジフェニ
ルエーテル、２゜ｉ（４，４’−ビス（ｐ−ヒドラジド
フェノキシ）ジフェニル〕プロパン、２．２− （４，
４’ビス（ｐ−ヒドラジドフェノキシ）ジフェニル〕へ
キサフルオロプロパン、シュウ酸ジヒドラジ】 ７
ド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グ
ルタル酸ジヒドラジド、アジピン酸ジヒドラジド、ピメ
リン酸ジヒドラジド、スペリン酸ジヒドラジド、アゼラ
イン酸ジヒドラジド、セバシン酸ジヒドラジド等があげ
られ、単独でもしくは併せて用いられる。CL CH3 Further, examples of the dibasic acid hydrazide compound include isophthalic acid dihydrazide, terephthalic acid dihydrazide, 4.
4'-dihydrazide diphenyl ether, 4.4'-dihydrazide diphenyl sulfone, 4,4'-dihydrazide diphenyl, 4°4'-dihydrazide diphenylmethane, 4.4' dihydrazide phenyl benzoate, 4.
4'-dihydrazido phenyl sulfide, 3.3' dihydrazido phenyl sulfone, 4.4'-bis(p-hydrazidophenoxy) diphenyl sulfone, 4.4'-bis(m-hydrazidophenoxy) diphenyl sulfone,
4.4'-bis(p-hydrazidophenoxy)diphenyl ether, 2゜i(4,4'-bis(p-hydrazidophenoxy)diphenyl]propane, 2.2-(4,
4'bis(p-hydrazidophenoxy)diphenyl]hexafluoropropane, oxalic acid dihydrazide] 7, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, superic acid dihydrazide, azelaic acid dihydrazide , sebacic acid dihydrazide, etc., which may be used alone or in combination.
その他の感光性ポリイミドおよびポリアミド酸としては
、特開昭５６−１１０７２８号公報に開示されているよ
うな下記の構造を有する活性環状イミドを合成し、それ
とジアミン化合物または二塩基酸ヒドラジドとからなる
ものがあげられる。As other photosensitive polyimides and polyamic acids, active cyclic imides having the following structure as disclosed in JP-A No. 56-110728 are synthesized, and those are composed of diamine compounds or dibasic acid hydrazides. can be given.
さらに、他の感光性ポリイミドおよびポリアミド酸とし
ては、テトラカルボン酸とジアミン化合物または二塩基
酸ヒドラジドから得られるポリアミド酸のカルボキシル
基に感光性基を有する三級アミンをイオン結合させてア
ンモニウム塩型としたもの（特開昭５４−１４５７９４
号公報）、また、ポリイミドおよびポリアミド酸に感光
性化合物を混合して感光性を付与したもの等があげられ
る。Furthermore, other photosensitive polyimides and polyamic acids can be made into ammonium salts by ionically bonding a tertiary amine having a photosensitive group to the carboxyl group of a polyamic acid obtained from a tetracarboxylic acid and a diamine compound or a dibasic acid hydrazide. (Japanese Unexamined Patent Publication No. 54-145794)
(No. 3, No. 3, No. 3, No. 3, No. 3, No. 2002-12), and those in which a photosensitive compound is mixed with polyimide and polyamic acid to impart photosensitivity.
上記感光性化合物としては、重クロム酸塩、芳香族ジア
ゾ化合物、芳香族アジド化合物および有機ハロゲン化合
物等があげられる。Examples of the photosensitive compounds include dichromates, aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds.
本発明に用いられる感光性ポリアミド酸は、例えばつぎ
のようにして得られる。すなわち、上記テトラカルボン
酸二無水物とジアミン化合物または二塩基酸ヒドラジド
を反応させポリアミド酸を合成し、その後得られたポリ
アミド酸に感光性基を導入するか、あるいは感光性化合
物を混合することにより得られる。または、予め感光性
基を上記テトラカルボン酸二無水物に導入し、その後ジ
アミン化合物または二塩基酸ヒドラジドを反応させて得
られる。The photosensitive polyamic acid used in the present invention can be obtained, for example, as follows. That is, by reacting the above tetracarboxylic dianhydride with a diamine compound or dibasic acid hydrazide to synthesize a polyamic acid, and then introducing a photosensitive group into the obtained polyamic acid, or by mixing a photosensitive compound. can get. Alternatively, it can be obtained by introducing a photosensitive group into the tetracarboxylic dianhydride in advance and then reacting it with a diamine compound or dibasic acid hydrazide.
また、本発明において、液晶配向膜に用いられる感光性
高分子として、上記感光性基を有するポリアミド酸およ
び感光性基を有するポリイミド以外に、感光性基を有す
るポリイソインドロキナゾリンジオン系樹脂、ポリイソ
インドロベンゾチアダイアシンジオキサイド系樹脂、ポ
リイミダゾピロロン系樹脂、ポリベンゾオキジノン系樹
脂等を用いることもできる。In addition, in the present invention, as the photosensitive polymer used in the liquid crystal alignment film, in addition to the above-mentioned polyamic acid having a photosensitive group and polyimide having a photosensitive group, polyisoindoquinazolinedione resin having a photosensitive group, Polyisoindrobenzothiadiacine dioxide-based resins, polyimidazopyrrolone-based resins, polybenzooxidinone-based resins, etc. can also be used.
このような有機高分子は、素材に応じて展開溶媒を選択
し、水面上に均一展開する系で薄膜形成される。Such organic polymers are formed into a thin film by selecting a developing solvent according to the material and uniformly developing them on the water surface.
上記展開溶媒としては、ポリアミド酸、ポリイミドを溶
解する不活性溶媒が用いられ、例えば、Ｎ−メチルピロ
リドン、ジメチルアセトアミド、ジメチルホルムアミド
、ジメチルスルホキシド、ジエチルホルムアミド、ジメ
チルスルホキサイドヘキサメヂルホスホルアミド、テト
ラメチレンスルホン等があげられ、単独でもしくは併せ
て用いられる。また、一種類の溶剤で充分な水面展開製
膜性が得られない場合には展開助剤として第２の有機溶
剤を添加することも有効である。このような展開助剤と
しては、脂肪族、脂環族またはケトン、エステル、アル
コール、アミン、アルデヒド、パーオキサイドならびに
これらの混合物があげられる。As the developing solvent, an inert solvent that dissolves polyamic acid and polyimide is used, such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, diethylformamide, dimethylsulfoxide hexamethylphosphoramide, Examples include tetramethylene sulfone, which can be used alone or in combination. Furthermore, when sufficient water surface spreadability cannot be obtained with one type of solvent, it is also effective to add a second organic solvent as a spreading aid. Such developing aids include aliphatic, cycloaliphatic or ketones, esters, alcohols, amines, aldehydes, peroxides and mixtures thereof.
この系では、上記展開助剤を１重量％（以下「％」と略
す）以上含有する溶液を用いることが好ましい。In this system, it is preferable to use a solution containing 1% by weight (hereinafter abbreviated as "%") or more of the above-mentioned developing aid.
本発明において、水面展開連続製膜に用いる有機高分子
溶液の濃度は、０．５〜３０％、好ましくは１〜２０％
である。ポリマー濃度が低すぎると均一な連続膜を得る
ことが難しく、逆に高すぎると水面上で溶液の展開性が
低下するため好ましくない。In the present invention, the concentration of the organic polymer solution used for continuous film formation on a water surface is 0.5 to 30%, preferably 1 to 20%.
It is. If the polymer concentration is too low, it will be difficult to obtain a uniform continuous film, whereas if it is too high, the spreadability of the solution on the water surface will decrease, which is not preferable.
なお、本発明に用いられる感光性有機高分子には、上記
成分以外にも、必要に応じて光増感剤。In addition to the above-mentioned components, the photosensitive organic polymer used in the present invention may optionally contain a photosensitizer.
顔料等その他の添加剤を用いることができる。Other additives such as pigments can be used.
上記光増感剤としては、例えば、ベンゾフェノン、アセ
トフェノン、アントロン、ｐ、ｐ’−テトラメチルジア
ミノベンゾフェノン（ミヒラーケトン）、フェナントレ
ン、ナフタレン、２−ニトロフルオレン、５−ニトロア
セナフテン、Ｎ−アセチル−４−ニトロ−１−ナフチル
アミン、４ニトロ−１−ナフチルアミン、ベンゾキノン
、ジベンザルアセトン、ベンジル、ｐ−ジアミノベンゾ
フェノン、ｐ、ｐ’ −ジメチル−アミノベンゾフェノ
ン、１．２−ナフトキノン、１．４−ナフトキノン、ア
ントラキノン、１．９−ベンゾアントロン等があげられ
、単独でもしくは併せて用いられる。上記光増感剤の含
有量は、光硬化性高分子成分に対して０．０１〜１０％
の割合で含有されるのが好ましく、顔料等の着色剤を添
加する場合には適宜増量される。Examples of the photosensitizer include benzophenone, acetophenone, anthrone, p, p'-tetramethyldiaminobenzophenone (Michler's ketone), phenanthrene, naphthalene, 2-nitrofluorene, 5-nitroacenaphthene, N-acetyl-4- Nitro-1-naphthylamine, 4-nitro-1-naphthylamine, benzoquinone, dibenzalacetone, benzyl, p-diaminobenzophenone, p,p'-dimethyl-aminobenzophenone, 1,2-naphthoquinone, 1,4-naphthoquinone, anthraquinone , 1,9-benzaanthrone, etc., which may be used alone or in combination. The content of the photosensitizer is 0.01 to 10% based on the photocurable polymer component.
It is preferably contained in a proportion of , and when a coloring agent such as a pigment is added, the amount is increased as appropriate.
また、本発明に用いられる感光性アミド酸系ポリマーお
よびイミド系ポリマーは、どのようなものでもよいが、
特に固有粘度（濃度０．５ｇ／１００ｍ１．温度３０°
Ｃで測定）が０．３〜５．０の範囲のものが好ましい。Further, the photosensitive amic acid-based polymer and imide-based polymer used in the present invention may be of any type, but
Especially the intrinsic viscosity (concentration 0.5g/100m1.Temperature 30°
C) is preferably in the range of 0.3 to 5.0.
本発明に用いる配向膜は、先に述べたように、電極を設
けた基板上に直接積層形成することができるが、電極の
下層または上層に無機絶縁膜としテＳ ｉｏｚ 、 Ａ
Ｉ！、ｚ Ｏ，およびＴｉＯ２等の膜を設けた基板に対
しても適用できる。また、−層強固な配向膜を得るため
に、エポキシ系およびアミノ系シランカップリング剤の
１種以上を併用することもできる。As mentioned above, the alignment film used in the present invention can be directly laminated on a substrate provided with an electrode, but it is also possible to form an inorganic insulating film as a layer below or above the electrode.
I! The present invention can also be applied to substrates provided with films such as , z O, and TiO2. Further, in order to obtain a strong alignment film, one or more of epoxy-based and amino-based silane coupling agents can be used in combination.
このようにして基材上に付設される配向膜は、マスクを
通して露光し未露光部分を適当な現像液で流出除去する
ことによりパターンが形成され、種々の基板上に微細な
画像を形成することができる。上記露光による光硬化法
は、光照射（紫外線、電子線、放射線等）によって行わ
れる。The alignment film attached to the substrate in this way is patterned by exposing it to light through a mask and removing the unexposed areas with a suitable developer, thereby forming fine images on various substrates. Can be done. The photocuring method using exposure is performed by light irradiation (ultraviolet rays, electron beams, radiation, etc.).
また、配向膜がポリアミド酸系のものは、必要に応じて
加熱または化学処理によりイミド化してもよい。Furthermore, if the alignment film is based on polyamic acid, it may be imidized by heating or chemical treatment, if necessary.
本発明は、上記のようにして得られた電極基板を用いて
液晶セルを形成し、この液晶セル中に液晶を封入するこ
とにより液晶表示素子を製造する。In the present invention, a liquid crystal display element is manufactured by forming a liquid crystal cell using the electrode substrate obtained as described above and sealing liquid crystal in this liquid crystal cell.
上記液晶としては、例えば、下記の式■〜■に示すネマ
チック液晶、弐〇〜＠に示す強誘電性液晶（Ｃ″は不斉
炭素原子を表す）および上記の混合物等があげられる。Examples of the above-mentioned liquid crystals include nematic liquid crystals shown in the following formulas (1) to (2), ferroelectric liquid crystals shown in (2) to (@) (C'' represents an asymmetric carbon atom), and mixtures of the above.
■ Ａ−Ｃン（コーＢ
■ １１−’８ヒＣとＢ
■ Ａ−（）−Ｃ０２（トＢ
■ ＾→ＳとＧ ＯＺ −Ｃ＞１
■
Ａ＋ン嵌コトＢ
＋＋
これらの液晶は、上記液晶セルに封入され液晶層を構成
する。■ A-Cn (ko B ■ 11-'8hi C and B ■ A-()-C02 (to B) ■ ^→S and G OZ -C>1 ■ A+n fitting B ++ These liquid crystals are It is sealed in the liquid crystal cell and constitutes a liquid crystal layer.
本発明の液晶表示素子における液晶層は、ネマチック液
晶物質を１種以上含有してもよい。その際、液晶表示素
子は両基板間の配向方向が８０〜２８０’捩じれた構造
を有するのが好ましい。また、一方の基板に薄膜トラン
ジスターまたはダイオード等のスイッチング素子を設け
てよい。さらに、液晶層は、強誘電性液晶物質（例えば
、前記式〇〜＠）を１種以上含有しても差し支えない。The liquid crystal layer in the liquid crystal display element of the present invention may contain one or more nematic liquid crystal substances. In this case, it is preferable that the liquid crystal display element has a structure in which the alignment direction between both substrates is twisted by 80 to 280'. Further, a switching element such as a thin film transistor or a diode may be provided on one of the substrates. Furthermore, the liquid crystal layer may contain one or more types of ferroelectric liquid crystal substances (for example, the above formulas ○ to @).
以上のように、本発明の液晶表示素子は、水面展開法に
よって形成された水面展開膜を液晶分子配向膜として用
いているため、従来のようなラビング処理による静電気
の発生や配向境界面の汚染ならびに膜厚不均一にもとづ
く表示むら等の問題を全く生じない。また、配向膜を予
め所定のパターン状に形成しておき、これを使用できる
ため、配向膜の不適正による点灯不良等の発生を防止す
ることができる。さらに、水面展開法により配向Ｇ
膜を形成しフォトエツチングにより配向膜をパターン状
に形成することは比較的容品で量産性に冨んでいること
から、本発明の方法によれば、上記液晶表示素子を容易
に量産しうるようになる。As described above, since the liquid crystal display element of the present invention uses a water surface development film formed by the water surface development method as a liquid crystal molecule alignment film, it is free from the generation of static electricity and contamination of the alignment interface due to the conventional rubbing process. Furthermore, problems such as display unevenness due to non-uniform film thickness do not occur at all. Further, since the alignment film can be formed in advance in a predetermined pattern and used, it is possible to prevent lighting failures and the like due to inappropriate alignment films. Furthermore, forming an oriented G film by the water surface development method and forming the oriented film in a pattern by photoetching is relatively simple and easy to mass produce. Devices can be easily mass-produced.
つぎに、実施例について比較例と併せて説明する。Next, examples will be described together with comparative examples.
〔実施例１〕
ピロメリット酸二無水物２４．１６ ｇと４，４′ジア
ミノジフ工ニルエーテル１５ｇを２００ｇのＮ−メチル
ピロリドン溶液中において、室温下で４時間撹拌し固有
粘度２．５のポリアミド酸溶液を合成した。その後、窒
素ガスを流しながら温度９０°Ｃに加熱して得られたポ
リアミド酸溶液にグリシジルシンナマート３．７８ ｇ
およびトリエチルベンジルアンモニウムクロライド０．
３７８ ｇを加えて９０°Ｃ下で５時間反応させた。得
られた感光性ポリアミド酸溶液に増感剤ｐ、ｐ’−テト
ラメチルジアミノベンゾフェノン２ｇを添加し、感光性
ポリアミド酸をＮ−メチルピロリドン／アセトフェノン
＝３０／７０（重量比）混合溶媒にポリマー濃度が５％
になるように希釈して展開溶液を作製した。上記展開溶
液を製膜速度１２ｍ／ｍｉｎで水面展開連続製膜を行い
、膜厚が３００人で赤外二色比カ月、３０（波長１５０
０ｃｍ”）のポリアミド酸配向膜を得た。つぎに、上記
配向膜をストライプ状の透明電極基板（電極幅２００μ
ｍ９間隔５０μｍ）に付設し、この基板に所定のパター
ンを描いたマスクを取り付は上記基板を高圧水銀灯（３
０ｃｍ／１ｋＶ）で６０秒間紫外線照射した。さらに、
上記基板状の未露光部分の未硬化樹脂をＮ−メチルピロ
リドンで溶解した後、温度８０°Ｃで１時間乾燥した。[Example 1] 24.16 g of pyromellitic dianhydride and 15 g of 4,4' diamino diphenyl ether were stirred in 200 g of N-methylpyrrolidone solution at room temperature for 4 hours to obtain a polyamic acid with an intrinsic viscosity of 2.5. A solution was synthesized. Thereafter, 3.78 g of glycidyl cinnamate was added to the polyamic acid solution obtained by heating to 90°C while flowing nitrogen gas.
and triethylbenzylammonium chloride 0.
378 g was added and reacted at 90°C for 5 hours. 2 g of the sensitizer p,p'-tetramethyldiaminobenzophenone was added to the obtained photosensitive polyamic acid solution, and the polymer concentration was adjusted by adding the photosensitive polyamic acid to a mixed solvent of N-methylpyrrolidone/acetophenone = 30/70 (weight ratio). is 5%
A developing solution was prepared by diluting the solution to the following. Continuous film formation was carried out using the above developing solution at a film formation speed of 12 m/min on the water surface, and the film thickness was 300 people and the infrared dichroic ratio was 30 months (wavelength: 150 m/min).
A polyamic acid alignment film of 0cm") was obtained. Next, the above alignment film was coated on a striped transparent electrode substrate (electrode width 200μ).
To attach a mask with a predetermined pattern on this board, place the above board under a high-pressure mercury lamp (3
Ultraviolet rays were irradiated for 60 seconds at a voltage of 0 cm/1 kV). moreover,
After dissolving the uncured resin in the unexposed portion of the substrate with N-methylpyrrolidone, it was dried at a temperature of 80° C. for 1 hour.
上記のような処理が施された基板を配向膜の製膜方向が
直交するように６μｍのスペーサを介して、フェニルシ
クロヘキサン系のネマチック液晶組成物を注入し外周部
をエポキシ樹脂でシールした後、偏光軸が配向膜の配向
方向と同じ方向に偏光板を貼り付は液晶表示素子を得た
。After injecting a phenylcyclohexane-based nematic liquid crystal composition through a 6 μm spacer so that the film forming direction of the alignment film is perpendicular to the substrate treated as described above, and sealing the outer periphery with an epoxy resin, A liquid crystal display element was obtained by attaching a polarizing plate so that the polarization axis was in the same direction as the alignment direction of the alignment film.
このようにして得られた液晶表示素子は、配向のムラは
見られず均一配向性を示した。また、点灯不良は全くみ
られなかった。さらに、電気光学特性の第５図に示す電
圧透過率特性（γ＝Ｖ、。／■、。）は１．４５であっ
た。なお、第５図に示すように、しきい値特性を電圧■
（横軸）と透過率％（縦軸）との関係で示した。また、
この液晶表示素子は静電気の発生がなく、電極間のショ
ート。The liquid crystal display element thus obtained exhibited uniform alignment without any unevenness in alignment. Furthermore, no lighting defects were observed. Furthermore, the voltage transmittance characteristic (γ=V, ./■, .) shown in FIG. 5 of the electro-optical characteristics was 1.45. In addition, as shown in Figure 5, the threshold characteristic is determined by changing the voltage
(horizontal axis) and transmittance% (vertical axis). Also,
This liquid crystal display element does not generate static electricity, and there is no short circuit between electrodes.
電極破壊が全く見られなかった。さらに、目視で観察し
た結果、ネサ見えも発生していなかった。No electrode breakdown was observed. Furthermore, as a result of visual observation, there was no appearance of Nesa.
〔実施例２〕
ポリアミド酸配向膜を温度２００°Ｃ下で１時間熱処理
してイミド化し、膜厚４００人で赤外二色比１．２５（
波長１５００ｃｍ−’）の薄膜を作製した。それ以外は
実施例１と同様にして液晶表示素子を得た。[Example 2] A polyamic acid alignment film was heat-treated at a temperature of 200°C for 1 hour to imidize it, and the infrared dichroic ratio was 1.25 (at a film thickness of 400 people).
A thin film with a wavelength of 1500 cm-' was produced. A liquid crystal display element was obtained in the same manner as in Example 1 except for the above.
得られた液晶表示素子は点灯不良が全くなく、また配向
性は良好で、電気光学特性のＴは１．５５であった。ま
た、この液晶表示素子は静電気の発生がなく、電極間の
ショート、電極破壊が全く見られなかった。さらに、目
視で観察した結果、ネサ見えも発生していなかった。The obtained liquid crystal display element had no lighting defects, had good alignment, and had an electro-optical characteristic T of 1.55. Further, this liquid crystal display element did not generate static electricity, and no short circuit between electrodes or electrode breakdown was observed. Furthermore, as a result of visual observation, there was no appearance of Nesa.
〔実施例３〕
３．３’、４．４’ −ベンゾフェノンテトラカルボン
酸二無水物と２．２− （４，４’−ビス（ｐ−アミノ
フェノキシ）ジフェニル〕へキサフルオロプロパンを用
いてポリアミド酸のメタクリル酸エステルからなる感光
性ポリアミド酸を作製した。この感光性ポリアミド酸を
、ジメチルアセトアミド／アセトフェノン−６０／４０
（重量比）混合溶媒にポリマー濃度が５％になるように
溶解して展開溶液を調整した。この調整溶液を、製膜速
度１５ｍ／ｎ＋ｉｎで水面展開連続製膜を行い、膜厚が
１００人、赤外二色比が１．５０（波長１５００ｃｍ−
’）のポリアミド酸配向膜を作製した。得られた配向膜
を用いて実施例１と同様にしてパターンが形成された基
板を作製した。つぎに、温度２００°Ｃで３０分間熱処
理してイミド化した上記基板を用いて配向膜の製膜方向
が直行するように４μｍのスペーサを介して、下記に示
す強誘電性液晶組成物
（余 白 ）
ＣＨ３
Ｃ６Ｈ＋ ａｏ−Ｑ−ＯｃＯ−Ｑ−Ｑ−０−Ｃ” Ｃ６
ＨＩ ３（５０モルχ）
ＣＩ＋。[Example 3] Preparation of polyamide using 3.3',4.4'-benzophenonetetracarboxylic dianhydride and 2.2-(4,4'-bis(p-aminophenoxy)diphenyl]hexafluoropropane) A photosensitive polyamic acid consisting of a methacrylic acid ester was prepared.This photosensitive polyamic acid was mixed with dimethylacetamide/acetophenone-60/40.
(Weight ratio) A developing solution was prepared by dissolving the polymer in a mixed solvent at a concentration of 5%. This adjusted solution was subjected to continuous film formation on the water surface at a film forming speed of 15 m/n+in, resulting in a film thickness of 100 mm and an infrared dichroic ratio of 1.50 (wavelength 1500 cm-
') polyamic acid alignment film was prepared. A patterned substrate was produced in the same manner as in Example 1 using the obtained alignment film. Next, using the above-mentioned substrate which had been heat-treated for 30 minutes at a temperature of 200°C and made into an imid, a ferroelectric liquid crystal composition shown below (the remainder White) CH3 C6H+ ao-Q-OcO-Q-Q-0-C” C6
HI 3 (50 mol χ) CI+.
Ｃ７ＨＩ、０−Ｑ−ＯＣＯ−Ｑ−０（Ｃ■２チ丁Ｃ”−
Ｃ２Ｈ＋。C7HI, 0-Q-OCO-Q-0 (C ■ 2 Chi Ding C"-
C2H+.
（２５モルχ）
ＣＨ３
ＣｅＨ，，０図コトＣ＞Ｃｏ２−ＣＨ２−Ｃ“−ｃ、ｕ
、 （２５モルχ）■
を注入し外周部をエポキシ樹脂でシールした後、偏光軸
が配向膜の製膜方向と同じ方向に偏光板を貼り付は液晶
表示素子を得た。このようにして得られた液晶表示素子
は、配向のむらは見られず均−配向性を示した。また、
電気光学特性も測定した。第６図（ａ）および第６図（
ｂ）は、このメモリー性評価特性を、時間と明るさおよ
び印加電圧の関係で示したグラフであり、図に示すよう
に、電界印加時のコントラスト比Ｃ，＝Ｂ４／Ｂ、メモ
リ−２状態間のコントラスト比Ｃ，’＝Ｂ３／Ｂ２とす
ると、両者の比はＭ−（Ｃ，’−１）／（ＣＩ−１）と
なる。すなわち、メモリー状態の安定性を表すパラメー
タとして、メモリ−２状態間のコントラスト比と電界印
加時のコントラス
ト
コントラスト比も１０：１と良好な値を有していた。ま
た、この液晶表示素子は点灯不良および静電気の発生が
なく、電極間のショート、電極破壊が全く見られなかっ
た。(25 mol χ) CH3 CeH,,0 figure C>Co2-CH2-C"-c, u
, (25 mol χ)■ was injected and the outer periphery was sealed with epoxy resin, and a polarizing plate was attached so that the polarization axis was in the same direction as the alignment film forming direction to obtain a liquid crystal display element. The liquid crystal display element thus obtained exhibited uniform alignment without any unevenness in alignment. Also,
Electro-optical properties were also measured. Figure 6(a) and Figure 6(
b) is a graph showing the memory evaluation characteristics in terms of the relationship between time, brightness, and applied voltage. If the contrast ratio between C,'=B3/B2, then the ratio between the two becomes M-(C,'-1)/(CI-1). That is, as parameters representing the stability of the memory state, the contrast ratio between memory-2 states and the contrast ratio when an electric field was applied also had good values of 10:1. In addition, this liquid crystal display element had no lighting failure or static electricity generation, and no short circuit between electrodes or electrode breakdown was observed.
〔実施例４〕
３、３’，４．４’ −ベンゾフェノンテトラカルボン
酸二無水物と４．４′−ビス（ｍ−アミノフェノキシ）
ジフェニルスルホンからなるポリアミド酸のメタクリル
酸エステルを感光性樹脂として用いて、ポリマー濃度が
３％になるように溶解して展開溶液を調整した。それ以
外は実施例３と同様にしてポリアミド酸水面展開法によ
る膜厚１００人で赤外二色比が１．４０（波長１５００
ｃｍ−’）のポリアミド酸系配向膜を作製した。つぎに
、実施例１と同様にして上記配向膜のパターン化処理を
行い、さらに温度２００°Ｃで１時間加熱しポリイミド
膜を作製した。そして、実施例３で用いた強誘電性液晶
に二色性色素（三菱化成社製，ＬＳＢ２３５）を３％混
入させ、目的の液晶表示素子を得た。このようにして得
られた液晶表示素子の配向性，メモリー性およびコント
ラスト比を評価した。その結果、点灯不良は全くなく、
また配向のむらも見られず均一配向性を示し、かつメモ
リー性（Ｍ）はＭ＝１と良好な値を示し、コントラスト
比もｌＯ：１を示した。また、得られた液晶表示素子は
静電気の発生がなく、電極間のショート、電極破壊が一
切見られなかった。[Example 4] 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-bis(m-aminophenoxy)
A developing solution was prepared by using methacrylic acid ester of polyamic acid consisting of diphenyl sulfone as a photosensitive resin and dissolving the polymer at a concentration of 3%. Other than that, the infrared dichroic ratio was 1.40 (wavelength 1500
A polyamic acid-based alignment film of cm-') was produced. Next, the alignment film was patterned in the same manner as in Example 1, and further heated at 200° C. for 1 hour to produce a polyimide film. Then, 3% of a dichroic dye (manufactured by Mitsubishi Kasei Corporation, LSB235) was mixed into the ferroelectric liquid crystal used in Example 3 to obtain the desired liquid crystal display element. The orientation, memory properties, and contrast ratio of the liquid crystal display element thus obtained were evaluated. As a result, there were no lighting defects at all.
Moreover, uniform alignment was exhibited without any unevenness in alignment, and the memory property (M) showed a good value of M=1, and the contrast ratio also showed 1O:1. Further, the obtained liquid crystal display element did not generate static electricity, and no short circuit between electrodes or electrode breakdown was observed.
〔実施例５〕
ピロメリット酸二無水物と２．２−（４，４’ビス（ｐ
−アミノフェノキシ）ジフェニル〕プロパンからなるポ
リアミド酸のベンザルアセトフェノンエステルを感光性
樹脂として用いて、Ｎメチルピロリドン／アセトフェノ
ン−８ ０７２ ０（重量比）混合溶媒にポリマー濃度
が６％になるように溶解して展開溶液を調整した。この
調整溶液を用いて、実施例１と同様にしてアモルファス
シリコン半導体基板上（画素数２０Ｘ２０）に水面展開
連続製膜法により膜厚５００人の配向膜を形成し配向膜
をパターン化した。さらに、温度１８０°Ｃで１時間加
熱を行った後、下記に示すネマチック液晶組成物
Ｃ．Ｈ？ｐＣＮ （６０モ，＋Ｌ，Ｘ）Ｃ
ｓＨｔ＋−３とＣＯ□（コトＦ （１０モルχ）Ｃ
ｘＨｙ＜Ｅｆ＞べＢヒＣ＞Ｃ３Ｈ？ （２０モル
χ）ＣｓＨ＋ ｒ Ｆ （１０
モ）Ｌｔχ）を注入し外周部をシールし、偏光軸が配向
膜の配向方向と同じ方向に偏光板を貼り付はアクティブ
マトリックス液晶表示素子を得た。このようにして得ら
れた液晶表示素子は、配向のむらは見られず均一配向性
を示し、かつＴＰＴ動作を行った結果、全画素が正常に
点灯することを確認した。したがって、この液晶表示素
子は静電気の発生がな（、ＴＰＴの損傷が全く見られな
かった。[Example 5] Pyromellitic dianhydride and 2,2-(4,4'bis(p)
Using benzalacetophenone ester of polyamic acid consisting of -aminophenoxy)diphenyl]propane as a photosensitive resin, it was dissolved in a mixed solvent of N-methylpyrrolidone/acetophenone-80720 (weight ratio) to a polymer concentration of 6%. A developing solution was prepared. Using this adjustment solution, an alignment film with a thickness of 500 layers was formed on an amorphous silicon semiconductor substrate (pixel count: 20×20) by a water surface continuous film forming method in the same manner as in Example 1, and the alignment film was patterned. Furthermore, after heating at a temperature of 180°C for 1 hour, a nematic liquid crystal composition C. H? pCN (60mo, +L,X)C
sHt+-3 and CO□(CotoF (10 moles χ)C
xHy＜Ef＞BeBhiC＞C3H? (20 mol χ)CsH+ r F (10
m) Ltχ) was injected to seal the outer periphery, and a polarizing plate was attached so that the polarization axis was in the same direction as the alignment direction of the alignment film to obtain an active matrix liquid crystal display element. It was confirmed that the thus obtained liquid crystal display element exhibited uniform alignment without any unevenness in alignment, and as a result of performing TPT operation, all pixels lit up normally. Therefore, this liquid crystal display element did not generate static electricity (and no damage to the TPT was observed).
〔実施例６〕
Ｎ、Ｎ’−ビス（メタクリロイル）ピロメリットイミド
と４，４′−ジアミノジフェニルエーテルからなる感光
性ポリアミド酸に、感光性重合体に対して２−メチルア
ントラキノンの８％溶液を作製した。上記感光性ポリア
ミド酸溶液を用いてジメチルアセトアミド／アセトフェ
ノン＝５０１５０（重量比）混合溶媒にポリマー濃度が
８％になるように溶解して展開溶液を調整した。この調
整溶液をストライプ状の透明電極基板（電極幅２００μ
ｍ、間隔５０μｍ）に実施例１と同じ条件で水面展開連
続製膜を行い、膜厚が約４００人。[Example 6] An 8% solution of 2-methylanthraquinone to the photosensitive polymer was prepared in a photosensitive polyamic acid consisting of N,N'-bis(methacryloyl)pyromellitimide and 4,4'-diaminodiphenyl ether. did. A developing solution was prepared by dissolving the above photosensitive polyamic acid solution in a mixed solvent of dimethylacetamide/acetophenone=50150 (weight ratio) so that the polymer concentration was 8%. This adjustment solution was applied to a striped transparent electrode substrate (electrode width 200 μm).
Continuous film formation was carried out on the water surface under the same conditions as in Example 1 at intervals of 50 μm, and the film thickness was approximately 400 μm.
赤外二色比が１．４５（波長１５００ｃｍ−’）の感光
性ポリアミド酸系配向膜を作製した。その後、温度２０
０°Ｃで３０分間加熱しポリイミドに閉環させた後、液
晶分子のねじれ角度を２００°になるよう基板と偏光板
の吸収軸を調製し６μｍのスペーサを介して、下記に示
すネマチック液晶組成物Ｃ３Ｈ１（）９口＞ ＣＮ
（４０モルχ）Ｃ６ＨＩ ３□ｃＨ
ｚｃＨｚ＜Ｅｉ＞ＣｓＨｚ ＋ （１５モルχ）Ｃ
７ＨＩ５ ０Ｃ５１１１１（２０モルχ）
ＣｓＨｚ−ぐ予−Ｃ０２−Ｏ＋−０Ｃ６ＨＩ３（２５モ
ルχ）を注入してシールした。その後、ＳＴＮ液晶素子
のスキャツタリングドメイン（光を散乱するドメイン）
を調べた結果、ドメインの発生は見られず全画素の領域
で安定な点灯状態になることを確認した。また、このＳ
ＴＮ液晶表示素子も静電気の発生がなく、電極間のショ
ート、電極破壊が全く見られなかった。さらに、目視で
観察した結果、ネサ見えも発生していなかった。A photosensitive polyamic acid alignment film having an infrared dichroic ratio of 1.45 (wavelength 1500 cm-') was produced. Then temperature 20
After heating at 0°C for 30 minutes to ring-close the polyimide, the absorption axes of the substrate and polarizing plate were adjusted so that the twist angle of the liquid crystal molecules was 200°, and the nematic liquid crystal composition shown below was prepared through a 6 μm spacer. C3H1 () 9 shares> CN
(40 mol χ)C6HI 3□cH
zcHz<Ei>CsHz + (15 mol χ)C
7HI5 0C51111 (20 mol χ)
CsHz-pre-C02-O+-0C6HI3 (25 mol χ) was injected and sealed. After that, the scattering domain (domain that scatters light) of the STN liquid crystal element
As a result of the investigation, it was confirmed that no domains were observed and a stable lighting state was achieved in all pixel areas. Also, this S
The TN liquid crystal display element also did not generate static electricity, and no short circuit between electrodes or electrode breakdown was observed. Furthermore, as a result of visual observation, there was no appearance of Nesa.
〔比較例１〕
ピロメリット酸二無水物と４．４′−ジアミノジフェニ
ルエーテルを用いてポリアミド酸を作製し、このポリア
ミド酸を用いてＮ−メチルピロリドン／アセトフェノン
＝３０／７０ （ｌｉｒ比） Ｎ釈によるポリマー濃度
５％の溶液を作製した。上記溶液を用いて製膜速度１２
ｍ／ｓｉｎで水面展開連続製膜を行い膜厚３００人、赤
外二色比１．３０（波長１５００ｃｍ＋−’）のポリア
ミド酸配向膜を作製した。上記配向膜をストライプ状の
透明電極基板（電極幅２００μｍ、間隔５０ｔＩＩ１１
）に付設し、基板全面に配向膜が存在する電極基板を用
いた。それ以外は実施例１と同様にして液晶表示素子を
得た。得られた液晶表示素子は、外部端子部と内部接続
部上の配向膜の絶縁性から電場印加時に点灯不良が生じ
、その結果、表示不良を起こした。[Comparative Example 1] Polyamic acid was produced using pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, and N-methylpyrrolidone/acetophenone = 30/70 (LIR ratio) was prepared using this polyamic acid. A solution with a polymer concentration of 5% was prepared. Film forming speed 12 using the above solution
A polyamic acid oriented film with a film thickness of 300 and an infrared dichroic ratio of 1.30 (wavelength 1500 cm+-') was produced by continuous film formation on the water surface at m/sin. The above alignment film was applied to a striped transparent electrode substrate (electrode width 200 μm, interval 50tII11
), and an electrode substrate with an alignment film on the entire surface of the substrate was used. A liquid crystal display element was obtained in the same manner as in Example 1 except for the above. In the obtained liquid crystal display element, lighting failure occurred when an electric field was applied due to the insulation of the alignment film on the external terminal portion and the internal connection portion, resulting in display failure.
〔比較例２〕
実施例１で作製した感光性ポリアミド酸溶液を用いて、
ジメチルアセトアミド希釈によりポリマー濃度３％の溶
液を作製した。つぎに、上記溶液を用いて、ストライプ
状の透明電極基板（電極幅２００μｍ２間隔５０μｍ）
にスピン塗布（３０００ｒｐｍ、６０秒）で約５００人
の配向膜を形成した。その後、実施例１と同様にして配
向膜をパターン化し、温度２００″Ｃで１時間加熱閉環
させた。そして、ＡＢレーベル布を巻いたロータを回転
（回転数６０Ｏｒｐｍ、切り込み量０．４ｓ）してラビ
ング処理を行いフェニルシクロヘキサン系のネマチック
液晶組成物を注入し外周部をエポキシ樹脂でシールして
液晶表示素子を得た。得られた液晶表示素子について評
価した結果、静電気の発生が見られ、電極間のショート
、電極破壊が起こり点灯不良が発生した。また、液晶素
子の各部でしきい値（ｖｔｈ）特性の変化および低下が
見られ、素子全体での安定性が劣ったものであった。[Comparative Example 2] Using the photosensitive polyamic acid solution prepared in Example 1,
A solution with a polymer concentration of 3% was prepared by dilution with dimethylacetamide. Next, using the above solution, a striped transparent electrode substrate (electrode width 200 μm 2 interval 50 μm) was prepared.
An alignment film of about 500 layers was formed by spin coating (3000 rpm, 60 seconds). Thereafter, the alignment film was patterned in the same manner as in Example 1, and the ring was closed by heating at a temperature of 200"C for 1 hour. Then, a rotor wrapped with AB label cloth was rotated (rotation speed: 60 rpm, cutting depth: 0.4 s). A phenylcyclohexane-based nematic liquid crystal composition was injected, and the outer periphery was sealed with epoxy resin to obtain a liquid crystal display element.As a result of evaluation of the obtained liquid crystal display element, generation of static electricity was observed. Short-circuits between electrodes and electrode breakage occurred, resulting in poor lighting.Also, changes and decreases in threshold (vth) characteristics were observed in various parts of the liquid crystal element, and the stability of the entire element was poor. .
第１図は水面展開連続製膜装置の一例の構成図、第２図
（Ａ）は水面上で高分子溶液の展開を示す平面模式図、
第２図（Ｂ）はその要部の拡大側面図、第３図はＦＴ−
Ｉ Ｒで測定した配向薄膜の赤外二色比の測定スペクト
ル図、第４図は引取速度を変えて作製した配向薄膜の赤
外二色比の変化の状態を示す図、第５図はしきい値特性
を示す図、第６図（ａ）および第６図（ｂ）はメモリー
性評価特性を示す図である。
特許出願人 日東電工株式会社
株式会社日立製作所
代理人 弁理士 西 藤 征 彦
ｌ教（ｃｍｌｌ）
第
図
〃、教達／！＜ｍ１分）
第
図
−快稠四
￥役イｊFig. 1 is a configuration diagram of an example of a continuous film forming apparatus developed on a water surface, and Fig. 2 (A) is a schematic plan view showing the development of a polymer solution on a water surface.
Figure 2 (B) is an enlarged side view of the main parts, Figure 3 is the FT-
Figure 4 is a measurement spectrum diagram of the infrared dichroic ratio of an oriented thin film measured by IR. Figures 6(a) and 6(b) showing threshold characteristics are diagrams showing memory evaluation characteristics. Patent Applicant Nitto Denko Co., Ltd. Hitachi, Ltd. Representative Patent Attorney Yukihiko Nishifuji (cmll) Figure 〃, Kyodatsu/! <m1 minute) Diagram - Kaidenshi yaku ij
Claims (9)
少なくとも液晶層および液晶分子配向膜を挟持してなる
液晶表示素子において、上記液晶分子配向膜の膜厚が０
．１μｍ以下であり、上記配向膜は、単層の膜厚が０．
００３μｍ以上の有機高分子の水面展開膜からなり、か
つ上記配向膜がパターン状に形成されていることを特徴
とする液晶表示素子。(1) between a pair of electrode substrates, at least one of which is translucent;
In a liquid crystal display element formed by sandwiching at least a liquid crystal layer and a liquid crystal molecule alignment film, the thickness of the liquid crystal molecule alignment film is 0.
．． 1 μm or less, and the alignment film has a single layer thickness of 0.
1. A liquid crystal display element comprising a water surface spread film of an organic polymer having a diameter of 0.03 μm or more, and wherein the alignment film is formed in a pattern.
極基板で挟持された液晶層の液晶分子の長軸方向が電界
ゼロにおいて上下電極基板間で８０〜２８０°ねじれた
構造を有する請求項（１）記載の液晶表示素子。(2) The liquid crystal layer is a nematic liquid crystal layer, and has a structure in which the long axis direction of the liquid crystal molecules in the liquid crystal layer sandwiched between the upper and lower electrode substrates is twisted by 80 to 280 degrees between the upper and lower electrode substrates when the electric field is zero. (1) The liquid crystal display element described.
項（１）記載の液晶表示素子。(3) The liquid crystal display element according to claim (1), wherein the liquid crystal layer is a ferroelectric liquid crystal composition layer.
ー、イミド系ポリマーまたはこれらの共重合体からなる
配向膜である請求項（１）ないし（３）のいずれか一項
に記載の液晶表示素子。(4) The liquid crystal according to any one of claims (1) to (3), wherein the liquid crystal molecule alignment film is an alignment film made of a photosensitive amic acid polymer, an imide polymer, or a copolymer thereof. display element.
ング剤層上の少なくとも一方に形成されている請求項（
１）ないし（４）のいずれか一項に記載の液晶表示素子
。(5) Claim (5) wherein the liquid crystal molecule alignment film is formed on at least one of the insulating layer and the coupling agent layer.
1) The liquid crystal display element according to any one of (4).
二色比の値が１．０５以上の膜である請求項（１）ない
し（５）のいずれか一項に記載の液晶表示素子。(6) The liquid crystal molecule alignment film according to any one of claims (1) to (5), wherein the infrared dichroic ratio in the vertical direction and the horizontal direction is a film having an infrared dichroic ratio of 1.05 or more. Liquid crystal display element.
えたものである請求項（１）ないし（６）のいずれか一
項に記載の液晶表示素子。(7) The liquid crystal display element according to any one of claims (1) to (6), wherein the electrode substrate includes an active matrix type electrode.
方向に引いて製膜し、得られた水面展開膜を電極基板上
の所定の部位に密着形成し、さらにフォトエッチングに
より配向膜をパターン状に形成した上記電極基板を用い
て作製した液晶セルに、液晶を封入することを特徴する
液晶表示素子の製造方法。(8) An organic polymer solution is supplied onto the water surface, the solution is pulled in one direction to form a film, the resulting water surface spread film is closely formed on a predetermined location on the electrode substrate, and then oriented by photo-etching. 1. A method for manufacturing a liquid crystal display element, comprising filling a liquid crystal cell into a liquid crystal cell manufactured using the electrode substrate on which a film is formed in a pattern.
複数個の電極基板を、上記膜に順次接触させる連続操作
により上記電極基板上に膜を密着形成する請求項（８）
記載の液晶表示素子の製造方法。(9) Claim (8), wherein the film is closely formed on the electrode substrate by a continuous operation in which a plurality of electrode substrates moving at the same speed as the take-up speed of the water surface-deployed film are sequentially brought into contact with the film.
A method for manufacturing the liquid crystal display element described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27817988A JPH02124534A (en) | 1988-11-02 | 1988-11-02 | Liquid crystal display element and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27817988A JPH02124534A (en) | 1988-11-02 | 1988-11-02 | Liquid crystal display element and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02124534A true JPH02124534A (en) | 1990-05-11 |
Family
ID=17593688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27817988A Pending JPH02124534A (en) | 1988-11-02 | 1988-11-02 | Liquid crystal display element and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02124534A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006350347A (en) * | 2005-06-14 | 2006-12-28 | Lg Phillips Lcd Co Ltd | Liquid crystal display device and method of fabricating the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245031A (en) * | 1988-03-25 | 1989-09-29 | Nitto Denko Corp | Oriented high polymer thin film and production thereof |
-
1988
- 1988-11-02 JP JP27817988A patent/JPH02124534A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01245031A (en) * | 1988-03-25 | 1989-09-29 | Nitto Denko Corp | Oriented high polymer thin film and production thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006350347A (en) * | 2005-06-14 | 2006-12-28 | Lg Phillips Lcd Co Ltd | Liquid crystal display device and method of fabricating the same |
| JP4564470B2 (en) * | 2005-06-14 | 2010-10-20 | エルジー ディスプレイ カンパニー リミテッド | Liquid crystal display element and manufacturing method thereof |
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