US20220315703A1 - Varnish for photo alignment film and liquid crystal display device - Google Patents
Varnish for photo alignment film and liquid crystal display device Download PDFInfo
- Publication number
- US20220315703A1 US20220315703A1 US17/842,922 US202217842922A US2022315703A1 US 20220315703 A1 US20220315703 A1 US 20220315703A1 US 202217842922 A US202217842922 A US 202217842922A US 2022315703 A1 US2022315703 A1 US 2022315703A1
- Authority
- US
- United States
- Prior art keywords
- polyamic acid
- based compound
- group
- skeleton
- liquid crystal
- 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
- 239000002966 varnish Substances 0.000 title claims abstract description 27
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 36
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 157
- 150000001875 compounds Chemical class 0.000 claims abstract description 135
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 40
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 29
- 150000001408 amides Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 125000001302 tertiary amino group Chemical group 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000004018 acid anhydride group Chemical group 0.000 claims 1
- 125000005462 imide group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 103
- 239000010410 layer Substances 0.000 description 67
- 239000000758 substrate Substances 0.000 description 29
- 206010047571 Visual impairment Diseases 0.000 description 28
- 150000004985 diamines Chemical class 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 229920001721 polyimide Polymers 0.000 description 22
- -1 aliphatic tertiary amine 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 16
- 238000002161 passivation Methods 0.000 description 15
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 15
- 125000004427 diamine group Chemical group 0.000 description 13
- 0 CC*(C)(C)NC Chemical compound CC*(C)(C)NC 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- XBGRQAGVGRSAMQ-UHFFFAOYSA-N COC(=O)C1C(C)(C=O)C(C(=O)OC)C1(C)C=O Chemical compound COC(=O)C1C(C)(C=O)C(C(=O)OC)C1(C)C=O XBGRQAGVGRSAMQ-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical group CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical group 0.000 description 4
- 230000009435 amidation Effects 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-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
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000001491 aromatic compounds Chemical group 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- SVULLAKRZSFIHX-UHFFFAOYSA-N CC(C)(C)OC(=O)NCc1cc(N)ccc1N Chemical compound CC(C)(C)OC(=O)NCc1cc(N)ccc1N SVULLAKRZSFIHX-UHFFFAOYSA-N 0.000 description 2
- VHDNYNSAZQPYSH-UHFFFAOYSA-N CC(C)(C)OC(=O)Nc1cc(N)ccc1NC(=O)c1ccccc1C(=O)O Chemical compound CC(C)(C)OC(=O)Nc1cc(N)ccc1NC(=O)c1ccccc1C(=O)O VHDNYNSAZQPYSH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 229910015202 MoCr Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FFTSAKMFNTZBBI-UHFFFAOYSA-N Nc1ccc(NC(=O)c2ccccc2C(=O)O)cc1 Chemical compound Nc1ccc(NC(=O)c2ccccc2C(=O)O)cc1 FFTSAKMFNTZBBI-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000001930 cyclobutanes Chemical group 0.000 description 2
- FBOFHVFMPNNIKN-UHFFFAOYSA-N dimethylquinoline Natural products C1=CC=C2N=C(C)C(C)=CC2=C1 FBOFHVFMPNNIKN-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229960004979 fampridine Drugs 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical group OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- VOSLIUIVGWBSOK-UHFFFAOYSA-N 1-n-phenylbenzene-1,2,4-triamine Chemical compound NC1=CC(N)=CC=C1NC1=CC=CC=C1 VOSLIUIVGWBSOK-UHFFFAOYSA-N 0.000 description 1
- SVUBJHQQHAKLCM-UHFFFAOYSA-N 2,2-bis(4-aminophenyl)propanedioic acid Chemical compound C1=CC(N)=CC=C1C(C(O)=O)(C(O)=O)C1=CC=C(N)C=C1 SVUBJHQQHAKLCM-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- IFFLKGMDBKQMAH-UHFFFAOYSA-N 2,4-diaminopyridine Chemical compound NC1=CC=NC(N)=C1 IFFLKGMDBKQMAH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- QAYVHDDEMLNVMO-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-diamine Chemical compound NC1=CC(Cl)=C(N)C=C1Cl QAYVHDDEMLNVMO-UHFFFAOYSA-N 0.000 description 1
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical group CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- YJSATLBWFLERNZ-MDZDMXLPSA-N 2-[(e)-2-(2-aminophenyl)ethenyl]aniline Chemical compound NC1=CC=CC=C1\C=C\C1=CC=CC=C1N YJSATLBWFLERNZ-MDZDMXLPSA-N 0.000 description 1
- CRDDNFACHODSOM-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;n,n-dimethyl-1-phenylmethanamine Chemical compound CN(C)CC1=CC=CC=C1.OCCN(CCO)CCO CRDDNFACHODSOM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- KPKOSOUTWDOOIW-UHFFFAOYSA-N 3,5-bis(4-aminophenoxy)benzoic acid Chemical compound C1=CC(N)=CC=C1OC1=CC(OC=2C=CC(N)=CC=2)=CC(C(O)=O)=C1 KPKOSOUTWDOOIW-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-UHFFFAOYSA-N 0.000 description 1
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- KOGDFDWINXIWHI-OWOJBTEDSA-N 4-[(e)-2-(4-aminophenyl)ethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1 KOGDFDWINXIWHI-OWOJBTEDSA-N 0.000 description 1
- ZSQIQUAKDNTQOI-UHFFFAOYSA-N 4-[1-(4-aminophenyl)cyclohexyl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)CCCCC1 ZSQIQUAKDNTQOI-UHFFFAOYSA-N 0.000 description 1
- NGMJQNYIDZLGFP-UHFFFAOYSA-N 4-[10-(4-aminophenoxy)decoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCCCCCCOC1=CC=C(N)C=C1 NGMJQNYIDZLGFP-UHFFFAOYSA-N 0.000 description 1
- MEKBJJDSFDITCS-UHFFFAOYSA-N 4-[10-(4-aminophenyl)decyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCCCCCCC1=CC=C(N)C=C1 MEKBJJDSFDITCS-UHFFFAOYSA-N 0.000 description 1
- ISESBQNCWCFFFR-UHFFFAOYSA-N 4-[2-(4-amino-2-methylphenyl)ethyl]-3-methylaniline Chemical group CC1=CC(N)=CC=C1CCC1=CC=C(N)C=C1C ISESBQNCWCFFFR-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
- HPUJEBAZZTZOFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)-2,2-dimethylpropoxy]aniline Chemical compound C=1C=C(N)C=CC=1OCC(C)(C)COC1=CC=C(N)C=C1 HPUJEBAZZTZOFL-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- KWFFEQXPFFDJER-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)propoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCOC1=CC=C(N)C=C1 KWFFEQXPFFDJER-UHFFFAOYSA-N 0.000 description 1
- BMIUMBLWVWZIHD-UHFFFAOYSA-N 4-[3-(4-aminophenyl)propyl]aniline Chemical compound C1=CC(N)=CC=C1CCCC1=CC=C(N)C=C1 BMIUMBLWVWZIHD-UHFFFAOYSA-N 0.000 description 1
- LAFZPVANKKJENB-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)butoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCOC1=CC=C(N)C=C1 LAFZPVANKKJENB-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- PZBWQICCJHUJGP-UHFFFAOYSA-N 4-[4-(4-aminophenyl)butyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCC1=CC=C(N)C=C1 PZBWQICCJHUJGP-UHFFFAOYSA-N 0.000 description 1
- DPDYBERBCHCODD-UHFFFAOYSA-N 4-[4-[10-[4-(4-aminophenoxy)phenoxy]decoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 DPDYBERBCHCODD-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- QZTURPSSWBAQMO-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]ethyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC(C=C1)=CC=C1CCC(C=C1)=CC=C1OC1=CC=C(N)C=C1 QZTURPSSWBAQMO-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HSDAXNMOGHTBPQ-UHFFFAOYSA-N 4-[4-[3-[4-(4-aminophenoxy)phenoxy]propoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 HSDAXNMOGHTBPQ-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- HOSAKYKXQPBPFJ-UHFFFAOYSA-N 4-[4-[4-[4-(4-aminophenoxy)phenoxy]butoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 HOSAKYKXQPBPFJ-UHFFFAOYSA-N 0.000 description 1
- ZUBYRLIOGYHFCP-UHFFFAOYSA-N 4-[4-[5-[4-(4-aminophenoxy)phenoxy]pentoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 ZUBYRLIOGYHFCP-UHFFFAOYSA-N 0.000 description 1
- KBVPANOLXOGZDY-UHFFFAOYSA-N 4-[4-[6-[4-(4-aminophenoxy)phenoxy]hexoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 KBVPANOLXOGZDY-UHFFFAOYSA-N 0.000 description 1
- PWMAGDIHKLEZLO-UHFFFAOYSA-N 4-[4-[7-[4-(4-aminophenoxy)phenoxy]heptoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PWMAGDIHKLEZLO-UHFFFAOYSA-N 0.000 description 1
- GGEQMFKXDPQHML-UHFFFAOYSA-N 4-[4-[8-[4-(4-aminophenoxy)phenoxy]octoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 GGEQMFKXDPQHML-UHFFFAOYSA-N 0.000 description 1
- CJZXARYPYYJHHT-UHFFFAOYSA-N 4-[4-[9-[4-(4-aminophenoxy)phenoxy]nonoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OCCCCCCCCCOC(C=C1)=CC=C1OC1=CC=C(N)C=C1 CJZXARYPYYJHHT-UHFFFAOYSA-N 0.000 description 1
- SLHXQWDUYXSTPA-UHFFFAOYSA-N 4-[5-(4-aminophenoxy)pentoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCOC1=CC=C(N)C=C1 SLHXQWDUYXSTPA-UHFFFAOYSA-N 0.000 description 1
- MJZXFMSIHMJQBW-UHFFFAOYSA-N 4-[5-(4-aminophenyl)-1,3,4-oxadiazol-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NN=C(C=2C=CC(N)=CC=2)O1 MJZXFMSIHMJQBW-UHFFFAOYSA-N 0.000 description 1
- SOKDIHGREPWQCY-UHFFFAOYSA-N 4-[5-(4-aminophenyl)pentyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCC1=CC=C(N)C=C1 SOKDIHGREPWQCY-UHFFFAOYSA-N 0.000 description 1
- GRFCDFDVGOXFPY-UHFFFAOYSA-N 4-[6-(4-aminophenoxy)hexoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCCOC1=CC=C(N)C=C1 GRFCDFDVGOXFPY-UHFFFAOYSA-N 0.000 description 1
- XLKGPJIGDHZIMW-UHFFFAOYSA-N 4-[6-(4-aminophenyl)hexyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCCC1=CC=C(N)C=C1 XLKGPJIGDHZIMW-UHFFFAOYSA-N 0.000 description 1
- JBXBSFFXAMVASC-UHFFFAOYSA-N 4-[7-(4-aminophenoxy)heptoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCCCOC1=CC=C(N)C=C1 JBXBSFFXAMVASC-UHFFFAOYSA-N 0.000 description 1
- JXPFXZXQRFXJAK-UHFFFAOYSA-N 4-[7-(4-aminophenyl)heptyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCCCC1=CC=C(N)C=C1 JXPFXZXQRFXJAK-UHFFFAOYSA-N 0.000 description 1
- SURHEQARWKWZMT-UHFFFAOYSA-N 4-[8-(4-aminophenoxy)octoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCCCCOC1=CC=C(N)C=C1 SURHEQARWKWZMT-UHFFFAOYSA-N 0.000 description 1
- YJPXABVNBBJWSP-UHFFFAOYSA-N 4-[8-(4-aminophenyl)octyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCCCCC1=CC=C(N)C=C1 YJPXABVNBBJWSP-UHFFFAOYSA-N 0.000 description 1
- DFXGPEKKMXWHQU-UHFFFAOYSA-N 4-[9-(4-aminophenoxy)nonoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCCCCCCCCOC1=CC=C(N)C=C1 DFXGPEKKMXWHQU-UHFFFAOYSA-N 0.000 description 1
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- FIIGXVURROMCRR-UHFFFAOYSA-N 4-[9-(4-aminophenyl)nonyl]aniline Chemical compound C1=CC(N)=CC=C1CCCCCCCCCC1=CC=C(N)C=C1 FIIGXVURROMCRR-UHFFFAOYSA-N 0.000 description 1
- OJXULZRBAPPHNY-UHFFFAOYSA-N 4-[[(4-aminophenyl)-dimethylsilyl]oxy-dimethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(N)C=C1 OJXULZRBAPPHNY-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- LVNDUJYMLJDECN-UHFFFAOYSA-N 5-methylbenzene-1,3-diamine Chemical compound CC1=CC(N)=CC(N)=C1 LVNDUJYMLJDECN-UHFFFAOYSA-N 0.000 description 1
- OOEGQLPPMITCBZ-UHFFFAOYSA-N 6-propan-2-yl-1,3,5-triazine-2,4-diamine Chemical compound CC(C)C1=NC(N)=NC(N)=N1 OOEGQLPPMITCBZ-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- YCZUWQOJQGCZKG-UHFFFAOYSA-N 9h-carbazole-3,6-diamine Chemical compound C1=C(N)C=C2C3=CC(N)=CC=C3NC2=C1 YCZUWQOJQGCZKG-UHFFFAOYSA-N 0.000 description 1
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- QACJLDDJMXDMTE-UHFFFAOYSA-N CC(=O)c1cc(C(=O)O)c(C(C)=O)cc1C(=O)O.COC(=O)C1(C)C(C)(C(C)=O)C(C)(C(=O)OC)C1(C)C(C)=O Chemical compound CC(=O)c1cc(C(=O)O)c(C(C)=O)cc1C(=O)O.COC(=O)C1(C)C(C)(C(C)=O)C(C)(C(=O)OC)C1(C)C(C)=O QACJLDDJMXDMTE-UHFFFAOYSA-N 0.000 description 1
- NFGMLRCKLLOYBL-UHFFFAOYSA-N CC(C)(C)OC(=O)NCc1cc(NC(=O)c2ccccc2C(=O)O)ccc1N Chemical compound CC(C)(C)OC(=O)NCc1cc(NC(=O)c2ccccc2C(=O)O)ccc1N NFGMLRCKLLOYBL-UHFFFAOYSA-N 0.000 description 1
- CYUYLTFAQSBBMY-UHFFFAOYSA-N CC(C)(C)OC(=O)Nc1cc(N)ccc1N Chemical compound CC(C)(C)OC(=O)Nc1cc(N)ccc1N CYUYLTFAQSBBMY-UHFFFAOYSA-N 0.000 description 1
- OZMFXQRJWRUBCX-UHFFFAOYSA-N CC(C)(C)OC(=O)Nc1cc(N)ccc1N.Nc1ccc(N)c2ncccc12 Chemical compound CC(C)(C)OC(=O)Nc1cc(N)ccc1N.Nc1ccc(N)c2ncccc12 OZMFXQRJWRUBCX-UHFFFAOYSA-N 0.000 description 1
- JEHZIZOLEPYFJX-UHFFFAOYSA-N CC(C)(C)OC(=O)Nc1cc(NC(=O)c2ccccc2C(=O)O)ccc1N Chemical compound CC(C)(C)OC(=O)Nc1cc(NC(=O)c2ccccc2C(=O)O)ccc1N JEHZIZOLEPYFJX-UHFFFAOYSA-N 0.000 description 1
- PXLBVDHRNXMWRL-UHFFFAOYSA-N CC.CC.CNC.CNC.c1ccccc1 Chemical compound CC.CC.CNC.CNC.c1ccccc1 PXLBVDHRNXMWRL-UHFFFAOYSA-N 0.000 description 1
- BRXYXUHMHWRXGO-UHFFFAOYSA-N CC1(C=O)C(C(=O)O)C(C)(C(=O)O)C1C(=O)O Chemical compound CC1(C=O)C(C(=O)O)C(C)(C(=O)O)C1C(=O)O BRXYXUHMHWRXGO-UHFFFAOYSA-N 0.000 description 1
- DSZSCNLNUSKDIM-UHFFFAOYSA-N CC1(C=O)C(C(=O)O)C(C)(C=O)C1C(=O)O Chemical compound CC1(C=O)C(C(=O)O)C(C)(C=O)C1C(=O)O DSZSCNLNUSKDIM-UHFFFAOYSA-N 0.000 description 1
- YSKQWYZHNXEBFG-UHFFFAOYSA-N COC(=O)C(C(C)=O)(C(C)=O)C(=O)OC Chemical compound COC(=O)C(C(C)=O)(C(C)=O)C(=O)OC YSKQWYZHNXEBFG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGMPVYSXXIOGJY-UHFFFAOYSA-N Fusaric acid Chemical compound CCCCC1=CC=C(C(O)=O)N=C1 DGMPVYSXXIOGJY-UHFFFAOYSA-N 0.000 description 1
- 244000126211 Hericium coralloides Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000006001 Methyl nonyl ketone Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZSXGLVDWWRXATF-UHFFFAOYSA-N N,N-dimethylformamide dimethyl acetal Chemical compound COC(OC)N(C)C ZSXGLVDWWRXATF-UHFFFAOYSA-N 0.000 description 1
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- UJERQIONQPNDIB-UHFFFAOYSA-N Nc1ccc(CC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(CCc2ccc(N)cc2)cc1.Nc1ccc(CN=NCc2ccc(N)cc2)cc1.Nc1ccc(CNC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(COC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(COCc2ccc(N)cc2)cc1.Nc1ccc(CS(=O)(=O)c2ccc(N)cc2)cc1.Nc1ccc(CS(=O)c2ccc(N)cc2)cc1.Nc1ccc(OCOc2ccc(N)cc2)cc1 Chemical compound Nc1ccc(CC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(CCc2ccc(N)cc2)cc1.Nc1ccc(CN=NCc2ccc(N)cc2)cc1.Nc1ccc(CNC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(COC(=O)Cc2ccc(N)cc2)cc1.Nc1ccc(COCc2ccc(N)cc2)cc1.Nc1ccc(CS(=O)(=O)c2ccc(N)cc2)cc1.Nc1ccc(CS(=O)c2ccc(N)cc2)cc1.Nc1ccc(OCOc2ccc(N)cc2)cc1 UJERQIONQPNDIB-UHFFFAOYSA-N 0.000 description 1
- VQGDWYKSSZWWML-UHFFFAOYSA-N Nc1ccc(CC(=O)c2ccc(N)cc2)cc1.Nc1ccc(CN=Nc2ccc(N)cc2)cc1.Nc1ccc(CNC(=O)c2ccc(N)cc2)cc1.Nc1ccc(COC(=O)c2ccc(N)cc2)cc1.Nc1ccc(COc2ccc(N)cc2)cc1.Nc1ccc(COc2ccc(N)cc2)cc1.Nc1ccc(CSc2ccc(N)cc2)cc1.Nc1ccc(Cc2ccc(N)cc2)cc1.Nc1ccc(Cc2ccc(N)cc2)cc1 Chemical compound Nc1ccc(CC(=O)c2ccc(N)cc2)cc1.Nc1ccc(CN=Nc2ccc(N)cc2)cc1.Nc1ccc(CNC(=O)c2ccc(N)cc2)cc1.Nc1ccc(COC(=O)c2ccc(N)cc2)cc1.Nc1ccc(COc2ccc(N)cc2)cc1.Nc1ccc(COc2ccc(N)cc2)cc1.Nc1ccc(CSc2ccc(N)cc2)cc1.Nc1ccc(Cc2ccc(N)cc2)cc1.Nc1ccc(Cc2ccc(N)cc2)cc1 VQGDWYKSSZWWML-UHFFFAOYSA-N 0.000 description 1
- CIAPBQJSZOAOEO-UHFFFAOYSA-N Nc1ccc(Cc2ccc(NC(=O)c3ccccc3C(=O)O)cc2)cc1 Chemical compound Nc1ccc(Cc2ccc(NC(=O)c3ccccc3C(=O)O)cc2)cc1 CIAPBQJSZOAOEO-UHFFFAOYSA-N 0.000 description 1
- JYFRBECAJLHOEK-UHFFFAOYSA-N Nc1ccc(N)c2ncccc12 Chemical compound Nc1ccc(N)c2ncccc12 JYFRBECAJLHOEK-UHFFFAOYSA-N 0.000 description 1
- YHAYNHKBPIHDJR-UHFFFAOYSA-N Nc1ccc(NC(=O)c2ccccc2C(=O)O)c2cccnc12 Chemical compound Nc1ccc(NC(=O)c2ccccc2C(=O)O)c2cccnc12 YHAYNHKBPIHDJR-UHFFFAOYSA-N 0.000 description 1
- CXNWGHWYUQGFEX-UHFFFAOYSA-N Nc1ccc(NC(=O)c2ccccc2C(=O)O)c2ncccc12 Chemical compound Nc1ccc(NC(=O)c2ccccc2C(=O)O)c2ncccc12 CXNWGHWYUQGFEX-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
- MBFCMFURFRNNNF-UHFFFAOYSA-N O=C1OC(=O)C12C(=O)OC2=O Chemical compound O=C1OC(=O)C12C(=O)OC2=O MBFCMFURFRNNNF-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Natural products CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000002862 amidating effect Effects 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- CYZQUDGGSNLUBU-UHFFFAOYSA-N benzo[f]phthalazine Chemical compound N1=NC=C2C3=CC=CC=C3C=CC2=C1 CYZQUDGGSNLUBU-UHFFFAOYSA-N 0.000 description 1
- YUFRAQHYKKPYLH-UHFFFAOYSA-N benzo[f]quinoxaline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=N1 YUFRAQHYKKPYLH-UHFFFAOYSA-N 0.000 description 1
- DMMLYDCVMZEUMT-UHFFFAOYSA-N benzo[h]cinnoline Chemical compound C1=NN=C2C3=CC=CC=C3C=CC2=C1 DMMLYDCVMZEUMT-UHFFFAOYSA-N 0.000 description 1
- FZICDBOJOMQACG-UHFFFAOYSA-N benzo[h]isoquinoline Chemical compound C1=NC=C2C3=CC=CC=C3C=CC2=C1 FZICDBOJOMQACG-UHFFFAOYSA-N 0.000 description 1
- PQIUGRLKNKSKTC-UHFFFAOYSA-N benzo[h]quinazoline Chemical compound N1=CN=C2C3=CC=CC=C3C=CC2=C1 PQIUGRLKNKSKTC-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- YMXKKAMHFCWWNZ-UHFFFAOYSA-N bis(4-aminophenyl) butanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCC(=O)OC1=CC=C(N)C=C1 YMXKKAMHFCWWNZ-UHFFFAOYSA-N 0.000 description 1
- GOKWZXBYDWJEEX-UHFFFAOYSA-N bis(4-aminophenyl) decanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCCCCCCC(=O)OC1=CC=C(N)C=C1 GOKWZXBYDWJEEX-UHFFFAOYSA-N 0.000 description 1
- IYZXLVMHFBPTFS-UHFFFAOYSA-N bis(4-aminophenyl) heptanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCCCC(=O)OC1=CC=C(N)C=C1 IYZXLVMHFBPTFS-UHFFFAOYSA-N 0.000 description 1
- AIQVJNFIUNHSOB-UHFFFAOYSA-N bis(4-aminophenyl) hexanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCCC(=O)OC1=CC=C(N)C=C1 AIQVJNFIUNHSOB-UHFFFAOYSA-N 0.000 description 1
- WIQCJWYOACZYRI-UHFFFAOYSA-N bis(4-aminophenyl) nonanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCCCCCC(=O)OC1=CC=C(N)C=C1 WIQCJWYOACZYRI-UHFFFAOYSA-N 0.000 description 1
- ABJJAQHJNDNNIN-UHFFFAOYSA-N bis(4-aminophenyl) octanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCCCCC(=O)OC1=CC=C(N)C=C1 ABJJAQHJNDNNIN-UHFFFAOYSA-N 0.000 description 1
- ZOIYKZIJKIJRCY-UHFFFAOYSA-N bis(4-aminophenyl) pentanedioate Chemical compound C1=CC(N)=CC=C1OC(=O)CCCC(=O)OC1=CC=C(N)C=C1 ZOIYKZIJKIJRCY-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- YCDUMXSNRLISHV-UHFFFAOYSA-N dibenzofuran-2,7-diamine Chemical compound C1=C(N)C=C2C3=CC=C(N)C=C3OC2=C1 YCDUMXSNRLISHV-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 108700003601 dimethylglycine Proteins 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NILJCGYQNXKIRL-UHFFFAOYSA-N n,n-dicyclopentylcyclopentanamine Chemical compound C1CCCC1N(C1CCCC1)C1CCCC1 NILJCGYQNXKIRL-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- CJYCVQJRVSAFKB-UHFFFAOYSA-N octadecane-1,18-diamine Chemical compound NCCCCCCCCCCCCCCCCCCN CJYCVQJRVSAFKB-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- WOFKFNZIJZWWPZ-UHFFFAOYSA-N pyrene-1,3-diamine Chemical compound C1=C2C(N)=CC(N)=C(C=C3)C2=C2C3=CC=CC2=C1 WOFKFNZIJZWWPZ-UHFFFAOYSA-N 0.000 description 1
- OWJJRQSAIMYXQJ-UHFFFAOYSA-N pyrene-1,6-diamine Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=C(N)C=CC2=C1 OWJJRQSAIMYXQJ-UHFFFAOYSA-N 0.000 description 1
- BLYOXQBERINFDU-UHFFFAOYSA-N pyrene-1,8-diamine Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=C(N)C2=C1 BLYOXQBERINFDU-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133354—Arrangements for aligning or assembling substrates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133397—Constructional arrangements; Manufacturing methods for suppressing after-image or image-sticking
Definitions
- Embodiments described herein relate generally to a varnish for a photo alignment film and a liquid crystal display device.
- Liquid crystal display devices comprise an array substrate provided with, for example, pixel electrodes and thin-film transistors (TFTs) arranged in a matrix and a counter-substrate arranged apart from and opposite to the array substrate and provided with, for example, color filters, formed thereon. Liquid crystal is sealed between the array substrate and the counter-substrate.
- TFTs thin-film transistors
- the liquid crystal is aligned by alignment films disposed on the array substrate and the counter-substrate, respectively.
- Polyimide films are frequently used as the alignment films.
- the polyimide films are obtained by baking polyamic acid at a high temperature of 230° C. or higher. But, in most of the cases, polyimide films obtained by baking at high temperature have deteriorated transmissivity due to coloring of film.
- polyamic acid is imidized in the presence of an amine-based imidization promotor. Imidization using an imidization promotor can be carried out at relatively low temperature, and therefore substantially no coloring of polyimide occurs.
- the photo-alignment technique comprises irradiating the polyimide film with ultraviolet (UV) light having a short wavelength of 254 to 365 nm to achieve the alignment.
- UV ultraviolet
- some main chains of the polyimide molecules are cut in a direction parallel to the direction of polarization, and the polyimide film is given uniaxial anisotropy in a direction perpendicular to the direction of polarization.
- Liquid crystal molecules are aligned along the remaining main chains of the polyimide molecules which have not been cut, and thus are kept long and linearly extend.
- FIG. 1 is a schematic cross-sectional view illustrating part of a display panel of a liquid crystal display device according to one embodiment.
- FIG. 2 is a plan view illustrating part of a pixel electrode in the liquid crystal display device shown in FIG. 1 .
- FIG. 3 is a perspective view illustrating a structure of an alignment film having a double-layer structure according to one embodiment.
- FIG. 4 is a view illustrating a pattern for inspection for a DC afterimage.
- a varnish for a photo alignment film comprising an imidization promotor and a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the imidization promotor has skeleton containing no primary amino group and no secondary amino group, and the first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- a varnish for a photo alignment film comprising a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the first polyamic acid-based compound has terminal skeletons containing no primary amino group, and also a diamine skeleton represented by Formula (7) below:
- L is an aromatic compound group
- Y 5 is an amino group containing an organic group which may leave by heat
- Y 6 is H or an amino group containing an organic group which may leave by heat
- II Y 5 and Y 6 are bonded together to form a cyclic group containing nitrogen.
- the present inventors have confirmed that when a liquid crystal display device incorporating a polyimide alignment film having been subjected to photo-alignment processing (photo alignment polyimide film) is turned on and an image is displayed, the photo alignment polyimide film becomes excited by the light emitted from the backlight as the lighting time of the backlight proceeds, producing a photoelectromotive force, as a result of which charge is accumulated in the photo alignment polyimide film, leading to an afterimage (DC afterimage).
- photo alignment polyimide film becomes excited by the light emitted from the backlight as the lighting time of the backlight proceeds, producing a photoelectromotive force, as a result of which charge is accumulated in the photo alignment polyimide film, leading to an afterimage (DC afterimage).
- the alignment film became to slightly absorb UV light emitted of 450 nm or less within the emission wavelength of the backlight.
- the present inventors have made intensive studies on the DC afterimage of the polyimide film imidized using the amine-based promotor. As a result, they found a technique of preventing DC afterimage completely from occurring or eliminating it to disappear in a short time even if it occurs by: 1) letting the imidization promotor to use include a skeleton other than a primary amino group and a secondary amino group or not using an imidization promotor, and 2) letting the polyimide contain groups other than a primary amino group at both terminals thereof.
- Making the polyimide to have groups other than primary amino groups at its both terminals can be achieved making a polyamic acid or a polyamic acid ester (usually provided in the form of varnish), which is a precursor of the polyimide, to have groups other than primary amino groups at its both terminals.
- Such a vanish for forming an photo alignment film can be provided, that DC afterimage can be prevented from occurring in a liquid crystal display device, or even DC afterimage occurs, it disappear in a short time.
- a varnish for a photo alignment film according to the first embodiment includes an imidization promotor and a first polyamic acid-based compound in an organic solvent.
- the first polyamic acid-based compound is a polyamic acid or a polyamic acid ester.
- the imidization promotor has skeleton containing no primary amino group and no secondary amino group.
- the first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- a varnish for a photo alignment film according to the first embodiment comprising an imidization promotor and a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the imidization promotor has skeleton containing no primary amino group and no secondary amino group, and the first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- An imidization promotor promotes the dehydration and cyclization reaction to the first polyamic acid-based compound.
- the imidization promotor is a pyridine-based compound, a quinoline-based compound, an isoquinoline-based compound, an imidazole-based compound, a benzimidazole-based compound or a tertiary amine.
- the pyridine-based compound is a compound which has a pyridine skeleton
- the quinoline-based compound, isoquinoline-based compound, imidazole-based compound and benzimidazole-based compound are compounds which have a quinoline skeleton, an isoquinoline skeleton, an imidazole skeleton and a benzimidazole skeleton, respectively.
- the tertiary amine is, for example, an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine, or a derivative such as an alkyl-substituted compound.
- aliphatic tertiary amine examples include trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamin, tricyclopentylamine, trihexylamine, benzyldimethylamine triethanolamine, etc.
- aromatic tertiary amine N,N-dimethylaniline.
- heterocyclic tertiary amine examples include pyridine, ⁇ -picoline, quinoline, isoquinoline, dipyridine, diquinoline, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenantolidine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzoisoxazole, thiazole, benzothiazole, oxadiazole, thiadiazole, benzoisoquinolizine, hexamethylenetetramine, N,N-dimethyl-4-aminopyr
- the imidization promotor should preferably be a such as N,N-dimethylaniline, pyridine, ⁇ -picoline, quinoline, isoquinoline or N,N-dimethyl-4-aminopyridine, or a derivative thereof.
- the derivative should preferably be an alkyl-substituted compound.
- the imidization promotor comprises an amine-reactive skeleton.
- the amine-reactive skeleton includes a halogen group, a diazo group, a carboxyl group, a hydroxyl group, an isocyanate group or an acid anhydride skeleton.
- Examples of the imidization promotor having an amine-reactive skeleton are dimethylglycine, picolinic acid, nicotinic acid and 5-butylpicolinic acid.
- the amine-reactive skeleton reacts with a primary amine which may exist at sites other than both terminals of the first polyamic acid-based compound and a secondary amine which may exist in the first polyamic acid-based compound, to produce amide.
- DC afterimage which occurs due to the primary and secondary amines can be substantially eliminated more reliably.
- the imidization promotor has a molecular weight of 130 or more.
- An imidization promotor having a molecular weight of 130 or more, which exists in a photo-alignment polyimide film is not able to easily respond to a general liquid crystal drive (of 1 Hz to 120 Hz) because of its ion weight. Therefore, it becomes possible to slow down the accumulation velocity of ions to a specific part in the display device, which may be caused by long drive, and thus the time until nonuniformity in display occurs and the life of the display device can be prolonged.
- the content of the imidization promotor in the varnish for photo alignment films should preferably be 5% by mass or more, and more preferably 10% by mass or more.
- the first polyamic acid-based compound has a structural unit (repeating unit) represented by Formula (1) below:
- each of R 1 and R 2 is independently —COOH or —COOR where R is an alkyl group, and Y 1 is an organic group.
- X is an alicyclic group, for example, a substituted or unsubstituted cyclobutane group.
- X is a benzene ring or a benzene ring-containing group, wherein the benzene ring may be substituted with an alkyl group or the like.
- X is the alicyclic group.
- the first polyamic acid-based compound has a diamine skeleton represented by Formula (2) below:
- M is an organic group, for example, a cyclic group-containing group.
- M is Ar 0 or Ar 1 —Z—Ar 2 , where Ar 0 is an aromatic group, each of Ar 1 and Ar 2 is independently an aromatic group, and Z is an organic group containing no primary amino group and no secondary amino group.
- An example of the aromatic group represented by Ar 1 , Ar 1 or Ar 2 is a benzene ring or a benzene ring-containing group.
- Z is constituted by oxygen, nitrogen, sulfur, carbon or hydrogen, or a combination of two or more of them.
- Z contains no hydroxyl group, no thiol group and no amino group other than tertiary amino group, i.e., no —NH nor >NH.
- the terminal skeletons of the first polyamic acid-based compound each comprise an imide skeleton, an amide skeleton, a urea skeleton, a tertiary amino skeleton, an azo bond or a carboxyl group.
- both terminal skeletons of the first polyamic acid-based compound are represented by Formula (3) below:
- Y 2 is H, S or an organic group, and Y 3 is an aliphatic group or an aromatic group; or Y 2 and Y 3 are bonded together to form a cyclic group, for example, imide; or Formula (4) below:
- R 3 and R 4 are independently hydrogen or an alkyl group.
- the polyamic acid can be produced by reacting a tetracarboxylic dianhydride with a diamine by an ordinary method.
- the tetracarboxylic dianhydride can be represented by Formula (A) below:
- X is a cyclic group as defined above with respect to Formula (1) above.
- the tetracarboxylic dianhydride having a substituted or unsubstituted cyclobutane group as X can be represented by Formula (B) below:
- each R b is independently hydrogen or an alkyl group.
- An example of the alkyl group is an alkyl group having one to six carbon atoms. Particularly preferably, the alkyl group is methyl group.
- tetracarboxylic dianhydride having a benzene ring as X is pyromellitic acid.
- the tetracarboxylic dianhydride is the one represented by Formula (B) above.
- the diamine to be reacted with the above tetracarboxylic dianhydride is an organic compound having two primary amino groups.
- the diamine can be represented by Formula (C):
- the diamine represented by Formula (C) includes an alicyclic diamine, a heterocyclic diamine, an aliphatic diamine and an aromatic diamine.
- Examples of the alicyclic diamine are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophoronediamine, etc.
- heterocyclic diamine examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole, etc.
- Examples of the aliphatic diamine are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooc
- aromatic diamine examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2, 5-dichlorobenzene, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-2,2′-dimethylbibenzyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diamino
- the aromatic diamine can be represented by Formula (D) or (E) below:
- An alignment film formed using the diamine represented by Formula (D) has a high photo-alignability, and is preferably used to produce a second polyamic acid-based compound described below.
- An alignment film formed using the diamine represented by Formula (E) does not contain thiol group or hydroxyl group, and thus is not greatly influenced by a hydrogen bond. Accordingly, its resistance tends to become high. Also, this diamine does not contain an amino group other than a tertiary amine in Z, i.e., does not contain —NH or >NH in Z, and DC afterimages can be prevented from generating.
- the diamine of Formula (E) be used to produce the first polyamic acid-based compound.
- an amide bond is distinguished from a secondary amino group, since their chemical properties are different from each other. That is, Z may be an organic group which forms an amide bond.
- a polyamic acid ester having —COOR can be produced by reacting, for example, N,N-dimethylformamide dialkyl acetal with the polyamic acid above.
- a polyamic acid ester can also be produced by the method disclosed in JP 2000-273172 A.
- the first polyamic acid-based compound has terminal skeletons represented by Formula (3), (4) or (5).
- the first polyamic acid-based compound noted above can be obtained by chemically modifying the terminal primary amino groups of the polyamic acid or the polyamic acid ester, which has the primary amino groups at its both terminals. This chemical modification is a capping of the primary amino groups.
- a method for chemically modifying a terminal primary amino group includes amidation.
- a capping agent (amidating agent) used for this purpose a compound having one halogenated carbonyl group in the molecule, i.e. a monofunctional acid halide, can be used.
- the halide includes chloride, bromide and fluoride.
- the monofunctional acid halide include benzoyl chloride, acetyl chloride, propionyl chloride, acryloyl chloride, methacryloyl chloride and tosyl chloride.
- a compound having one acid anhydride i.e., a monofunctional acid anhydride
- a monofunctional acid anhydride examples include phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic-1,2-anhydrid, cyclohexene-1,2-dicarboxylic anhydride, etc.
- the terminal primary groups are chemically modified with these compounds, ordinarily, the terminals are converted into polyamic acids. Thereafter, the resulting compound is formed into a film, and baked to be imidized.
- esterification into amic acid esters may be used.
- an amino-reactive group such as carboxyl group or an acid halide (halogenated carbonyl group) and a known aromatic compound having an ester skeleton are used as capping agents.
- the conversion of the terminals into amic acid esters can be effected by reacting the compound having its terminals converted into amic acid by the above method with, for example, N,N-dimethylformamide dialkyl acetal.
- the terminal primary amino groups are chemically modified with these compounds, ordinarily, the terminals become polyamic acid esters. Thereafter, the resulting compound is formed into a film, and baked to be imidized.
- the terminals may be in imidized state.
- the above capped compound having the terminals converted into polyamic acid or polyamic acid ester is heated to be dehydration-condensed.
- a chemical modification other than amidation and imidization may be applied, for example, azotization, ureation or tertiary amination may be applied.
- a diazonium salt-based diazo coupling agent can be used as a capping agent (azotization agent).
- azotization agent an isocyanate-based compound can be used as a capping agent.
- the isocyanate are phenyl isocyanate, naphthyl isocyanate, etc.
- tertiary amination a compound having a halogen group (especially, chlorine) or hydroxyl group can be used as a capping agent (tertiary amination agent). It should be noted that substances other than the above capping agents can be used for the azotization, ureation or tertiary amination.
- a polyamic acid-based compound having terminal skeletons not containing a primary amino group can be produced by using, in the reaction of the tetracarboxylic dianhydride and the diamine note above, the tetracarboxylic dianhydride in an amount larger than the amount of the diamine (for example, in a molar amount 1.1 to 1.5 times larger than the amount of the diamine). This reaction produces a polyamic acid having carboxyl groups at its terminals.
- the total amount of the polyamic acid-based compounds each having carboxyl groups at the both terminals occupy 80% by mass or more, more preferably 90% by mass or more of the sum of the total amount of the polyamic acid-based compounds.
- the first polyamic acid-based compound having groups other than primary amino groups at its both terminals can have an acid skeleton represented by Formula (6) below:
- the acid skeleton represented by the formula (6) includes acid skeletons represented by Formulas (6-1) and (6-2) below:
- R a is an alkyl group, for example, an alkyl group having 1 to 6 carbon atoms
- R b is hydrogen or an alkyl group as defined with respect to Formula (B) above.
- the amine skeleton is as described above.
- the first polyamic acid-based compound can have the structural unit (repeating unit) represented by Formula (1) above, and its terminal skeletons can comprise an imide skeleton, an amide skeleton, a urea skeleton, a tertiary amino skeleton, an azo bond or a carboxyl group.
- the structural unit represented by Formula (1) includes a structural unit represented by Formulas (1-1) or (1-2) below:
- Ar is Ar 0 or Ar 1 —Z-Art as defined with respect to Formula (2) above.
- R a and R b are as defined with respect to Formula (6-1) above.
- Z is as defined with respect to Formula (2) above.
- a requirement for the imidization promotor not to substantially produce DC afterimage is to avoid the imidization promotor from having skeletons of a primary amino group and a secondary amino group. This can be ultimately achieved by not using an imidization promotor substantially.
- imidization promotor without an imidization promotor, imidization cannot be promoted, and therefore the first polyamic acid-based compound (having terminal skeletons containing no primary amino group) is incorporated with a skeleton which can promote imidization.
- a varnish for a photo alignment film according to the second embodiment comprising a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the first polyamic acid-based compound has terminal skeletons containing no primary amino group, and also a diamine skeleton represented by Formula (7) below:
- L is an aromatic compound group
- Y 5 is an amino group containing an organic group which may leave by heat
- Y 6 is H or an amino group containing an organic group which may leave by heat
- II Y 5 and Y 6 are bonded together to form a cyclic group containing nitrogen.
- the varnish according to the second embodiment further comprises an imidization promotor, an amount of the imidization promotor being less than 1.0% by mass based on an amount of the first polyamic acid-based compound.
- the diamine skeleton represented by Formula (7) contains a diamine skeleton is represented by Formula (8) below:
- Y 4 is a —N(H)A group, A being an amino group containing an organic group which may leave by heat
- Y 5 is H or a —N(H)A group
- amino groups or —NH— groups being located at a meta position or para position with respect to each other, and Y 4 and Y 5 are located at ortho positions to one amino group or —NH— group.
- the first polyamic acid-based compound having a diamine skeleton represented by Formula (7) has an acid skeleton represented by Formula (9) below:
- each of R 1 and R 2 is independently —COOH or —COOR where R is an alkyl group.
- Less than the 1.0% by mass of imidization promotor means, for example, that an amount of the imidization promotor being less than 1.0% by mass based on an amount of the first polyamic acid-based compound and this amount is a quantity which does not substantially exhibit the function of promoting imidization.
- the content of the imidization promotor in the organic solvent is less than 1.0% by mass, preferably, less than 0.1% by mass, and more preferably, 0° by mass.
- the first polyamic acid-based compound contained in the varnish for photo alignment films according to the second aspect can be produced by using as a diamine which derives a diamine skeleton represented by Formula (7) (including Formula (8)) as the diamine in the production of the first polyamic acid-based compound contained in the varnish for photo alignment films according to the first aspect.
- a diamine includes an aromatic diamine represented by Formula (F) or (G) below.
- the polyamic acid-based compound obtained by reacting a diamine represented by Formula (F) or (G) with tetracarboxylic dianhydride by an ordinary method comprises an amine site having an imidization promoting function in a skeleton thereof.
- the polyamic acid-based compound obtained by reacting a diamine of Formula (F) with tetracarboxylic dianhydride by the ordinary method forms an imidazole skeleton as a protective group (tert-butoxycarbonyl group) leaves by heating at the time of baking for imidization, thus promoting the imidization.
- each of R 1 and R 2 is independently —COOH or —COOR where R is an alkyl group as defined in Formula (1) above.
- the varnish for a photo alignment film according to the second contains a first polyamic acid-based compound which is a polyamic acid or a polymide acid ester in an organic solvent. Further, the content of the imidization promotor is less than 1.0% by mass, and the first polyamic acid-based compound has a terminal skeleton containing a carboxyl group.
- the first polyamic acid-based compound which has a terminal skeleton containing a carboxyl group can be produced by using, in the reaction of the tetracarboxylic dianhydride and the diamine noted above, the tetracarboxylic dianhydride in an amount larger than the amount of the diamine (for example, in a molar amount 1.1 to 1.5 times larger than the amount of the diamine).
- the first polyamic acid-based compound which has an terminal skeleton containing a carboxyl group can promote imidization at the time of baking for imidization by the carboxyl group.
- the varnish further comprises a second polyamic acid-based compound which is a polyamic acid or a polyamic acid ester, in addition to the first polyamic acid-based compound.
- the first polyamic acid-based compound has a polarity higher than, or a surface energy higher than, that of the second polyamic acid-based compound. Therefore, in the case where the first and second polyamic acid-based compounds coexist in the varnish, they are phase-separated from each other.
- the first polyamic acid-based compound has a higher affinity for indium tin oxide (ITO) which forms pixel electrodes, inorganic passivation films such as SiO 2 or SiN x and organic passivation films using organic resins in a liquid crystal display device.
- ITO indium tin oxide
- the first polyamic acid-based compound forms a lower layer.
- the polyamic acid ester and a polyamic acid coexist, the polyamic acid ester forms an upper layer, and the polyamic acid forms a lower layer.
- the diamine skeleton of one of these polyamic acid-based compounds contains oxygen or fluorine
- the diamine skeleton of the other polyamic acid-based compound contains neither oxygen nor fluorine or the diamine skeleton of the above other polyamic acid-based compound contains oxygen or fluorine, the amount of which is, however, less than that of the oxygen or fluorine in the diamine skeleton of the above one of the polyamic acid-based compounds
- the above one of the polyamic acid-based compounds forms a lower layer
- the other polyamic acid-based compound forms an upper layer.
- the first polyamic acid-based compound is used as the polyamic acid-based compound.
- the second polyamic acid-based compound can be selected from the compounds indicated above as the first polyamic acid-based compound. Alternatively, it can be selected from polyamic acid-based compounds each of which has not yet subjected to the capping of terminal primary amino groups for the production of the first polyamic acid-based compound, i.e., from polyamic acids and polyamic acid esters, each having primary amino groups at the both terminals. However, it is preferable that the second polyamic acid-based compound, as well as the first polyamic acid-based compound, have no primary amino groups at its both terminals.
- neither the first polyamic acid-based compound nor the second polyamic acid-based compound has a secondary amino group (excluding a secondary amino group forming an amide), regardless of whether the alignment film has a single-layer structure or a two-layer structure.
- a lower layer means a layer which is in direct contact with an item (for example, an ITO film, an inorganic passivation film or an organic passivation film) to which the varnish is applied
- an upper layer means a layer which is in contact with the lower layer.
- the first polyamic acid-based compound which has a higher polarity, is included in the lower layer and contacts with pixel electrodes. That is, in order to suppress a DC afterimage, it is necessary to prevent accumulation of charge due to the photo-charge of the lower-layer film. Therefore, it is preferable that the first polyamic acid-based compound contained at least in the lower-layer film have no primary amino groups at its both terminals.
- the varnish according to some embodiments can use as solvents for dissolving or dispersing the polyamic acid-based compound or compounds, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, M-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramehylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, ethylamylketone, methylnonylketone, methylethylketone, methylisoamylketone, methylisopropylketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone.
- the varnish according to some embodiments described herein is applied to an item or object to be coated, and is imidized by heating at about 200° C. More specifically, in a varnish containing, as the polyamic acid-based compound, the first polyamic acid-based compound alone, the first polyamic acid-based compound is imidized. In a varnish containing, as the polyamic acid-based compounds, both the first polyamic acid-based compound and the second polyamic acid-based compound, they are phase-separated into two layers after coating, and they are both imidized by the heating.
- Photo-alignment processing is carried out on the resultant imidized film, providing a photo alignment film.
- the photo-alignment processing can be carried out by radiating the film with a short-wavelength UV light having a wavelength of 254 or 365 nm.
- the alignment film after photo alignment process may be washed using an oxidizing solvent or an organic solvent. By washing the photo alignment film, the imidization promotor remaining in the film can be removed.
- oxidizing solvent examples include hydrogen peroxide water, hypochlorous acid solution, ozone water, hypoiodous acid water, permanganic acid water, etc.
- organic solvent examples include a ketone-based solvent, an ester-based solvent, an ether-based solvent, an alcohol-based solvent, a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent, etc.
- ketone-based solvent examples include acetone, methylethylketone, methylisobutylketone, cyclohexanone, diacetone alcohol, etc.
- ester-based solvent examples include ethyl acetate, ethyl formate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc.
- ether-based solvent examples include diethyl ether, isopropyl ether, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, methyl tertiary butylether (MTBE), butylcarbitol, etc.
- alcohol-based solvent examples include methanol, ethanol, butanol, isopropyl alcohol, normal propyl alcohol, butanediol, ethylhexanol, benzyl alcohol, etc.
- hydrocarbon-based solvent examples include aliphatics or aliphatic hydrocarbons such as hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene.
- halogenated hydrocarbon-based solvent examples include alkyl halides such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane; alkenyl halides such as trichloroethylene and tetrachloroethylene; and aryl halides such as monochlorobenzene and dichlorobenzene.
- a liquid crystal display device comprising an alignment film comprising an imidized product of the varnish according to some embodiments.
- FIG. 1 is a cross-sectional view partially illustrating a display panel PNL of a lateral electric field type liquid crystal display device.
- the display panel PNL includes an array substrate ARS and an opposite substrate OPS disposed opposite to, and spaced apart from, the array substrate ARS.
- a liquid crystal layer 300 is provided between the array substrate ARS and the opposite substrate OPS.
- the array substrate ARS includes a first glass substrate 100 .
- a gate electrode 101 is provided on the first glass substrate 100 .
- the gate electrode 101 has the same thickness as each of scanning lines (not shown) provided on the first glass substrate 100 .
- the gate electrode 101 can have a two-layer structure, with a lower layer, which is in direct contact with the first glass substrate 100 , being formed of, for example, an AlNd alloy, and an upper layer being formed of, for example, a MoCr alloy.
- a gate insulating film 102 is provided, covering the gate electrode 101 .
- the gate insulating film 102 is formed of, for example, SiN.
- a semiconductor layer 103 is provided at a location opposite to the gate electrode 101 .
- the semiconductor layer 103 is formed of, for example, amorphous silicon (a-Si film).
- the semiconductor layer 103 forms the channel portion of a TFT (not shown).
- a drain electrode 104 and a source electrode 105 are provided through the above channel portion. Between the semiconductor layer 103 and the drain electrode 104 or the source electrode 105 , an n + —Si layer (not shown) is provided in order to establish an ohmic contact between them.
- An image signal line doubles as the drain electrode 104 , and the source electrode 105 is connected to a pixel electrode 110 .
- the drain electrode 104 and the source electrode 105 are formed of, for example, a MoCr alloy.
- An inorganic passivation film 106 is provided, covering the TFT.
- the inorganic passivation film 106 is formed of, for example, SiN.
- the inorganic passivation film 106 protects the TFT, especially, the channel portion thereof, from impurities.
- An organic passivation film 107 is provided on the inorganic passivation film 106 .
- the organic passivation film 107 serves to protect the TFT, and also to planarize the surfaces. Therefore, the organic passivation film 107 is formed to be thick, for example, in a thickness of 1 to 4 ⁇ m.
- the organic passivation film is formed of, for example, “OPTMER PC Series” available from JSR Corporation.
- a counter-electrode 108 is provided on the organic passivation film 107 .
- the counter-electrode 108 is formed of a transparent electrically conductive material, for example, ITO.
- the counter-electrode 108 is formed planarly over the entire display area.
- the interlayer insulating film 109 is provided, covering the counter-electrode 108 .
- the interlayer insulating film 109 is formed of, for example, SiN.
- the pixel electrode 110 is provided, covering the interlayer insulating film 109 , and also covering the inner side surface and the bottom surface of the through hole 111 .
- the pixel electrode 110 is formed of, for example, ITO.
- the pixel electrode 110 is connected to the portion of the source electrode 105 which is partially exposed by the through hole 111 .
- the pixel electrode 110 and the source electrode 105 which extends from the TFT, are electrically connected to each other, and an image signal is supplied to the pixel electrode 110 .
- FIG. 2 partially illustrates an example of the pixel electrode 110 .
- the pixel electrode 110 is a comb-tooth electrode. On both sides of the pixel electrode 110 , image signal lines 1041 are provided. Slits 112 are provided between the comb-teeth of the pixel electrode 110 . Also, the planar counter-electrode 108 is provided below the pixel electrode 110 .
- an image signal is supplied to the pixel electrode 110 , liquid crystal molecules are rotated by an electric flux produced between the pixel electrode 110 and the counter-electrode 108 through the slits 112 . Accordingly, light passing through the liquid crystal layer 300 is controlled to form an image.
- the opposite substrate OPS comprises a second glass substrate 200 .
- Color filers 201 including red, green and blue filter segments are provided on the inner surface of the second glass substrate 200 .
- a black matrix 202 is formed, and improves the contrast of the image.
- the black matrix 202 also serves as a light-shielding film for the TFT, and prevents photocurrent from flowing into the TFT.
- An overcoat film 203 is formed, covering the color filters 201 and the black matrix 202 .
- the overcoat film 203 planarizes the surfaces of the color filters 201 and the black matrix 202 .
- An alignment film 113 b is provided on the overcoat film 203 to cause, together with the alignment film 113 a , the liquid crystals to be aligned in an initial alignment state.
- the construction of the alignment film 113 b will be described later.
- An external electrically conductive film 210 is formed on an outer surface of the second glass substrate 200 to stabilize the potential inside the liquid crystal display panel PNL. A predetermined voltage is applied to the external electrically conductive film 210 .
- each of the alignment films 113 a and 113 b is a single layer film, and comprises the imidized product of the first polyamic acid-based compound. In another embodiment, each of the alignment films 113 a and 113 b is of a two-layer structure provided with a film comprising the imidized product of the first polyamic acid-based compound and a film comprising the imidized product of the second polyamic acid-based compound.
- one of the alignment films 113 a and 113 b is a single layer film which comprises the imidized product of the first polyamic acid-based compound, while the other alignment film is of a two-layer structure provided with a film comprising the imidized product of the first polyamic acid-based compound as the lower layer and a film comprising the imidized product of the second polyamic acid-based compound as the upper layer.
- the alignment films 113 a and 113 b will be collectively denoted as alignment film 113 hereinafter.
- FIG. 3 is a schematic view illustrating the alignment film 113 having a two-layer structure according to one embodiment.
- the alignment film 113 is formed on the pixel electrode 110 .
- the alignment film 113 is provided with an upper film 1131 and a lower film 1132 . It should be noted that the boundary between the upper film 1131 and the lower film 1132 of the alignment film 113 is not clear, so the boundary is indicated by a dotted line in FIG. 3 .
- the lower layer in the alignment film having a two-layer structure occupy 30% by weight or more but 60% by weight or less of the total amount of the two-layer alignment film.
- the drive frequency (the number of times the image signal is supplied to the pixel electrodes per frame) of the liquid crystal display device fall within the range of 40 Hz or less, preferably 1 Hz or more, which leads to reduction in the power consumption.
- the resistance of the alignment film be high in order to suppress the lowering of the brightness during the voltage is held by the pixel electrode.
- the volume resistivity of the alignment film is preferably 5 ⁇ 10 13 ⁇ cm or more, more preferably 1 ⁇ 10 16 ⁇ cm or less, most preferably 5 ⁇ 10 15 ⁇ cm or less.
- a solution of 100 parts by mol of pyromellitic dianhydride in NMP and a solution of 110 parts by mol of 4,4′-diaminodiphenyl ether in NMP were mixed together, and the mixture was reacted at room temperature for 8 hours, producing a polyamic acid having primary amines at its both terminals.
- a solution of 5 parts by mol of phthalic anhydride in NMP was added, and reacted at room temperature for 8 hours, capping the primary amino groups at both terminals of the polyamic acid into amic acids.
- the unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- a solution of 100 parts by mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride in NMP and a solution of 90 parts by mol of p-phenylenediamine in NMP were mixed together, and the mixture was reacted at room temperature for 8 hours, producing a polyamic acid having carboxyl groups at its both terminals.
- the unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- a solution of 100 parts by mol of pyromellitic dianhydride in NMP and a solution of 90 parts by mol of 4,4′-diaminodiphenyl ether in NMP were mixed together, and the mixture was reacted with at room temperature for 8 hours, producing a polyamic acid having carboxyl groups at its both terminals.
- the unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- the acid skeletons, diamine skeletons and terminal skeletons of the polyamic acid-based compounds produced in Synthetic Examples 1 to 8 noted above are shown in Table 1 below.
- the mark “*” added to an acid skeleton represents a binding site to the amine skeleton
- the mark “*” added to an amine skeleton represents a binding site to the acid skeleton.
- the mark “*” added to the terminal skeleton represents a binding site to the acid skeleton if the terminal skeletons have amides and represents a binding site to the amine skeleton if the terminal skeletons have carboxyl groups.
- Coating liquids were prepared by adding, to the polyamic acid-based compounds of Examples 1 to 10 and Comparative Examples 1 to 4 shown in Table 2 below, the imidization promotors, respectively as indicated in the table (note in some cases, no promotor is added), followed by agitation for homogenization, and then mixing the upper-layer components and lower-layer components at the mass ratio of 1:1.
- the coating liquids were applied to the areas of the array substrate and the opposite substrate, which were to be coated with alignment films 113 , and were imidized by heating at 200° C.
- the imidization degree in all the Examples was 80%. Photo-alignment processing was conducted on each of the resultant imidized films using short wavelength UV light.
- the liquid crystal display devices provided with the display panels having the structure as illustrated in FIG. 1 were fabricated by the ordinary method, using array substrates and opposite substrates provided with alignment films thus formed.
- a nematic liquid crystal material (MLC-2039 available from Merk & Co., Inc.) having negative dielectric anisotropy A the value of which was ⁇ 4.1 (1 kHz, 20° C.) and refractive anisotropy ⁇ n the value of which was 0.0821 (wavelength of 590 nm, 20° C.) was used as the liquid crystal.
- the fabricated liquid crystal display devices were operated to display a white and black (shaded) checkered flag pattern as illustrated in FIG. 4 for 100 hours.
- Each of checkers forming the checkered flag pattern was a square having four sides of equal length of 5 mm.
- White is the maximum luminance (256th level of 256 levels of gray)
- black is the minimum luminance (0th level of 256 levels of gray).
- the liquid crystal display devices were each operated to display gray at the 31st level of 256 levels of gray on the entire screen of each liquid crystal display device, it was observed that the areas corresponding to the white checkers which had displayed white for 100 hours exhibited luminance different from that of the areas corresponding to the black checkers which had displayed black for 100 hours.
- the change rate of the luminance of the both areas noted above is calculated by the following formula:
- a is the luminance of the areas corresponding to the white checkers which had displayed white for 100 hours
- b is the luminance of the areas corresponding to the black checkers which had displayed black for 100 hours.
- the change rate is defined as the intensity of afterimage. If a numeral value obtained by the above formula is greater than or equal to 1%, afterimage is recognized by human's eyes.
- the change of the afterimage intensity over time was measured when the gray was displayed after the checkered flag pattern was continuously displayed for 100 hours, and was evaluated on a scale in 5 levels below.
- the fabricated liquid crystal display devices were operated to display 10 different kinds of patterns for 1,000 hours in a thermostatic bath at 70° C. while switching the patterns one from another every 30 seconds.
- the liquid crystal displays were taken out of the thermostatic bath every 250 hours and operated to display a gray pattern (64th level of 256 levels of gray) in normal temperature environment. In each device, the entire area of the screen was observed as to whether nonuniformity had occurred, and evaluated on a scale of five levels below.
- C A nonuniformity not generated before 500 hours, but after 1,000 hours, a nonuniformity in brightness of 1 mm or more in diameter, which is visible at first sight, occurred on a part of the screen, which corresponds to the outer circumference of the substrate.
- D A small nonuniformity in brightness of 1 mm or less in diameter occurred on a part of the screen, which corresponds to the outer circumference of the substrate before 500 hours.
- E A nonuniformity in brightness of 1 mm or more in diameter, which is visible at first sight, occurred on a part of the screen, which corresponds to the outer circumference of the substrate before 500 hours.
- a varnish for producing photo alignment films which does not cause a DC afterimage on a liquid crystal display device or causes an DC afterimage to disappear in a short period of time even if the DC afterimage is generated, and also a liquid crystal display device is provided, in which a DC afterimage is not generated or disappears within a short period of time even if the afterimage is generated.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
- This application is a continuation of and claims the benefit of priority under 35 U.S.C. § 120 from U.S. application Ser. No. 17/164,973 filed Feb. 2, 2021, which is a continuation of U.S. application Ser. No. 15/647,322 filed Jul. 12, 2017 (now U.S. Pat. No. 10,947,345 issued Mar. 16, 2021), and claims the benefit of priority under 35 U.S.C. § 119 from Japanese Patent Application No. 2016-141379 filed Jul. 19, 2016, the entire contents of each of which are incorporated herein by reference.
- Embodiments described herein relate generally to a varnish for a photo alignment film and a liquid crystal display device.
- Liquid crystal display devices comprise an array substrate provided with, for example, pixel electrodes and thin-film transistors (TFTs) arranged in a matrix and a counter-substrate arranged apart from and opposite to the array substrate and provided with, for example, color filters, formed thereon. Liquid crystal is sealed between the array substrate and the counter-substrate.
- The liquid crystal is aligned by alignment films disposed on the array substrate and the counter-substrate, respectively. Polyimide films are frequently used as the alignment films. The polyimide films are obtained by baking polyamic acid at a high temperature of 230° C. or higher. But, in most of the cases, polyimide films obtained by baking at high temperature have deteriorated transmissivity due to coloring of film. As a solution to this, such a technique is employed that polyamic acid is imidized in the presence of an amine-based imidization promotor. Imidization using an imidization promotor can be carried out at relatively low temperature, and therefore substantially no coloring of polyimide occurs.
- Recently, a photo-alignment technique, which can impart the alignment control capability to polyimide films in a non-contact manner, has been adopted, in addition to rubbing treatment. The photo-alignment technique comprises irradiating the polyimide film with ultraviolet (UV) light having a short wavelength of 254 to 365 nm to achieve the alignment. In the polyimide film irradiated with the polarized light, some main chains of the polyimide molecules are cut in a direction parallel to the direction of polarization, and the polyimide film is given uniaxial anisotropy in a direction perpendicular to the direction of polarization. Liquid crystal molecules are aligned along the remaining main chains of the polyimide molecules which have not been cut, and thus are kept long and linearly extend.
-
FIG. 1 is a schematic cross-sectional view illustrating part of a display panel of a liquid crystal display device according to one embodiment. -
FIG. 2 is a plan view illustrating part of a pixel electrode in the liquid crystal display device shown inFIG. 1 . -
FIG. 3 is a perspective view illustrating a structure of an alignment film having a double-layer structure according to one embodiment. -
FIG. 4 is a view illustrating a pattern for inspection for a DC afterimage. - In general, according to first embodiment, there is provided a varnish for a photo alignment film comprising an imidization promotor and a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the imidization promotor has skeleton containing no primary amino group and no secondary amino group, and the first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- According to second embodiment, there is provided a varnish for a photo alignment film comprising a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the first polyamic acid-based compound has terminal skeletons containing no primary amino group, and also a diamine skeleton represented by Formula (7) below:
- where L is an aromatic compound group, and I) Y5 is an amino group containing an organic group which may leave by heat, Y6 is H or an amino group containing an organic group which may leave by heat, or II) Y5 and Y6 are bonded together to form a cyclic group containing nitrogen.
- The present inventors have confirmed that when a liquid crystal display device incorporating a polyimide alignment film having been subjected to photo-alignment processing (photo alignment polyimide film) is turned on and an image is displayed, the photo alignment polyimide film becomes excited by the light emitted from the backlight as the lighting time of the backlight proceeds, producing a photoelectromotive force, as a result of which charge is accumulated in the photo alignment polyimide film, leading to an afterimage (DC afterimage).
- In recent years, alignment films have been required to have a higher resistance in order to improve a voltage holding ratio of a pixel electrode. However, more recently, it has been found that only in the case where a high-resistance alignment film is subjected to photo-alignment process, a specific DC afterimage phenomenon occurs. In this phenomenon, when the light of a liquid crystal display device is continuously turned on, a DC voltage is created by photo-charge of the alignment film in liquid crystal cells, and the afterimage does not disappear even when the application of a voltage to pixel electrodes is stopped. As a result of the present inventors' investigation, it has been confirmed that before and after the photo-alignment processing, in which short-wavelength UV irradiation is used, an absorption wavelength of the alignment film changes. More specifically, as a result of the alignment processing noted above, the alignment film became to slightly absorb UV light emitted of 450 nm or less within the emission wavelength of the backlight. The inventors investigated its cause in detail and conjectured that the cause is the primary amines present at the terminals of the chemical structure of the polyimide. It is inferred that the primary amines are displaced in the photo-alignment process, leading to the change in the absorption wavelength of the polyimide film, though it is uncertain exactly why so. This phenomenon has been confirmed to occur also in a polyimide film obtained by imidization using an imidization promotor having a primary or secondary amine skeleton.
- The present inventors have made intensive studies on the DC afterimage of the polyimide film imidized using the amine-based promotor. As a result, they found a technique of preventing DC afterimage completely from occurring or eliminating it to disappear in a short time even if it occurs by: 1) letting the imidization promotor to use include a skeleton other than a primary amino group and a secondary amino group or not using an imidization promotor, and 2) letting the polyimide contain groups other than a primary amino group at both terminals thereof. Making the polyimide to have groups other than primary amino groups at its both terminals can be achieved making a polyamic acid or a polyamic acid ester (usually provided in the form of varnish), which is a precursor of the polyimide, to have groups other than primary amino groups at its both terminals.
- Thus, such a vanish for forming an photo alignment film can be provided, that DC afterimage can be prevented from occurring in a liquid crystal display device, or even DC afterimage occurs, it disappear in a short time.
- A varnish for a photo alignment film according to the first embodiment includes an imidization promotor and a first polyamic acid-based compound in an organic solvent. The first polyamic acid-based compound is a polyamic acid or a polyamic acid ester. The imidization promotor has skeleton containing no primary amino group and no secondary amino group. The first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- In some embodiments, a varnish for a photo alignment film according to the first embodiment comprising an imidization promotor and a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the imidization promotor has skeleton containing no primary amino group and no secondary amino group, and the first polyamic acid-based compound has terminal skeletons containing no primary amino group.
- [Imidization Promotor]
- An imidization promotor promotes the dehydration and cyclization reaction to the first polyamic acid-based compound.
- In some embodiments, the imidization promotor is a pyridine-based compound, a quinoline-based compound, an isoquinoline-based compound, an imidazole-based compound, a benzimidazole-based compound or a tertiary amine.
- The pyridine-based compound is a compound which has a pyridine skeleton, whereas the quinoline-based compound, isoquinoline-based compound, imidazole-based compound and benzimidazole-based compound are compounds which have a quinoline skeleton, an isoquinoline skeleton, an imidazole skeleton and a benzimidazole skeleton, respectively.
- The tertiary amine is, for example, an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine, or a derivative such as an alkyl-substituted compound.
- Examples of the aliphatic tertiary amine are trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, tributylamine, tripentylamin, tricyclopentylamine, trihexylamine, benzyldimethylamine triethanolamine, etc.
- An example of the aromatic tertiary amine is N,N-dimethylaniline.
- Examples of the heterocyclic tertiary amine are pyridine, β-picoline, quinoline, isoquinoline, dipyridine, diquinoline, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenantolidine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzoisoxazole, thiazole, benzothiazole, oxadiazole, thiadiazole, benzoisoquinolizine, hexamethylenetetramine, N,N-dimethyl-4-aminopyridine, 4-hydroxypyridine etc.
- In some embodiments, the imidization promotor should preferably be a such as N,N-dimethylaniline, pyridine, β-picoline, quinoline, isoquinoline or N,N-dimethyl-4-aminopyridine, or a derivative thereof. The derivative should preferably be an alkyl-substituted compound.
- In some embodiments, the imidization promotor comprises an amine-reactive skeleton.
- The amine-reactive skeleton includes a halogen group, a diazo group, a carboxyl group, a hydroxyl group, an isocyanate group or an acid anhydride skeleton.
- Examples of the imidization promotor having an amine-reactive skeleton are dimethylglycine, picolinic acid, nicotinic acid and 5-butylpicolinic acid.
- In the imidization, the amine-reactive skeleton reacts with a primary amine which may exist at sites other than both terminals of the first polyamic acid-based compound and a secondary amine which may exist in the first polyamic acid-based compound, to produce amide. Thus, DC afterimage which occurs due to the primary and secondary amines can be substantially eliminated more reliably.
- In some embodiments, the imidization promotor has a molecular weight of 130 or more. An imidization promotor having a molecular weight of 130 or more, which exists in a photo-alignment polyimide film is not able to easily respond to a general liquid crystal drive (of 1 Hz to 120 Hz) because of its ion weight. Therefore, it becomes possible to slow down the accumulation velocity of ions to a specific part in the display device, which may be caused by long drive, and thus the time until nonuniformity in display occurs and the life of the display device can be prolonged.
- Note that the content of the imidization promotor in the varnish for photo alignment films should preferably be 5% by mass or more, and more preferably 10% by mass or more.
- [First Polyamic Acid-Based Compound]
- In some embodiments, the first polyamic acid-based compound has a structural unit (repeating unit) represented by Formula (1) below:
- where X is a cyclic group, each of R1 and R2 is independently —COOH or —COOR where R is an alkyl group, and Y1 is an organic group.
- In one embodiment, X is an alicyclic group, for example, a substituted or unsubstituted cyclobutane group. In another embodiment, X is a benzene ring or a benzene ring-containing group, wherein the benzene ring may be substituted with an alkyl group or the like. Preferably, X is the alicyclic group.
- In some embodiments, the first polyamic acid-based compound has a diamine skeleton represented by Formula (2) below:
-
—HN-M-NH— (2) - where M is an organic group, for example, a cyclic group-containing group. In some embodiments, M is Ar0 or Ar1—Z—Ar2, where Ar0 is an aromatic group, each of Ar1 and Ar2 is independently an aromatic group, and Z is an organic group containing no primary amino group and no secondary amino group. An example of the aromatic group represented by Ar1, Ar1 or Ar2 is a benzene ring or a benzene ring-containing group. Alternatively, Z is constituted by oxygen, nitrogen, sulfur, carbon or hydrogen, or a combination of two or more of them. Z contains no hydroxyl group, no thiol group and no amino group other than tertiary amino group, i.e., no —NH nor >NH.
- In some embodiments, the terminal skeletons of the first polyamic acid-based compound each comprise an imide skeleton, an amide skeleton, a urea skeleton, a tertiary amino skeleton, an azo bond or a carboxyl group.
- In some embodiments, both terminal skeletons of the first polyamic acid-based compound are represented by Formula (3) below:
- where Y2 is H, S or an organic group, and Y3 is an aliphatic group or an aromatic group; or Y2 and Y3 are bonded together to form a cyclic group, for example, imide; or Formula (4) below:
-
—N═N—Y4 (4) - where Y4 is an organic group; or Formula (5) below:
- where X is as defined above, and each of R3 and R4 is independently hydrogen or an alkyl group.
- The polyamic acid can be produced by reacting a tetracarboxylic dianhydride with a diamine by an ordinary method.
- The tetracarboxylic dianhydride can be represented by Formula (A) below:
- where X is a cyclic group as defined above with respect to Formula (1) above.
- The tetracarboxylic dianhydride having a substituted or unsubstituted cyclobutane group as X can be represented by Formula (B) below:
- where each Rb is independently hydrogen or an alkyl group. An example of the alkyl group is an alkyl group having one to six carbon atoms. Particularly preferably, the alkyl group is methyl group.
- An example of the tetracarboxylic dianhydride having a benzene ring as X is pyromellitic acid.
- Preferably, the tetracarboxylic dianhydride is the one represented by Formula (B) above.
- [Diamine]
- The diamine to be reacted with the above tetracarboxylic dianhydride is an organic compound having two primary amino groups. The diamine can be represented by Formula (C):
-
H2N-M-NH2 (C) - where M is as defined with respect to Formula (2) above.
- The diamine represented by Formula (C) includes an alicyclic diamine, a heterocyclic diamine, an aliphatic diamine and an aromatic diamine.
- Examples of the alicyclic diamine are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophoronediamine, etc.
- Examples of the heterocyclic diamine are 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole, etc.
- Examples of the aliphatic diamine are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, etc.
- Examples of the aromatic diamine are o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2, 5-dichlorobenzene, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-2,2′-dimethylbibenzyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4′-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]ulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 1,1-bis(4-aminophenyl)cyclohexane, α,α′-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4′-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis(4-aminophenyl)tetramethyldisiloxane, benzidine, 2,2′-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)nonane, 1,10-bis(4-aminophenyl)decane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy) decane, di(4-aminophenyl)propane-1,3-dioate, di(4-aminophenyl)butane-1,4-dioate, di(4-aminophenyl)pentane-1,5-dioate, di(4-aminophenyl)hexane-1,6-dioate, di(4-aminophenyl)heptane-1,7-dioate, di(4-aminophenyl)octane-1,8-dioate, di(4-aminophenyl)nonane-1,9-dioate, di(4-aminophenyl)decane-1,10-dioate, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, etc. Further examples of the aromatic diamine are listed below (in the further examples below, n denotes an integer of 1 to 10):
- The aromatic diamine can be represented by Formula (D) or (E) below:
-
H2N—Ar0—NH2 (D) -
H2N—Ar1—Z—Ar2—NH2 (E) - where Ar0, Ar1, Ar2 and Z are as defined with respect to Formula (2) above. An alignment film formed using the diamine represented by Formula (D) has a high photo-alignability, and is preferably used to produce a second polyamic acid-based compound described below. An alignment film formed using the diamine represented by Formula (E) does not contain thiol group or hydroxyl group, and thus is not greatly influenced by a hydrogen bond. Accordingly, its resistance tends to become high. Also, this diamine does not contain an amino group other than a tertiary amine in Z, i.e., does not contain —NH or >NH in Z, and DC afterimages can be prevented from generating. Accordingly, it is preferable that the diamine of Formula (E) be used to produce the first polyamic acid-based compound. It should be noted that an amide bond is distinguished from a secondary amino group, since their chemical properties are different from each other. That is, Z may be an organic group which forms an amide bond.
- Note that a polyamic acid ester having —COOR can be produced by reacting, for example, N,N-dimethylformamide dialkyl acetal with the polyamic acid above. Alternatively, a polyamic acid ester can also be produced by the method disclosed in JP 2000-273172 A.
- [Terminal Skeleton of Polyamic Acid-Based Compound]
- In some embodiments, preferably, the first polyamic acid-based compound has terminal skeletons represented by Formula (3), (4) or (5).
- In the reaction of the tetracarboxylic dianhydride and the diamine, when the diamine is used in an amount slightly larger than the amount of the tetracarboxylic dianhydride (for example, in a molar amount 1.1 to 1.5 times larger than the molar amount of the tetracarboxylic dianhydride), a polyamic acid having primary amino groups at its both terminals, or a polyamic acid having primary amines as the terminal skeletons, is produced.
- The first polyamic acid-based compound noted above can be obtained by chemically modifying the terminal primary amino groups of the polyamic acid or the polyamic acid ester, which has the primary amino groups at its both terminals. This chemical modification is a capping of the primary amino groups.
- A method for chemically modifying a terminal primary amino group includes amidation. As a capping agent (amidating agent) used for this purpose, a compound having one halogenated carbonyl group in the molecule, i.e. a monofunctional acid halide, can be used. The halide includes chloride, bromide and fluoride. Examples of the monofunctional acid halide include benzoyl chloride, acetyl chloride, propionyl chloride, acryloyl chloride, methacryloyl chloride and tosyl chloride.
- Furthermore, as another capping agent which achieves the amidation, a compound having one acid anhydride, i.e., a monofunctional acid anhydride, may be used. Examples of the monofunctional acid anhydride are phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic-1,2-anhydrid, cyclohexene-1,2-dicarboxylic anhydride, etc. In the case where the terminal primary groups are chemically modified with these compounds, ordinarily, the terminals are converted into polyamic acids. Thereafter, the resulting compound is formed into a film, and baked to be imidized.
- Furthermore, for amidation, esterification into amic acid esters may be used. To convert the terminals into amic acid esters, it suffices that an amino-reactive group such as carboxyl group or an acid halide (halogenated carbonyl group) and a known aromatic compound having an ester skeleton are used as capping agents. Also, the conversion of the terminals into amic acid esters can be effected by reacting the compound having its terminals converted into amic acid by the above method with, for example, N,N-dimethylformamide dialkyl acetal. In the case where the terminal primary amino groups are chemically modified with these compounds, ordinarily, the terminals become polyamic acid esters. Thereafter, the resulting compound is formed into a film, and baked to be imidized.
- Also, the terminals may be in imidized state. In order to obtain the imidized terminals, it suffices that the above capped compound having the terminals converted into polyamic acid or polyamic acid ester is heated to be dehydration-condensed.
- It should be noted that a chemical modification other than amidation and imidization may be applied, for example, azotization, ureation or tertiary amination may be applied.
- For azotization, a diazonium salt-based diazo coupling agent can be used as a capping agent (azotization agent). For ureation, an isocyanate-based compound can be used as a capping agent. Examples of the isocyanate are phenyl isocyanate, naphthyl isocyanate, etc. For tertiary amination, a compound having a halogen group (especially, chlorine) or hydroxyl group can be used as a capping agent (tertiary amination agent). It should be noted that substances other than the above capping agents can be used for the azotization, ureation or tertiary amination.
- In another embodiment, a polyamic acid-based compound having terminal skeletons not containing a primary amino group can be produced by using, in the reaction of the tetracarboxylic dianhydride and the diamine note above, the tetracarboxylic dianhydride in an amount larger than the amount of the diamine (for example, in a molar amount 1.1 to 1.5 times larger than the amount of the diamine). This reaction produces a polyamic acid having carboxyl groups at its terminals.
- In the case where the varnish contains two or more polyamic acid-based compounds, it is preferable that the total amount of the polyamic acid-based compounds each having carboxyl groups at the both terminals occupy 80% by mass or more, more preferably 90% by mass or more of the sum of the total amount of the polyamic acid-based compounds.
- [Acid Skeleton]
- As is clear from the above explanation, the first polyamic acid-based compound having groups other than primary amino groups at its both terminals can have an acid skeleton represented by Formula (6) below:
- where X is as described above with respect to Formula (1) above.
- The acid skeleton represented by the formula (6) includes acid skeletons represented by Formulas (6-1) and (6-2) below:
- In Formula (6-1), Ra is an alkyl group, for example, an alkyl group having 1 to 6 carbon atoms, and Rb is hydrogen or an alkyl group as defined with respect to Formula (B) above.
- The amine skeleton is as described above.
- Furthermore, as is clear from the above, the first polyamic acid-based compound can have the structural unit (repeating unit) represented by Formula (1) above, and its terminal skeletons can comprise an imide skeleton, an amide skeleton, a urea skeleton, a tertiary amino skeleton, an azo bond or a carboxyl group. The structural unit represented by Formula (1) includes a structural unit represented by Formulas (1-1) or (1-2) below:
- In Formulas (1-1) and (1-2), Ar is Ar0 or Ar1—Z-Art as defined with respect to Formula (2) above. In Formula (1-1), Ra and Rb are as defined with respect to Formula (6-1) above. Z is as defined with respect to Formula (2) above.
- As described above, a requirement for the imidization promotor not to substantially produce DC afterimage is to avoid the imidization promotor from having skeletons of a primary amino group and a secondary amino group. This can be ultimately achieved by not using an imidization promotor substantially. However, without an imidization promotor, imidization cannot be promoted, and therefore the first polyamic acid-based compound (having terminal skeletons containing no primary amino group) is incorporated with a skeleton which can promote imidization.
- That is, a varnish for a photo alignment film according to the second embodiment comprising a first polyamic acid-based compound in an organic solvent, the first polyamic acid-based compound being a polyamic acid or a polyamic acid ester, wherein the first polyamic acid-based compound has terminal skeletons containing no primary amino group, and also a diamine skeleton represented by Formula (7) below:
- where L is an aromatic compound group, and I) Y5 is an amino group containing an organic group which may leave by heat, Y6 is H or an amino group containing an organic group which may leave by heat, or II) Y5 and Y6 are bonded together to form a cyclic group containing nitrogen.
- The varnish according to the second embodiment further comprises an imidization promotor, an amount of the imidization promotor being less than 1.0% by mass based on an amount of the first polyamic acid-based compound.
- The diamine skeleton represented by Formula (7) contains a diamine skeleton is represented by Formula (8) below:
- where Y4 is a —N(H)A group, A being an amino group containing an organic group which may leave by heat, and Y5 is H or a —N(H)A group, amino groups or —NH— groups being located at a meta position or para position with respect to each other, and Y4 and Y5 are located at ortho positions to one amino group or —NH— group.
- The first polyamic acid-based compound having a diamine skeleton represented by Formula (7), has an acid skeleton represented by Formula (9) below:
- where X is a cyclic group as defined in Formula (1) above, each of R1 and R2 is independently —COOH or —COOR where R is an alkyl group.
- Less than the 1.0% by mass of imidization promotor means, for example, that an amount of the imidization promotor being less than 1.0% by mass based on an amount of the first polyamic acid-based compound and this amount is a quantity which does not substantially exhibit the function of promoting imidization.
- In some embodiments, the content of the imidization promotor in the organic solvent is less than 1.0% by mass, preferably, less than 0.1% by mass, and more preferably, 0° by mass.
- The first polyamic acid-based compound contained in the varnish for photo alignment films according to the second aspect can be produced by using as a diamine which derives a diamine skeleton represented by Formula (7) (including Formula (8)) as the diamine in the production of the first polyamic acid-based compound contained in the varnish for photo alignment films according to the first aspect. Such a diamine includes an aromatic diamine represented by Formula (F) or (G) below.
- The polyamic acid-based compound obtained by reacting a diamine represented by Formula (F) or (G) with tetracarboxylic dianhydride by an ordinary method comprises an amine site having an imidization promoting function in a skeleton thereof.
- The polyamic acid-based compound obtained by reacting a diamine of Formula (F) with tetracarboxylic dianhydride by the ordinary method forms an imidazole skeleton as a protective group (tert-butoxycarbonyl group) leaves by heating at the time of baking for imidization, thus promoting the imidization.
- The reaction for forming an imidazole skeleton is expressed by Scheme (I) below:
- where X is a cyclic group as defined in Formula (1) above, each of R1 and R2 is independently —COOH or —COOR where R is an alkyl group as defined in Formula (1) above.
- In some embodiments, the varnish for a photo alignment film according to the second contains a first polyamic acid-based compound which is a polyamic acid or a polymide acid ester in an organic solvent. Further, the content of the imidization promotor is less than 1.0% by mass, and the first polyamic acid-based compound has a terminal skeleton containing a carboxyl group.
- The first polyamic acid-based compound which has a terminal skeleton containing a carboxyl group can be produced by using, in the reaction of the tetracarboxylic dianhydride and the diamine noted above, the tetracarboxylic dianhydride in an amount larger than the amount of the diamine (for example, in a molar amount 1.1 to 1.5 times larger than the amount of the diamine).
- The first polyamic acid-based compound which has an terminal skeleton containing a carboxyl group can promote imidization at the time of baking for imidization by the carboxyl group.
- [Second Polyamic Acid-Based Compound]
- In another embodiment, the varnish further comprises a second polyamic acid-based compound which is a polyamic acid or a polyamic acid ester, in addition to the first polyamic acid-based compound. In this case, the first polyamic acid-based compound has a polarity higher than, or a surface energy higher than, that of the second polyamic acid-based compound. Therefore, in the case where the first and second polyamic acid-based compounds coexist in the varnish, they are phase-separated from each other. Here, the first polyamic acid-based compound has a higher affinity for indium tin oxide (ITO) which forms pixel electrodes, inorganic passivation films such as SiO2 or SiNx and organic passivation films using organic resins in a liquid crystal display device. Thus, the first polyamic acid-based compound forms a lower layer. Ordinarily, in the case where a polyamic acid ester and a polyamic acid coexist, the polyamic acid ester forms an upper layer, and the polyamic acid forms a lower layer. Further, in the case where two kinds of polyamic acid-based compounds coexist, the diamine skeleton of one of these polyamic acid-based compounds contains oxygen or fluorine, the diamine skeleton of the other polyamic acid-based compound contains neither oxygen nor fluorine or the diamine skeleton of the above other polyamic acid-based compound contains oxygen or fluorine, the amount of which is, however, less than that of the oxygen or fluorine in the diamine skeleton of the above one of the polyamic acid-based compounds, the above one of the polyamic acid-based compounds forms a lower layer, and the other polyamic acid-based compound forms an upper layer.
- Needless to say, in the case where the alignment film is of a single layer, the first polyamic acid-based compound is used as the polyamic acid-based compound.
- The second polyamic acid-based compound can be selected from the compounds indicated above as the first polyamic acid-based compound. Alternatively, it can be selected from polyamic acid-based compounds each of which has not yet subjected to the capping of terminal primary amino groups for the production of the first polyamic acid-based compound, i.e., from polyamic acids and polyamic acid esters, each having primary amino groups at the both terminals. However, it is preferable that the second polyamic acid-based compound, as well as the first polyamic acid-based compound, have no primary amino groups at its both terminals. Also, it is preferable that neither the first polyamic acid-based compound nor the second polyamic acid-based compound has a secondary amino group (excluding a secondary amino group forming an amide), regardless of whether the alignment film has a single-layer structure or a two-layer structure.
- As is clear from the above explanation, with respect to the alignment film having a two-layer structure, a lower layer means a layer which is in direct contact with an item (for example, an ITO film, an inorganic passivation film or an organic passivation film) to which the varnish is applied, and an upper layer means a layer which is in contact with the lower layer.
- In the alignment film having a two-layer structure, the first polyamic acid-based compound, which has a higher polarity, is included in the lower layer and contacts with pixel electrodes. That is, in order to suppress a DC afterimage, it is necessary to prevent accumulation of charge due to the photo-charge of the lower-layer film. Therefore, it is preferable that the first polyamic acid-based compound contained at least in the lower-layer film have no primary amino groups at its both terminals.
- The varnish according to some embodiments can use as solvents for dissolving or dispersing the polyamic acid-based compound or compounds, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, M-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramehylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethylamylketone, methylnonylketone, methylethylketone, methylisoamylketone, methylisopropylketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone.
- The varnish according to some embodiments described herein is applied to an item or object to be coated, and is imidized by heating at about 200° C. More specifically, in a varnish containing, as the polyamic acid-based compound, the first polyamic acid-based compound alone, the first polyamic acid-based compound is imidized. In a varnish containing, as the polyamic acid-based compounds, both the first polyamic acid-based compound and the second polyamic acid-based compound, they are phase-separated into two layers after coating, and they are both imidized by the heating.
- [Processing after Imidization]
- Photo-alignment processing is carried out on the resultant imidized film, providing a photo alignment film. The photo-alignment processing can be carried out by radiating the film with a short-wavelength UV light having a wavelength of 254 or 365 nm.
- The alignment film after photo alignment process (photo alignment film) may be washed using an oxidizing solvent or an organic solvent. By washing the photo alignment film, the imidization promotor remaining in the film can be removed.
- Examples of the oxidizing solvent are hydrogen peroxide water, hypochlorous acid solution, ozone water, hypoiodous acid water, permanganic acid water, etc.
- Examples of the organic solvent are a ketone-based solvent, an ester-based solvent, an ether-based solvent, an alcohol-based solvent, a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent, etc.
- Examples of the ketone-based solvent are acetone, methylethylketone, methylisobutylketone, cyclohexanone, diacetone alcohol, etc.
- Examples of the ester-based solvent are ethyl acetate, ethyl formate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc.
- Examples of the ether-based solvent are diethyl ether, isopropyl ether, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, methyl tertiary butylether (MTBE), butylcarbitol, etc.
- Examples of the alcohol-based solvent are methanol, ethanol, butanol, isopropyl alcohol, normal propyl alcohol, butanediol, ethylhexanol, benzyl alcohol, etc.
- Examples of the hydrocarbon-based solvent are aliphatics or aliphatic hydrocarbons such as hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene.
- Examples of the halogenated hydrocarbon-based solvent are alkyl halides such as methylene chloride, chloroform, carbon tetrachloride and dichloroethane; alkenyl halides such as trichloroethylene and tetrachloroethylene; and aryl halides such as monochlorobenzene and dichlorobenzene.
- According to the third embodiment, there is provided a liquid crystal display device comprising an alignment film comprising an imidized product of the varnish according to some embodiments.
-
FIG. 1 is a cross-sectional view partially illustrating a display panel PNL of a lateral electric field type liquid crystal display device. - Referring to
FIG. 1 , the display panel PNL includes an array substrate ARS and an opposite substrate OPS disposed opposite to, and spaced apart from, the array substrate ARS. Aliquid crystal layer 300 is provided between the array substrate ARS and the opposite substrate OPS. - The array substrate ARS includes a
first glass substrate 100. Agate electrode 101 is provided on thefirst glass substrate 100. Thegate electrode 101 has the same thickness as each of scanning lines (not shown) provided on thefirst glass substrate 100. Thegate electrode 101 can have a two-layer structure, with a lower layer, which is in direct contact with thefirst glass substrate 100, being formed of, for example, an AlNd alloy, and an upper layer being formed of, for example, a MoCr alloy. - A
gate insulating film 102 is provided, covering thegate electrode 101. Thegate insulating film 102 is formed of, for example, SiN. On thegate insulating film 102, asemiconductor layer 103 is provided at a location opposite to thegate electrode 101. Thesemiconductor layer 103 is formed of, for example, amorphous silicon (a-Si film). Thesemiconductor layer 103 forms the channel portion of a TFT (not shown). On thesemiconductor layer 103, adrain electrode 104 and asource electrode 105 are provided through the above channel portion. Between thesemiconductor layer 103 and thedrain electrode 104 or thesource electrode 105, an n+—Si layer (not shown) is provided in order to establish an ohmic contact between them. - An image signal line doubles as the
drain electrode 104, and thesource electrode 105 is connected to apixel electrode 110. Thedrain electrode 104 and thesource electrode 105 are formed of, for example, a MoCr alloy. - An
inorganic passivation film 106 is provided, covering the TFT. Theinorganic passivation film 106 is formed of, for example, SiN. Theinorganic passivation film 106 protects the TFT, especially, the channel portion thereof, from impurities. Anorganic passivation film 107 is provided on theinorganic passivation film 106. Theorganic passivation film 107 serves to protect the TFT, and also to planarize the surfaces. Therefore, theorganic passivation film 107 is formed to be thick, for example, in a thickness of 1 to 4 μm. The organic passivation film is formed of, for example, “OPTMER PC Series” available from JSR Corporation. - A counter-electrode 108 is provided on the
organic passivation film 107. The counter-electrode 108 is formed of a transparent electrically conductive material, for example, ITO. The counter-electrode 108 is formed planarly over the entire display area. - An interlayer insulating
film 109 is provided, covering the counter-electrode 108. Theinterlayer insulating film 109 is formed of, for example, SiN. - A through
hole 111 is provided, penetrating theinterlayer insulating film 109, the counter-electrode 108, theorganic passivation film 107 and theinorganic passivation film 106 to partially expose the surface of thesource electrode 105. - The
pixel electrode 110 is provided, covering theinterlayer insulating film 109, and also covering the inner side surface and the bottom surface of the throughhole 111. Thepixel electrode 110 is formed of, for example, ITO. Thepixel electrode 110 is connected to the portion of thesource electrode 105 which is partially exposed by the throughhole 111. Thus, in the throughhole 111, thepixel electrode 110 and thesource electrode 105, which extends from the TFT, are electrically connected to each other, and an image signal is supplied to thepixel electrode 110. -
FIG. 2 partially illustrates an example of thepixel electrode 110. Thepixel electrode 110 is a comb-tooth electrode. On both sides of thepixel electrode 110,image signal lines 1041 are provided.Slits 112 are provided between the comb-teeth of thepixel electrode 110. Also, theplanar counter-electrode 108 is provided below thepixel electrode 110. When an image signal is supplied to thepixel electrode 110, liquid crystal molecules are rotated by an electric flux produced between thepixel electrode 110 and the counter-electrode 108 through theslits 112. Accordingly, light passing through theliquid crystal layer 300 is controlled to form an image. - Referring back to
FIG. 1 , analignment film 113 a which aligns liquid crystal molecules is provided on thepixel electrode 110. The construction of thealignment film 113 a will be described later. - The opposite substrate OPS comprises a
second glass substrate 200.Color filers 201 including red, green and blue filter segments are provided on the inner surface of thesecond glass substrate 200. Between thecolor filters 201, ablack matrix 202 is formed, and improves the contrast of the image. Theblack matrix 202 also serves as a light-shielding film for the TFT, and prevents photocurrent from flowing into the TFT. - An
overcoat film 203 is formed, covering thecolor filters 201 and theblack matrix 202. Theovercoat film 203 planarizes the surfaces of thecolor filters 201 and theblack matrix 202. - An
alignment film 113 b is provided on theovercoat film 203 to cause, together with thealignment film 113 a, the liquid crystals to be aligned in an initial alignment state. The construction of thealignment film 113 b will be described later. - An external electrically
conductive film 210 is formed on an outer surface of thesecond glass substrate 200 to stabilize the potential inside the liquid crystal display panel PNL. A predetermined voltage is applied to the external electricallyconductive film 210. - In one embodiment, each of the
alignment films alignment films alignment films alignment films alignment film 113 hereinafter. -
FIG. 3 is a schematic view illustrating thealignment film 113 having a two-layer structure according to one embodiment. In the Figure, thealignment film 113 is formed on thepixel electrode 110. Thealignment film 113 is provided with anupper film 1131 and a lower film 1132. It should be noted that the boundary between theupper film 1131 and the lower film 1132 of thealignment film 113 is not clear, so the boundary is indicated by a dotted line inFIG. 3 . - It is preferable that the lower layer in the alignment film having a two-layer structure occupy 30% by weight or more but 60% by weight or less of the total amount of the two-layer alignment film.
- Further, it is preferable that the drive frequency (the number of times the image signal is supplied to the pixel electrodes per frame) of the liquid crystal display device fall within the range of 40 Hz or less, preferably 1 Hz or more, which leads to reduction in the power consumption. Furthermore, in the case of a low frequency driving, it is preferable that the resistance of the alignment film be high in order to suppress the lowering of the brightness during the voltage is held by the pixel electrode. The volume resistivity of the alignment film is preferably 5×1013 Ωcm or more, more preferably 1×1016 Ωcm or less, most preferably 5×1015 Ωcm or less.
- Some Examples will be described below, but firstly Synthetic Examples of polyamic acid-based compounds will be described.
- A solution of 100 parts by mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride in N-methyl-2-pyrrolidone (NMP) and a solution of 110 parts by mol of p-phenylenediamine in NMP were mixed together, and the mixture was reacted at room temperature for 8 hours, producing a polyamic acid having primary amines at its both terminals. To the reaction mixture, 100 parts by mol of N,N-dimethylformamide dimethyl acetal were added dropwise, and the mixture was reacted at 50° C. for 2 hours, methyl-esterifying the two carboxyl groups in each acid skeleton. To the resulting reaction mixture, a solution of 5 parts by mol of phthalic anhydride in NMP was added, and the mixture was reacted at room temperature for 8 hours, capping the primary amino groups at the both terminals of the polyamic acid into amic acids. The unreacted monomers and low-molecular-weight components were removed, giving a solution of a desired polyamic acid ester having both terminals capped and a solids concentration of 15% by mass.
- A solution of 100 parts by mol of pyromellitic dianhydride in NMP and a solution of 110 parts by mol of 4,4′-diaminodiphenyl ether in NMP were mixed together, and the mixture was reacted at room temperature for 8 hours, producing a polyamic acid having primary amines at its both terminals. To the reaction mixture, a solution of 5 parts by mol of phthalic anhydride in NMP was added, and reacted at room temperature for 8 hours, capping the primary amino groups at both terminals of the polyamic acid into amic acids. The unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- The same procedures were taken as in Synthetic Example 1 except that 4-[(4-aminophenyl)methyl]aniline was used instead of p-phenylenediamine, giving a solution of a polyamic acid having the primary amino groups at both terminals amidated.
- A solution of 100 parts by mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride in NMP and a solution of 90 parts by mol of p-phenylenediamine in NMP were mixed together, and the mixture was reacted at room temperature for 8 hours, producing a polyamic acid having carboxyl groups at its both terminals. The unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- A solution of 100 parts by mol of pyromellitic dianhydride in NMP and a solution of 90 parts by mol of 4,4′-diaminodiphenyl ether in NMP were mixed together, and the mixture was reacted with at room temperature for 8 hours, producing a polyamic acid having carboxyl groups at its both terminals. The unreacted monomers and low-molecular-weight components were removed, giving a polyamic acid solution having a solids concentration of 15% by mass.
- The same procedures were taken as in Synthetic Example 1 except that a diamine represented by Formula (G) above was used instead of p-phenylenediamine, giving a solution of a polyamic acid having the primary amino groups at both terminals amidated.
- The same procedures were taken as in Synthetic Example 1 except that a diamine represented by Formula (F) above was used instead of p-phenylenediamine, giving a solution of a polyamic acid having the primary amino groups at both terminals amidated.
- The same procedures were taken as in Synthetic Example 1 except that a diamine represented by Formula (H) below was used instead of p-phenylenediamine, giving a solution of a polyamic acid having the primary amino groups at both terminals amidated:
- The acid skeletons, diamine skeletons and terminal skeletons of the polyamic acid-based compounds produced in Synthetic Examples 1 to 8 noted above are shown in Table 1 below. In Table 1, the mark “*” added to an acid skeleton represents a binding site to the amine skeleton, and the mark “*” added to an amine skeleton represents a binding site to the acid skeleton. The mark “*” added to the terminal skeleton represents a binding site to the acid skeleton if the terminal skeletons have amides and represents a binding site to the amine skeleton if the terminal skeletons have carboxyl groups.
- Coating liquids were prepared by adding, to the polyamic acid-based compounds of Examples 1 to 10 and Comparative Examples 1 to 4 shown in Table 2 below, the imidization promotors, respectively as indicated in the table (note in some cases, no promotor is added), followed by agitation for homogenization, and then mixing the upper-layer components and lower-layer components at the mass ratio of 1:1. In the liquid crystal display device having the structure as illustrated in
FIG. 1 , the coating liquids were applied to the areas of the array substrate and the opposite substrate, which were to be coated withalignment films 113, and were imidized by heating at 200° C. The imidization degree in all the Examples was 80%. Photo-alignment processing was conducted on each of the resultant imidized films using short wavelength UV light. Then, the alignment films were washed. Thus, the liquid crystal display devices provided with the display panels having the structure as illustrated inFIG. 1 were fabricated by the ordinary method, using array substrates and opposite substrates provided with alignment films thus formed. A nematic liquid crystal material (MLC-2039 available from Merk & Co., Inc.) having negative dielectric anisotropy A the value of which was −4.1 (1 kHz, 20° C.) and refractive anisotropy Δn the value of which was 0.0821 (wavelength of 590 nm, 20° C.) was used as the liquid crystal. - The fabricated liquid crystal display devices were operated to display a white and black (shaded) checkered flag pattern as illustrated in
FIG. 4 for 100 hours. Each of checkers forming the checkered flag pattern was a square having four sides of equal length of 5 mm. White is the maximum luminance (256th level of 256 levels of gray), and black is the minimum luminance (0th level of 256 levels of gray). Then, when the liquid crystal display devices were each operated to display gray at the 31st level of 256 levels of gray on the entire screen of each liquid crystal display device, it was observed that the areas corresponding to the white checkers which had displayed white for 100 hours exhibited luminance different from that of the areas corresponding to the black checkers which had displayed black for 100 hours. The change rate of the luminance of the both areas noted above is calculated by the following formula: -
{(a−b)/b}×100 - where a is the luminance of the areas corresponding to the white checkers which had displayed white for 100 hours, and b is the luminance of the areas corresponding to the black checkers which had displayed black for 100 hours. The change rate is defined as the intensity of afterimage. If a numeral value obtained by the above formula is greater than or equal to 1%, afterimage is recognized by human's eyes.
- The change of the afterimage intensity over time was measured when the gray was displayed after the checkered flag pattern was continuously displayed for 100 hours, and was evaluated on a scale in 5 levels below.
- A: No afterimage generated from the initial stage of the above gray-displaying operation.
- B: An afterimage slightly visible from an oblique direction, generated at the initial stage of the gray-displaying operation, but disappeared within one hour.
- C: An afterimage visible from a front view, generated at the initial stage of the gray-displaying operation, but disappeared within one hour.
- D: An afterimage visible from a front view, generated at the initial stage of the gray-displaying operation, and reduced to an afterimage slightly visible from an oblique direction after one hour.
- E: An afterimage visible from a front view, generated at the initial stage of the gray-displaying operation, but did not disappear even after one hour.
- Furthermore, the fabricated liquid crystal display devices were operated to display 10 different kinds of patterns for 1,000 hours in a thermostatic bath at 70° C. while switching the patterns one from another every 30 seconds. The liquid crystal displays were taken out of the thermostatic bath every 250 hours and operated to display a gray pattern (64th level of 256 levels of gray) in normal temperature environment. In each device, the entire area of the screen was observed as to whether nonuniformity had occurred, and evaluated on a scale of five levels below.
- A: Nonuniformity in display not generated even after 1,000 hours.
- B: A nonuniformity not generated before 750 hours, but after 1,000 hours, a small nonuniformity in brightness (nonuniformity in display) of 1 mm or less in diameter occurred on a part of the screen, which corresponds to the outer circumference of the substrate.
- C: A nonuniformity not generated before 500 hours, but after 1,000 hours, a nonuniformity in brightness of 1 mm or more in diameter, which is visible at first sight, occurred on a part of the screen, which corresponds to the outer circumference of the substrate.
- D: A small nonuniformity in brightness of 1 mm or less in diameter occurred on a part of the screen, which corresponds to the outer circumference of the substrate before 500 hours.
- E: A nonuniformity in brightness of 1 mm or more in diameter, which is visible at first sight, occurred on a part of the screen, which corresponds to the outer circumference of the substrate before 500 hours.
- The results are indicated in Table 2. Note that Table 2 indicate briefly the skeletons at both terminals in the polyamic acid-based compounds produced in the Synthetic Examples.
-
TABLE 2 Polyamic acid-based Terminal Imidization DC Nonuniformity compound skeleton promotor afterimage in display Ex. 1 Upper layer Synthetic Amide N,N-dimethyl- B B component Ex. 1 4-aminopyridine Lower layer Synthetic Amide component Ex. 2 Ex. 2 Upper layer Synthetic Amide β-picoline B C component Ex. 3 Lower layer Synthetic Amide component Ex. 2 Ex. 3 Upper layer Synthetic Amide Nicotinic acid A B component Ex. 1 Lower layer Synthetic Amide component Ex. 2 Ex. 4 Upper layer Synthetic Amide 2,2′-dipyridyl B A component Ex. 1 Lower layer Synthetic Amide component Ex. 2 Ex. 5 Upper layer Synthetic Amide 2,6- B A component Ex. 1 dimethylquinoline Lower layer Synthetic Amide component Ex. 2 Ex. 6 Upper layer Synthetic Amide 5-butylpicolinic A A component Ex. 1 acid Lower layer Synthetic Amide component Ex. 2 Ex. 7 Upper layer Synthetic Carboxylic Absent C A component Ex. 4 acid Lower layer Synthetic Carboxylic component Ex. 5 acid Ex. 8 Upper layer Synthetic Amide Absent C A component Ex. 1 Lower layer Synthetic Carboxylic component Ex. 5 acid Ex. 9 Upper layer Synthetic Amide Absent B A component Ex. 6 Lower layer Synthetic Amide component Ex. 2 Ex. 10 Upper layer Synthetic Amide Absent C A component Ex. 7 Lower layer Synthetic Carboxylic component Ex. 5 acid Comp. Upper layer Synthetic Amide 4-aminopyridine E C Ex. 1 component Ex. 3 Lower layer Synthetic Amide component Ex. 2 Comp. Upper layer Synthetic Amide Histidine E A Ex. 2 component Ex. 1 Lower layer Synthetic Amide component Ex. 2 Comp. Upper layer Synthetic Amide Absent E A Ex. 3 component Ex. 1 Lower layer Synthetic Amide component Ex. 2 Comp. Upper layer Synthetic Amide Absent E A Ex. 4 component Ex. 8 Lower layer Synthetic Carboxylic component Ex. 2 acid - As described in detail above, according to one or more embodiments described above, a varnish for producing photo alignment films is provided, which does not cause a DC afterimage on a liquid crystal display device or causes an DC afterimage to disappear in a short period of time even if the DC afterimage is generated, and also a liquid crystal display device is provided, in which a DC afterimage is not generated or disappears within a short period of time even if the afterimage is generated.
- While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/842,922 US20220315703A1 (en) | 2016-07-19 | 2022-06-17 | Varnish for photo alignment film and liquid crystal display device |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-141379 | 2016-07-19 | ||
JP2016141379A JP7076939B2 (en) | 2016-07-19 | 2016-07-19 | Varnish for photo-alignment film and liquid crystal display device |
US15/647,322 US10947345B2 (en) | 2016-07-19 | 2017-07-12 | Varnish for photo alignment film and liquid crystal display device |
US17/164,973 US11384204B2 (en) | 2016-07-19 | 2021-02-02 | Varnish for photo alignment film and liquid crystal display device |
US17/842,922 US20220315703A1 (en) | 2016-07-19 | 2022-06-17 | Varnish for photo alignment film and liquid crystal display device |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/164,973 Continuation US11384204B2 (en) | 2016-07-19 | 2021-02-02 | Varnish for photo alignment film and liquid crystal display device |
Publications (1)
Publication Number | Publication Date |
---|---|
US20220315703A1 true US20220315703A1 (en) | 2022-10-06 |
Family
ID=60987919
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/647,322 Active 2038-01-04 US10947345B2 (en) | 2016-07-19 | 2017-07-12 | Varnish for photo alignment film and liquid crystal display device |
US17/164,973 Active US11384204B2 (en) | 2016-07-19 | 2021-02-02 | Varnish for photo alignment film and liquid crystal display device |
US17/842,922 Pending US20220315703A1 (en) | 2016-07-19 | 2022-06-17 | Varnish for photo alignment film and liquid crystal display device |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/647,322 Active 2038-01-04 US10947345B2 (en) | 2016-07-19 | 2017-07-12 | Varnish for photo alignment film and liquid crystal display device |
US17/164,973 Active US11384204B2 (en) | 2016-07-19 | 2021-02-02 | Varnish for photo alignment film and liquid crystal display device |
Country Status (3)
Country | Link |
---|---|
US (3) | US10947345B2 (en) |
JP (1) | JP7076939B2 (en) |
CN (2) | CN107632461B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7076939B2 (en) * | 2016-07-19 | 2022-05-30 | 株式会社ジャパンディスプレイ | Varnish for photo-alignment film and liquid crystal display device |
CN112055832B (en) * | 2018-05-29 | 2023-12-05 | Jsr株式会社 | Liquid crystal aligning agent and manufacturing method thereof, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element |
JP7218101B2 (en) * | 2018-06-01 | 2023-02-06 | 株式会社ジャパンディスプレイ | Varnish for photo-alignment film and liquid crystal display device |
JP7218100B2 (en) * | 2018-06-01 | 2023-02-06 | 株式会社ジャパンディスプレイ | Varnish for photo-alignment film and liquid crystal display device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013115228A1 (en) * | 2012-02-01 | 2013-08-08 | 日産化学工業株式会社 | Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same |
WO2013157586A1 (en) * | 2012-04-18 | 2013-10-24 | 日産化学工業株式会社 | Liquid-crystal alignment material for use in photo-alignment method, liquid-crystal alignment film, and liquid-crystal display element |
US10947345B2 (en) * | 2016-07-19 | 2021-03-16 | Japan Display Inc. | Varnish for photo alignment film and liquid crystal display device |
Family Cites Families (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09302225A (en) * | 1996-03-14 | 1997-11-25 | Toshiba Corp | Polyimide precursor composition, method of forming polyimide film, electronic part and liquid crystal element |
JP3978755B2 (en) * | 1997-12-29 | 2007-09-19 | チッソ株式会社 | Polyamic acid composition, liquid crystal alignment film, and liquid crystal display element |
US6949281B1 (en) * | 1999-06-25 | 2005-09-27 | Chisso Corporation | Varnish composition and liquid-crystal display element |
JP4686954B2 (en) * | 1999-06-28 | 2011-05-25 | チッソ株式会社 | Varnish composition and liquid crystal display element |
JP4336922B2 (en) * | 2000-04-12 | 2009-09-30 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JPWO2005118686A1 (en) * | 2004-06-01 | 2008-04-03 | 株式会社カネカ | Soluble polyimide and optical compensation member using the same |
JP2006056956A (en) | 2004-08-19 | 2006-03-02 | Jsr Corp | Method for producing polyimide film |
JP4844721B2 (en) * | 2006-03-22 | 2011-12-28 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
JP4716061B2 (en) * | 2007-03-01 | 2011-07-06 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
KR101482070B1 (en) * | 2008-04-15 | 2015-01-14 | 삼성디스플레이 주식회사 | A photo-based alignment material and method of manufacturing display substrate using the same |
JP5129107B2 (en) * | 2008-05-16 | 2013-01-23 | 旭化成イーマテリアルズ株式会社 | Polyamic acid varnish composition, polyimide resin and metal-polyimide composite |
CN102197091B (en) * | 2008-10-31 | 2013-11-06 | 宇部兴产株式会社 | Polyimide precursor solution composition |
JP5368250B2 (en) * | 2009-10-23 | 2013-12-18 | 株式会社ジャパンディスプレイ | Liquid crystal display |
JP5915523B2 (en) | 2010-03-15 | 2016-05-11 | 日産化学工業株式会社 | Polyamic acid ester-containing liquid crystal aligning agent and liquid crystal aligning film |
WO2011115077A1 (en) * | 2010-03-15 | 2011-09-22 | 日産化学工業株式会社 | Liquid crystal alignment agent containing end-modified polyamic acid ester, and liquid crystal alignment film |
CN102445790B (en) * | 2010-10-06 | 2016-05-18 | 株式会社日本显示器 | Alignment films, composition for forming alignment film and liquid crystal indicator |
WO2012053525A1 (en) * | 2010-10-19 | 2012-04-26 | 日産化学工業株式会社 | Liquid crystal aligning agent suitable for photo-alignment process, and liquid crystal alignment film using same |
EP2634220B1 (en) | 2010-10-28 | 2017-05-03 | Kaneka Corporation | Process for production of electrically conductive polyimide film |
JP5285729B2 (en) * | 2011-03-03 | 2013-09-11 | 株式会社ジャパンディスプレイ | Liquid crystal display |
JP5292438B2 (en) * | 2011-05-23 | 2013-09-18 | 株式会社ジャパンディスプレイ | Liquid crystal display |
KR101848962B1 (en) | 2011-06-21 | 2018-04-13 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal orientation agent for photo-orientation treatment method and liquid crystal orientation film using same |
SG10201607603VA (en) * | 2011-10-10 | 2016-11-29 | Brewer Science Inc | Spin-on carbon compositions for lithographic processing |
WO2013054858A1 (en) | 2011-10-12 | 2013-04-18 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
KR101988067B1 (en) * | 2011-12-28 | 2019-06-11 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal display element, method for manufacturing liquid crystal display element, and polymerizable compound |
TWI486335B (en) * | 2011-12-29 | 2015-06-01 | Eternal Materials Co Ltd | Base generator |
WO2013111836A1 (en) * | 2012-01-26 | 2013-08-01 | 日産化学工業株式会社 | Method for preparing polyimide varnish, and liquid crystal aligning agent |
WO2014208704A1 (en) * | 2013-06-27 | 2014-12-31 | 宇部興産株式会社 | Polyimide precursor and polyimide |
JP6147148B2 (en) * | 2013-09-03 | 2017-06-14 | 株式会社ジャパンディスプレイ | Alignment film material and liquid crystal display device using the same |
JP6400284B2 (en) | 2013-10-22 | 2018-10-03 | 株式会社ジャパンディスプレイ | Liquid crystal display |
JP6329380B2 (en) | 2014-02-07 | 2018-05-23 | 株式会社ジャパンディスプレイ | Manufacturing method and manufacturing apparatus for liquid crystal display device |
CN106795283B (en) * | 2014-09-02 | 2020-07-10 | 东丽株式会社 | Resin and photosensitive resin composition |
CN105446012A (en) | 2014-09-19 | 2016-03-30 | 株式会社日本显示器 | Liquid crystal display device and material for alignment film |
JP2016066053A (en) | 2014-09-19 | 2016-04-28 | 株式会社ジャパンディスプレイ | Liquid crystal display device and material for alignment film |
JP6461544B2 (en) * | 2014-10-08 | 2019-01-30 | 株式会社ジャパンディスプレイ | Liquid crystal display device and manufacturing method thereof |
JP6701635B2 (en) * | 2014-10-08 | 2020-05-27 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
JP6461548B2 (en) * | 2014-10-14 | 2019-01-30 | 株式会社ジャパンディスプレイ | Liquid crystal display device and manufacturing method thereof |
TWI701270B (en) | 2014-12-22 | 2020-08-11 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
JP2017090781A (en) * | 2015-11-13 | 2017-05-25 | 株式会社ジャパンディスプレイ | Varnish for optical alignment film and liquid crystal display |
KR20180103120A (en) * | 2016-01-20 | 2018-09-18 | 제이엑스티지 에네루기 가부시키가이샤 | Process for producing polyimide film, polyimide film, polyamic acid solution and photosensitive composition |
JP6747091B2 (en) * | 2016-06-23 | 2020-08-26 | 富士ゼロックス株式会社 | Porous film and method for producing the same |
WO2018051888A1 (en) * | 2016-09-13 | 2018-03-22 | Jxtgエネルギー株式会社 | Polyimide, polyamic acid, solutions thereof, and film using polyimide |
JP6873790B2 (en) * | 2017-03-31 | 2021-05-19 | 株式会社ジャパンディスプレイ | Varnish for photoalignment film and liquid crystal display device |
-
2016
- 2016-07-19 JP JP2016141379A patent/JP7076939B2/en active Active
-
2017
- 2017-07-12 US US15/647,322 patent/US10947345B2/en active Active
- 2017-07-18 CN CN201710589519.1A patent/CN107632461B/en active Active
- 2017-07-18 CN CN202110198214.4A patent/CN112764274A/en active Pending
-
2021
- 2021-02-02 US US17/164,973 patent/US11384204B2/en active Active
-
2022
- 2022-06-17 US US17/842,922 patent/US20220315703A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013115228A1 (en) * | 2012-02-01 | 2013-08-08 | 日産化学工業株式会社 | Novel diamine, polymer, liquid crystal alignment agent, and liquid crystal alignment film, and liquid crystal display element using same |
WO2013157586A1 (en) * | 2012-04-18 | 2013-10-24 | 日産化学工業株式会社 | Liquid-crystal alignment material for use in photo-alignment method, liquid-crystal alignment film, and liquid-crystal display element |
US10947345B2 (en) * | 2016-07-19 | 2021-03-16 | Japan Display Inc. | Varnish for photo alignment film and liquid crystal display device |
US11384204B2 (en) * | 2016-07-19 | 2022-07-12 | Japan Display Inc. | Varnish for photo alignment film and liquid crystal display device |
Also Published As
Publication number | Publication date |
---|---|
JP7076939B2 (en) | 2022-05-30 |
JP2018013532A (en) | 2018-01-25 |
US20180022874A1 (en) | 2018-01-25 |
CN112764274A (en) | 2021-05-07 |
US20210155755A1 (en) | 2021-05-27 |
US11384204B2 (en) | 2022-07-12 |
CN107632461B (en) | 2021-07-27 |
US10947345B2 (en) | 2021-03-16 |
CN107632461A (en) | 2018-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11384204B2 (en) | Varnish for photo alignment film and liquid crystal display device | |
TWI407211B (en) | A liquid crystal alignment agent and a liquid crystal display device using the liquid crystal display device | |
JP5773177B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
JP4404090B2 (en) | Liquid crystal aligning agent for photo-alignment and liquid crystal display device using the same | |
US20170137667A1 (en) | Varnish for photo alignment film and liquid crystal display device | |
JP6702373B2 (en) | Liquid crystal aligning agent | |
US6294639B1 (en) | Liquid crystal aligning agent | |
US20110109857A1 (en) | Liquid crystal display device | |
US20150323837A1 (en) | Liquid crystal display device and method for fabticating the same | |
KR101589328B1 (en) | Liquid crystal aligning agent and liquid crystal display element using same | |
TWI628232B (en) | Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element | |
JP6314827B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
JPWO2006070819A1 (en) | Liquid crystal aligning agent for vertical alignment, liquid crystal alignment film, and liquid crystal display device using the same | |
JP5751171B2 (en) | Liquid crystal alignment treatment agent and liquid crystal display element using the same | |
TW201736440A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
KR101613755B1 (en) | Liquid crystal aligning agent and liquid crystal element using same | |
TWI359175B (en) | ||
JP4171851B2 (en) | Liquid crystal alignment treatment agent | |
WO2018043326A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
TWI756256B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same | |
KR19980048480A (en) | A photo-alignment composition, an alignment film formed therefrom, and a liquid crystal display element having the alignment film | |
JP6888071B2 (en) | Varnish for photoalignment film and liquid crystal display device | |
CN108690493B (en) | Varnish for photo-alignment film and liquid crystal display device | |
JP2006243595A (en) | Liquid crystal alignment film and its evaluating method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
AS | Assignment |
Owner name: JAPAN DISPLAY INC., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SONODA, HIDEHIRO;HIROTA, TAKENORI;TOMIOKA, YASUSHI;AND OTHERS;SIGNING DATES FROM 20170614 TO 20170620;REEL/FRAME:065267/0218 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: AWAITING TC RESP., ISSUE FEE NOT PAID |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: WITHDRAW FROM ISSUE AWAITING ACTION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |