JP7010850B2 - Azo compounds or salts thereof, and dye-based polarizing films and dye-based polarizing plates containing them. - Google Patents
Azo compounds or salts thereof, and dye-based polarizing films and dye-based polarizing plates containing them. Download PDFInfo
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- JP7010850B2 JP7010850B2 JP2018562447A JP2018562447A JP7010850B2 JP 7010850 B2 JP7010850 B2 JP 7010850B2 JP 2018562447 A JP2018562447 A JP 2018562447A JP 2018562447 A JP2018562447 A JP 2018562447A JP 7010850 B2 JP7010850 B2 JP 7010850B2
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- carbon atoms
- dye
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- polarizing film
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- 150000003839 salts Chemical class 0.000 title claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 102
- 239000000975 dye Substances 0.000 claims description 93
- 125000003545 alkoxy group Chemical group 0.000 claims description 65
- -1 azo compound Chemical class 0.000 claims description 62
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 49
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 48
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 230000007935 neutral effect Effects 0.000 claims description 20
- 239000004973 liquid crystal related substance Substances 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 10
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- ALGIYXGLGIECNT-UHFFFAOYSA-N 3h-benzo[e]indole Chemical group C1=CC=C2C(C=CN3)=C3C=CC2=C1 ALGIYXGLGIECNT-UHFFFAOYSA-N 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 35
- 230000010287 polarization Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 238000002834 transmittance Methods 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 229920006254 polymer film Polymers 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 5
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 description 4
- CKAGMVXJHAZUBL-UHFFFAOYSA-N 2-amino-1,3-benzothiazole-6-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2SC(N)=NC2=C1 CKAGMVXJHAZUBL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- VKCPLNCNTDLLHJ-UHFFFAOYSA-N 2-amino-7-methoxy-1,3-benzothiazole-6-sulfonic acid Chemical compound NC=1SC2=C(N1)C=CC(=C2OC)S(=O)(=O)O VKCPLNCNTDLLHJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXWCDTXEKCVRRO-UHFFFAOYSA-N para-Cresidine Chemical compound COC1=CC=C(C)C=C1N WXWCDTXEKCVRRO-UHFFFAOYSA-N 0.000 description 3
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 3
- BQVLLTHCZQAJNH-UHFFFAOYSA-N 4-hydroxy-7-[(5-hydroxy-7-sulfonaphthalen-2-yl)amino]naphthalene-2-sulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(NC=3C=C4C=C(C=C(C4=CC=3)O)S(O)(=O)=O)=CC=C21 BQVLLTHCZQAJNH-UHFFFAOYSA-N 0.000 description 2
- OXQJOAGKNHVOAI-UHFFFAOYSA-N 5-amino-6-methoxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=C(N)C(OC)=CC=C21 OXQJOAGKNHVOAI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229950003476 aminothiazole Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- XPKFTIYOZUJAGA-UHFFFAOYSA-N 2,5-diethoxyaniline Chemical compound CCOC1=CC=C(OCC)C(N)=C1 XPKFTIYOZUJAGA-UHFFFAOYSA-N 0.000 description 1
- XHNDTWIUBZHABC-UHFFFAOYSA-N 2,6-diethoxyaniline Chemical compound CCOC1=CC=CC(OCC)=C1N XHNDTWIUBZHABC-UHFFFAOYSA-N 0.000 description 1
- HQBJSEKQNRSDAZ-UHFFFAOYSA-N 2,6-dimethoxyaniline Chemical compound COC1=CC=CC(OC)=C1N HQBJSEKQNRSDAZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 1
- UCVWMHNZPBEORR-UHFFFAOYSA-N 2-amino-7-methoxy-1,3-benzothiazole-4,6-disulfonic acid Chemical compound NC=1SC2=C(N1)C(=CC(=C2OC)S(=O)(=O)O)S(=O)(=O)O UCVWMHNZPBEORR-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical class C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- IRRIDSMXMHAYOV-UHFFFAOYSA-N 2-ethoxy-5-methoxyaniline Chemical compound CCOC1=CC=C(OC)C=C1N IRRIDSMXMHAYOV-UHFFFAOYSA-N 0.000 description 1
- TUOWYJFPLMIKCX-UHFFFAOYSA-N 2-ethoxynaphthalen-1-amine Chemical compound C1=CC=CC2=C(N)C(OCC)=CC=C21 TUOWYJFPLMIKCX-UHFFFAOYSA-N 0.000 description 1
- WGJDJIOVBVNPAU-UHFFFAOYSA-N 4-hydroxy-6-[(8-hydroxy-6-sulfonaphthalen-2-yl)amino]naphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(NC3=CC=C4C=C(C=C(C4=C3)O)S(O)(=O)=O)=CC=C21 WGJDJIOVBVNPAU-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- WBSMIPLNPSCJFS-UHFFFAOYSA-N 5-chloro-2-methoxyaniline Chemical compound COC1=CC=C(Cl)C=C1N WBSMIPLNPSCJFS-UHFFFAOYSA-N 0.000 description 1
- GDAIYFAMMVNXNI-UHFFFAOYSA-N 5-ethoxy-2-methoxyaniline Chemical compound CCOC1=CC=C(OC)C(N)=C1 GDAIYFAMMVNXNI-UHFFFAOYSA-N 0.000 description 1
- JUMINRWBSYTVFG-UHFFFAOYSA-N 8-amino-7-ethoxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=C(N)C(OCC)=CC=C21 JUMINRWBSYTVFG-UHFFFAOYSA-N 0.000 description 1
- WDCKALMBICTILQ-UHFFFAOYSA-N 8-amino-7-methoxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=C(N)C(OC)=CC=C21 WDCKALMBICTILQ-UHFFFAOYSA-N 0.000 description 1
- PHALDJXMGPQIGO-UHFFFAOYSA-N C1=C(S(O)(=O)=O)C=C2SC(N)=NC2=C1S(O)(=O)=O Chemical compound C1=C(S(O)(=O)=O)C=C2SC(N)=NC2=C1S(O)(=O)=O PHALDJXMGPQIGO-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- IQFVPQOLBLOTPF-UHFFFAOYSA-L Congo Red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-UHFFFAOYSA-L 0.000 description 1
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000006239 protecting group Chemical group 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
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- FIXVWFINKCQNFG-UHFFFAOYSA-M sodium;4-[(4-aminophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FIXVWFINKCQNFG-UHFFFAOYSA-M 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012192 staining solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/28—Disazo or polyazo compounds containing copper
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Description
本発明は、新規なアゾ化合物又はその塩、及びそれらを含有してなる染料系偏光膜に関するものである。 The present invention relates to a novel azo compound or a salt thereof, and a dye-based polarizing film containing them.
光の透過・遮へい機能を有する偏光板は、光のスイッチング機能を有する液晶とともに液晶ディスプレイ（Ｌｉｑｕｉｄ Ｃｒｙｓｔａｌ Ｄｉｓｐｌａｙ：ＬＣＤ）等の表示装置に用いられる。このＬＣＤの適用分野も初期の頃の電卓及び時計等の小型機器から、ノートパソコン、ワープロ、液晶プロジェクター、液晶テレビ、カーナビゲーション、及び屋内外の情報表示装置、計測機器等が挙げられる。また偏光機能を有するレンズへの適用も可能であり、視認性の向上したサングラスや、近年では３Ｄテレビなどに対応する偏光メガネなどへの応用がなされている。近年では、表示用途だけでなく、真偽判定用デバイスにおける精度向上のための応用や、ＣＣＤやＣＭＯＳなどのイメージセンサーにおける反射光カットによるＳ／Ｎ比向上への応用がなされている。 A polarizing plate having a light transmitting / shielding function is used in a display device such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function. The fields of application of this LCD include small devices such as calculators and watches in the early days, notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, indoor / outdoor information display devices, measuring devices, and the like. It can also be applied to lenses having a polarizing function, and has been applied to sunglasses with improved visibility and, in recent years, polarized glasses compatible with 3D televisions and the like. In recent years, it has been applied not only to display applications but also to improve accuracy in authenticity determination devices and to improve S / N ratio by cutting reflected light in image sensors such as CCD and CMOS.
一般的な偏光板は、延伸配向したポリビニルアルコール又はその誘導体のフィルムあるいは、ポリ塩化ビニルフィルムの脱塩酸又はポリビニルアルコール系フィルムの脱水によりポリエンを生成して配向させたポリエン系のフィルムなどの偏光膜基材に、偏光素子としてヨウ素や二色性染料を染色させて又は含有させて製造される。これらのうち、偏光素子としてヨウ素を用いたヨウ素系偏光膜は、偏光性能には優れるものの、水及び熱に対して弱く、高温、高湿の状態で長時間使用する場合にはその耐久性に問題がある。一方、偏光素子として二色性染料を用いた染料系偏光膜はヨウ素系偏光膜に比べ、耐湿性及び耐熱性は優れるものの、一般に偏光性能が十分でない。 A general polarizing plate is a polarizing film such as a stretch-oriented polyvinyl alcohol or a derivative film thereof, or a polyene-based film in which polyene is generated and oriented by dehydrogenating a polyvinyl chloride film or dehydrating a polyvinyl alcohol-based film. It is manufactured by dyeing or impregnating a base material with iodine or a dichroic dye as a polarizing element. Of these, iodine-based polarizing films that use iodine as the polarizing element are excellent in polarizing performance, but are vulnerable to water and heat, and are durable when used for a long time in high temperature and high humidity conditions. There's a problem. On the other hand, a dye-based polarizing film using a dichroic dye as a polarizing element is superior in moisture resistance and heat resistance to an iodine-based polarizing film, but generally has insufficient polarizing performance.
近年では、タッチパネル向け認識光源や防犯カメラ、センサー、偽造防止、通信機器等の用途において、可視域波長向けの偏光板だけでなく、赤外線領域に用いられる偏光板が求められている。そういった要望に対して、特許文献１のようにヨウ素系偏光板をポリエン化した赤外偏光板や、特許文献２又は３のようなワイヤーグリットを応用した赤外偏光板や、特許文献４のような微粒子を含んだガラスを延伸した赤外偏光子や、特許文献５又は６のようなコレステリック液晶を用いたタイプが報告されている。特許文献１では耐久性が弱く、耐熱性、湿熱耐久性、及び耐光性も弱く、実用に至っていない。特許文献２又は３のようなワイヤグリッドタイプは、フィルムタイプにも加工が可能であると同時に、製品として安定していることから普及が進みつつある。しかしながら、表面にナノレベルの凹凸がないと光学特性を維持でないことから、表面に触れてはならず、そのため使用される用途は制限され、さらには反射防止（ＡＲ）や防呟（アンチグレア）加工をすることが難しい。特許文献４のような微粒子を含んだガラス延伸タイプは高い耐久性を有し、高い二色性を有していることから実用に至っている。しかしながら、微粒子を含みながら延伸されたガラスであるため、素子そのものが割れやすく、もろく、かつ、従来の偏光板のような柔軟性が無く、そのために表面加工や他の基板との貼合が難しいという問題点があった。特許文献５と特許文献６の技術は、古くから公開されている円偏光を用いた技術ではあるが、視認する角度によって色が変わってしまうことや、基本的に、反射を利用した偏光板であるため、迷光や絶対偏光光を形成させることが難しかった。つまり、一般的なヨウ素系偏光板のように吸収型偏光素子であって、フィルムタイプで柔軟性があり、かつ、高い耐久性を有する赤外線波長領域に対応した染料系偏光板は無かった。これは、従来の二色性染料が可視波長域のみの吸収であって、赤外波長域の吸収が無いことに起因する。 In recent years, not only polarizing plates for visible wavelengths but also polarizing plates used in the infrared region have been required in applications such as recognition light sources for touch panels, security cameras, sensors, anti-counterfeiting, and communication devices. In response to such a request, an infrared polarizing plate obtained by polyenizing an iodine-based polarizing plate as in Patent Document 1, an infrared polarizing plate applying a wire grit such as Patent Document 2 or 3, and Patent Document 4 such as Patent Document 4. A type using an infrared polarizing element obtained by stretching a glass containing fine particles and a cholesteric liquid crystal as in Patent Document 5 or 6 has been reported. In Patent Document 1, the durability is weak, the heat resistance, the wet heat durability, and the light resistance are also weak, and it has not been put into practical use. The wire grid type such as Patent Document 2 or 3 can be processed into a film type, and at the same time, it is stable as a product, so that it is becoming widespread. However, since the optical properties cannot be maintained unless the surface has nano-level irregularities, the surface must not be touched, which limits the applications in which it can be used, and also has anti-reflection (AR) and anti-glare (anti-glare) processing. Difficult to do. The stretched glass type containing fine particles as in Patent Document 4 has high durability and high dichroism, and thus has been put into practical use. However, since the glass is stretched while containing fine particles, the element itself is fragile, brittle, and does not have the flexibility of a conventional polarizing plate, so that surface treatment and bonding with other substrates are difficult. There was a problem that it was difficult. The techniques of Patent Document 5 and Patent Document 6 are techniques using circularly polarized light that have been published for a long time, but the color changes depending on the viewing angle, and basically, a polarizing plate using reflection is used. Therefore, it was difficult to form stray light or absolutely polarized light. That is, there has been no dye-based polarizing plate that is an absorption-type polarizing element like a general iodine-based polarizing plate, is a film type, has flexibility, and has high durability and is compatible with the infrared wavelength region. This is because the conventional dichroic dye absorbs only in the visible wavelength region and does not absorb in the infrared wavelength region.
本発明は、赤外域に吸収を有する二色性染料を用いた延伸フィルムでありながら、赤外域の波長の光線に対して機能する高性能な偏光膜及び偏光板、並びにその製造を可能とするアゾ化合物又はその塩を提供することを目的とする。 The present invention enables the production of a high-performance polarizing film and a polarizing plate that function against light having a wavelength in the infrared region, and a polarizing film thereof, while being a stretched film using a dichroic dye having absorption in the infrared region. It is an object of the present invention to provide an azo compound or a salt thereof.
本発明者らは、かかる目的を達成すべく鋭意研究を進めた結果、赤外域に吸収を有する色素を含むフィルムであって、かつ、その色素がフィルム中で配向を成すことによって赤外線波長の光線に対して機能する偏光板を達成しうることを新規に見出し、本発明の完成するに至った。 As a result of diligent research to achieve this object, the present inventors have made a film containing a dye having absorption in the infrared region, and the dye forms an orientation in the film to form an infrared ray having an infrared wavelength. We have newly found that a polarizing plate that functions for the above can be achieved, and have completed the present invention.
すなわち、本発明は、以下の［１］～［１３］に関する。
［１］
下記式（１）：
（式中、Ａ１及びＡ２は各々独立に水素原子又は下記式（２）：
（式中、Ｒ１及びスルホ基が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環であり、Ｒ１は塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より（複数ある場合には各々独立して）選択され、
Ｒ２は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｍは１～３の整数を示す）、
又は、下記式（３）：
（式中、Ｒ３及びスルホ基が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環であり、Ｒ３は式（２）におけるＲ１と同じものを表し、
Ｒ４及びＲ５は各々独立に水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｎは１～３の整数を示す）
で表され、但し、Ａ１及びＡ２の両方が水素原子であるものは除き、
Ａ１が水素原子であるときＲａはヒドロキシ基であり、Ａ１が式（２）又は式（３）で表されるときＲａはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成し、
Ａ２が水素原子であるときＲｂはヒドロキシ基であり、Ａ２が式（２）又は式（３）で表されるときＲｂはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成し、
－ＮＨ－の２結合は、各々独立してａ又はｂで示す置換位置に結合している）
で表されるアゾ又はその塩。
［２］
Ａ１及びＡ２が各々独立に式（２）又は式（３）で表される［１］に記載のアゾ化合物又はその塩。
［３］
Ａ１が式（２）又は式（３）で表され、Ａ２が水素原子である［１］に記載のアゾ化合物又はその塩。
［４］
－ＮＨ－の置換位置がａである［１］～［３］のいずれかに記載のアゾ化合物又はその塩。
［５］
下記式（４）：
（式中、Ｒ６は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｘは、１～３の整数を表す。）
で表される［１］に記載のアゾ化合物又はその塩。
［６］
［１］～［５］のいずれかに記載のアゾ化合物又はその塩と、偏光膜基材とを含む、少なくとも近赤外域に吸収を有する染料系偏光膜。
［７］
［１］～［５］のいずれかに記載のアゾ化合物又はその塩、並びにこれら以外の有機染料を１種類以上含有する偏光膜基材を含む、染料系偏光膜。
［８］
［１］～［５］のいずれかに記載のアゾ化合物又はその塩を２種類以上及びこれら以外の有機染料を１種類以上と、偏光膜基材とを含む、染料系偏光膜。
［９］
偏光膜基材がポリビニルアルコール樹脂又はその誘導体から形成されるフィルムである、［６］～［８］のいずれかに記載の染料系偏光膜。
［１０］
［６］～［９］のいずれかに記載の染料系偏光膜の少なくとも一方の面に透明保護層を貼合して得られる染料系偏光板。
［１１］
［６］～［９］のいずれかに記載の染料系偏光膜又は［１０］に記載の染料系偏光板を備える液晶表示装置。
［１２］
ニュートラルグレーを呈する［６］～［９］のいずれかに記載の染料系偏光膜。
［１３］
［１２］に記載の染料系偏光膜、又は前記染料系偏光膜の少なくとも一方の面に透明保護層を貼合して得られる染料系偏光板を備える車載用表示装置又は屋外表示装置。
That is, the present invention relates to the following [1] to [13].
[1]
The following formula (1):
(In the formula, A 1 and A 2 are independently hydrogen atoms or the following formula (2):
(In the formula, the ring substituted with R1 and the sulfo group is a benzothiazole ring when the ring represented by the broken line is not present, and the naphthoazole ring when the ring represented by the broken line is present. R 1 is a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms having a carboxy group (independently if there are a plurality of groups).
R2 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms having a carboxy group.
m indicates an integer from 1 to 3),
Or, the following formula (3):
( In the formula, the ring substituted with R3 and the sulfo group is a benzothiazole ring when the ring represented by the broken line does not exist, and the naphthoazole ring when the ring represented by the broken line exists. And R 3 represents the same thing as R 1 in the equation (2).
R 4 and R 5 each independently have a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 1 carbon atoms. An alkyl group of 4, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group. It is selected from the group consisting of an alkoxy group having 1 to 4 alkoxy groups and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
n indicates an integer of 1 to 3)
, Except for those in which both A 1 and A 2 are hydrogen atoms.
When A 1 is a hydrogen atom, Ra is a hydroxy group, and when A 1 is represented by the formula (2) or the formula (3 ), Ra is combined with R c or R d - O -Cu. Forming -O-
When A 2 is a hydrogen atom, R b is a hydroxy group, and when A 2 is represented by the formula (2) or the formula (3), R b is combined with R c or R d -O-Cu. Forming -O-
The two -NH- bonds are independently bound to the substitution positions indicated by a or b).
Azo or a salt thereof represented by.
[2]
The azo compound or salt thereof according to [1], wherein A 1 and A 2 are independently represented by the formula (2) or the formula (3).
[3]
The azo compound or salt thereof according to [1], wherein A 1 is represented by the formula (2) or the formula (3), and A 2 is a hydrogen atom.
[4]
The azo compound or salt thereof according to any one of [1] to [3], wherein the substitution position of -NH- is a.
[5]
The following formula (4):
(In the formula, R 6 has a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 4 carbon atoms. An alkyl group, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and 1 to 4 carbon atoms having a hydroxy group. It is selected from the group consisting of an alkoxy group having 4 alkoxy groups and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
x represents an integer of 1 to 3. )
The azo compound or salt thereof according to [1] represented by.
[6]
A dye-based polarizing film having absorption in at least the near infrared region, which comprises the azo compound according to any one of [1] to [5] or a salt thereof and a polarizing film substrate.
[7]
A dye-based polarizing film containing the azo compound according to any one of [1] to [5] or a salt thereof, and a polarizing film substrate containing one or more kinds of organic dyes other than these.
[8]
A dye-based polarizing film containing two or more kinds of the azo compound or a salt thereof according to any one of [1] to [5], one or more kinds of organic dyes other than these, and a polarizing film base material.
[9]
The dye-based polarizing film according to any one of [6] to [8], wherein the polarizing film substrate is a film formed of a polyvinyl alcohol resin or a derivative thereof.
[10]
A dye-based polarizing plate obtained by laminating a transparent protective layer on at least one surface of the dye-based polarizing film according to any one of [6] to [9].
[11]
A liquid crystal display device including the dye-based polarizing film according to any one of [6] to [9] or the dye-based polarizing plate according to [10].
[12]
The dye-based polarizing film according to any one of [6] to [9], which exhibits neutral gray.
[13]
An in-vehicle display device or an outdoor display device provided with the dye-based polarizing film according to [12] or a dye-based polarizing plate obtained by laminating a transparent protective layer on at least one surface of the dye-based polarizing film.
本発明は、赤外域に吸収を有する二色性染料を用いた延伸フィルムでありながら、赤外域の波長の光線に対して機能する高性能な偏光膜及び偏光板、並びにその製造を可能とするアゾ化合物又はその塩を提供することができる。本発明に係る偏光板は、従来の染料系偏光板と同様な取扱いが可能な赤外線波長域の光線向け偏光板である。一態様において、本発明の偏光板は柔軟性及び／又は物理的安定を有する。一態様において、本発明の偏光板は吸収型であるために迷光が発生しない。一態様において、本発明の偏光板は高い耐候性（耐熱性、耐湿熱性、耐光性）を有する。 The present invention enables the production of a high-performance polarizing film and a polarizing plate that function against light having a wavelength in the infrared region, and a polarizing film thereof, while being a stretched film using a dichroic dye having absorption in the infrared region. An azo compound or a salt thereof can be provided. The polarizing plate according to the present invention is a polarizing plate for light rays in the infrared wavelength range that can be handled in the same manner as a conventional dye-based polarizing plate. In one aspect, the polarizing plate of the present invention has flexibility and / or physical stability. In one aspect, since the polarizing plate of the present invention is an absorption type, stray light does not occur. In one aspect, the polarizing plate of the present invention has high weather resistance (heat resistance, moisture heat resistance, light resistance).
＜アゾ化合物又はその塩＞
本発明のアゾ化合物は、下記式（１）：
で表されるアゾ化合物又はその塩である。
式（１）において、－ＮＨ－の２結合は、各々独立してａ又はｂで示す置換位置、好ましくはａで示す置換位置に結合している。<Azo compound or its salt>
The azo compound of the present invention has the following formula (1):
It is an azo compound represented by, or a salt thereof.
In the formula (1), the two bonds of -NH- are independently bonded to the substitution position represented by a or b, preferably the substitution position represented by a.
式（１）において、Ａ１及びＡ２は、水素原子、又は下記式（２）：
又は、下記式（３）：
で表される。但し、Ａ１及びＡ２の両方が水素原子である場合は除く。Ａ１及びＡ２の一方が水素原子であり他方が式（２）で表されるか、又は、Ａ１及びＡ２の両方が式（２）で表される。好ましくは、Ａ１及びＡ２の両方が式（２）で表される。
In the formula (1), A 1 and A 2 are hydrogen atoms, or the following formula (2):
Or, the following formula (3):
It is represented by. However, this excludes cases where both A 1 and A 2 are hydrogen atoms. One of A 1 and A 2 is a hydrogen atom and the other is represented by the formula (2), or both A 1 and A 2 are represented by the formula (2). Preferably, both A 1 and A 2 are represented by the formula (2).
式（２）において、Ｒ１及びスルホ基が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環である。破線で表される環が存在しない場合、すなわちＲ１が置換している環がベンゾチアゾール環である場合、Ｒ１及びスルホ基の置換位置は特に限定されないが、４位のみ、６位のみ、４位と６位の組合せ、及び６位と７位の組合せが好ましく、６位のみ及び４位と６位の組合せがより好ましい。破線で表される環が存在する場合、すなわちＲ１が置換している環がナフトチアゾール環である場合、置換位置は特に限定されないが、６位と８位の組合せ、４位と６位と８位の組合せ、及び、４位と７位と９位の組合せが好ましく、より好ましくは６位と８位の組合せである。In formula (2), the ring substituted with R1 and the sulfo group is a benzothiazole ring when the ring represented by the broken line is not present, and naphtho when the ring represented by the broken line is present. It is a thiazole ring. When the ring represented by the broken line does not exist, that is, when the ring substituted by R 1 is a benzothiazole ring, the substitution positions of R 1 and the sulfo group are not particularly limited, but only the 4-position and the 6-position, The combination of the 4th and 6th positions and the combination of the 6th and 7th positions are preferable, and the combination of only the 6th position and the 4th and 6th positions is more preferable. When the ring represented by the broken line exists, that is, when the ring substituted by R 1 is a naphthozol ring, the substitution position is not particularly limited, but the combination of the 6-position and the 8-position and the 4-position and the 6-position are used. The combination of the 8th position and the combination of the 4th position, the 7th position and the 9th position are preferable, and the combination of the 6th position and the 8th position is more preferable.
Ｒ１は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択される。好ましくはスルホ基、炭素数１～４のアルコキシ基である。Ｒ１が複数ある場合、それらは各々独立に選択される。R 1 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And a group consisting of an alkoxy group having 1 to 4 carbon atoms having a carboxy group. It is preferably a sulfo group or an alkoxy group having 1 to 4 carbon atoms. If there are multiple R1 , they are selected independently.
ヒドロキシ基を有する炭素数１～４のアルコキシ基は、好ましくはアルコキシ基末端がヒドロキシ基で置換された直鎖アルコキシ基であり、より好ましくは４－ヒドロキシプロポキシ基又は４－ヒドロキシブトキシ基である。カルボキシ基を有する炭素数１～４のアルコキシ基は、好ましくはアルコキシ基末端がカルボキシ基で置換された直鎖アルコキシ基であり、より好ましくは４－カルボキシプロポキシ基又は４－カルボキシブトキシ基である。スルホ基を有する炭素数１～４のアルコキシ基は、好ましくはアルコキシ基末端がスルホ基で置換された直鎖アルコキシ基であり、より好ましくは４－スルホプロポキシ基又は４－スルホブトキシ基である。 The alkoxy group having a hydroxy group and having 1 to 4 carbon atoms is preferably a linear alkoxy group in which the end of the alkoxy group is substituted with a hydroxy group, and more preferably a 4-hydroxypropoxy group or a 4-hydroxybutoxy group. The alkoxy group having 1 to 4 carbon atoms having a carboxy group is preferably a linear alkoxy group in which the end of the alkoxy group is substituted with a carboxy group, and more preferably a 4-carboxypropoxy group or a 4-carboxybutoxy group. The alkoxy group having 1 to 4 carbon atoms having a sulfo group is preferably a linear alkoxy group in which the end of the alkoxy group is substituted with a sulfo group, and more preferably a 4-sulfopropoxy group or a 4-sulfobutoxy group.
Ｒ２は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択される。好ましくは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基である。置換位置は特に限定されないが、ＲＣのパラ位が好ましい。 R2 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And a group consisting of an alkoxy group having 1 to 4 carbon atoms having a carboxy group. A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms having a sulfo group are preferable. The substitution position is not particularly limited, but the para position of RC is preferable.
ｍは１～３の整数を示す。 m represents an integer of 1 to 3.
式（３）において、Ｒ３が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環である。破線で表される環が存在しない場合、すなわちＲ３が置換している環がベンゾチアゾール環である場合、Ｒ３の置換位置は特に限定されないが、４位のみ、６位のみ、４位と６位の組合せ、及び６位と７位の組合せが好ましく、６位のみ及び４位と６位の組合せがより好ましい。破線で表される環が存在する場合、すなわちＲ３が置換している環がナフトチアゾール環である場合、置換位置は特に限定されないが、６位と８位の組合せ、４位と６位と８位の組合せ、及び４位と７位と９位の組合せが好ましく、より好ましくは６位と８位の組合せである。２位のみ、６位のみ、７位のみ、２位と６位の組合せ、及び２位と７位の組合せが好ましく、２位のみ及び２位と７位の組合せが特に好ましい。In formula ( 3 ), the ring substituted by R3 is a benzothiazole ring when the ring represented by the broken line is not present, and a naphthoazole ring when the ring represented by the broken line is present. be. When the ring represented by the broken line does not exist, that is, when the ring substituted by R 3 is a benzothiazole ring, the substitution position of R 3 is not particularly limited, but only the 4-position, the 6-position only, and the 4-position. The 6-position combination and the 6-position and 7-position combinations are preferable, and the 6-position only and the 4-position and 6-position combinations are more preferable. When the ring represented by the broken line exists, that is, when the ring substituted by R3 is a naphthozol ring, the substitution position is not particularly limited, but the combination of the 6-position and the 8-position and the 4-position and the 6-position The combination of the 8-position and the combination of the 4-position, the 7-position and the 9-position are preferable, and the combination of the 6-position and the 8-position is more preferable. Only the 2nd place, only the 6th place, only the 7th place, the combination of the 2nd place and the 6th place, and the combination of the 2nd place and the 7th place are preferable, and the combination of the 2nd place only and the 2nd place and the 7th place are particularly preferable.
Ｒ３は式（２）におけるＲ１と同じ意味を表し、Ｒ１から独立して選択される。R 3 has the same meaning as R 1 in the equation (2) and is selected independently of R 1 .
Ｒ４及びＲ５は各々独立に水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択される。好ましくはスルホ基、ヒドロキシ基、炭素数１～４のアルキル基、又は、炭素数１～４のアルコキシ基である。置換位置は特に限定されないが、６位のみ、及び７位のみが好ましい。R 4 and R 5 each independently have a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 1 carbon atoms. An alkyl group of 4, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group. It is selected from the group consisting of 1 to 4 alkoxy groups and 1 to 4 carbon atoms having an alkoxy group having a carboxy group. It is preferably a sulfo group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The substitution position is not particularly limited, but only the 6-position and the 7-position are preferable.
ｎは１～３の整数を示す。 n represents an integer of 1 to 3.
Ａ１が水素原子であるときＲａはヒドロキシ基であり、Ａ１が式（２）又は式（３）で表されるときＲａはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成する。Ａ２が水素原子であるときＲｂはヒドロキシ基であり、Ａ２が式（２）又は式（３）で表されるときＲｂはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成する。When A 1 is a hydrogen atom, Ra is a hydroxy group, and when A 1 is represented by the formula (2) or the formula (3 ), Ra is combined with R c or R d - O -Cu. Forming -O-. When A 2 is a hydrogen atom, R b is a hydroxy group, and when A 2 is represented by the formula (2) or the formula (3), R b is combined with R c or R d -O-Cu. Forming -O-.
式（１）で表されるアゾ化合物は、好ましくは、式（４）：
で表される。
式（４）において、Ｒ６は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択される。
ｘは、１～３の整数を表す。The azo compound represented by the formula (1) is preferably the formula (4) :.
It is represented by.
In the formula (4), R 6 has a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 1 carbon atoms. Alkyl group of 4, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group. It is selected from the group consisting of 1 to 4 alkoxy groups and 1 to 4 carbon atoms having an alkoxy group having a carboxy group.
x represents an integer of 1 to 3.
式（１）で表されるアゾ化合物は遊離形態であっても、塩の形態であってもよい。塩は、例えば、リチウム塩、ナトリウム塩、及びカリウム塩等のアルカリ金属塩、又は、アンモニウム塩やアルキルアミン塩等の有機塩であり得る。塩は、好ましくは、ナトリウム塩である。 The azo compound represented by the formula (1) may be in the free form or in the salt form. The salt may be, for example, an alkali metal salt such as a lithium salt, a sodium salt, and a potassium salt, or an organic salt such as an ammonium salt or an alkylamine salt. The salt is preferably a sodium salt.
次に、式（１）で表されるアゾ化合物の具体例を以下に挙げる。なお、式中のスルホ基、カルボキシ基及びヒドロキシ基は遊離酸の形態で表す。
式（１）で表されるアゾ化合物又はその塩は、例えば、染料化学（細田豊著、１９５７年出版、６２１ページ）等に記載されるような通常のアゾ染料の製造方法に従って、ジアゾ化、カップリングを行うことにより製造することができる。 The azo compound represented by the formula (1) or a salt thereof is diazotized according to an ordinary method for producing an azo dye as described in, for example, dye chemistry (Yutaka Hosoda, published in 1957, p. 621). It can be manufactured by coupling.
具体的な製造方法の例としては次の方法が挙げられる。
下記式（Ａ）で表されるアミノチアゾール類をジアゾ化し、下記式（Ｂ）で表されるアニリン類又は下記式（Ｃ）で表されるアミノナフタレン類と一次カップリングさせ、下記式（Ｄ）又は下記式（Ｅ）で表されるモノアゾアミノ化合物を得る。
The aminothiazoles represented by the following formula (A) are diazotized and primaryly coupled with the anilines represented by the following formula (B) or the aminonaphthalene represented by the following formula (C), and the following formula (D) is used. ) Or a monoazoamino compound represented by the following formula (E).
このモノアゾアミノ化合物（Ｄ）又は（Ｅ）をそれぞれジアゾ化し、下記式（Ｆ）のナフトール類とそれぞれ二次カップリングさせ、得られたアゾ化合物に銅塩を加えて銅錯体化することにより式（１）のアゾ化合物が得られる。
式（Ａ）～（Ｆ）において、Ｒ０及びＲ０が置換している環は式（２）においてＲ１又は式（３）におけるＲ３について説明したのと同じ意味を表し、Ｒ２は式（２）におけるものと同じ意味を表し、Ｒ４及びＲ５は式（３）におけるものと同じ意味を表し、ｌは式（２）におけるｍ又は式（３）におけるｎと同じ意味を表す。Ｒｐ及びＲｑは銅錯塩化前の前駆体である酸素原子を持つ置換基であり、一般的にはヒドロキシ基又は炭素数１～４のアルコキシ基である。In formulas (A) to (F), the rings in which R 0 and R 0 are substituted have the same meanings as described for R 1 in formula (2) or R 3 in formula (3), where R 2 has the same meaning. It has the same meaning as that in the formula (2), R 4 and R 5 have the same meaning as those in the formula (3), and l has the same meaning as m in the formula (2) or n in the formula (3). .. Rp and Rq are substituents having an oxygen atom which is a precursor before copper complex chloride, and are generally hydroxy groups or alkoxy groups having 1 to 4 carbon atoms.
上記製造方法において、ジアゾ化工程は、ジアゾ成分の塩酸、硫酸などの鉱酸水溶液又はけん濁液に亜硝酸ナトリウムなどの亜硝酸塩を混合するという順法によるか、あるいはジアゾ成分の中性又は弱アルカリ性の水溶液に亜硝酸塩を加えておき、これと鉱酸を混合するという逆法によって行うことが好ましい。ジアゾ化の温度は、－１０～４０℃が適当である。また、アニリン類とのカップリング工程は塩酸、酢酸などの酸性水溶液と上記各ジアゾ液を混合し、温度が－１０～４０℃でｐＨ２～７の酸性条件で行うことが好ましい。 In the above production method, the diazotization step is carried out by a normal method of mixing a mineral acid aqueous solution such as hydrochloric acid or sulfuric acid or a turbid solution of the diazo component with a nitrite such as sodium nitrite, or the diazo component is neutral or weak. It is preferable to add nitrite to an alkaline aqueous solution and mix it with mineral acid by the reverse method. The temperature of diazotization is preferably −10 to 40 ° C. Further, it is preferable that the coupling step with anilines is performed by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo solutions at a temperature of −10 to 40 ° C. and acidic conditions of pH 2 to 7.
カップリングして得られた式（Ｄ）又は式（Ｅ）のモノアゾ化合物は、そのまま濾過するか、酸析や塩析により析出させ濾過して取り出すか、溶液又はけん濁液のまま次の工程へ進むこともできる。ジアゾニウム塩が難溶性でけん濁液となっている場合は濾過し、プレスケーキとして次のカップリング工程で使うこともできる。 The monoazo compound of the formula (D) or the formula (E) obtained by coupling can be filtered as it is, precipitated by acidation or salting out and filtered out, or the solution or turbid solution can be used as the next step. You can also proceed to. If the diazonium salt is sparingly soluble and a suspension, it can be filtered and used as a press cake in the next coupling step.
式（Ｄ）又は式（Ｅ）のモノアゾ化合物のジアゾ化物と、式（Ｆ）で表されるナフトール類との二次カップリング反応は、温度が－１０～４０℃でｐＨ７～１０の中性からアルカリ性条件で行われることが好ましい。反応終了後、得られたアゾ化合物又はその塩を、好ましくは塩析により析出させ濾過して取り出す。また、精製が必要な場合には、塩析を繰り返すか又は有機溶媒を使用して水中から析出させればよい。精製に使用する有機溶媒としては、例えばメタノール、エタノール等のアルコール類、アセトン等のケトン類等の水溶性有機溶媒が挙げられる。 The secondary coupling reaction between the diazodized monoazo compound of the formula (D) or the formula (E) and the naphthols represented by the formula (F) is neutral at a temperature of -10 to 40 ° C. and a pH of 7 to 10. It is preferable to carry out under alkaline conditions. After completion of the reaction, the obtained azo compound or a salt thereof is preferably precipitated by salting out and filtered out. If purification is required, salting out may be repeated or precipitation may be performed from water using an organic solvent. Examples of the organic solvent used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
銅錯体化の反応では、上記二次カップリング反応で得られたアゾ化合物又はその塩を含む水溶液に、硫酸銅、塩化銅、及び酢酸銅等の銅塩を加え、アンモニア、モノエタノールアミン、及びジエタノールアミン等のアミン類存在下、例えば７０～１００℃で反応させる。反応終了後、得られたアゾ化合物又はその塩を－好ましくは塩析により析出させ濾過して－取り出すことにより、式（１）で表されるアゾ化合物又はその塩が得られる。 In the copper complexation reaction, copper salts such as copper sulfate, copper chloride, and copper acetate are added to an aqueous solution containing the azo compound or a salt thereof obtained in the above secondary coupling reaction, and ammonia, monoethanolamine, and The reaction is carried out in the presence of amines such as diethanolamine at, for example, 70 to 100 ° C. After completion of the reaction, the obtained azo compound or a salt thereof-preferably precipitated by salting out and filtered-is taken out to obtain an azo compound represented by the formula (1) or a salt thereof.
式（Ａ）で表されるアミノチアゾール化合物は、破線で表される環が存在しない場合には、２－アミノベンゾチアゾール類として表され、例えば、２－アミノ－６－スルホベンゾチアゾール、２－アミノ－７－メトキシ－６－スルホベンゾチアゾール、２－アミノ－４，６－ジスルホベンゾチアゾール、２－アミノ－７－メトキシ－４，６－ジスルホベンゾチアゾールが挙げられる。式（Ａ）で表されるアミノチアゾール化合物は、破線で表される環が存在する場合には、２－アミノナフトチアゾール類として表され、例えば、２－アミノ－６，８－ジスルホナフトチアゾール、２－アミノ－４，６，８－トリスルホナフトチアゾール、２－アミノ－４－クロロ－６，８－ジスルホナフトチアゾール、２－アミノ－６－スルホプロポキシ－４，８－ジスルホナフトチアゾール、２－アミノ－６－スルホプロポキシ－４，７，８－トリスルホナフトチアゾール、２－アミノ－６－メトキシ－４，７，８－トリスルホナフトチアゾール、２－アミノ－７－スルホプロポキシ－４，９－ジスルホナフトチアゾール、２－アミノ－４－スルホプロポキシ－５，７，９－トリスルホナフトチアゾール、等が挙げられ、２－アミノ－６－スルホベンゾチアゾール、２－アミノ－７－メトキシ－６－スルホベンゾチアゾール、２－アミノ－６，８－ジスルホナフトチアゾールが好ましい。 The aminothiazole compound represented by the formula (A) is represented as 2-aminobenzothiazoles in the absence of the ring represented by the broken line, and is represented by, for example, 2-amino-6-sulfobenzothiazole, 2-. Examples thereof include amino-7-methoxy-6-sulfobenzothiazole, 2-amino-4,6-disulfobenzothiazole, and 2-amino-7-methoxy-4,6-disulfobenzothiazole. The aminothiazole compound represented by the formula (A) is represented as 2-aminonaphthiazoles in the presence of a ring represented by a broken line, and is represented by, for example, 2-amino-6,8-disulfonaphthiazole. , 2-Amino-4,6,8-trisulfonaphthiazole, 2-amino-4-chloro-6,8-disulfonaphthiazole, 2-amino-6-sulfopropoxy-4,8-disulfonaphthiazole , 2-Amino-6-sulfopropoxy-4,7,8-trisulfonaphthiazole, 2-amino-6-methoxy-4,7,8-trisulfonaphthiazole, 2-amino-7-sulfopropoxy-4 , 9-Disulfonaphthiazole, 2-amino-4-sulfopropoxy-5,7,9-trisulfonaphthiazole, etc., 2-amino-6-sulfobenzothiazole, 2-amino-7-methoxy, etc. -6-sulfobenzothiazole and 2-amino-6,8-disulfonaphthiazole are preferred.
式（Ｂ）のアニリン類としては、例えば２－メトキシアニリン、２－メトキシ－５－メチルアニリン、２，５－ジメトキシアニリン、２，６－ジメトキシアニリン、２－エトキシアニリン、２－エトキシ－５－メチルアニリン、２，５－ジエトキシアニリン、２，６－ジエトキシアニリン、２－メトキシ－５－エトキシアニリン、２－エトキシ－５－メトキシアニリン、又は２－メトキシ－５－クロロアニリン等が挙げられる。好ましくは２－メトキシ－５－メチルアニリン及び２，５－ジメトキシアニリンが挙げられる。これらのアニリン類はアミノ基が保護されていてもよい。式（Ｃ）のアミノナフタレン類としては、例えば、１－アミノ－２－メトキシナフタレン－６－スルホン酸、１－アミノ－２－メトキシナフタレン－７－スルホン酸、１－アミノ－２－エトキシナフタレン－６－スルホン酸、及び１－アミノ－２－エトキシナフタレン－７－スルホン酸が挙げられる。好ましくは１－アミノ－２－メトキシナフタレン－６－スルホン酸が挙げられる。これらのアミノナフタレン類はアミノ基が保護されていてもよい。保護基としては、例えばそのω－メタンスルホン基が挙げられる。 Examples of the anilines of the formula (B) include 2-methoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2,6-dimethoxyaniline, 2-ethoxyaniline and 2-ethoxy-5-. Examples thereof include methylaniline, 2,5-diethoxyaniline, 2,6-diethoxyaniline, 2-methoxy-5-ethoxyaniline, 2-ethoxy-5-methoxyaniline, 2-methoxy-5-chloroaniline and the like. .. Preferred examples include 2-methoxy-5-methylaniline and 2,5-dimethoxyaniline. These anilines may have an amino group protected. Examples of the aminonaphthalene of the formula (C) include 1-amino-2-methoxynaphthalen-6-sulfonic acid, 1-amino-2-methoxynaphthalen-7-sulfonic acid, and 1-amino-2-ethoxynaphthalene-. 6-Sulfonic acid and 1-amino-2-ethoxynaphthalene-7-sulfonic acid can be mentioned. Preferred are 1-amino-2-methoxynaphthalene-6-sulfonic acid. These aminonaphthalene may have an amino group protected. Examples of the protecting group include the ω-methanesulfon group.
本発明に係るアゾ化合物又はその塩は、近赤外域に吸収を有する。本発明に係るアゾ化合物又はその塩は、フィルムに染色、延伸することで配向し、異方性を有する吸収を発現させることができ、偏光膜用の染料として有用である。ここで、赤外域は一般的に７００～３００００ｎｍを指し、近赤外線の波長は７００～１５００ｎｍの波長を指す。本発明に係るアゾ化合物又はその塩によれば、近赤外域に偏光性能を有する高性能な染料系近赤外吸収偏光板を製造することができる。また、可視光領域に偏光性能を有する染料を併用することにより、これまでの可視光領域だけでなく、近赤外域まで制御できるニュートラルグレーの高性能な染料系偏光板を実現することができる。一態様において、本発明に係るアゾ化合物又はその塩は、高温高湿条件下で使用される車載用又は屋外表示用のニュートラルグレー偏光板や近赤外域の制御が必要な各種センサー向けの近赤外吸収偏光板の製造に好適である。 The azo compound or a salt thereof according to the present invention has absorption in the near infrared region. The azo compound or a salt thereof according to the present invention can be oriented by dyeing and stretching a film to exhibit anisotropic absorption, and is useful as a dye for a polarizing film. Here, the infrared region generally refers to a wavelength of 700 to 30,000 nm, and the wavelength of near infrared rays refers to a wavelength of 700 to 1500 nm. According to the azo compound or a salt thereof according to the present invention, a high-performance dye-based near-infrared absorbing polarizing plate having polarization performance in the near-infrared region can be produced. Further, by using a dye having polarization performance in combination in the visible light region, it is possible to realize a neutral gray high-performance dye-based polarizing plate that can control not only the conventional visible light region but also the near infrared region. In one embodiment, the azo compound or salt thereof according to the present invention is a neutral gray polarizing plate for in-vehicle or outdoor display used under high temperature and high humidity conditions, and near-red for various sensors requiring control in the near-infrared region. It is suitable for manufacturing an external absorption polarizing plate.
＜染料系偏光膜＞
染料系偏光膜は、式（１）で表されるアゾ化合物又はその塩を少なくとも含む二色性色素と、偏光膜基材とを含み、少なくとも近赤外域に吸収を有する。染料系偏光膜は、カラー偏光膜、ニュートラルグレー偏光膜、及び近赤外吸収偏光膜のいずれでもあり得、好ましくは近赤外吸収偏光膜である。ここで、本願明細書及び特許請求の範囲において、「ニュートラルグレー」は、２枚の偏光膜をその配向方向が互いに直交するように重ね合わせた状態（直交位）で、可視光領域及び近赤外域における特定波長の光漏れ（色漏れ）が少ないことを意味する。<Dye-based polarizing film>
The dye-based polarizing film contains a dichroic dye containing at least an azo compound represented by the formula (1) or a salt thereof, and a polarizing film substrate, and has absorption at least in the near infrared region. The dye-based polarizing film can be any of a color polarizing film, a neutral gray polarizing film, and a near-infrared absorbing polarizing film, and is preferably a near-infrared absorbing polarizing film. Here, in the present specification and claims, "neutral gray" is a state in which two polarizing films are overlapped so that their orientation directions are orthogonal to each other (orthogonal position), and is in the visible light region and near-red. It means that there is little light leakage (color leakage) of a specific wavelength in the outer region.
染料系偏光膜は、二色性色素として、式（１）で表されるアゾ化合物又はその塩を１種類又は２種類以上含み、必要に応じて他の有機染料を１種以上さらに含むことができる。併用される他の有機染料は、特に制限はないが、式（１）で表されるアゾ化合物又はその塩の吸収波長領域と異なる波長領域に吸収特性を有する染料であって二色性の高いものであることが好ましい。併用する有機染料としては、例えばシー．アイ．ダイレクト．イエロー１２、シー．アイ．ダイレクト．イエロー２８、シー．アイ．ダイレクト．イエロー４４、シー．アイ．ダイレクト．オレンジ２６、シー．アイ．ダイレクト．オレンジ３９、シー．アイ．ダイレクト．オレンジ７１、シー．アイ．ダイレクト．オレンジ１０７、シー．アイ．ダイレクト．レッド２、シー．アイ．ダイレクト．レッド３１、シー．アイ．ダイレクト．レッド７９、シー．アイ．ダイレクト．レッド８１、シー．アイ．ダイレクト．レッド２４７、シー．アイ．ダイレクト．ブルー６７、シー．アイ．ダイレクト．ブルー２３７、シー．アイ．ダイレクト．ブルー２７３、シー．アイ．ダイレクト．ブルー２７４、シー．アイ．ダイレクト．グリーン８０、及びシー．アイ．ダイレクト．グリーン５９、などの染料等が代表例として挙げられる。これらの色素は、遊離酸として、あるいはアルカリ金属塩（例えばＮａ塩、Ｋ塩、Ｌｉ塩）、アンモニウム塩、又はアミン類の塩として染料系偏光膜に含有される。 The dye-based polarizing film may contain one or more azo compounds represented by the formula (1) or salts thereof as dichroic dyes, and may further contain one or more other organic dyes as necessary. can. The other organic dyes used in combination are not particularly limited, but are dyes having absorption characteristics in a wavelength region different from the absorption wavelength region of the azo compound represented by the formula (1) or a salt thereof, and have high dichroism. It is preferable that it is a thing. Examples of the organic dye used in combination include C.I. Ai. direct. Yellow 12, Sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, Sea. Ai. direct. Orange 71, Sea. Ai. direct. Orange 107, Sea. Ai. direct. Red 2, Sea. Ai. direct. Red 31, Sea. Ai. direct. Red 79, Sea. Ai. direct. Red 81, Sea. Ai. direct. Red 247, Sea. Ai. direct. Blue 67, Sea. Ai. direct. Blue 237, Sea. Ai. direct. Blue 273, Sea. Ai. direct. Blue 274, Sea. Ai. direct. Green 80 and Sea. Ai. direct. Typical examples are dyes such as Green 59. These dyes are contained in the dye-based polarizing film as free acids or as salts of alkali metal salts (for example, Na salt, K salt, Li salt), ammonium salts, or amines.
他の有機染料を併用する場合、目的とする染料系偏光膜が、近赤外吸収偏光膜、ニュートラルグレーの偏光膜、液晶プロジェクター用カラー偏光膜、その他のカラー偏光膜であるかよって、それぞれ配合される他の有機染料の種類は異なる。他の有機染料の配合割合は特に限定されるものではないが、式（１）のアゾ化合物又はその塩１００質量部に対し、１種類又は複数種類の有機染料の合計が０．１～１０質量部の範囲であることが好ましい。 When other organic dyes are used in combination, the target dye-based polarizing film may be a near-infrared absorbing polarizing film, a neutral gray polarizing film, a color polarizing film for a liquid crystal projector, or another color polarizing film. The types of other organic dyes used are different. The blending ratio of the other organic dyes is not particularly limited, but the total of one or more organic dyes is 0.1 to 10% by mass with respect to 100 parts by mass of the azo compound of the formula (1) or a salt thereof. It is preferably in the range of parts.
ニュートラルグレーの偏光膜の場合、得られた偏光膜が可視光領域及び近赤外域の波長領域における色漏れが少なくなるように、併用される他の有機染料の種類及びその配合割合の調整が行われる。 In the case of a neutral gray polarizing film, the types of other organic dyes used in combination and their blending ratios are adjusted so that the obtained polarizing film has less color leakage in the visible light region and the near infrared region. Will be.
染料系偏光膜は、式（１）で表されるアゾ化合物又はその塩を少なくとも含み、必要に応じて他の有機染料をさらに含む二色性色素を、偏光膜基材（例えば、高分子フィルム）に公知の方法で吸着させ配向させる、液晶と共に混合させる、又は塗工方法により配向させることにより製造することができる。 The dye-based polarizing film contains a dichroic dye containing at least an azo compound represented by the formula (1) or a salt thereof, and further containing another organic dye, if necessary, as a polarizing film substrate (for example, a polymer film). ) Can be produced by adsorbing and orienting by a known method, mixing with a liquid crystal, or orienting by a coating method.
偏光膜基材は、好ましくは高分子フィルムであり、より好ましくはポリビニルアルコール樹脂又はその誘導体からなるフィルムである。偏光膜基材の具体例としてはポリビニルアルコール又はその誘導体、及びこれらのいずれかをエチレン、プロピレン等のオレフィンや、クロトン酸、アクリル酸、メタクリル酸、マレイン酸等の不飽和カルボン酸などで変性したもの等が挙げられる。偏光膜基材としては、ポリビニルアルコール又はその誘導体からなるフィルムが、染料の吸着性及び配向性の観点から好適に用いられる。偏光膜基材の厚さは通常３０～１００μｍ、好ましくは５０～８０μｍ程度である。 The polarizing film base material is preferably a polymer film, and more preferably a film made of a polyvinyl alcohol resin or a derivative thereof. Specific examples of the polarizing film base material include polyvinyl alcohol or a derivative thereof, and any of these modified with olefins such as ethylene and propylene, and unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid. Things etc. can be mentioned. As the polarizing film base material, a film made of polyvinyl alcohol or a derivative thereof is preferably used from the viewpoint of dye adsorptivity and orientation. The thickness of the polarizing film substrate is usually about 30 to 100 μm, preferably about 50 to 80 μm.
偏光膜基材が高分子フィルムである場合、式（１）のアゾ化合物又はその塩を少なくとも含む二色性色素を含有せしめるにあたっては、通常、高分子フィルムを染色する方法を採用することができる。染色は、例えば次のように行うことができる。まず、本発明のアゾ化合物又はその塩、及び必要によりこれ以外の有機染料を水に溶解して染浴を調製する。染浴中の染料濃度は特に制限されないが、通常は０．００１～１０質量％程度の範囲から選択される。また、必要により染色助剤を用いてもよく、例えば、芒硝を０．１～１０質量％程度の濃度で用いるのが好適である。このようにして調製した染浴に高分子フィルムを例えば１～１０分間浸漬し、染色を行う。染色温度は、好ましくは４０～８０℃程度である。 When the polarizing film substrate is a polymer film, a method of dyeing the polymer film can usually be adopted in order to contain a dichroic dye containing at least the azo compound of the formula (1) or a salt thereof. .. The dyeing can be performed, for example, as follows. First, the azo compound of the present invention or a salt thereof, and if necessary, other organic dyes are dissolved in water to prepare a dyeing bath. The dye concentration in the dyeing bath is not particularly limited, but is usually selected from the range of about 0.001 to 10% by mass. Further, a dyeing aid may be used if necessary, and for example, it is preferable to use Glauber's salt at a concentration of about 0.1 to 10% by mass. The polymer film is immersed in the dyeing bath thus prepared for, for example, 1 to 10 minutes for dyeing. The dyeing temperature is preferably about 40 to 80 ° C.
式（１）のアゾ化合物又はその塩を含む二色性色素の配向は、染色された高分子フィルムを延伸することによって行われる。延伸する方法としては、例えば湿式法、乾式法など、任意の公知の方法を用いることができる。高分子フィルムの延伸は、場合により、染色の前に行ってもよい。この場合には、染色の時点で水溶性染料の配向が行われる。水溶性染料を含有及び配向せしめた高分子フィルムは、必要に応じて公知の方法によりホウ酸処理などの後処理が施される。このような後処理は、染料系偏光膜の光線透過率及び偏光度を向上させる目的で行われる。ホウ酸処理の条件は、用いる高分子フィルムの種類や用いる染料の種類によって異なるが、一般的にはホウ酸水溶液のホウ酸濃度を０．１～１５質量％、好ましくは１～１０質量％の範囲とし、処理は例えば３０～８０℃、好ましくは４０～７５℃の温度範囲で、例えば０．５～１０分間浸漬して行われる。さらに必要に応じて、カチオン系高分子化合物を含む水溶液で、フィックス処理を併せて行ってもよい。 The orientation of the dichroic dye containing the azo compound of the formula (1) or a salt thereof is performed by stretching the dyed polymer film. As the stretching method, any known method such as a wet method or a dry method can be used. In some cases, the polymer film may be stretched before dyeing. In this case, the orientation of the water-soluble dye is performed at the time of dyeing. The polymer film containing and oriented the water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method, if necessary. Such post-treatment is performed for the purpose of improving the light transmittance and the degree of polarization of the dye-based polarizing film. The conditions for boric acid treatment vary depending on the type of polymer film used and the type of dye used, but in general, the boric acid concentration of the boric acid aqueous solution is 0.1 to 15% by mass, preferably 1 to 10% by mass. The treatment is carried out in a temperature range of, for example, 30 to 80 ° C., preferably 40 to 75 ° C., for example, by immersing for 0.5 to 10 minutes. Further, if necessary, an aqueous solution containing a cationic polymer compound may be used in combination with a fixing treatment.
得られた染料系偏光膜は、保護膜を付けることにより偏光板として使用され得、必要に応じて保護層又はＡＲ（反射防止）層及び支持体等をさらに設けることができる。 The obtained dye-based polarizing film can be used as a polarizing plate by attaching a protective film, and if necessary, a protective layer or an AR (antireflection) layer, a support, and the like can be further provided.
カラー及びニュートラルグレーの染料系偏光膜は、例えば、液晶プロジェクター、電卓、時計、ノートパソコン、ワープロ、液晶テレビ、カーナビゲーション、屋内外の計測器や車等の表示器等、及びレンズやメガネ等に適用されることが好ましい。赤外域吸収偏光膜は、真偽判定用デバイス、ＣＣＤやＣＭＯＳなどのイメージセンサー等に好適に用いられる。染料系偏光膜は、ヨウ素を用いた偏光膜に匹敵する高い偏光性能を有し、かつ、耐久性にも優れる。このため、高い偏光性能と耐久性を必要とする各種液晶表示体用、液晶プロジェクター用、車載用、及び屋外表示用（例えば、工業計器類の表示用途やウェアラブル用途）、高信頼性が必要なセキュリティデバイス等に特に好適である。 Color and neutral gray dye-based polarizing films are used in, for example, liquid crystal projectors, calculators, watches, laptop computers, word processors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring instruments, displays for cars, lenses, glasses, etc. It is preferable to be applied. The infrared absorption polarizing film is suitably used for a device for authenticity determination, an image sensor such as a CCD or CMOS, and the like. The dye-based polarizing film has high polarization performance comparable to that of a polarizing film using iodine, and is also excellent in durability. Therefore, high reliability is required for various liquid crystal displays, liquid crystal projectors, in-vehicle use, and outdoor displays (for example, display applications and wearable applications of industrial instruments) that require high polarization performance and durability. It is particularly suitable for security devices and the like.
＜染料系偏光板＞
染料系偏光板は、染料系偏光膜の片面又は両面に透明保護膜を貼合することにより得ることができる。染料系偏光板は、上記の染料系偏光膜を備えるため、優れた偏光性能及び耐湿性・耐熱性・耐光性を有する。透明保護膜を形成する材料としては、光学的透明性及び機械的強度に優れる材料が好ましく、例えば、セルロースアセテート系フィルムやアクリル系フィルムのほか、四フッ化エチレン／六フッ化プロピレン系共重合体等のフッ素系フィルム、ポリエステル樹脂、ポリオレフィン樹脂又はポリアミド系樹脂からなるフィルム等が用いられる。透明保護膜は、好ましくはトリアセチルセルロース（ＴＡＣ）フィルム又はシクロオレフィン系フィルムである。保護膜の厚さは通常４０～２００μｍであることが好ましい。<Dye-based polarizing plate>
The dye-based polarizing plate can be obtained by laminating a transparent protective film on one side or both sides of the dye-based polarizing film. Since the dye-based polarizing plate includes the above-mentioned dye-based polarizing film, it has excellent polarization performance and moisture resistance, heat resistance, and light resistance. As the material for forming the transparent protective film, a material having excellent optical transparency and mechanical strength is preferable. For example, a cellulose acetate film or an acrylic film, or an ethylene tetrafluoride / propylene hexafluoride copolymer is used. Etc., a film made of a fluororesin, a polyester resin, a polyolefin resin, a polyamide resin, or the like is used. The transparent protective film is preferably a triacetyl cellulose (TAC) film or a cycloolefin-based film. The thickness of the protective film is usually preferably 40 to 200 μm.
偏光膜と保護膜を貼り合わせるのに用い得る接着剤としては、ポリビニルアルコール系接着剤、ウレタンエマルジョン系接着剤、アクリル系接着剤、及びポリエステルーイソシアネート系接着剤等が挙げられ、ポリビニルアルコール系接着剤が好適である。 Examples of the adhesive that can be used to bond the polarizing film and the protective film include polyvinyl alcohol-based adhesives, urethane emulsion-based adhesives, acrylic adhesives, polyester-isocyanate-based adhesives, and the like, and polyvinyl alcohol-based adhesives. The agent is suitable.
染料系偏光板の表面には、さらに透明な保護層を設けてもよい。さらなる透明保護層としては、例えばアクリル系やポリシロキサン系のハードコート層やウレタン系の保護層等が挙げられる。また、単板光透過率をより向上させるために、この保護層の上にＡＲ層を設けることが好ましい。ＡＲ層は、例えば二酸化珪素、酸化チタン等の物質を蒸着又はスパッタリング処理によって形成することができ、またフッ素系物質を薄く塗布することにより形成することができる。染料系偏光板は、表面に位相差板をさらに貼付し、楕円偏光板として使用することもできる。 A more transparent protective layer may be provided on the surface of the dye-based polarizing plate. Further examples of the transparent protective layer include an acrylic or polysiloxane-based hard coat layer and a urethane-based protective layer. Further, in order to further improve the light transmittance of the veneer, it is preferable to provide an AR layer on the protective layer. The AR layer can be formed by depositing or sputtering a substance such as silicon dioxide or titanium oxide, or by applying a thin coat of a fluorine-based substance. The dye-based polarizing plate can also be used as an elliptical polarizing plate by further attaching a retardation plate to the surface.
染料系偏光板は、用途に応じて上記の近赤外吸収偏光板、ニュートラル偏光板、及びカラー偏光板のいずれであってもよい。 The dye-based polarizing plate may be any of the above-mentioned near-infrared absorbing polarizing plate, neutral polarizing plate, and color polarizing plate depending on the application.
ニュートラルグレー偏光板は、可視光領域及び近赤外域において直交位の色漏れが少なく、偏光性能に優れ、さらに高温高湿状態でも変色や偏光性能の低下が防止され、可視光領域における直交位での光漏れが少ないという特徴を有し、車載用又は屋外表示用、高信頼性が必要なセキュリティデバイス等に特に好適である。 The neutral gray polarizing plate has less color leakage at the orthogonal position in the visible light region and the near infrared region, has excellent polarization performance, and is prevented from discoloration and deterioration of the polarization performance even in a high temperature and high humidity state, and at the orthogonal position in the visible light region. It has a feature that there is little light leakage, and is particularly suitable for in-vehicle or outdoor display, security devices that require high reliability, and the like.
車載用又は屋外表示用のニュートラルグレー偏光板は、偏光膜と保護膜からなる偏光板に、単板光透過率をより向上させるために、ＡＲ層を設け、ＡＲ層付き偏光板としたものが好ましく、さらに透明樹脂などの支持体を設けたＡＲ層及び支持体付きの偏光板がより好ましい。ＡＲ層は、偏光板の片面又は両面に設けることができる。支持体は、偏光板の片面に設けることが好ましく、偏光板上にＡＲ層を介して設けられていても直接設けられていてもよい。支持体は偏光板を貼付するための平面部を有しているものが好ましく、また光学用途であるため、透明基板であること好ましい。透明基板としては、大きく分けて無機基板と有機基板があり、ソーダガラス、ホウ珪酸ガラス、水晶基板、サファイヤ基板、及びスピネル基板等の無機基板、並びにアクリル、ポリカーボネート、ポリエチレンテレフタレート、ポリエチレンナフタレート、及びシクロオレフィンポリマー等の有機基板が挙げられるが、有機基板が好ましい。透明基板の厚さや大きさは所望のサイズでよい。 The neutral gray polarizing plate for in-vehicle use or outdoor display is a polarizing plate composed of a polarizing film and a protective film, which is provided with an AR layer in order to further improve the light transmittance of a single plate to form a polarizing plate with an AR layer. More preferably, an AR layer provided with a support such as a transparent resin and a polarizing plate with the support are more preferable. The AR layer can be provided on one side or both sides of the polarizing plate. The support is preferably provided on one side of the polarizing plate, and may be provided on the polarizing plate via the AR layer or may be provided directly. The support preferably has a flat surface portion for attaching the polarizing plate, and is preferably a transparent substrate because it is used for optics. Transparent substrates are broadly divided into inorganic substrates and organic substrates. Inorganic substrates such as soda glass, borosilicate glass, crystal substrates, sapphire substrates, and spinel substrates, as well as acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and Examples thereof include an organic substrate such as a cycloolefin polymer, but an organic substrate is preferable. The thickness and size of the transparent substrate may be a desired size.
近赤外吸収偏光板は、偏光性能に優れ、高温高湿状態でも変色や偏光性能の低下を起こさないため、液晶プロジェクター用、車載用、屋外表示用、高信頼性が必要なセキュリティデバイス用に好適である。これらの偏光板は、染料系偏光膜に保護膜を付け偏光板とし、必要に応じて保護層又はＡＲ層及び支持体等を設けて用いられる。 Near-infrared polarizing polarizing plates have excellent polarization performance and do not cause discoloration or deterioration of polarization performance even in high temperature and high humidity conditions, so they are used for liquid crystal projectors, in-vehicle use, outdoor display, and security devices that require high reliability. Suitable. These polarizing plates are used by attaching a protective film to a dye-based polarizing film to form a polarizing plate, and if necessary, providing a protective layer, an AR layer, a support, or the like.
単板平均光透過率は、偏光膜、又はＡＲ層及び透明ガラス板等の支持体の設けていない１枚の偏光板（以下、単に偏光板と言うときは同様な意味で使用する）に自然光を入射したときの特定波長領域における光線透過率の平均値である。直交位の平均光透過率は、配向方向を直交になるように配置した２枚の偏光膜又は偏光板に自然光を入射したときの特定波長領域における光透過率の平均値である。 The average light transmittance of a single plate is determined by natural light on a single polarizing plate (hereinafter, simply referred to as a polarizing plate is used in the same meaning) without a support such as a polarizing film or an AR layer and a transparent glass plate. It is the average value of the light transmittance in a specific wavelength region when the light is incident. The average light transmittance at the orthogonal position is the average value of the light transmittance in a specific wavelength region when natural light is incident on two polarizing films or polarizing plates arranged so that the orientation directions are orthogonal to each other.
車載用又は屋外用表示装置のための支持体付カラー偏光板は、例えば、支持体平面部に透明な接着（粘着）剤を塗布し、次いでこの塗布面に染料系偏光板を貼付することにより製造することができる。また、染料系偏光板に透明な接着（粘着）剤を塗布し、ついでこの塗布面に支持体を貼付してもよい。ここで使用する接着（粘着）剤は、例えばアクリル酸エステル系のものが好ましい。なお、この染料系偏光板を楕円偏光板として使用する場合、位相差板側を支持体側に貼付するのが通常であるが、偏光板側を透明基板に貼付してもよい。 A color polarizing plate with a support for an in-vehicle or outdoor display device is obtained by, for example, applying a transparent adhesive (adhesive) agent to the flat surface portion of the support and then attaching a dye-based polarizing plate to the coated surface. Can be manufactured. Further, a transparent adhesive (adhesive) may be applied to the dye-based polarizing plate, and then a support may be attached to the applied surface. As the adhesive (adhesive) used here, for example, an acrylic acid ester-based adhesive is preferable. When this dye-based polarizing plate is used as an elliptical polarizing plate, the retardation plate side is usually attached to the support side, but the polarizing plate side may be attached to the transparent substrate.
＜液晶表示装置＞
液晶表示装置は、上記の染料系偏光膜又は染料系偏光板を備える。液晶表示装置は、例えば電卓、時計、ノートパソコン、ワープロ、液晶テレビ、カーナビゲーション、及び屋内外の計測器や表示器等用のディスプレイ用であり、特に、高い偏光性能と耐久性を必要とする各種液晶表示体、例えば車載用及び屋外表示用（例えば、工業計器類の表示用途やウェアラブル用途）に好適に用いられる。<Liquid crystal display device>
The liquid crystal display device includes the above-mentioned dye-based polarizing film or dye-based polarizing plate. Liquid crystal displays are for, for example, calculators, watches, laptops, word processors, LCD TVs, car navigation systems, and displays for indoor and outdoor measuring instruments and displays, and in particular, require high polarization performance and durability. It is suitably used for various liquid crystal displays, for example, for in-vehicle and outdoor displays (for example, display applications and wearable applications of industrial instruments).
車載用又は屋外用の液晶表示装置には、ニュートラルグレーの偏光膜又は偏光板が備えられていることが好適である。ニュートラルグレー偏光膜又は偏光板が明るさと優れた偏光性能、耐久性及び耐光性を有するため、車内や屋外の高温高湿状態でも変色や偏光性能の低下を起こし難く、信頼性が高い車載用又は屋外用表示装置を実現することができる。 It is preferable that the liquid crystal display device for automobiles or outdoors is provided with a neutral gray polarizing film or a polarizing plate. Since the neutral gray polarizing film or polarizing plate has brightness and excellent polarization performance, durability and light resistance, it is unlikely to cause discoloration or deterioration of polarization performance even in high temperature and high humidity conditions inside or outdoors, and is highly reliable for in-vehicle use or. An outdoor display device can be realized.
以下、実施例により本発明をさらに詳細に説明するが、これらは例示的なものであって、本発明を限定するものではない。％及び部は、特にことわらないかぎり質量基準である。 Hereinafter, the present invention will be described in more detail by way of examples, but these are exemplary and are not intended to limit the present invention. % And parts are based on mass unless otherwise specified.
［実施例１］
２－アミノナフトチアゾール－６，８－ジスルホン酸３６．０部を９８％硫酸１００部に加え、５０℃で溶解させたのち、６０％硝酸１２．６部を加え、５～１０℃で４０％ニトロシル硫酸５０部を約１０分間で滴下し、１時間反応することによりジアゾ反応液を得た。次に、２，５－ジメトキシアニリン１５．３部を、３５％塩酸１０．４部を水１００部で希釈した酸性水溶液に加えて溶解させた。この水溶液に先ほどのジアゾ反応液を３時間かけて滴下し、終夜撹拌してカップリング反応を完結させた。その後、濾過を行い、下記式（４５）で表されるモノアゾアミノ化合物４１．９部を得た。
Add 36.0 parts of 2-aminonaphthiazole-6,8-disulfonic acid to 100 parts of 98% sulfuric acid, dissolve at 50 ° C, add 12.6 parts of 60% nitric acid, and add 40% at 5-10 ° C. 50 parts of nitrosylsulfuric acid was added dropwise in about 10 minutes, and the reaction was carried out for 1 hour to obtain a diazo reaction solution. Next, 15.3 parts of 2,5-dimethoxyaniline was dissolved by adding 10.4 parts of 35% hydrochloric acid to an acidic aqueous solution diluted with 100 parts of water. The above diazo reaction solution was added dropwise to this aqueous solution over 3 hours, and the mixture was stirred overnight to complete the coupling reaction. Then, filtration was performed to obtain 41.9 parts of a monoazoamino compound represented by the following formula (45).
得られたモノアゾアミノ化合物（４５）４１．９部を水２００部に加え、そこに２５％水酸化ナトリウムを加えて、モノアゾアミノ化合物（４５）を溶解させた。４０％亜硝酸ナトリウム水溶液を１３．８部加え、次に２０～３０℃で３５％塩酸２５．０部を加え、２０～３０℃で１時間攪拌し、ジアゾ化物を得た。一方、６，６’－イミノビス（１－ヒドロキシナフタレン－３－スルホン酸）３６．９部を水１００部に加え、そこに２５％水酸化ナトリウム水溶液を加えて弱アルカリ性として、６，６’－イミノビス（１－ヒドロキシナフタレン－３－スルホン酸）を溶解した。この液に、先に得られたジアゾ化物をｐＨ８～１０に保って滴下し、攪拌してカップリング反応を完結させた。その後、塩化ナトリウムで塩析させた後、濾過して式（４６）で表されるジスアゾ化合物６３．７部を得た。
得られたジスアゾアミノ化合物（４６）６３．７部を水２００部に加えて溶解したのち、硫酸銅五水和物１９．２部、モノエタノールアミン３９．０部を加え、９５℃で３時間反応させた。反応終了後、放冷したのち塩化ナトリウムで塩析し、濾過して前記式（８）で表される化合物５３．５部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は７５２ｎｍ であった。 63.7 parts of the obtained disazoamino compound (46) was added to 200 parts of water to dissolve it, then 19.2 parts of copper sulfate pentahydrate and 39.0 parts of monoethanolamine were added, and the temperature was 95 ° C. for 3 hours. It was reacted. After completion of the reaction, the mixture was allowed to cool, salted out with sodium chloride, and filtered to obtain 53.5 parts of the compound represented by the above formula (8). The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 752 nm.
［実施例２］
６，６’－イミノビス（１－ヒドロキシナフタレン－３－スルホン酸）３６．９部を７，７’－イミノビス（１－ヒドロキシナフタレン－３－スルホン酸）３６．９部に替える以外は実施例１と同様にして、式（９）で表される化合物５３．５部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は７５６ｎｍであった。[Example 2]
Example 1 except that 36.9 parts of 6,6'-iminobis (1-hydroxynaphthalene-3-sulfonic acid) is replaced with 36.9 parts of 7,7'-iminobis (1-hydroxynaphthalene-3-sulfonic acid). In the same manner as above, 53.5 parts of the compound represented by the formula (9) was obtained. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 756 nm.
［実施例３］
２－アミノナフトチアゾール－６，８－ジスルホン酸３６．０部を２－アミノ－７－メトキシベンゾチアゾール－６－スルホン酸２６．０部に替える以外は実施例１と同様にして、式（１５）で表される化合物４６．７部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は６９２ｎｍであった。[Example 3]
The formula (15) was the same as in Example 1 except that 36.0 parts of 2-aminonaphthiazole-6,8-disulfonic acid was replaced with 26.0 parts of 2-amino-7-methoxybenzothiazole-6-sulfonic acid. ) Was obtained in 46.7 parts. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 692 nm.
［実施例４］
前記式（４５）で表される化合物４１．９部を実施例１と同様にジアゾ化し、前記式（４６）で表される化合物７９．６部を水２００部に加えて溶解させた水溶液にｐＨ９～１１に保って滴下し、攪拌してカップリング反応を完結させた。その後、塩化ナトリウムで塩析させた後、濾過して式（４７）で表されるテトラキスアゾ化合物７８．４部を得た。
41.9 parts of the compound represented by the formula (45) were diazotized in the same manner as in Example 1, and 79.6 parts of the compound represented by the formula (46) was added to 200 parts of water and dissolved in an aqueous solution. The pH was maintained at 9 to 11 and the solution was added dropwise, and the mixture was stirred to complete the coupling reaction. Then, it was salted out with sodium chloride and then filtered to obtain 78.4 parts of the tetrakisazo compound represented by the formula (47).
得られたテトラキスアゾアミノ化合物（４７）７８．４部を水２００部に加えて溶解したのち、硫酸銅五水和物３０．７部、モノエタノールアミン３１．２部を加え、９５℃で３時間反応させた。反応終了後、放冷したのち塩化ナトリウムで塩析し、濾過して前記式（１７）で表される化合物６６．６部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は８０２ｎｍ であった。 78.4 parts of the obtained tetrakisazoamino compound (47) was added to 200 parts of water to dissolve it, then 30.7 parts of copper sulfate pentahydrate and 31.2 parts of monoethanolamine were added, and 3 at 95 ° C. Reacted for time. After completion of the reaction, the mixture was allowed to cool, salted out with sodium chloride, and filtered to obtain 66.6 parts of the compound represented by the above formula (17). The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 802 nm.
［実施例５］
前記式（８）で表される化合物を前記式（９）で表される化合物に替える以外は実施例４と同様にして、式（１８）で表される化合物を６６．６部得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は８０６ｎｍであった。[Example 5]
66.6 parts of the compound represented by the formula (18) was obtained in the same manner as in Example 4 except that the compound represented by the formula (8) was replaced with the compound represented by the formula (9). The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 806 nm.
［実施例６］
２－アミノナフトチアゾール－６，８－ジスルホン酸３６．０部を２－アミノベンゾチアゾール－６－スルホン酸２３．０部に替える以外は実施例１、実施例４と同様にして、式（２７）で表される化合物５５．９部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は７０６ｎｍであった。[Example 6]
The formula (27) was the same as in Example 1 and Example 4 except that 36.0 parts of 2-aminonaphthiazole-6,8-disulfonic acid was replaced with 23.0 parts of 2-aminobenzothiazole-6-sulfonic acid. ) Was obtained in 55.9 parts. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 706 nm.
［実施例７］
２－アミノナフトチアゾール－６，８－ジスルホン酸３６．０部を２－アミノ－７－メトキシベンゾチアゾール－６－スルホン酸２６．０部に替える以外は実施例１、実施例４と同様にして、式（２９）で表される化合物５５．９部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は７２３ｎｍであった。[Example 7]
Same as in Examples 1 and 4 except that 36.0 parts of 2-aminonaphthiazole-6,8-disulfonic acid is replaced with 26.0 parts of 2-amino-7-methoxybenzothiazole-6-sulfonic acid. , 55.9 parts of the compound represented by the formula (29) were obtained. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 723 nm.
［実施例８］
２，５－ジメトキシアニリン１５．３部を２－メトキシ－５－メチルアニリン１３．７部に替える以外は実施例１と同様にして式（４８）で表されるモノアゾ化合物４０．６部を得た。
40.6 parts of the monoazo compound represented by the formula (48) was obtained in the same manner as in Example 1 except that 15.3 parts of 2,5-dimethoxyaniline was replaced with 13.7 parts of 2-methoxy-5-methylaniline. rice field.
式（４５）で表される化合物４１．９部を式（４８）で表される化合物４０．６部に替える以外は実施例４と同様にして、式（３５）で表される化合物６５．９部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は７９４ｎｍ であった。 Compound 65. Compound represented by formula (35) in the same manner as in Example 4 except that 41.9 parts of the compound represented by the formula (45) is replaced with 40.6 parts of the compound represented by the formula (48). I got 9 copies. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 794 nm.
［実施例９］
２－アミノナフトチアゾール－６，８－ジスルホン酸３６．０部を２－アミノベンゾチアゾール－６－スルホン酸２３．０部に替える以外は実施例１と同様にして、式（１３）で表される化合物４６．７部を得た。２０％ピリジン水溶液中のその化合物の極大吸収波長は６５２ｎｍであった。[Example 9]
It is represented by the formula (13) in the same manner as in Example 1 except that 36.0 parts of 2-aminonaphthiazole-6,8-disulfonic acid is replaced with 23.0 parts of 2-aminobenzothiazole-6-sulfonic acid. 46.7 parts of the compound was obtained. The maximum absorption wavelength of the compound in the 20% aqueous pyridine solution was 652 nm.
［作製例１：偏光膜］
実施例１で得られた式（８）の化合物を０．０３％及び芒硝を０．１％の濃度とした４５℃の水溶液からなる染色液に、厚さ７５μｍのポリビニルアルコールを４分間浸漬した。このフィルムを３％ホウ酸水溶液中で５０℃で５倍に延伸し、緊張状態を保ったまま水洗、乾燥して偏光膜を得た。[Production Example 1: Polarizing film]
A 75 μm-thick polyvinyl alcohol was immersed in a staining solution consisting of an aqueous solution of the formula (8) obtained in Example 1 at a concentration of 0.03% and Glauber's salt at a concentration of 0.1% at 45 ° C. for 4 minutes. .. This film was stretched 5 times at 50 ° C. in a 3% aqueous boric acid solution, washed with water and dried while maintaining a tense state to obtain a polarizing film.
［作製例２～８：偏光膜］
式（８）の化合物に代えて、実施例２～８で得られた式（９）、（１５）、（１７）、（１８）、（２７）、（２９）、（３５）のアゾ化合物を用いた点以外は作製例１と同様にして偏光膜を得た。[Production Examples 2 to 8: Polarizing Film]
Instead of the compound of the formula (8), the azo compound of the formulas (9), (15), (17), (18), (27), (29), (35) obtained in Examples 2 to 8 A polarizing film was obtained in the same manner as in Production Example 1 except that the above was used.
（偏光膜の極大吸収波長及び偏光率の測定）
偏光膜の作製例１～９で得られた偏光膜について、極大吸収波長及び偏光率を測定した。偏光膜の極大吸収波長の測定及び偏光率の算出は、偏光入射時の平行透過率、ならびに直交透過率を分光光度計（日立製作所製；Ｕ－４１００）を用いて測定し、算出した。ここで平行透過率（Ｋｙ）とは、絶対偏光子の吸収軸と偏光膜の吸収軸が、平行時の透過率であり、直交透過率（Ｋｚ）とは、絶対偏光子の吸収軸と偏光膜の吸収軸が、直交時の透過率を示す。各波長の平行透過率及び直交透過率は、３８０～１１００ｎｍにおいて、１ｎｍ間隔で測定した。それぞれ測定した値を用いて、下記式（ｉ）より各波長の偏光率を算出し、３８０～１１００ｎｍにおける最も大きい偏光率と、その時の吸収波長（ｎｍ）を得た。結果を表１に示す。
偏光率（％）＝［（Ｋｙ－Ｋｚ）／（Ｋｙ＋Ｋｚ）］×１００ （ｉ）
(Measurement of maximum absorption wavelength and polarization rate of polarizing film)
The maximum absorption wavelength and the polarization rate of the polarizing films obtained in Production Examples 1 to 9 of the polarizing film were measured. The maximum absorption wavelength of the polarizing film and the calculation of the polarization rate were calculated by measuring the parallel transmittance and the orthogonal transmittance at the time of incident polarization using a spectrophotometer (manufactured by Hitachi, Ltd .; U-4100). Here, the parallel transmittance (Ky) is the transmittance when the absorption axis of the absolute modulator and the absorption axis of the polarizing film are parallel, and the orthogonal transmittance (Kz) is the absorption axis of the absolute polarizing element and the polarization. The absorption axis of the film shows the transmittance when it is orthogonal. The parallel transmittance and the orthogonal transmittance of each wavelength were measured at 380 to 1100 nm at 1 nm intervals. The polarization rate of each wavelength was calculated from the following formula (i) using the measured values, and the maximum polarization rate in 380 to 1100 nm and the absorption wavelength (nm) at that time were obtained. The results are shown in Table 1.
Polarization rate (%) = [(Ky-Kz) / (Ky + Kz)] x 100 (i)
表１の通り、これらの化合物を用いて作成した偏光膜は、いずれも近赤外域に吸収を有しており、かつ高い偏光率を有していた。 As shown in Table 1, all the polarizing films prepared by using these compounds had absorption in the near infrared region and had a high polarization rate.
［作製例９：ニュートラルグレー偏光板］
染色液として、式（１７）の化合物を０．２％、シー・アイ・ダイレクト・オレンジ３９を０．０７％、シー・アイ・ダイレクト・レッド８１を０．０２％、シー・アイ・ダイレクト・ブルー２７４を０．０３％、及び芒硝を０．１％の濃度とした４５℃の水溶液を用いた点以外は、作製例１と同様にして偏光膜を作製した。得られた偏光膜は３８０～８５０ｎｍにおける単板平均透過率が３８％、直交位の平均光透過率は０．０２％であり、広帯域にわたり高い偏光度を有していた。さらに、平行位及び直交位ともに可視光領域における透過率がほぼ一定であり、ニュートラルグレーの色相を呈していた。
この偏光膜の両面に、１枚ずつのトリアセチルセルロースフィルム（ＴＡＣフィルム；富士写真フィルム社製；商品名ＴＤ－８０Ｕ）をポリビニルアルコール水溶液の接着剤を介してラミネートした。次いで、片方のＴＡＣフィルム上に、粘着剤を用いてＡＲ支持体（日油社製；リアルックＸ４０１０）を積層させて、ＡＲ支持体付きのニュートラルグレーの染料系偏光板を得た。得られた偏光板は、偏光膜と同様に、ニュートラルグレーの色相を呈し、かつ、高い偏光率を有していた。
さらに、データは示していないが、得られた偏光板は、高温且つ高湿の状態でも長時間にわたる耐久性を示し、また、長時間暴露に対する耐光性も優れていた。[Production Example 9: Neutral Gray Polarizing Plate]
As the dyeing solution, 0.2% of the compound of the formula (17), 0.07% of C.I.Direct Orange 39, 0.02% of C.I.Direct Red 81, and C.I.Direct. A polarizing film was prepared in the same manner as in Preparation Example 1 except that an aqueous solution at 45 ° C. having a concentration of Blue 274 at 0.03% and Glauber's salt at 0.1% was used. The obtained polarizing film had a single plate average transmittance of 38% at 380 to 850 nm and an average light transmittance of 0.02% at the orthogonal position, and had a high degree of polarization over a wide band. Further, the transmittance in the visible light region was almost constant in both the parallel position and the orthogonal position, and the hue was neutral gray.
One triacetyl cellulose film (TAC film; manufactured by Fuji Photo Film Co., Ltd .; trade name TD-80U) was laminated on both sides of this polarizing film via an adhesive of a polyvinyl alcohol aqueous solution. Next, an AR support (manufactured by NOF CORPORATION; Realc X4010) was laminated on one of the TAC films using an adhesive to obtain a neutral gray dye-based polarizing plate with the AR support. The obtained polarizing plate exhibited a neutral gray hue and had a high polarization ratio, similar to the polarizing film.
Furthermore, although no data are shown, the obtained polarizing plate showed durability over a long period of time even in a high temperature and high humidity state, and also had excellent light resistance to long-term exposure.
Claims (13)
（式中、Ａ１及びＡ２は各々独立に水素原子又は下記式（２）：
（式中、Ｒ１及びスルホ基が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環であり、Ｒ１は塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より（複数ある場合には各々独立して）選択され、
Ｒ２は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｍは１～３の整数を示す）、
又は、下記式（３）：
（式中、Ｒ３及びスルホ基が置換している環は、破線で表される環が存在しない場合にはベンゾチアゾール環であり、破線で表される環が存在する場合にはナフトチアゾール環であり、Ｒ３は式（２）におけるＲ１と同じものを表し、
Ｒ４及びＲ５は各々独立に水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｎは１～３の整数を示す）
で表され、但し、Ａ１及びＡ２の両方が水素原子であるものは除き、
Ａ１が水素原子であるときＲａはヒドロキシ基であり、Ａ１が式（２）又は式（３）で表されるときＲａはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成し、
Ａ２が水素原子であるときＲｂはヒドロキシ基であり、Ａ２が式（２）又は式（３）で表されるときＲｂはＲｃ又はＲｄと一緒になって－Ｏ－Ｃｕ－Ｏ－を形成し、
Ａ １ 及びＡ ２ が各々独立に式（２）又は式（３）で表されるとき、
・Ｒ ａ はＲ ｃ 又はＲ ｄ と一緒になってーＯーＣｕ－Ｏ－を形成し、Ｒ ｂ はＲ ｃ 又はＲ ｄ と一緒になってーＯ－Ｃｕ－Ｏ－を形成するか、
・Ｒ ａ はＲ ｃ 又はＲ ｄ と一緒になってーＯーＣｕ－Ｏ－を形成し、Ｒ ｂ は水酸基を表し、Ａ ２ 中のＲ ｃ 又はＲ ｄ はメトキシ基を表すか、又は
・Ｒ ａ は水酸基を表し、Ａ １ 中のＲ ｃ 又はＲ ｄ はメトキシ基を表し、Ｒ ｂ はＲ ｃ 又はＲ ｄ と一緒になってーＯ－Ｃｕ－Ｏ－を形成し、
－ＮＨ－の２結合は、各々独立してａ又はｂで示す置換位置に結合している）
で表されるアゾ又はその塩。 The following formula (1):
(In the formula, A 1 and A 2 are independently hydrogen atoms or the following formula (2):
(In the formula, the ring substituted with R1 and the sulfo group is a benzothiazole ring when the ring represented by the broken line is not present, and the naphthoazole ring when the ring represented by the broken line is present. R 1 is a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms having a carboxy group (independently if there are a plurality of groups).
R2 is a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a sulfo group, and hydroxy. An alkyl group having 1 to 4 carbon atoms having a group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and an alkoxy group having 1 to 4 carbon atoms having a hydroxy group. , And selected from the group consisting of alkoxy groups having 1 to 4 carbon atoms having a carboxy group.
m indicates an integer from 1 to 3),
Or, the following formula (3):
( In the formula, the ring substituted with R3 and the sulfo group is a benzothiazole ring when the ring represented by the broken line does not exist, and the naphthoazole ring when the ring represented by the broken line exists. And R 3 represents the same thing as R 1 in the equation (2).
R 4 and R 5 each independently have a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 1 carbon atoms. An alkyl group of 4, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and a carbon number having a hydroxy group. It is selected from the group consisting of an alkoxy group having 1 to 4 alkoxy groups and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
n indicates an integer of 1 to 3)
, Except for those in which both A 1 and A 2 are hydrogen atoms.
When A 1 is a hydrogen atom, Ra is a hydroxy group, and when A 1 is represented by the formula (2) or the formula (3 ), Ra is combined with R c or R d - O -Cu. Forming -O-
When A 2 is a hydrogen atom, R b is a hydroxy group, and when A 2 is represented by the formula (2) or the formula (3), R b is combined with R c or R d -O-Cu. Forming -O-
When A 1 and A 2 are independently represented by Eq. (2) or Eq. (3), respectively.
R a together with R c or R d to form -O-Cu-O-, and R b together with R c or R d to form -O-Cu-O-.
R a together with R c or R d form —O—Cu—O—, R b represents a hydroxyl group, and R c or R d in A 2 represents a methoxy group or
R a represents a hydroxyl group, R c or R d in A 1 represents a methoxy group, and R b together with R c or R d forms —O—Cu—O—.
The two -NH- bonds are independently bound to the substitution positions indicated by a or b).
Azo or a salt thereof represented by.
（式中、Ｒ６は水素原子、塩素原子、スルホ基、ニトロ基、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、スルホ基を有する炭素数１～４のアルキル基、ヒドロキシ基を有する炭素数１～４のアルキル基、カルボキシ基を有する炭素数１～４のアルキル基、スルホ基を有する炭素数１～４のアルコキシ基、ヒドロキシ基を有する炭素数１～４のアルコキシ基、及びカルボキシ基を有する炭素数１～４のアルコキシ基からなる群より選択され、
ｘは、１～３の整数を表す。）
で表される請求項１に記載のアゾ化合物又はその塩。 The following formula (4):
(In the formula, R 6 has a hydrogen atom, a chlorine atom, a sulfo group, a nitro group, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a sulfo group having 1 to 4 carbon atoms. An alkyl group, an alkyl group having 1 to 4 carbon atoms having a hydroxy group, an alkyl group having 1 to 4 carbon atoms having a carboxy group, an alkoxy group having 1 to 4 carbon atoms having a sulfo group, and 1 to 4 carbon atoms having a hydroxy group. It is selected from the group consisting of an alkoxy group having 4 alkoxy groups and an alkoxy group having 1 to 4 carbon atoms having a carboxy group.
x represents an integer of 1 to 3. )
The azo compound according to claim 1 or a salt thereof.
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| PCT/JP2018/001588 WO2018135618A1 (en) | 2017-01-20 | 2018-01-19 | Azo compound or salt thereof, as well as dye-type polarizer film and dye-type polarizer plate including same |
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| WO2020203640A1 (en) * | 2019-04-05 | 2020-10-08 | 株式会社ポラテクノ | Polarizing element containing cellulose nanofibers (cnf) and polarizing plate |
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| WO2012165223A1 (en) | 2011-05-30 | 2012-12-06 | 日本化薬株式会社 | Dye-based polarizing element and polarizing plate |
| WO2015186681A1 (en) | 2014-06-03 | 2015-12-10 | 日本化薬株式会社 | Achromatic polarizing plate with high-transmissivity and high-degree of polarization |
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| JPS61145284A (en) * | 1984-12-19 | 1986-07-02 | Mitsubishi Chem Ind Ltd | Liquid crystal composition |
| JPS6279271A (en) * | 1986-09-12 | 1987-04-11 | Casio Comput Co Ltd | Trisazo based compound |
| DE69228591T2 (en) * | 1991-12-26 | 1999-07-01 | Mitsui Chemicals, Inc., Tokio/Tokyo | Water-soluble azo dyes and polarizing films containing these dyes |
| JP3852966B2 (en) * | 1994-06-22 | 2006-12-06 | 三井化学株式会社 | Azo compound and polarizing film using the compound |
| JP3624961B2 (en) * | 1994-10-31 | 2005-03-02 | 三井化学株式会社 | Azoxy compound and polarizing film using the compound |
| JP2004086100A (en) | 2002-08-29 | 2004-03-18 | Arisawa Mfg Co Ltd | Polarizing glass and its manufacture method |
| MY139010A (en) * | 2005-01-21 | 2009-08-28 | Ciba Holding Inc | 6-azo-5, 5'-dihydroxy -7,7'-disulfo-2-2'-dinaphthylamine derivatives |
| JPWO2009078253A1 (en) * | 2007-12-14 | 2011-04-28 | 日本化薬株式会社 | Trisazo compound, ink composition, recording method and colored body |
| JPWO2010109843A1 (en) * | 2009-03-27 | 2012-09-27 | 日本化薬株式会社 | Azo compound, ink composition, recording method and colored body |
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| WO2012165223A1 (en) | 2011-05-30 | 2012-12-06 | 日本化薬株式会社 | Dye-based polarizing element and polarizing plate |
| WO2015186681A1 (en) | 2014-06-03 | 2015-12-10 | 日本化薬株式会社 | Achromatic polarizing plate with high-transmissivity and high-degree of polarization |
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