JP2007133184A - Photo-alignment film for novel polarizing element - Google Patents
Photo-alignment film for novel polarizing element Download PDFInfo
- Publication number
- JP2007133184A JP2007133184A JP2005326637A JP2005326637A JP2007133184A JP 2007133184 A JP2007133184 A JP 2007133184A JP 2005326637 A JP2005326637 A JP 2005326637A JP 2005326637 A JP2005326637 A JP 2005326637A JP 2007133184 A JP2007133184 A JP 2007133184A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- photo
- compound
- composition
- alignment
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 60
- -1 Bisamide compound Chemical class 0.000 claims description 58
- 239000004973 liquid crystal related substance Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 3
- 239000002052 molecular layer Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 60
- 239000010409 thin film Substances 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 4
- 230000002535 lyotropic effect Effects 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- KOQYGXVZECYCFC-UHFFFAOYSA-N 2-[4-[[4-(dimethylamino)phenyl]diazenyl]phenoxy]undecanoic acid Chemical compound CN(C1=CC=C(C=C1)N=NC1=CC=C(OC(C(=O)O)CCCCCCCCC)C=C1)C KOQYGXVZECYCFC-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CQKQINNUKSBEQR-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]diazenyl]phenol Chemical compound CN(C)c1ccc(cc1)N=Nc1ccc(O)cc1 CQKQINNUKSBEQR-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007699 photoisomerization reaction Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- DQFMPTUTAAIXAN-UHFFFAOYSA-N 4,4-dimethyl-1h-imidazol-5-one Chemical compound CC1(C)NC=NC1=O DQFMPTUTAAIXAN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NOLJPCPMOUBRJN-UHFFFAOYSA-N 2-bromoundecanoic acid Chemical compound CCCCCCCCCC(Br)C(O)=O NOLJPCPMOUBRJN-UHFFFAOYSA-N 0.000 description 3
- STOOUUMSJPLRNI-UHFFFAOYSA-N 5-amino-4-hydroxy-3-[[4-[4-[(4-hydroxyphenyl)diazenyl]phenyl]phenyl]diazenyl]-6-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC(=CC=3)C=3C=CC(=CC=3)N=NC=3C=CC(O)=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 STOOUUMSJPLRNI-UHFFFAOYSA-N 0.000 description 3
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229940043264 dodecyl sulfate Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- RZRILSWMGXWSJY-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;sulfuric acid Chemical compound OS(O)(=O)=O.OCCN(CCO)CCO RZRILSWMGXWSJY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PTIWCWYYGIRDIZ-UHFFFAOYSA-K Durazol blue 4R Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(cc3cc(cc(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O PTIWCWYYGIRDIZ-UHFFFAOYSA-K 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 2
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- PHBXSOKXCTZJBO-UHFFFAOYSA-L disodium 7-amino-4-hydroxy-3-[[4-[4-[(1-hydroxy-4-sulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(ccc1N=Nc1cc(c2ccccc2c1O)S([O-])(=O)=O)-c1ccc(N=Nc2c(O)c3ccc(N)cc3cc2S([O-])(=O)=O)c(OC)c1 PHBXSOKXCTZJBO-UHFFFAOYSA-L 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- AVERNFJXXRIVQN-XSDYUOFFSA-N 5-[(4-ethoxyphenyl)diazenyl]-2-[(e)-2-[4-[(4-ethoxyphenyl)diazenyl]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C1=CC(OCC)=CC=C1N=NC(C=C1S(O)(=O)=O)=CC=C1\C=C\C1=CC=C(N=NC=2C=CC(OCC)=CC=2)C=C1S(O)(=O)=O AVERNFJXXRIVQN-XSDYUOFFSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- UFUQRRYHIHJMPB-DUCFOALUSA-L Sirius red 4B Chemical compound [Na+].[Na+].OS(=O)(=O)c1cc2cc(NC(=O)c3ccccc3)ccc2c([O-])c1\N=N\c1ccc(cc1)\N=N\c1ccc(cc1)S([O-])(=O)=O UFUQRRYHIHJMPB-DUCFOALUSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- IJPIIGZZYMQGNJ-UHFFFAOYSA-N [4-(2-phenylethenyl)-1-prop-2-enoyloxycyclohexa-2,4-dien-1-yl] prop-2-enoate Chemical compound C1=CC(OC(=O)C=C)(OC(=O)C=C)CC=C1C=CC1=CC=CC=C1 IJPIIGZZYMQGNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- BPHHNXJPFPEJOF-UHFFFAOYSA-J chembl296966 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=C(N)C2=C(O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=C4C(N)=C(C=C(C4=CC=3)S([O-])(=O)=O)S([O-])(=O)=O)O)OC)=CC=C21 BPHHNXJPFPEJOF-UHFFFAOYSA-J 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- JWTNYFWHDZSFKD-UHFFFAOYSA-G dicopper trisodium 7-[[4-[4-[(6-anilino-1-oxido-3-sulfonatonaphthalen-2-yl)diazenyl]-3-oxidophenyl]-2-oxidophenyl]diazenyl]-8-oxidonaphthalene-1,6-disulfonate Chemical compound C1=CC=C(C=C1)NC2=CC3=CC(=C(C(=C3C=C2)[O-])N=NC4=C(C=C(C=C4)C5=CC(=C(C=C5)N=NC6=C(C=C7C=CC=C(C7=C6[O-])S(=O)(=O)[O-])S(=O)(=O)[O-])[O-])[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Cu+2].[Cu+2] JWTNYFWHDZSFKD-UHFFFAOYSA-G 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- PBOIUUROGJVVNC-UHFFFAOYSA-L disodium 2-hydroxy-5-[[4-[[2-methoxy-4-[(3-sulfonatophenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].COc1cc(ccc1NC(=O)Nc1ccc(cc1)N=Nc1ccc(O)c(c1)C([O-])=O)N=Nc1cccc(c1)S([O-])(=O)=O PBOIUUROGJVVNC-UHFFFAOYSA-L 0.000 description 1
- FCCOTXHFDDRSDO-UHFFFAOYSA-L disodium 5-[[4-[[4-[(3-carboxylato-4-hydroxyphenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]-2-hydroxybenzoate Chemical compound [Na+].[Na+].Oc1ccc(cc1C([O-])=O)N=Nc1ccc(NC(=O)Nc2ccc(cc2)N=Nc2ccc(O)c(c2)C([O-])=O)cc1 FCCOTXHFDDRSDO-UHFFFAOYSA-L 0.000 description 1
- SLZCDQVDTBWJND-UHFFFAOYSA-L disodium 8-[[4-[4-[(4-ethoxyphenyl)diazenyl]-3-methylphenyl]-2-methylphenyl]diazenyl]-7-hydroxynaphthalene-1,3-disulfonate Chemical compound CCOC1=CC=C(C=C1)N=NC2=C(C=C(C=C2)C3=CC(=C(C=C3)N=NC4=C(C=CC5=CC(=CC(=C54)S(=O)(=O)O)S(=O)(=O)[O-])[O-])C)C.[Na+].[Na+] SLZCDQVDTBWJND-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical group C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OLSOUGWNONTDCK-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=CC4=CC(=CC(N)=C4C=3O)S([O-])(=O)=O)S([O-])(=O)=O)OC)=C(O)C2=C1N OLSOUGWNONTDCK-UHFFFAOYSA-J 0.000 description 1
- XRFRTDKENRGSSX-UHFFFAOYSA-J tetrasodium;3-[[4-[[4-[(4,8-disulfonatonaphthalen-2-yl)diazenyl]-3-methylphenyl]carbamoylamino]-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N=NC3=CC=C(NC(=O)NC=4C=C(C)C(N=NC=5C=C6C(=CC=CC6=C(C=5)S([O-])(=O)=O)S([O-])(=O)=O)=CC=4)C=C3C)=CC(S([O-])(=O)=O)=C21 XRFRTDKENRGSSX-UHFFFAOYSA-J 0.000 description 1
- WNQPPENQFWLADQ-UHFFFAOYSA-J tetrasodium;4-hydroxy-5-[[4-[[4-[(8-hydroxy-3,6-disulfonatonaphthalen-1-yl)diazenyl]-2-methoxy-5-methylphenyl]carbamoylamino]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(O)=C2C(N=NC3=C(C)C=C(C(=C3)OC)NC(=O)NC3=CC(C)=C(N=NC=4C5=C(O)C=C(C=C5C=C(C=4)S([O-])(=O)=O)S([O-])(=O)=O)C=C3OC)=CC(S([O-])(=O)=O)=CC2=C1 WNQPPENQFWLADQ-UHFFFAOYSA-J 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は、ビスアミド化合物、それを含有する光配向膜用組成物、その製造方法、光配向膜、これを用いる偏光素子および液晶表示装置に関する。
二色性分子を配向させる方法として延伸法と塗布法がある。塗布法は、例えばガラス基板上にポリイミド膜を形成し、ラビング処理により配向膜としたのち、二色性分子溶液を塗布することにより該分子を配向させるラビング法などが知られている。しかし、ラビング法ではラビング処理の際に生ずる塵や静電気により、調製された配向膜の配向特性が低下する問題があった。そこで近年ラビング処理を行わない液晶配向制御技術が注目されている。とりわけ、偏光を利用した光配向法は簡便であり、盛んに研究が行われている。この光配向法は、基板上に設けられた光配向性の膜に偏光を照射して、該膜に液晶配向性を持たせた後、二色性分子溶液を塗布することによって自己組織化的に該分子を配向させる方法である。
例えば特許文献１では光異性化可能であって、二色性を有する基を含む樹脂の皮膜に偏光を照射してなる液晶配向膜が開示されている。
特許文献２ではアクリレートの高分子の側鎖に適当なスペーサーを介してアゾベンゼンのような光配向性基を導入した高分子材料が開示されている。
特許文献３では１分子中に２個以上の重合性基を有する二色性染料を含有する光配向膜用材料を基板上に塗布し、偏光を照射して光配向機能を付与した後、加熱又は光を照射することにより重合性基を重合させることによって光配向膜を得る方法が開示されている。
また特許文献４では４，４−ビスアクリロイルオキシスチルベン等のモノマーを基板上に塗布し、偏光を照射して反応させることによって光配向膜を得る方法が開示されている。
またnagaseらは非特許文献１において芳香族ポリアミドのような耐熱性のある高分子に光配向性基を導入した場合に直線偏光照射によりアミド結合部が光酸化反応によって異方性をもち配向することを報告している。
The present invention relates to a bisamide compound, a composition for a photo-alignment film containing the same, a method for producing the same, a photo-alignment film, a polarizing element using the same, and a liquid crystal display device.
There are a stretching method and a coating method as methods for orienting the dichroic molecules. As a coating method, for example, a rubbing method is known in which a polyimide film is formed on a glass substrate, an alignment film is formed by rubbing treatment, and then the molecules are aligned by applying a dichroic molecule solution. However, the rubbing method has a problem that the alignment characteristics of the prepared alignment film deteriorate due to dust and static electricity generated during the rubbing treatment. Therefore, in recent years, a liquid crystal alignment control technique that does not perform rubbing has been attracting attention. In particular, a photo-alignment method using polarized light is simple and actively researched. In this photo-alignment method, a photo-alignment film provided on a substrate is irradiated with polarized light to give the film a liquid crystal orientation, and then a dichroic molecule solution is applied to form a self-organizing method. In which the molecules are oriented.
For example, Patent Document 1 discloses a liquid crystal alignment film that is photoisomerizable and is formed by irradiating polarized light onto a resin film containing a dichroic group.
Patent Document 2 discloses a polymer material in which a photoalignable group such as azobenzene is introduced into a side chain of a polymer of acrylate via a suitable spacer.
In Patent Document 3, a material for a photo-alignment film containing a dichroic dye having two or more polymerizable groups in one molecule is applied on a substrate and irradiated with polarized light to give a photo-alignment function, followed by heating. Or the method of obtaining a photo-alignment film | membrane by polymerizing a polymeric group by irradiating light is disclosed.
Patent Document 4 discloses a method of obtaining a photo-alignment film by applying a monomer such as 4,4-bisacryloyloxystilbene on a substrate and reacting it by irradiating polarized light.
Also, in Non-Patent Document 1, nagase et al., When a photo-alignment group is introduced into a heat-resistant polymer such as an aromatic polyamide, the amide bond portion is oriented with anisotropy by a photo-oxidation reaction by linearly polarized light irradiation. It is reported that.
特許文献１で開示された方法によれば二色性を有する基を含む樹脂溶液を基板上に塗布して得られる樹脂の皮膜に偏光を照射して配向させた後、樹脂を架橋することにより配向の状態を固定化するが、偏光照射によって二色性を有する構成単位を配向させる際に、樹脂構造が妨げとなって十分な配向性が得られないといった問題がある。 According to the method disclosed in Patent Document 1, a resin solution containing a dichroic group is applied on a substrate, and the resin film is oriented by irradiating polarized light and then crosslinking the resin. Although the state of orientation is fixed, there is a problem that when the structural unit having dichroism is oriented by irradiation with polarized light, the resin structure is obstructed and sufficient orientation cannot be obtained.
特許文献２ではアクリレートの高分子の側鎖に適当なスペーサーを介してアゾベンゼンのような光配向性基を導入した高分子材料を用いるが、高分子主鎖の耐熱性が低いこと及び水溶性の液晶を配向させて偏光膜を形成する場合、アクリレート高分子の脂溶性の高さから液晶の濡れ性が悪く均一に塗膜できないという問題がある。 In Patent Document 2, a polymer material in which a photo-alignment group such as azobenzene is introduced into a side chain of an acrylate polymer via an appropriate spacer is used, but the heat resistance of the polymer main chain is low and water-soluble When the polarizing film is formed by aligning the liquid crystal, there is a problem that the wettability of the liquid crystal is poor due to the high lipophilicity of the acrylate polymer, and the film cannot be uniformly coated.
特許文献３では偏光を照射して光配向機能を付与した後に配向性基を固定化しているので、重合過程における分子揺らぎの影響により、配向が一部乱され、液晶配向能に影響がでる問題がある。 In Patent Document 3, since the orientation group is fixed after irradiating polarized light and imparting the photo-alignment function, the alignment is partially disturbed by the influence of molecular fluctuation in the polymerization process, and the liquid crystal alignment ability is affected. There is.
特許文献４では偏光で重合反応を行うので重合が均一に進まず、未反応のモノマーが一部残存することがあり、液晶の配向特性が一部低下する問題がある。 In Patent Document 4, since the polymerization reaction is carried out with polarized light, the polymerization does not proceed uniformly, and some unreacted monomers may remain, and there is a problem that the alignment characteristics of the liquid crystal partially deteriorate.
非特許文献１では芳香族ポリアミドのような耐熱性のある高分子に光配向性基を導入した場合には、直線偏光照射による光酸化反応によってアミド結合部が異方性をもち配向するが、主鎖及び側鎖に光配向性基が共存するとその配向特性が著しく低下することが報告されている。さらに本配向法においては偏光方向の光を吸収することにより光酸化反応が起きるため直線偏光方向に対して平行に異方性を持つようになり、光異性化を伴わない液晶分子は直線偏向方向に対して平行に配向する。しかしアゾベンゼンのような光異性化を伴う光配向性基の場合、直線偏光を吸収しない方向すなわち直線偏光に対して垂直に配向するため、光分解の場合とクロスしてしまい配向特性を大きく損なってしまう問題がある。 In Non-Patent Document 1, when a photo-alignment group is introduced into a heat-resistant polymer such as an aromatic polyamide, the amide bond part is oriented with anisotropy by a photo-oxidation reaction by linearly polarized light irradiation. It has been reported that when photo-alignment groups coexist in the main chain and the side chain, the alignment characteristics are remarkably deteriorated. Furthermore, in this alignment method, a photo-oxidation reaction takes place by absorbing light in the polarization direction, so that it has anisotropy parallel to the linear polarization direction, and the liquid crystal molecules without photoisomerization are in the linear deflection direction. Oriented parallel to However, in the case of a photo-alignable group with photoisomerization such as azobenzene, it is aligned perpendicularly to the direction of linearly polarized light that does not absorb linearly polarized light. There is a problem.
本発明が解決しようとする課題は、リオトロピック液晶性二色性色素の配向性の優れる塗布型偏光膜に用いられる光配向膜とその製造方法およびこれを用いた偏光素子による液晶表示装置を提供することにある。 The problem to be solved by the present invention is to provide a photo-alignment film used for a coating-type polarizing film having excellent orientation of a lyotropic liquid crystalline dichroic dye, a manufacturing method thereof, and a liquid crystal display device using a polarizing element using the same. There is.
本発明者等は斯かる観点から、鋭意検討した結果、本発明に至った。
すなわち本発明は、
（１）
一般式（１）
（２）
上記式（１）においてｐが１のビスアミド化合物を含み、さらにｐが２ないし５のビスアミド化合物を少なくとも一種類含有する光配向膜用組成物
（３）
上記式（１）においてｐが１のビスアミド化合物の比率が４０〜６０％であり、残分がｐが２ないし５のビスアミド化合物である（２）に記載の光配向膜用組成物
（４）
下記式（ａ）
（５）
一般式（ａ）、（ｂ）および（ｃ）で表される化合物の比率がモル比で式（ａ）の化合物が１に対して式（ｂ）の化合物が１．１ないし２であり、式（ｃ）の化合物が０．５ないし０．６である（４）に記載の光配向膜用組成物の製造方法
（６）
一般式（２）
（７）
一般式（１）で表されるアミド化合物および一般式（２）で表されるアミド化合物を含有する光配向膜用組成物
（８）
一般式（１）で表されるアミド化合物および一般式（２）で表されるアミド化合物の比率が重量比で後者が１に対して前者が１ないし２である（７）に記載の光配向膜用組成物
（９）
（２）、（３）、（７）、（８）のいずれか一項に記載の組成物からなる光配向膜
（１０）
基板上に（９）に記載の配向膜を有し、さらにその上に二色性分子層を有することを特徴とする偏光素子
（１１）
対向する上下基板を有する液晶表示装置であって、該上下基板の少なくとも一方が（１０）に記載の偏光素子を有する基板である液晶表示装置
に関する。
As a result of intensive studies from such a viewpoint, the present inventors have arrived at the present invention.
That is, the present invention
(1)
General formula (1)
A photoalignment film composition (3) comprising a bisamide compound wherein p is 1 in the above formula (1) and further containing at least one bisamide compound wherein p is 2 to 5
The composition for a photoalignment film (4) according to (2), wherein the ratio of the bisamide compound in which p is 1 in the formula (1) is 40 to 60%, and the balance is a bisamide compound in which p is 2 to 5
The following formula (a)
The ratio of the compounds represented by the general formulas (a), (b) and (c) is 1.1 to 2 in terms of the molar ratio of the compound of the formula (a) to 1 in the compound of the formula (a), (6) The method for producing a composition for photo-alignment films according to (4), wherein the compound of formula (c) is 0.5 to 0.6
General formula (2)
Composition for photoalignment film (8) containing amide compound represented by general formula (1) and amide compound represented by general formula (2)
The photo-alignment according to (7), wherein the ratio of the amide compound represented by the general formula (1) and the amide compound represented by the general formula (2) is a weight ratio, the latter being 1 and the former being 1 to 2 Film composition (9)
(2), (3), (7), a photo-alignment film (10) comprising the composition according to any one of (8)
A polarizing element (11) having the alignment film according to (9) on a substrate and further having a dichroic molecular layer thereon
The present invention relates to a liquid crystal display device having opposing upper and lower substrates, wherein at least one of the upper and lower substrates is a substrate having the polarizing element described in (10).
本発明により、親水性の二色性物質の配向に使用でき、耐熱性も良好で、可視光偏光で配向し、その結果光分解が少なく、かつ低エネルギーで配向させることができる偏光素子用配向膜が得られる。また本発明の配向膜用化合物は非重合性化合物なので合成と精製が簡便である。さらにこの配向膜を用いた偏光素子は塗布型偏光素子としては良好な二色性比を示す。 According to the present invention, it can be used for the alignment of hydrophilic dichroic substances, has good heat resistance, is aligned with visible light polarization, and as a result, has little photodecomposition and can be aligned with low energy. A membrane is obtained. In addition, since the alignment film compound of the present invention is a non-polymerizable compound, synthesis and purification are simple. Furthermore, a polarizing element using this alignment film exhibits a good dichroic ratio as a coating type polarizing element.
本発明の光配向膜用組成物は一分子中に少なくとも一つ以上のジアルキルアミノ基および光異性化により配向性を示す光配向性基を有する低分子もしくはオリゴマーアミド化合物の組成物であり、分子の長さの異なる物質同士が絡み合うことによってアモルファス薄膜を形成するものである。すなわち高分子主鎖中に光配向性基を有する場合に生じる高分子構造に特有の配向特性の低下を、オリゴマーとすることにより改善し、スムーズに光異性化を生じさせることができるようにしたものである。またアミド化合物であることからガラス基板上などに設けた薄膜に、水溶性色素を直接塗布する際の濡れ性を向上させることができ、その結果として均一な配向膜を形成することも可能となった。さらにポリアミドにおいては光酸化分解が３１３ｎｍより短い波長の紫外光で顕著に起こることから、深色基であるジアルキルアミノ基をオリゴマーアミド化合物に導入し、オリゴマーアミド化合物を含有する組成物の吸収光波長を長波長化することにより、可視光の照射で光異性化を行うことができるように改良し、この結果、光分解を抑えることが可能となった。 The composition for a photoalignment film of the present invention is a composition of a low-molecular or oligomeric amide compound having at least one dialkylamino group in one molecule and a photoalignment group that exhibits orientation by photoisomerization, An amorphous thin film is formed by intertwining substances having different lengths. In other words, the degradation of the alignment characteristics peculiar to the polymer structure that occurs when the polymer main chain has a photo-alignment group has been improved by using an oligomer, so that photoisomerization can be caused smoothly. Is. In addition, since it is an amide compound, it is possible to improve wettability when a water-soluble dye is directly applied to a thin film provided on a glass substrate or the like, and as a result, a uniform alignment film can be formed. It was. Furthermore, in polyamide, photo-oxidative decomposition occurs remarkably with ultraviolet light having a wavelength shorter than 313 nm. Therefore, a dialkylamino group that is a deep color group is introduced into the oligomer amide compound, and the absorbed light wavelength of the composition containing the oligomer amide compound By making the wavelength longer, it was improved so that photoisomerization can be performed by irradiation with visible light, and as a result, it became possible to suppress photolysis.
従って本発明の偏光素子は、光配向性基を有するオリゴマー組成物を用いて調整した薄膜の高度な配向性を利用し、その上に形成されるリオトロピック液晶性を有する二色性分子層の配向をも十分に制御し得るものであることを特徴とするものである。 Therefore, the polarizing element of the present invention utilizes the high degree of orientation of the thin film prepared using the oligomer composition having a photo-orienting group, and the orientation of the dichroic molecular layer having lyotropic liquid crystal properties formed thereon. It is also possible to sufficiently control the above.
本発明の第一の発明であるビスアミド化合物は、上記式（１）で表される化合物である。この化合物は、直線偏光照射により光配向性基の分子軸配向変化を起こすものである。ここで言う分子軸配向変化とは、直線偏光の光エネルギーを吸収した後に、その分子軸の方向がその直線偏光に応じて一定方向に変わる現象を意味する。 The bisamide compound which is the first invention of the present invention is a compound represented by the above formula (1). This compound causes a change in the molecular axis orientation of the photoalignable group by irradiation with linearly polarized light. The term “change in molecular axis orientation” as used herein means a phenomenon in which the direction of the molecular axis changes in a certain direction according to the linearly polarized light after absorbing the light energy of the linearly polarized light.
上記一般式（１）においてＲ1〜Ｒ4およびＲ7〜Ｒ10は各々独立に、Ｃ１〜Ｃ４アルキル基を表す。ｎは８〜１２までの整数を、ｐは１〜５までの整数を表す。Ｒ1〜Ｒ4およびＲ7〜Ｒ10として好ましい基はＣ１〜Ｃ４からなる直鎖、分岐鎖及び環状のアルキル基であり、具体例としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、２−ブチル基、イソブチル基、ｔ−ブチル基、シクロブチル基が挙げられる。より好ましいＲ1〜Ｒ4およびＲ7〜Ｒ10はメチル基またはエチル基であり、より好ましいｐは１または２であり、より好ましいｎは９〜１１である。特に好ましくは下記式（３）においてＲ1〜Ｒ4がメチル基であり、ｐが１でｎが１０である。 In the general formula (1), R 1 to R 4 and R 7 to R 10 each independently represent a C 1 to C 4 alkyl group. n represents an integer from 8 to 12, and p represents an integer from 1 to 5. Preferred groups as R 1 to R 4 and R 7 to R 10 are linear, branched and cyclic alkyl groups composed of C1 to C4, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , Cyclopropyl group, n-butyl group, 2-butyl group, isobutyl group, t-butyl group, and cyclobutyl group. More preferable R 1 to R 4 and R 7 to R 10 are a methyl group or an ethyl group, more preferable p is 1 or 2, and more preferable n is 9 to 11. Particularly preferably, in the following formula (3), R 1 to R 4 are methyl groups, p is 1 and n is 10.
本発明の第二の発明である光配向膜用組成物は、上記式（１）におけるｐが１のビスアミド化合物を含み、さらにｐが２ないし５のビスアミド化合物を少なくとも一種類含有する。ｐが１のビスアミド化合物の比率が４０〜６０％であり、残分がｐが２ないし５のビスアミド化合物であるものが好ましい。この配合比率はＬＣ−ＭＳの面積比により分析できる。 The composition for photo-alignment films according to the second invention of the present invention contains a bisamide compound in which p in the above formula (1) is 1, and further contains at least one bisamide compound in which p is 2 to 5. It is preferable that the ratio of the bisamide compound in which p is 1 is 40 to 60%, and the remainder is a bisamide compound in which p is 2 to 5. This blending ratio can be analyzed by the LC-MS area ratio.
本発明の第三の発明である光配向膜用組成物の製造方法は上記式（ａ）で示される化合物と上記式（ｂ）で示される化合物を縮合して得られた化合物と、上記式（ｃ）で示される化合物とをさらに縮合することを特徴とする。上記式（ａ）におけるＲ12およびＲ13は前記式（１）におけるＲ1〜Ｒ4と同じものが好ましい。上記式（ｂ）におけるＧはハロゲン原子を、ｎは８〜１２の整数を表す。ハロゲン原子としては臭素、塩素が好ましい。ｎは９〜１１が好ましい。上記式（ｃ）におけるＲ7およびＲ10は前記式（１）におけるＲ1〜Ｒ4と同じものが好ましい。上記式（ａ）で示される化合物の製造方法としては例えばアミノフェノールのアミノ基をジアゾ化し、ジアルキルアニリンに酸性下でカップリングすることなどにより得られる。アルキル基としてはメチル基、エチル基が好ましい。カップリング反応時における反応系内のｐＨは３から６が好ましく、より好ましくは４程度である。上記式（ａ）と上記式（ｂ）との縮合反応は通常、式（ａ）と式（ｂ）をモル比で式（ａ）が１に対して、式（ｂ）を２の比率で縮合する。好ましくは式（ａ）が１に対して式（ｂ）を１．５の比率で、より好ましくは式（ａ）が１に対して式（ｂ）を１．２の比率で縮合する。溶媒としてはＣ１〜Ｃ４アルコールなどが好ましく、より好ましくはエタノール、ＩＰＡ（イソプロパノール）などである。触媒としてはアルカリ金属水酸化物などの強塩基が用いられ、好ましくは水酸化カリウム、水酸化ナトリウムなどである。また上記式（ａ）と上記式（ｂ）との縮合により得られた化合物と上記式（ｃ）との縮合反応はモル比で式（ａ）と式（ｂ）との縮合により得られた化合物が１に対して式（ｃ）の化合物を０．５または０．６として行うのが好ましい。縮合剤としてはリン系縮合剤が好ましく、具体例としては亜燐酸トリフェニルが挙げられる。この際、添加剤として芳香族アミンなど、例えばピリジンを用いることが好ましい。反応溶媒としては非プロトン性アミド系などの極性溶媒が好ましく、具体例としてはジメチルホルムアミド、Ｎ−メチルピロリジノン、ジメチルアセトアミド、ジメチルイミダゾリノンおよびジメチルスルホキシド等が挙げられる。 A method for producing a composition for a photoalignment film, which is the third invention of the present invention, comprises a compound obtained by condensing a compound represented by the above formula (a) and a compound represented by the above formula (b), and the above formula. The compound represented by (c) is further condensed. R 12 and R 13 in the formula (a) are preferably the same as R 1 to R 4 in the formula (1). In the above formula (b), G represents a halogen atom, and n represents an integer of 8-12. The halogen atom is preferably bromine or chlorine. n is preferably 9 to 11. R 7 and R 10 in the formula (c) are preferably the same as R 1 to R 4 in the formula (1). As a method for producing the compound represented by the above formula (a), for example, the amino group of aminophenol is diazotized and coupled to dialkylaniline under acidic conditions. The alkyl group is preferably a methyl group or an ethyl group. The pH in the reaction system during the coupling reaction is preferably 3 to 6, more preferably about 4. In the condensation reaction of the above formula (a) and the above formula (b), the formula (a) and the formula (b) are usually in a molar ratio, the formula (a) is 1 and the formula (b) is 2 in ratio. To condense. Preferably, formula (a) is condensed at a ratio of 1.5 to formula (b), more preferably formula (a) at a ratio of 1.2 to formula (b). As a solvent, C1-C4 alcohol etc. are preferable, More preferably, they are ethanol, IPA (isopropanol), etc. As the catalyst, a strong base such as an alkali metal hydroxide is used, and potassium hydroxide, sodium hydroxide and the like are preferable. The condensation reaction between the compound obtained by the condensation of the above formula (a) and the above formula (b) and the above formula (c) was obtained by the condensation of the formula (a) and the formula (b) in a molar ratio. It is preferred to carry out the compound of formula (c) as 0.5 or 0.6 with respect to 1. The condensing agent is preferably a phosphorus condensing agent, and specific examples include triphenyl phosphite. At this time, it is preferable to use an aromatic amine such as pyridine as an additive. The reaction solvent is preferably a polar solvent such as an aprotic amide, and specific examples include dimethylformamide, N-methylpyrrolidinone, dimethylacetamide, dimethylimidazolinone and dimethylsulfoxide.
本発明の第四の発明であるアミド化合物は上記一般式（２）で表される。上記一般式（２）においてＲ5およびＲ6は各々独立にＣ１〜Ｃ４アルキル基を表し、前記式（１）におけるＲ1〜Ｒ4と同じものが好ましい。ｍは８〜１２までの整数を表し、より好ましいｍは９〜１１である。ｐは１〜５までの整数を表し、より好ましいｐは１または２である。Ｘは−ＮＨ−または−ＮＲ11−で表される連結基を表し、Ｒ11はＣ１〜Ｃ４アルキル基を表す。Ｘとしては−ＮＨ−が好ましい。ＱはＣ１〜Ｃ４アルキル基を表し、具体例としては前記式（１）におけるＲ1〜Ｒ4と同じものが挙げられる。またＱとしては置換基を有しても良いアリール基も好ましく、具体例としてはフェニル、ナフチルなどがあげられる。Ｑとしてはフェニル基がさらに好ましい。 The amide compound according to the fourth aspect of the present invention is represented by the general formula (2). In the general formula (2), R 5 and R 6 each independently represent a C1 to C4 alkyl group, and the same as R 1 to R 4 in the formula (1) is preferable. m represents an integer of 8 to 12, and more preferably m is 9 to 11. p represents an integer of 1 to 5, and more preferably p is 1 or 2. X represents a linking group represented by —NH— or —NR 11 —, and R 11 represents a C1-C4 alkyl group. X is preferably -NH-. Q represents a C1~C4 alkyl group include the same R 1 to R 4 in Formula (1) as examples. Q is preferably an aryl group which may have a substituent, and specific examples thereof include phenyl and naphthyl. Q is more preferably a phenyl group.
本発明の第五の発明である光配向膜用組成物は一般式（１）で表されるアミド化合物および一般式（２）で表されるアミド化合物を含有する。一般式（１）で表されるアミド化合物および一般式（２）で表されるアミド化合物の比率が例えば重量比で後者が１に対して前者が１ないし２が好ましい。 The composition for photo-alignment films according to the fifth aspect of the present invention contains an amide compound represented by the general formula (1) and an amide compound represented by the general formula (2). The ratio of the amide compound represented by the general formula (1) and the amide compound represented by the general formula (2) is, for example, preferably 1 to 2 with respect to 1 for the latter and 1 to 2 for the latter.
本発明の光配向膜を調製するためには一般式（１）の化合物および一般式（１）で示されるｎの値が異なる化合物または一般式（２）で示される化合物のいずれかを少なくとも二種類以上特定の組成で配合しオリゴマー組成物とする必要がある。これらは任意の組成で配合することができるが好ましくは一般式（１）および一般式（２）の配合においてはｎ＝ｍであり、一般式（１）におけるｐ＝１と一般式（２）におけるｐ＝１を重量比で一般には２：１、好ましくは５：３、特に好ましくは３：２の組成で配合する。
またｎの値が異なる一般式（１）の化合物同士を配合する場合においては、一般式（１）のｐ＝２の化合物と一般式（１）のｐ＝１またはｐ＝４の化合物との配合のように、一方の化合物分子長にたいしておよそ半分もしくは倍の長さをもつような化合物を配合することが特に好ましい。このように分子長が異なる物質を配合することにより分子同士が絡み合いアモルファス状態を形成し製膜することができるものと考えられる。また配向特性を向上させるためには光配向性基の動くことができる自由な空間を確保する必要があるが、これは上記したような最適な配合を行うことにより実現することができる。
In order to prepare the photo-alignment film of the present invention, at least two of the compound represented by the general formula (1) and the compound represented by the general formula (1) having different values of n or the compound represented by the general formula (2) are used. It is necessary to mix more than one kind with a specific composition to make an oligomer composition. These can be blended in an arbitrary composition, but preferably n = m in the blends of the general formulas (1) and (2), and p = 1 in the general formula (1) and the general formula (2) P = 1 is generally blended in a weight ratio of 2: 1, preferably 5: 3, particularly preferably 3: 2.
When compounds of general formula (1) having different values of n are blended, the compound of p = 2 of general formula (1) and the compound of p = 1 or p = 4 of general formula (1) It is particularly preferable to blend a compound having a length approximately half or twice the molecular length of one compound, as in the blending. Thus, it is thought that by blending substances having different molecular lengths, molecules can be entangled to form an amorphous state to form a film. Further, in order to improve the alignment characteristics, it is necessary to secure a free space in which the photoalignable group can move. This can be realized by performing the optimum blending as described above.
これらの光配向性基を有するオリゴマーの吸収する光の波長は、可視光域のものにとどまらず紫外線や赤外線の領域のものも含まれる。これらの光配向性基を含有する薄膜に、該化合物が吸収する波長範囲を含む直線偏光を照射すると容易に分子軸配向変化を起こす。 The wavelength of light absorbed by the oligomer having these photo-alignment groups is not limited to the visible light region, but includes those in the ultraviolet or infrared region. When a thin film containing these photo-alignable groups is irradiated with linearly polarized light including a wavelength range that is absorbed by the compound, the molecular axis orientation is easily changed.
本発明の第六の発明である光配向膜において光配向性基を有する化合物の薄膜を基板上（基板としては、ガラス、或いはポリカーボネート、ポリエステルのようなプラスチック基板が用いられる）に設ける方法としては、回転塗布法が好ましい。又、この種のオリゴマー組成物薄膜をラングミュアーブロジェット法によって基板上に設けても良い。更には、これらのオリゴマー組成物溶液に基板を浸漬して吸着させても良い。膜厚は、通常０．００１〜５μｍ、好ましくは０．０１〜１μｍである。これらの薄膜を設ける場合、通常該オリゴマー組成物を適当な溶媒に溶解させて使用する。溶液中の該オリゴマー組成物の濃度は該オリゴマー組成物の種類、塗布方法、希望する膜厚等により適当な濃度は異なるので一概に言えないが、通常０．１〜１０重量％程度であり、好ましくは０．５〜５重量％程度である。適当な濃度は使用する塗布方法で予備的な試験をして容易に決定することが出来る。使用される溶媒としては該オリゴマー組成物を溶解するものであれば特に限定されないが、ピリジン、ジメチルホルムアミド、Ｎ−メチルピロリジノン、ジメチルアセトアミド、ジメチルイミダゾリノン等の非プロトン性極性溶媒やジメチルスルホキシドなどが好ましい例として挙げられる。 In the photo-alignment film according to the sixth aspect of the present invention, a method of providing a thin film of a compound having a photo-alignment group on a substrate (a glass substrate or a plastic substrate such as polycarbonate or polyester is used as the substrate) The spin coating method is preferred. Further, this type of oligomer composition thin film may be provided on the substrate by the Langmuir Blodget method. Furthermore, the substrate may be immersed and adsorbed in these oligomer composition solutions. The film thickness is usually 0.001 to 5 μm, preferably 0.01 to 1 μm. When these thin films are provided, the oligomer composition is usually used after being dissolved in a suitable solvent. The concentration of the oligomer composition in the solution cannot be generally stated because the appropriate concentration varies depending on the type of the oligomer composition, the coating method, the desired film thickness, etc., but is usually about 0.1 to 10% by weight, Preferably, it is about 0.5 to 5% by weight. Appropriate concentrations can be readily determined by preliminary testing with the application method used. The solvent used is not particularly limited as long as it dissolves the oligomer composition, and examples thereof include aprotic polar solvents such as pyridine, dimethylformamide, N-methylpyrrolidinone, dimethylacetamide, dimethylimidazolinone, and dimethyl sulfoxide. A preferred example is given.
基板上に設けられた光配向性基を有するオリゴマー組成物薄膜に直線偏光を照射する方法としては公知の様々な方法が適用できる。偏光素子を製造するためには、直線偏光を該薄膜に照射すればよい。露光エネルギーは０．１ｍＪ／ｃｍ2から１０Ｊ／ｃｍ2の範囲が好ましい。該薄膜の直線偏光照射による分子軸配向変化は可逆的であり、マスクパターンなどを用いることによって異なる偏光軸のパターンを自由に重ね書きすることも出来る。 Various known methods can be applied as a method of irradiating the linearly polarized light to the oligomer composition thin film having a photo-alignable group provided on the substrate. In order to manufacture a polarizing element, the thin film may be irradiated with linearly polarized light. The exposure energy is preferably in the range of 0.1 mJ / cm 2 to 10 J / cm 2 . The change in molecular axis orientation of the thin film due to irradiation with linearly polarized light is reversible, and patterns with different polarization axes can be freely overwritten by using a mask pattern or the like.
本発明の第七の発明である偏光素子は一定方向に分子軸の配列した光配向性基を有するオリゴマー組成物薄膜に二色性色素分子を塗布するだけで、即ち、該薄膜上に二色性色素層を設けるだけで、二色性色素分子の分子軸が光配向性基の分子軸の配列方向、即ち該薄膜に照射した直線偏光の偏光軸で規定された方向に配列し、かつ偏光軸が固定することによって形成される。この事を更に具体的に説明すると、一定方向に分子軸の配列した光配向性基を有するオリゴマー組成物薄膜を有する基板上に、二色性色素の溶液を塗布し、所望の温度および湿度条件下に溶媒を蒸発させ該色素薄膜を形成する。この際該色素の分子軸は、光配向性基を有するオリゴマー組成物薄膜に照射した直線偏光の偏光軸で規定された方向に配列し該色素薄膜の光の吸収軸が固定されて偏光素子としての性質が発揮される。 The polarizing element according to the seventh aspect of the present invention is that a dichroic dye molecule is simply applied to an oligomer composition thin film having a photo-alignable group in which molecular axes are arranged in a certain direction, that is, a dichroic dye is applied on the thin film. The dichroic dye molecules are arranged in the alignment direction of the molecular axes of the photo-alignment group, that is, in the direction defined by the polarization axis of the linearly polarized light irradiated to the thin film. It is formed by fixing the shaft. This will be explained more specifically. A dichroic dye solution is applied to a substrate having an oligomer composition thin film having a photo-alignable group in which molecular axes are arranged in a certain direction, and the desired temperature and humidity conditions are applied. The solvent is evaporated underneath to form the dye thin film. At this time, the molecular axis of the dye is arranged in a direction defined by the polarization axis of the linearly polarized light irradiated to the oligomer composition thin film having a photo-alignment group, and the light absorption axis of the dye thin film is fixed to form a polarizing element. The properties of.
本発明で用いる二色性色素溶液は、塗布の際に基板に平行なズリ応力を加えるとその応力方向に配向し易い性質を持っている。光配向による配向潜像を作製した基板であっても、二色性色素溶液の塗布の際にズリ応力が加わった部分はズリ応力による配向規制力が光配向規制力を上回ることもあるため塗布時の基板に平行なズリ応力を如何に軽減するかが重要な技術となる。即ち、光配向性基を有するオリゴマー組成物の薄膜に直線偏光を照射して配向膜とした後、該膜上に二色性分子を配列させる工程において、基板に対して平行なズリ応力が加わらず且つ垂直方向に０．０１ＭＰａ〜１．０ＭＰａ、好ましくは０．０５ＭＰａ〜０．５ＭＰａの圧力が懸かるように二色性分子溶液を塗布する製造方法によって偏光素子を得ることが可能となった。このような圧力を制御する上で有利な塗工方法としてはロールコーター塗布、フレキソ印刷、スクリーン印刷、カーテンコーター塗布、スプレイコーター塗布等があるが、特にロールコーター塗布、カーテンコーター塗布、スプレイコーター塗布等が好ましい。 The dichroic dye solution used in the present invention has the property of being easily oriented in the stress direction when a shear stress parallel to the substrate is applied during coating. Even if the substrate has an alignment latent image created by photo-alignment, the portion where shear stress is applied during coating of the dichroic dye solution can be applied because the orientation-regulating force due to shear stress may exceed the photo-alignment regulating force. An important technique is how to reduce the shear stress parallel to the substrate at the time. That is, after a thin film of an oligomer composition having a photo-alignment group is irradiated with linearly polarized light to form an alignment film, shear stress parallel to the substrate is applied in the step of arranging dichroic molecules on the film. In addition, a polarizing element can be obtained by a production method in which a dichroic molecular solution is applied so that a pressure of 0.01 MPa to 1.0 MPa, preferably 0.05 MPa to 0.5 MPa is applied in the vertical direction. Examples of coating methods advantageous in controlling such pressure include roll coater coating, flexographic printing, screen printing, curtain coater coating, spray coater coating, etc., but in particular roll coater coating, curtain coater coating, spray coater coating. Etc. are preferred.
本発明で用いる二色性色素（分子）溶液は、一定の濃度及び温度範囲において液晶性を示す。ある種の界面活性剤は二色性色素溶液のネマチック液晶性を高める効果を示し、一方、芳香族化合物である二色性色素は液晶相ではカラム積層構造をとっている。界面活性剤もリオトロピック液晶相を示すことが知られているが芳香族化合物のリオトロピック液晶相とは異なった相をとる場合が多い。そのため界面活性剤を含む二色性色素溶液が高濃度になると色素液晶相と界面活性剤液晶相とが相分離を起こし色素を含まない界面活性剤のみの領域が生じる。この現象は、二色性色素溶液の塗布膜において色素の無いピンホールとして観察されるが、これは界面活性剤、殊にアニオン界面活性剤により顕著に改善される。アニオン界面活性剤のうちでも好ましい物として例えばポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ラウリル硫酸塩、高級アルコール硫酸塩などが挙げられる。ポリオキシエチレンアルキルエーテル硫酸塩の場合、アルカリ金属塩または低級アルカノールアミン塩が好ましい。これらの具体例としては、例えばポリオキシエチレンラウリルエーテル硫酸ナトリウム（エマール２０Ｃ、エマールＥ−２７Ｃ、エマールＥ−７０Ｃ等：いずれも商品名：花王（株）製）及びその他のポリオキシエチレンアルキルエーテル硫酸ナトリウムとしては例えばエマール２０ＣＭ、レベノールＷＸ、ラテムルＷＸ等（いずれも商品名：花王（株）製）、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン（エマール２０Ｔ（商品名）等、花王（株）製）が挙げられる。ポリオキシエチレンアルキルフェニルエーテル硫酸塩の場合、アルカリ金属塩が好ましく、具体例としては、例えばポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム（エマールＮＣ−３５、レベノールＷＺ等、いずれも商品名：花王（株）製）が挙げられる。ラウリル硫酸塩の場合、ラウリル硫酸アルカリ金属塩、アンモニウム塩または低級アルカノールアミン塩が好ましい。これらの具体例としては、例えばラウリル硫酸ナトリウム（エマール１０、エマール０等、花王（株）製）、ラウリル硫酸アンモニウム（エマールＡＤ−２５Ｒ、エマールＡＤ−２５等、いずれも商品名：花王（株）製）、ラウリル硫酸トリエタノールアミンが挙げられる。高級アルコール硫酸塩の場合、高級アルコール硫酸アルカリ金属塩が好ましく、具体例としては、高級アルコール硫酸ナトリウム（エマール４０パウダー（商品名）等、花王（株））等が挙げられる。これらのうちより好ましいものとしては、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ラウリル硫酸トリエタノールアミンが挙げられ、これらは単独にて又は２種以上を併用することもできる。好ましい界面活性剤の添加量は、二色性色素溶液中０．０１〜１重量％、より好ましくは０．０５〜０．５重量％の範囲で含有させる。 The dichroic dye (molecule) solution used in the present invention exhibits liquid crystallinity in a certain concentration and temperature range. Certain surfactants have the effect of enhancing the nematic liquid crystal properties of the dichroic dye solution, while the dichroic dyes that are aromatic compounds have a column stack structure in the liquid crystal phase. Surfactants are also known to exhibit a lyotropic liquid crystal phase, but often have a phase different from the lyotropic liquid crystal phase of an aromatic compound. Therefore, when the concentration of the dichroic dye solution containing the surfactant becomes high, the dye liquid crystal phase and the surfactant liquid crystal phase undergo phase separation, resulting in a region containing only the surfactant containing no dye. This phenomenon is observed as a pinhole without a dye in the coating film of the dichroic dye solution, and this is remarkably improved by a surfactant, particularly an anionic surfactant. Preferred examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, lauryl sulfate, and higher alcohol sulfate. In the case of polyoxyethylene alkyl ether sulfates, alkali metal salts or lower alkanolamine salts are preferred. Specific examples thereof include, for example, sodium polyoxyethylene lauryl ether sulfate (Emar 20C, Emar E-27C, Emar E-70C, etc .: all trade names: manufactured by Kao Corporation) and other polyoxyethylene alkyl ether sulfates. Examples of sodium include EMAL 20CM, LEVENOL WX, LATEMUL WX, etc. (all trade names: manufactured by Kao Corporation), polyoxyethylene alkyl ether sulfate triethanolamine (EMAL 20T (trade name), etc., manufactured by Kao Corporation) Is mentioned. In the case of polyoxyethylene alkylphenyl ether sulfate, an alkali metal salt is preferable, and specific examples thereof include, for example, sodium polyoxyethylene alkylphenyl ether sulfate (Emar NC-35, Lebenol WZ, etc., both trade names: Kao Corporation) Manufactured). In the case of lauryl sulfate, alkali metal lauryl sulfate, ammonium salt or lower alkanolamine salt is preferred. Specific examples thereof include, for example, sodium lauryl sulfate (Emar 10, Emar 0, etc., manufactured by Kao Corporation), ammonium lauryl sulfate (Emar AD-25R, Emar AD-25, etc.), both of which are trade names: Kao Corporation ), Lauryl sulfate triethanolamine. In the case of a higher alcohol sulfate, a higher alcohol sulfate alkali metal salt is preferred, and specific examples thereof include higher alcohol sodium sulfate (Emar 40 powder (trade name), Kao Corporation) and the like. Among these, more preferred are sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium lauryl sulfate, ammonium lauryl sulfate. And lauryl sulfate triethanolamine, and these may be used alone or in combination of two or more. A preferable addition amount of the surfactant is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight in the dichroic dye solution.
二色性色素を溶解する溶媒としては、水および／またはアルコール類、エーテル類、ピリジン、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルフォキシド（ＤＭＳＯ）、Ｎ−メチルピロリジノン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡＣ）、ジメチルイミダゾリノン（ＤＭＩ）等の非プロトン性極性溶媒が好ましい。特に水を主体とする混合溶媒が好ましい。非プロトン性極性溶媒の混合量は任意であるが、０〜７０重量％特に０〜５０重量％が好ましい。好ましい二色性色素の濃度は二色性色素溶液全体に対して通常０．１〜３０重量％以下、好ましくは０．５〜２０重量％以下、より好ましくは０．８〜１５重量％以下程度ある。二色性色素溶液の溶媒を蒸発させ該色素薄膜を形成する温度および湿度条件は、該色素薄膜の偏光素子としての性能を左右する。この条件は溶媒組成、色素の種類、色素濃度および塗工膜厚等により決められるが、温度は０〜２００℃、好ましくは５〜５０℃、湿度は２０〜８０％ＲＨ、好ましくは４０〜７０％ＲＨ程度が良い。 Solvents for dissolving the dichroic dye include water and / or alcohols, ethers, pyridine, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidinone (NMP), dimethylacetamide (DMAC). An aprotic polar solvent such as dimethylimidazolinone (DMI) is preferred. Particularly preferred is a mixed solvent mainly composed of water. The mixing amount of the aprotic polar solvent is arbitrary, but is preferably 0 to 70% by weight, particularly preferably 0 to 50% by weight. The concentration of the preferable dichroic dye is usually 0.1 to 30% by weight or less, preferably 0.5 to 20% by weight or less, more preferably about 0.8 to 15% by weight or less with respect to the entire dichroic dye solution. is there. The temperature and humidity conditions for evaporating the solvent of the dichroic dye solution to form the dye thin film influence the performance of the dye thin film as a polarizing element. The conditions are determined by the solvent composition, the type of pigment, the pigment concentration, the coating film thickness, etc., but the temperature is 0 to 200 ° C., preferably 5 to 50 ° C., and the humidity is 20 to 80% RH, preferably 40 to 70. % RH is good.
本発明で用いられる二色性色素は、一定の溶媒組成、色素濃度および温度条件下でリオトロピック液晶性を示す化合物でありクロモニック液晶相といわれる会合した集合体を形成しており、この集合体が一定方向に配列することにより偏光性を示す。又、複数の分子が会合しているために耐光堅牢性に優れるという特徴を有している。このような性質を示すニ色性色素としては、例えば芳香環を有する化合物が好ましい。芳香環としては、ベンゼン、ナフタレン、アントラセン、フェナントレンの他にチアゾール、ピリジン、ピリミジン、ピリダジン、ピラジン、キノリン等の複素環或いはこれらの４級塩、更にはこれらとベンゼンやナフタレン等との縮合環が特に好ましい。又、これらの芳香環にスルホン酸基、カルボン酸基、アミノ基、水酸基等の親水性置換基が導入されていることが好ましい。 The dichroic dye used in the present invention is a compound that exhibits lyotropic liquid crystallinity under a certain solvent composition, dye concentration and temperature condition, and forms an associated aggregate called a chromonic liquid crystal phase. Polarization is exhibited by arranging in a certain direction. Further, since a plurality of molecules are associated with each other, the light fastness is excellent. As the dichroic dye exhibiting such properties, for example, a compound having an aromatic ring is preferable. As the aromatic ring, in addition to benzene, naphthalene, anthracene, phenanthrene, a heterocyclic ring such as thiazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, or a quaternary salt thereof, or a condensed ring of these with benzene, naphthalene, or the like Particularly preferred. Further, it is preferable that a hydrophilic substituent such as a sulfonic acid group, a carboxylic acid group, an amino group, or a hydroxyl group is introduced into these aromatic rings.
二色性色素としては、例えばアゾ系色素、シアニン系色素、インダンスロン等の縮合環を含むアントラキノン系色素、スチルベン系色素、ピラゾロン系色素、ペリレン系色素、ナフタルイミド系色素、トリフェニルメタン系色素、キノリン系色素、オキサジン系色素、チアジン系色素、キノフタロン系色素、インジゴ系色素、チオインジゴ系色素等が挙げられる。水溶性の色素が好ましいがこの限りではない。二色性色素の具体例としては、例えばＣ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ １、Ｃ．Ｉ．ＤｉｒｅｃｔＢｌｕｅ １５、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ６７、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ７８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ９０、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ９８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ １５１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ １６８、 Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ２０２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ５１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ５９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｇｒｅｅｎ ８５、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｖｉｏｌｅｔ ４８、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ７９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８１、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｒｅｄ ８９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ４１、 Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ４９、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｏｒａｎｇｅ ７２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ １２、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ２６、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ４４、Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ５０、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ３７、 Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｙｅｌｌｏｗ ２８、Ｃ．Ｉ．Ｎｏ．２７８６５、Ｃ．Ｉ．Ｎｏ．２７９１５、Ｃ．Ｉ．Ｎｏ．２７９２０、Ｃ．Ｉ．Ｎｏ．２９０５８、Ｃ．Ｉ．Ｎｏ．２９０６０、ｄｉｓｕｌｆｏｉｎｄａｎｔｈｒｏｎｅ、 ｄｉｓｕｌｆｏ−Ｎ，Ｎ’−ｄｉｘｙｌｙｌｐｅｒｙｌｅｎｅｔｅｔｒａｃａｒｂｏｄｉｉｍｉｄｅ等が挙げられる。 Examples of dichroic dyes include azo dyes, cyanine dyes, anthraquinone dyes containing condensed rings such as indanthrone, stilbene dyes, pyrazolone dyes, perylene dyes, naphthalimide dyes, and triphenylmethane dyes. Examples thereof include dyes, quinoline dyes, oxazine dyes, thiazine dyes, quinophthalone dyes, indigo dyes, and thioindigo dyes. A water-soluble dye is preferable, but not limited thereto. Specific examples of the dichroic dye include C.I. I. Direct Blue 1, C.I. I. DirectBlue 15, C.I. I. Direct Blue 67, C.I. I. Direct Blue 78, C.I. I. Direct Blue 83, C.I. I. Direct Blue 90, C.I. I. Direct Blue 98, C.I. I. Direct Blue 151, C.I. I. Direct Blue 168, C.I. I. Direct Blue 202, C.I. I. Direct Green 51, C.I. I. Direct Green 59, C.I. I. Direct Green 85, C.I. I. Direct Violet 9, C.I. I. Direct Violet 48, C.I. I. Direct Red 2, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Orange 39, C.I. I. Direct Orange 41, C.I. I. Direct Orange 49, C.I. I. Direct Orange 72, C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 26, C.I. I. Direct Yellow 44, C.I. I. Direct Yellow 50, C.I. I. Acid Red 37, C.I. I. Direct Yellow 28, C.I. I. No. 27865, C.I. I. No. 27915, C.I. I. No. 27920, C.I. I. No. 29058, C.I. I. No. 29060, disulfondanthrone, disulfo-N, N'-dilylyperylenetetrabosidemide.
以下実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例中、部は特に限定しない限り重量部を表す。又、％は断りのない限り重量％を意味する。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, parts represent parts by weight unless otherwise specified. Further,% means% by weight unless otherwise specified.
実施例１
４−（４−ジメチルアミノフェニルアゾ）フェノール（４）の合成
氷水１００部中に５−アミノフェノール９．０５部、６規定塩酸１７部を加え氷水で冷却した。亜硝酸ソーダ３．４５部を水１０部に溶解し、５℃以下で添加してジアゾ化した。別に、Ｎ、Ｎ−ジメチルアニリン６．３部、６Ｎ塩酸８．５部、氷水６０部のカップリング溶液を調製し氷水で冷却した。このカップリング溶液中に５℃以下で上記ジアゾ化溶液を添加し、２％炭酸ソーダ溶液を加えてｐＨ４〜６を保ちながら１０℃以下で終夜攪拌した。析出した結晶を濾取し水洗、乾燥することにより目的化合物（４）１５．５部を得た。
Ｍａｓｓ：ｍ／ｚ ２４１
Synthesis of 4- (4-dimethylaminophenylazo) phenol (4) To 100 parts of ice water, 9.05 parts of 5-aminophenol and 17 parts of 6N hydrochloric acid were added and cooled with ice water. 3.45 parts of sodium nitrite was dissolved in 10 parts of water and added at 5 ° C. or less to diazotize. Separately, a coupling solution of 6.3 parts of N, N-dimethylaniline, 8.5 parts of 6N hydrochloric acid and 60 parts of ice water was prepared and cooled with ice water. The diazotization solution was added to the coupling solution at 5 ° C. or lower, and a 2% sodium carbonate solution was added thereto, and the mixture was stirred overnight at 10 ° C. or lower while maintaining pH 4-6. The precipitated crystals were collected by filtration, washed with water and dried to obtain 15.5 parts of the target compound (4).
Mass: m / z 241
実施例２
４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸（５）の合成
４−（４−ジメチルアミノフェニルアゾ）フェノール（４）１４．５部とブロモウンデカン酸１５．９部を水酸化ナトリウム６．０部をエタノール２００部中で溶解させた溶液中に加え８０℃で２時間攪拌反応させた。反応終了後放冷したのち酢酸１６．９部を加えて析出した固体をろ取した。これを水洗、メタノール洗浄し乾燥することにより目的化合物（５）１９．１部を得た。少量のＤＭＦに加熱溶解しメタノールで再結晶精製することにより、目的化合物（５）１７．０部を得た。
Ｍａｓｓ：ｍ／ｚ ４２５
Synthesis of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid (5) 14.5 parts of 4- (4-dimethylaminophenylazo) phenol (4) and 15.9 parts of bromoundecanoic acid were added to sodium hydroxide 6. 0 part was added to a solution obtained by dissolving in 200 parts of ethanol, and the reaction was stirred at 80 ° C. for 2 hours. After allowing the reaction to cool, 16.9 parts of acetic acid was added and the precipitated solid was collected by filtration. This was washed with water, washed with methanol and dried to obtain 19.1 parts of the target compound (5). By heating and dissolving in a small amount of DMF and recrystallizing and purifying with methanol, 17.0 parts of the target compound (5) was obtained.
Mass: m / z 425
実施例３
４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸組成物（６）の合成
４−（４−ジメチルアミノフェニルアゾ）フェノール（４）１２．１部とブロモウンデカン酸１５．９部を水酸化カリウム６．３部をエタノール２００部中で溶解させた溶液中に加え８０℃で１６時間攪拌反応した。反応終了後放冷したのち酢酸１６．９部を加え、析出固体を濾取した。これを水洗、メタノール洗浄し乾燥することにより、ｐ＝１の化合物を主成分とし、ｐ＝１から５までの混合物である目的組成物（６）２０．３部を得た。
なお得られた混合物はＨＰＬＣ面比でｐ＝１が６５％、ｐ＝２が２２％、ｐ＝３が９％、ｐ＝４が２％およびｐ＝５が０．２％の組成であった。
Synthesis of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid composition (6) 12.1 parts of 4- (4-dimethylaminophenylazo) phenol (4) and 15.9 parts of bromoundecanoic acid were mixed with potassium hydroxide. 6.3 parts was added to a solution obtained by dissolving in 200 parts of ethanol, and the reaction was stirred at 80 ° C. for 16 hours. After allowing the reaction to cool, 16.9 parts of acetic acid was added, and the precipitated solid was collected by filtration. This was washed with water, washed with methanol and dried to obtain 20.3 parts of the target composition (6) which is a mixture of p = 1 as a main component and p = 1 to 5.
The obtained mixture had an HPLC aspect ratio of 65% p = 1, 22% p = 2, 9% p = 3, 2% p = 4 and 0.2% p = 5. It was.
実施例４
４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸組成物（７）の合成
４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸（５）１．１部、ブロモウンデカン酸０．７部および炭酸カリウム０．７部をＤＭＦ１０部に加え、６０℃で７時間攪拌反応した。反応終了後放冷し、酢酸０．３５部を加えて析出した固体を濾取した。これを水洗、メタノール洗浄し乾燥することにより、ｐ＝１の化合物を主成分とし、ｐ＝１から５までの混合物である目的組成物（７）１．３部を得た。
得られたはＨＰＬＣ面比でｐ＝１が５３％、ｐ＝２が２７％、ｐ＝３が１１％、ｐ＝４が３％、ｐ＝５が０．３％の組成であった。
Synthesis of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid composition (7) 1.1 parts of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid (5), 0.7 part of bromoundecanoic acid and carbonic acid 0.7 part of potassium was added to 10 parts of DMF, and the mixture was stirred at 60 ° C. for 7 hours. After completion of the reaction, the mixture was allowed to cool, 0.35 parts of acetic acid was added, and the precipitated solid was collected by filtration. This was washed with water, washed with methanol and dried to obtain 1.3 parts of the target composition (7) which is a mixture of p = 1 as a main component and p = 1 to 5.
The composition obtained by HPLC was such that p = 1 was 53%, p = 2 was 27%, p = 3 was 11%, p = 4 was 3%, and p = 5 was 0.3%.
実施例５
ビス[（４−ジメチルアミノフェニルアゾ）フェノキシウンデカノイルイミノ−１，４−（３，５−ジエチル）フェニレン]メタン（１０１）の合成
（一般式（１）においてＲ1〜Ｒ4はメチル、Ｒ7〜Ｒ10はエチル、ｎ＝１０、ｐ＝１である化合物）
ＮＭＰ１０部中に４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸（５）２．１部、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルメタン（ＴＥＤＰＭ：日本化薬（株）製）１．５部を加え攪拌溶解した。次いでトリフェニルフォスファイト３．１部、ピリジン２．５部を加え、１００℃にて６時間攪拌反応した。反応終了後、水１５０部で希釈し、さらに２％炭酸ソーダ水溶液１００部およびメタノール１００部を加えた。析出結晶を濾取し乾燥することにより固体２．２部を得た。得られた固体を少量のＤＭＦに加熱溶解しメタノールで再結晶精製することにより、目的化合物（１０１）１．８部を得た。
Ｍａｓｓ：ｍ／ｚ １１２４
Example 5
Synthesis of bis [(4-dimethylaminophenylazo) phenoxyundecanoylimino-1,4- (3,5-diethyl) phenylene] methane (101) (in the general formula (1), R 1 to R 4 are methyl, R 7 to R 10 are compounds in which ethyl, n = 10, and p = 1)
2.1 parts of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid (5) in 10 parts of NMP, 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane (TEDPM: Nippon Kayaku) 1.5 parts) was added and dissolved by stirring. Next, 3.1 parts of triphenyl phosphite and 2.5 parts of pyridine were added, and the reaction was stirred at 100 ° C. for 6 hours. After completion of the reaction, the reaction mixture was diluted with 150 parts of water, and 100 parts of 2% aqueous sodium carbonate solution and 100 parts of methanol were further added. The precipitated crystals were collected by filtration and dried to obtain 2.2 parts of a solid. The obtained solid was dissolved by heating in a small amount of DMF and recrystallized and purified with methanol to obtain 1.8 parts of the target compound (101).
Mass: m / z 1124
実施例６
〔４−（ジメチルアミノ）フェニルアゾ〕ウンデカノイルイミノ−１，４−（３，５−ジエチル）フェニレンメチレン−１，４−（３，５ージエチル）フェニレン（１０２）の合成
（一般式（２）においてＲ5〜Ｒ6はメチル、ｍ＝１０、ｐ＝１、Ｘは−ＮＨ−、Ｑはフェニルである化合物）
ＮＭＰ１０部中に４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸（５）２．１部、アニリン０．５部を加え攪拌溶解した。次いでトリフェニルフォスファイト１．５部、ピリジン２．５部を加え、１００℃にて６時間攪拌反応した。反応終了後水１５０部中で希釈し沈殿した結晶をさらに２％炭酸ソーダ水溶液１００部およびメタノール１００部で洗浄する。生成した結晶を濾取し乾燥することにより固体（１０２）５．９部を得た。得られた固体を少量のＤＭＦに加熱溶解しメタノールで希釈して再沈殿精製することにより、目的化合物５．１部を得た。
Ｍａｓｓ：ｍ／ｚ ５００
Example 6
Synthesis of [4- (dimethylamino) phenylazo] undecanoylimino-1,4- (3,5-diethyl) phenylenemethylene-1,4- (3,5-diethyl) phenylene (102) (general formula (2) Wherein R 5 to R 6 are methyl, m = 10, p = 1, X is —NH—, and Q is phenyl)
In 10 parts of NMP, 2.1 parts of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid (5) and 0.5 parts of aniline were added and dissolved by stirring. Next, 1.5 parts of triphenyl phosphite and 2.5 parts of pyridine were added, and the mixture was stirred at 100 ° C. for 6 hours. After completion of the reaction, the precipitated crystals diluted with 150 parts of water are further washed with 100 parts of 2% aqueous sodium carbonate solution and 100 parts of methanol. The produced crystals were collected by filtration and dried to obtain 5.9 parts of a solid (102). The obtained solid was dissolved by heating in a small amount of DMF, diluted with methanol, and purified by reprecipitation to obtain 5.1 parts of the target compound.
Mass: m / z 500
実施例７
光配光膜用組成物（８）の合成
ＮＭＰ１０部中に４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸組成物（６）２．１部、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルメタン（ＴＥＤＰＭ：日本化薬（株）製）１．５部を加え攪拌溶解した。次いでトリフェニルフォスファイト３．１部、ピリジン２．５部を加え、１００℃にて１０時間攪拌反応した。反応終了後水１５０部で希釈し、さらに２％炭酸ソーダ水溶液１００部およびメタノール１００部を加えた。析出固体を濾取し、乾燥することにより目的組成物（８）３．２部を得た。
Example 7
Synthesis of composition for light distribution film (8) In 10 parts of NMP, 2.1 parts of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid composition (6), 4,4′-diamino-3,3 ′ , 5,5′-tetraethyldiphenylmethane (TEDPM: Nippon Kayaku Co., Ltd.) 1.5 parts was added and dissolved by stirring. Next, 3.1 parts of triphenyl phosphite and 2.5 parts of pyridine were added, and the reaction was stirred at 100 ° C. for 10 hours. After completion of the reaction, the reaction mixture was diluted with 150 parts of water, and 100 parts of 2% aqueous sodium carbonate solution and 100 parts of methanol were further added. The precipitated solid was collected by filtration and dried to obtain 3.2 parts of the target composition (8).
実施例８
光配光膜用組成物（９）の合成
ＮＭＰ１０部中に４−（４−ジメチルアミノフェニルアゾ）フェノキシウンデカン酸組成物（７）２．１部、４，４’−ジアミノ−３，３’，５，５’−テトラエチルジフェニルメタン（ＴＥＤＰＭ：日本化薬（株）製）１．５部を加え攪拌溶解した。次いでトリフェニルフォスファイト３．１部、ピリジン２．５部を加え、１００℃にて１０時間攪拌反応した。反応終了後水１５０部で希釈し、さらに２％炭酸ソーダ水溶液１００部およびメタノール１００部を加えた。生成した結晶を濾取し乾燥することにより目的組成物（９）２．８部を得た。
Example 8
Synthesis of composition for light distribution film (9) In 10 parts of NMP, 2.1 parts of 4- (4-dimethylaminophenylazo) phenoxyundecanoic acid composition (7), 4,4′-diamino-3,3 ′ , 5,5′-tetraethyldiphenylmethane (TEDPM: Nippon Kayaku Co., Ltd.) 1.5 parts was added and dissolved by stirring. Next, 3.1 parts of triphenyl phosphite and 2.5 parts of pyridine were added, and the reaction was stirred at 100 ° C. for 10 hours. After completion of the reaction, the reaction mixture was diluted with 150 parts of water, and 100 parts of 2% aqueous sodium carbonate solution and 100 parts of methanol were further added. The produced crystals were collected by filtration and dried to obtain 2.8 parts of the target composition (9).
実施例９
光配向膜の調製
上記実施例７にて得られた光配向膜用組成物（８）の精製品１部をＮＭＰ９９部に溶解し、１％溶液を調製した。次にガラス基板上に乾燥膜厚約４０-５０ｎｍとなるようにスピンコートし、１００℃にて２時間加熱乾燥して上記組成物の薄膜を形成した。超高圧水銀ランプ（５００Ｗ／ｈｒ）を使用し５００ｎｍカットオフフィルターで可視光とし更に偏光板を通して直線偏光とした後、該ポリアミド薄膜を形成したガラス基板の膜面上に５０ｃｍの距離から１分間照射した後、ストライプ状のマスクを介して異なる偏光軸を有する直線偏光を同じように照射することにより、部分的に光配向性基の分子軸を異なる方向に配列させた光配向膜を調製した。
Example 9
Preparation of photo-alignment film 1 part of the purified product of the photo-alignment film composition (8) obtained in Example 7 was dissolved in 99 parts of NMP to prepare a 1% solution. Next, it spin-coated so that it might become a dry film thickness of about 40-50 nm on a glass substrate, and it heat-dried at 100 degreeC for 2 hours, and formed the thin film of the said composition. Using an ultra-high pressure mercury lamp (500 W / hr), the light is made visible with a 500 nm cut-off filter and further linearly polarized through a polarizing plate. After that, linearly polarized light having different polarization axes was irradiated in the same way through a striped mask to prepare a photoalignment film in which the molecular axes of the photoalignable groups were partially arranged in different directions.
実施例１０
実施例８にて得られた光配向膜用組成物（９）を用いる以外は実施例９と同様の操作を行うことにより光配向膜を調整した。
Example 10
A photo-alignment film was prepared by performing the same operation as in Example 9 except that the photo-alignment film composition (9) obtained in Example 8 was used.
実施例１１
上記実施例５で得た式（１０１）の精製品０.６部および上記実施例６で得た式（１０２）の精製品０.４部をＮＭＰ９９部に溶解し、１％溶液を作製した。次にガラス基板上に乾燥膜厚約４０-５０ｎｍとなるようにスピンコートし、１００℃にて２時間加熱乾燥して薄膜を形成した。超高圧水銀ランプ（５００Ｗ／ｈｒ）を使用し５００ｎｍカットオフフィルターで可視光とし更に偏光板を通して直線偏光とした後、該ポリアミド薄膜を形成したガラス基板の膜面上に５０ｃｍの距離から１分間照射した後、ストライプ状のマスクを介して異なる偏光軸を有する直線偏光を同じように照射することにより、部分的に光配向性基の分子軸を異なる方向に配列させた光配向膜を調製した。
Example 11
0.6 part of the purified product of formula (101) obtained in Example 5 and 0.4 part of the purified product of formula (102) obtained in Example 6 were dissolved in 99 parts of NMP to prepare a 1% solution. . Next, it spin-coated so that it might become a dry film thickness of about 40-50 nm on a glass substrate, and it heat-dried at 100 degreeC for 2 hours, and formed the thin film. Using an ultra-high pressure mercury lamp (500 W / hr), it is made visible light with a 500 nm cut-off filter and further linearly polarized through a polarizing plate, and then irradiated for 1 minute from a distance of 50 cm onto the film surface of the glass substrate on which the polyamide thin film is formed. After that, linearly polarized light having different polarization axes was irradiated in the same way through a striped mask to prepare a photoalignment film in which the molecular axes of the photoalignable groups were partially arranged in different directions.
実施例１２
偏向素子の調製
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ６７を５部、エマール２０Ｃ（アニオン界面活性剤：花王（株）製）０．２部を脱イオン水９４．８部に加熱溶解し色素溶液を調製した。この色素溶液を上記実施例９〜１１にて調製した光配光膜上に、それぞれ枚葉基板用ロールコーターを用いて塗布した。ロールコーターはあらかじめコーティングロールと基板間の位置を微調整してロールと基板間の押し圧を０．３ＭＰａに調整した。圧力の測定は富士フィルムプレスケールによって測定した。塗布した基板は３０℃、６０％ＲＨの条件下に乾燥して対応する本発明のストライプ状の偏光素子をそれぞれ得た。これらの偏向素子の吸収極大波長における二色性比は上記実施例９に記載の光配向膜を用いた場合２３、上記実施例１０に記載の光配向膜を用いた場合２５、上記実施例１１に記載の光配向膜を用いた場合１９であった。
Example 12
Preparation of deflection element I. A dye solution was prepared by heating and dissolving 5 parts Direct Blue 67 and 0.2 part Emar 20C (anionic surfactant: manufactured by Kao Corporation) in 94.8 parts deionized water. This dye solution was applied onto the light distribution film prepared in Examples 9 to 11 using a roll coater for a single wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance to adjust the pressure between the roll and the substrate to 0.3 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain the corresponding stripe-shaped polarizing elements of the present invention. The dichroic ratio at the absorption maximum wavelength of these deflecting elements is 23 when the photo-alignment film described in Example 9 is used, 25 when the photo-alignment film described in Example 10 is used, and in Example 11 above. 19 when the photo-alignment film described in 1 was used.
本発明によれば、水溶性二色性色素の濡れ性がよく光により分解しない配向膜を形成することによって高い二色比をもつ偏光素子の調製が可能となった。直線偏光を照射した光配向性基を有するアモルファス薄膜層に二色性分子を配列させるだけで液晶セル内に直接偏光素子を作り込むことが可能となった。又、照射する直線偏光の偏光軸を変えるだけで二色性分子の配列を変えることが可能であり、そのため基板上に偏光軸が異なるマイクロパターン偏光素子の製造が可能となった。この基板を使用した液晶表示素子は容易に立体画像表示が可能となる。 According to the present invention, it is possible to prepare a polarizing element having a high dichroic ratio by forming an alignment film in which the water-soluble dichroic dye has good wettability and is not decomposed by light. It has become possible to build a polarizing element directly in a liquid crystal cell simply by arranging dichroic molecules in an amorphous thin film layer having a photoalignable group irradiated with linearly polarized light. Further, it is possible to change the arrangement of the dichroic molecules only by changing the polarization axis of the linearly polarized light to be irradiated. Therefore, it is possible to manufacture a micropattern polarizing element having a different polarization axis on the substrate. A liquid crystal display element using this substrate can easily display a stereoscopic image.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005326637A JP2007133184A (en) | 2005-11-10 | 2005-11-10 | Photo-alignment film for novel polarizing element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005326637A JP2007133184A (en) | 2005-11-10 | 2005-11-10 | Photo-alignment film for novel polarizing element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007133184A true JP2007133184A (en) | 2007-05-31 |
Family
ID=38154897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005326637A Pending JP2007133184A (en) | 2005-11-10 | 2005-11-10 | Photo-alignment film for novel polarizing element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007133184A (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2293122A2 (en) | 2009-08-28 | 2011-03-09 | Fujifilm Corporation | Polarizing film, laminate, and liquid crystal display device |
| WO2011030883A1 (en) | 2009-09-14 | 2011-03-17 | Fujifilm Corporation | Color filter and light-emitting display element |
| JP2011169958A (en) * | 2010-02-16 | 2011-09-01 | Nitto Denko Corp | Polarizing film |
| WO2011125622A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Light-absorbable anisotropic film, polarizing film, process for producing same, and display device using same |
| WO2011125621A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Polarizing film, display device, and process for producing same |
| WO2011125620A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Liquid crystalline compound, liquid crystalline composition, anisotropically light-absorbing film, and liquid crystal display device |
| WO2015056671A1 (en) | 2013-10-15 | 2015-04-23 | 日東電工株式会社 | Optical layered body and dimmable window |
| WO2020008961A1 (en) | 2018-07-02 | 2020-01-09 | 富士フイルム株式会社 | Decorative film, decoration method, decorative molded body production method, and decorative molded film |
| WO2020175527A1 (en) | 2019-02-27 | 2020-09-03 | 富士フイルム株式会社 | Layered body |
| WO2020196306A1 (en) | 2019-03-28 | 2020-10-01 | 東洋紡株式会社 | Anti-reflection circular polariser and image display device using same |
| WO2020241312A1 (en) | 2019-05-30 | 2020-12-03 | 東洋紡株式会社 | Polarization plate for folding display |
| WO2020241313A1 (en) | 2019-05-30 | 2020-12-03 | 東洋紡株式会社 | Foldable display |
| WO2020262474A1 (en) | 2019-06-27 | 2020-12-30 | 富士フイルム株式会社 | Decorative film for molding, molded article, and display |
| JP2022085847A (en) * | 2020-11-27 | 2022-06-08 | 三菱ケミカル株式会社 | Polyester film for flexible displays, laminate film for flexible displays, flexible display, and flexible display device |
| JP2022113634A (en) * | 2021-01-25 | 2022-08-04 | 三菱ケミカル株式会社 | Polyester film for flexible displays, laminate film for flexible displays, flexible display and flexible display device |
| US11899167B2 (en) | 2019-05-28 | 2024-02-13 | Toyobo Co., Ltd. | Polyester film, laminated film, and use thereof |
| US11926720B2 (en) | 2019-05-28 | 2024-03-12 | Toyobo Co., Ltd. | Polyester film and application therefor |
| US11934226B2 (en) | 2019-02-08 | 2024-03-19 | Toyobo Co., Ltd. | Foldable display and portable terminal device |
| US11939499B2 (en) | 2019-05-28 | 2024-03-26 | Toyobo Co., Ltd. | Multilayer film and use of same |
| US11997916B2 (en) | 2019-02-08 | 2024-05-28 | Toyobo Co., Ltd. | Polyester film and use thereof |
| WO2025013901A1 (en) | 2023-07-11 | 2025-01-16 | 富士フイルム株式会社 | Liquid crystal composition, optically anisotropic layer, cured film, diffraction element, and compound |
| WO2025013896A1 (en) | 2023-07-11 | 2025-01-16 | 富士フイルム株式会社 | Composition, optically anisotropic layer, cured film, and diffraction element |
| US12319801B2 (en) | 2019-07-12 | 2025-06-03 | Toyobo Co., Ltd. | Hard coating film for foldable display, and application of said film |
| US12354504B2 (en) | 2019-05-28 | 2025-07-08 | Toyobo Co., Ltd. | Transparent conductive polyester film and use of same |
| US12351730B2 (en) | 2019-07-12 | 2025-07-08 | Toyobo Co., Ltd. | Hard coat film for foldable display and use thereof |
| US12548477B2 (en) | 2019-05-30 | 2026-02-10 | Toyobo Co., Ltd. | Polarization plate for folding display |
-
2005
- 2005-11-10 JP JP2005326637A patent/JP2007133184A/en active Pending
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2293122A2 (en) | 2009-08-28 | 2011-03-09 | Fujifilm Corporation | Polarizing film, laminate, and liquid crystal display device |
| WO2011030883A1 (en) | 2009-09-14 | 2011-03-17 | Fujifilm Corporation | Color filter and light-emitting display element |
| JP2011169958A (en) * | 2010-02-16 | 2011-09-01 | Nitto Denko Corp | Polarizing film |
| WO2011125622A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Light-absorbable anisotropic film, polarizing film, process for producing same, and display device using same |
| WO2011125621A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Polarizing film, display device, and process for producing same |
| WO2011125620A1 (en) | 2010-03-31 | 2011-10-13 | 富士フイルム株式会社 | Liquid crystalline compound, liquid crystalline composition, anisotropically light-absorbing film, and liquid crystal display device |
| WO2015056671A1 (en) | 2013-10-15 | 2015-04-23 | 日東電工株式会社 | Optical layered body and dimmable window |
| WO2020008961A1 (en) | 2018-07-02 | 2020-01-09 | 富士フイルム株式会社 | Decorative film, decoration method, decorative molded body production method, and decorative molded film |
| US11934226B2 (en) | 2019-02-08 | 2024-03-19 | Toyobo Co., Ltd. | Foldable display and portable terminal device |
| US11997916B2 (en) | 2019-02-08 | 2024-05-28 | Toyobo Co., Ltd. | Polyester film and use thereof |
| WO2020175527A1 (en) | 2019-02-27 | 2020-09-03 | 富士フイルム株式会社 | Layered body |
| WO2020196306A1 (en) | 2019-03-28 | 2020-10-01 | 東洋紡株式会社 | Anti-reflection circular polariser and image display device using same |
| US11939499B2 (en) | 2019-05-28 | 2024-03-26 | Toyobo Co., Ltd. | Multilayer film and use of same |
| US11926720B2 (en) | 2019-05-28 | 2024-03-12 | Toyobo Co., Ltd. | Polyester film and application therefor |
| US12354504B2 (en) | 2019-05-28 | 2025-07-08 | Toyobo Co., Ltd. | Transparent conductive polyester film and use of same |
| US11899167B2 (en) | 2019-05-28 | 2024-02-13 | Toyobo Co., Ltd. | Polyester film, laminated film, and use thereof |
| WO2020241312A1 (en) | 2019-05-30 | 2020-12-03 | 東洋紡株式会社 | Polarization plate for folding display |
| WO2020241313A1 (en) | 2019-05-30 | 2020-12-03 | 東洋紡株式会社 | Foldable display |
| US12298547B2 (en) | 2019-05-30 | 2025-05-13 | Toyobo Co., Ltd. | Foldable display |
| US12548477B2 (en) | 2019-05-30 | 2026-02-10 | Toyobo Co., Ltd. | Polarization plate for folding display |
| WO2020262474A1 (en) | 2019-06-27 | 2020-12-30 | 富士フイルム株式会社 | Decorative film for molding, molded article, and display |
| US12319801B2 (en) | 2019-07-12 | 2025-06-03 | Toyobo Co., Ltd. | Hard coating film for foldable display, and application of said film |
| US12351730B2 (en) | 2019-07-12 | 2025-07-08 | Toyobo Co., Ltd. | Hard coat film for foldable display and use thereof |
| JP2022085847A (en) * | 2020-11-27 | 2022-06-08 | 三菱ケミカル株式会社 | Polyester film for flexible displays, laminate film for flexible displays, flexible display, and flexible display device |
| JP2022113634A (en) * | 2021-01-25 | 2022-08-04 | 三菱ケミカル株式会社 | Polyester film for flexible displays, laminate film for flexible displays, flexible display and flexible display device |
| WO2025013901A1 (en) | 2023-07-11 | 2025-01-16 | 富士フイルム株式会社 | Liquid crystal composition, optically anisotropic layer, cured film, diffraction element, and compound |
| WO2025013896A1 (en) | 2023-07-11 | 2025-01-16 | 富士フイルム株式会社 | Composition, optically anisotropic layer, cured film, and diffraction element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007133184A (en) | Photo-alignment film for novel polarizing element | |
| KR100881982B1 (en) | Dichroic dye for polarizing film, polarizing film composition comprising the same, durable polarizing plate manufacturing method using the same, and polarizing plate manufactured accordingly | |
| TWI510541B (en) | Thermosetting film forming composition having photo-alignment property | |
| KR101023182B1 (en) | Optical element formation composition and optical element manufactured using the same | |
| JP4175455B2 (en) | Manufacturing method of novel micro-pattern polarizing element and stereoscopic display liquid crystal display device using the same | |
| TWI506080B (en) | Thermosetting film forming composition having photo-alignment property | |
| KR100927853B1 (en) | Dichroic dye for color filter, color filter formation composition comprising same, and color filter array substrate made therefrom | |
| CN102822705A (en) | Light-absorbable anisotropic film, polarizing film, process for producing same, and display device using same | |
| TWI564350B (en) | Composition for forming dye type polarizer and dye type polarizer | |
| JP7389147B2 (en) | Novel polymerizable liquid crystal | |
| TW200914585A (en) | Lyotropic liquid crystalline mixture, coating liquid, and optically anisotropic film | |
| JP4168173B2 (en) | Novel micro-pattern polarizer | |
| KR102442596B1 (en) | Polymerizable compound, mixture, polymerizable liquid crystal composition, polymer, optical film, optically anisotropic body, polarizing plate, display device and anti-reflection film | |
| US6541185B1 (en) | Micropattern polarized element | |
| JP5296866B2 (en) | Lyotropic liquid crystal systems based on bisacenaphthopyrazinoquinoxaline derivatives and methods for their production | |
| TWI640580B (en) | Composition for anisotropic pigment film, anisotropic pigment film, and optical element | |
| CN110520769A (en) | anisotropic light absorbing film and laminate | |
| JP2008031133A (en) | New lyotropic liquid-crystalline compound and its aqueous solution, method for producing polarized element using the same | |
| JP2007186428A (en) | Novel lyotropic liquid crystalline compound, aqueous solution thereof, and method for producing polarizing element using the same | |
| JP2006047966A (en) | Dye for anisotropic dye film, dye composition for anisotropic dye film, anisotropic dye film, and polarizing element | |
| JP2008150517A (en) | Novel compound, its aqueous solution and manufacturing method of polarizor element using the same | |
| TW200528543A (en) | Liquid crystal layer containing azolium salt | |
| JP2009115866A (en) | Coating liquid, polarizing film and method for producing polarizing film | |
| JP2009223140A (en) | Composition for photo-alignment layer, photo-alignment layer and its manufacturing method, liquid crystal cell, and liquid crystal display | |
| JP2008069300A (en) | New lyotropic liquid crystal compound, aqueous solution of the same and method for producing polarizing element using the same |