CA2006427A1 - Light-polarizing films or sheets containing stilbene dyestuffs - Google Patents
Light-polarizing films or sheets containing stilbene dyestuffsInfo
- Publication number
- CA2006427A1 CA2006427A1 CA002006427A CA2006427A CA2006427A1 CA 2006427 A1 CA2006427 A1 CA 2006427A1 CA 002006427 A CA002006427 A CA 002006427A CA 2006427 A CA2006427 A CA 2006427A CA 2006427 A1 CA2006427 A1 CA 2006427A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- dyestuffs
- dyestuff
- light
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 title abstract description 6
- 235000021286 stilbenes Nutrition 0.000 title abstract description 6
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 title abstract description 5
- -1 heterocyclic radical Chemical class 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910006069 SO3H Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000000975 dye Substances 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000005859 coupling reaction Methods 0.000 description 32
- 230000008878 coupling Effects 0.000 description 27
- 238000010168 coupling process Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001989 diazonium salts Chemical class 0.000 description 11
- 235000011167 hydrochloric acid Nutrition 0.000 description 11
- 229960000443 hydrochloric acid Drugs 0.000 description 11
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 239000012954 diazonium Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 7
- YGNDWDUEMICDLW-UHFFFAOYSA-N 7-anilino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C=1C=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=1NC1=CC=CC=C1 YGNDWDUEMICDLW-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000006193 diazotization reaction Methods 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 4
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 description 4
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 230000011987 methylation Effects 0.000 description 4
- 238000007069 methylation reaction Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZFRBZRZEKIOGQI-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=CC(O)=C2C(N)=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 ZFRBZRZEKIOGQI-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PEMGGJDINLGTON-UHFFFAOYSA-N n-(3-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(N)=C1 PEMGGJDINLGTON-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 2
- MFMGIQZTZDNZTD-UHFFFAOYSA-N 3-amino-7-benzoyl-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C2C=C(S(O)(=O)=O)C(N)=C(O)C2=CC=C1C(=O)C1=CC=CC=C1 MFMGIQZTZDNZTD-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- GHBWBMDGBCKAQU-OWOJBTEDSA-N 5-amino-2-[(e)-2-(4-nitro-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O GHBWBMDGBCKAQU-OWOJBTEDSA-N 0.000 description 2
- IZNPFDIKQHGNSK-UHFFFAOYSA-N 5-amino-6-ethoxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=C(N)C(OCC)=CC=C21 IZNPFDIKQHGNSK-UHFFFAOYSA-N 0.000 description 2
- SEMRCUIXRUXGJX-UHFFFAOYSA-N 6-aminonaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(N)=CC=C21 SEMRCUIXRUXGJX-UHFFFAOYSA-N 0.000 description 2
- ZLHGMJOGMLVDFS-UHFFFAOYSA-N 7-benzamido-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C=1C=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=1NC(=O)C1=CC=CC=C1 ZLHGMJOGMLVDFS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- FIWILGQIZHDAQG-UHFFFAOYSA-N NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F Chemical compound NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F FIWILGQIZHDAQG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- QKZIVVMOMKTVIK-UHFFFAOYSA-N anilinomethanesulfonic acid Chemical compound OS(=O)(=O)CNC1=CC=CC=C1 QKZIVVMOMKTVIK-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- WXWCDTXEKCVRRO-UHFFFAOYSA-N para-Cresidine Chemical compound COC1=CC=C(C)C=C1N WXWCDTXEKCVRRO-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- AFHIIJICYLMCSH-UHFFFAOYSA-N 5-amino-2-[2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C=CC(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-UHFFFAOYSA-N 0.000 description 1
- STOOUUMSJPLRNI-UHFFFAOYSA-N 5-amino-4-hydroxy-3-[[4-[4-[(4-hydroxyphenyl)diazenyl]phenyl]phenyl]diazenyl]-6-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC(=CC=3)C=3C=CC(=CC=3)N=NC=3C=CC(O)=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 STOOUUMSJPLRNI-UHFFFAOYSA-N 0.000 description 1
- OJFOBFYCFDJPKU-UHFFFAOYSA-N 5-benzamido-2-[2-(4-nitro-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound C=1C=C(C=CC=2C(=CC(=CC=2)[N+]([O-])=O)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(=O)C1=CC=CC=C1 OJFOBFYCFDJPKU-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- PZASAAIJIFDWSB-CKPDSHCKSA-N 8-[(1S)-1-[8-(trifluoromethyl)-7-[4-(trifluoromethyl)cyclohexyl]oxynaphthalen-2-yl]ethyl]-8-azabicyclo[3.2.1]octane-3-carboxylic acid Chemical compound FC(F)(F)C=1C2=CC([C@@H](N3C4CCC3CC(C4)C(O)=O)C)=CC=C2C=CC=1OC1CCC(C(F)(F)F)CC1 PZASAAIJIFDWSB-CKPDSHCKSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000478345 Afer Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 244000172533 Viola sororia Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000005574 benzylation reaction Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- BPHHNXJPFPEJOF-UHFFFAOYSA-J chembl296966 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=C(N)C2=C(O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=C4C(N)=C(C=C(C4=CC=3)S([O-])(=O)=O)S([O-])(=O)=O)O)OC)=CC=C21 BPHHNXJPFPEJOF-UHFFFAOYSA-J 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- DSARWKALPGYFTA-UHFFFAOYSA-L disodium 4-hydroxy-7-[(5-hydroxy-6-phenyldiazenyl-7-sulfonatonaphthalen-2-yl)carbamoylamino]-3-phenyldiazenylnaphthalene-2-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(NC(=O)NC=3C=C4C=C(C(N=NC=5C=CC=CC=5)=C(O)C4=CC=3)S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=CC=C1 DSARWKALPGYFTA-UHFFFAOYSA-L 0.000 description 1
- TWKKUWBBCHHMLT-UHFFFAOYSA-N disodium;sulfide;trihydrate Chemical compound O.O.O.[Na+].[Na+].[S-2] TWKKUWBBCHHMLT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940045681 other alkylating agent in atc Drugs 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- BQHRKYUXVHKLLZ-UHFFFAOYSA-M sodium 7-amino-2-[[4-[(4-aminophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-3-sulfonaphthalen-1-olate Chemical compound [Na+].COc1cc(N=Nc2ccc(N)cc2)c(C)cc1N=Nc1c(O)c2cc(N)ccc2cc1S([O-])(=O)=O BQHRKYUXVHKLLZ-UHFFFAOYSA-M 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 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
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000012800 visualization Methods 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/205—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene
- C09B35/215—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene of diarylethane or diarylethene
-
- 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
- C09B56/00—Azo dyes containing other chromophoric systems
- C09B56/04—Stilbene-azo dyes
Abstract
Light-polarizing films or sheets containing stilbene dyestuffs Abstract Light-polarizing films or sheets, preferably based on vinyl alcohol homopolymers or copolymers contain dyestuffs of the formula in which X and Y have the meanings given in the description.
Le A 26 394 -US
Le A 26 394 -US
Description
The invention relates to stilbene dyestuffs and light-polarizing films or sheets containing stilbene dyestuffs.
Films based on polyvinyl alcohol (PVA) containing iodine or dichroic dyestuffs as polarizing agents are known.
Until now, it has been very predominantly the iodine-containing polarizers which have found industrial appli-cations, for example in passive liquid crystal displays for the visualization of information. In the absence of moisture, these polarizers are characterized by excellent light fastness and outstanding dichroic properties in the long-wave region of the visible spectrum. The active agent of these films is the iodine/PVA complex (M.M.
Zwick. J. Appl. Polym. Sci. 9, 2393-2424 ~1965)), which admittedly absorbs a wide band of the daylight spectrum, but not all of it. In the short-wave region, a ~hole", i.e. a region of diminished extinction, is present, which is the reason that the sheets have a characteristic blue .. . .. . . . ..
colour.
This has disadvantageous consequences, if it is desired to produce white light. The light transmitted in unpolar-ized form diminishes the dichroism and thus the polariza-tion performance in this region. To increase it again, it is necessary to increase the concentration of iodine complex. However, this correction in the short-wave region results in excessive extinction in the long-wave Le A 26 394 - 1 -~ 7 region. This leads to a significant decrease of the transmitted light in the transmission setting in combina-tion with a decrease in the brightness of the display which is equipped with this sheet. To achieve acceptable degrees of brightness, compromises must be made.
An important critical parameter of a display is its readability under various illumination conditions; it is usually stated as ~perceived contrast ratio" (PCR =
Tl/TIl); this ratio should be as large as possible. From this follows that the transmission on the one hand has to made as small as possible in the blocked setting (T¦¦) (readability in the dark) and, on the other hand as large as possible in the transmission setting (Tl) (readability in the light). This requires a very uniform polarizing performance of the filter over the entire spectral range, which can usually not be achieved by means of the iodine sheet.
There has not been a lack of attempts to replace iodine by dyestuff triples of dichroic dyestuffs to produce a neutral grey colour having a uniform dichroism. However, this requires a range of high-performance dyestuffs. In addition to good light and weather fastness, they must have a high extinction and a high dichroism in the matrix; in addition, they must not have secondary den-sities which have lower dichroism. ~hus, preferablypolyazo dyestuffs have been proposed, for example based on 4 nitro-4' stilbenedisulfonic acid (JA 59/145,255, JA
60/156,759, JA 60/168,743) or of substituted benzidine.
Le A 26 394 - 2 -2~ 2~7 In addition, numerous individual dyestuffs have been mentioned, for example Direct Red 2, 31, 81, Direct Orange 26, 107, Direct Green 85, Direct Blue 1, 106, 107, 109, 190, 202, Direct Black 17, 19, Direct Yellow 12,44 etc. (JA 60/230,606, JA 60~159,705, EP 182, 632). How-ever, although dichroism is a wide-spread property with dyestuffs (cf. W. Hanle, H. Scherer, Zeitschr. Natur-forsch. 6a, 437-439 (1951)), it has sofar not been possible to achieve or surpass the spectral properties of the iodine sheet. This can be attributed, on the one hand, to the lack of good blue shades, and, on the other hand, to the requirement of high dichroism of the system dyestuff/ matrix.
Surprisingly, it has now been found that certain novel stilbene dyestuffs have excellent dichroic properties and are highly suitable for the production of light-polariz-ing films or sheets.
(In what follows, a definition of a radical or index once given is maintained in the further text).
... . . .. . ... . ... ... . .
The invention relates to light-polarizing films or sheets containing dyestuffs which, in the form of their free acid, conform to the formula X ~ H=CH ~ =N-Y
~~ SO~H HO~S
Le A 26 394 - 3 -;7 in which X signifies -CN, -CF3, halogen, -NH2, -NHRl~ -NRlR2~
RlCONH-, -COOH, -CONH2, -CONHRl, -CONR~R2, -COORl, -OH, -OR1, -O-CO-R1, -N=N-Y1, or a substituted or S unsubstituted heterocyclic radical, Rl, R2 signify alkyl, cycloalkyl, aryl or aralkyl, which may be interrupted by O and/or S, and Yr Ylsignify a substituted or unsubstituted aryl or heterocyclic radical, in particular ~ R3 ~6 in which R3 signifies H, -OH, -ORl, -NH2, -NHRl, -NRlR2, -NH-COR1, -O-COR', -N=N=R1l, a heterocyclic radical, R4, R5, R7, R8, R9, RlD s ignify H, halogen, -OH, -ORl, -NH2, -NHRl, -NRlR2, -Rl, -S03H, -NH-CO-Rl, -O-CO-Rl, -SO2-NH2, -SO2-NHRl, -SO2-NRlR2, R6 - ~~ signifies H, -N=N=Rll, heterocyclic radical and Rll signifies a substituted or unsubstituted aryl radical, preferably a substituted or unsubstitut-ed phenyl or naphthyl radical or a substituted or unsubstituted heterocyclic radical containing a maximum of eight azobridges.
Preferred radicals y, yl and Rll of the benzene series are as follows:
Le A 26 394 _ 4 _ . . .... . - :
In particular, suitable radicals are those which are derived from phenol and aniline and its substitution products, if appropriate subsequently alkylated or acylated. Examples are:
H , ~ CH3 ~ ~ C2H5 -CH2-CH2-OH , ~ H , ~ H
H2 ' ~ `CH3 ~ `CH2-CH2-OH
,CH3 ~ ,CH3 `c}l2-cH2-ocH3 `CH2-CH2-CN
.
~1~ . --~3N5N_Rl 1 ~=N-Rl 1 , Le A 26 394 - 5 -=N-RIl ~ =N-Rll ~ =N-Rl _Ri 1 ~N_Rl 1 , ~
OCH3 HN~ 503H
COCH~
Preferred radicals y, yl and Rll of the naphthalene series are listed below:
~ R9 Rl2 = -OH, -NH2 _ ~ ~4 . . ~ . . .
R8~R9 Rl3 i8 H, if Rl~ = -N=N-Rll or H, and is -N=N-Rl1, if R14 = -OH, -NH2, R14 is -OH, -NH2, -N=N-R , Le A 26 394 - 6 -.... _ . _ .. .. ... . . . . . . .
R 15 R ~ 5 6 ' ~R14 R15)~R16 Rl5, Rl6 are H, -OH, -ORl, -O-CORl, -NH2, -NH-R1, -NR1R2, -NH-CO-Rl, -S03H, Rl7 is H, -SO3H.
In particular, the following radicals y, yl and R11 of the naphthalene series are preferred:
~ 18 ~ R17 Rl8 is H, OH, NH2, -NH-CO-Rl, -NH-Rl, -N=N-Rl1, -S03H, R2 R2 1 R2 o - ~ 3H
R1~ is H, -N=N-R11, R20, R2l are OH, NH2, -O-CO-R1, -NH-CO-Rl, Le A 26 394 ~ 7 ~
D~:27 OH OH R20 OH Rl 7 \~ ' ~ ' ~ 18 Preferably, Y, Y~ and Rll are derived from the (sub-stituted) I acid:
OH
HO ~5 ~R
R is -NH-Rl, -NH-CO-Rl, -N=N-Rll Halogen preferably represents F, Cl, Br, I.
Alkyl (Rl, R2) preferably represents Cl-C6-alkyl (methyl, ethyl).
Cycloalkyl (Rl, R2) preferably represents C3-C7-cvcloalkyl (cyclopentyl, cyclohexyl).
Aryl (Rl, R2) preferably represents phenyl and naphthyl.
Aralkyl (Rl, R2) preferably represents phenyl-C,-C4-alkyl (benzyl, phenethyl).
Suitable substituents for the alkyl and cycloalkyl radicals (Rl, RZ) are, for example, halogen (Cl, Br, F), -OH, -CN, Cl-C4-alkoxy and the like.
Suitable substituents for the aryl and aralkyl radicals (Rl, R2) are, for example, halogen (Cl, Br, F), -OH~ Cl-C4-Le A 26 394 - 8 -.. , _ . .... ..
alkoxy (methoxy), Cl-C4-alkyl (methyl), CF3, NO2, CN.
Preferred radicals X, R3 and R6 of the heterocyclic series have the formula:
; ~ R
-X jz ; in which . 5 X is a C or an N atom, where the free valence of ; carbon has been saturated by a double bound, and Z represents the remaining members of a preferably 5- or 6-membered monocyclic or bicyclic or tricyclic ring 10 which can contain 1 to 3 heteroatoms from the series con-sisting of N, O, S and is substituted or unsubstituted.
In particular, they are derived from the following heterocyclic systems:
triazole, pyrazole, benzotriazole, naphthotriazole, oxazole, imidazole, thiazole, oxadiazole.
Preferred radicals y, yl and Rll of the heterocyclic series have the formula ~'Rl 9 -C z in which Z represents the remaining members of a preferably Le A 26 394 - 9 -..
2~ 27 5- or 6-membered monocyclic or bicyclic or tricyclic ring, which can contain 1 to 3 heteroatoms from the series con-sisting of N, 0, S and is substituted or unsubstituted, S the free valence of carbon being saturated by a double bond.
In particular, Y, Y~ and R11 are derived from the follow-ing heterocyclic systems:
thiophene, triazole, pyrazole, pyridine, benzotriazole, pyridone, naphthotriazole.
In addition, R11 is derived from the following hetero-cyclic systems:
thiadiazole, thiazole, benzothiazole.
Suitable heterocyclic radicals (Y, Y~ and R11) are in particular a substituted 5-amino- or 5-hydroxypyrazole radical, for example R2 2~T=N
~N_R23 in which R12 R22 is H, C~-C4-alkyl (methyl), -COOH, R23 is ~ 503H ~ 503H, ~ =N ~ S03H
Further preferred radicals Y, Y~ and R~1 are those of the Le A 26 394 - 10 -formula:
~ A-N=N ~ L
in which A is a substituted or unsubstituted phenylene or naphthalene radical, L is a substituted or unsubstituted phenyl or naphthyl radical and p is 1, 2, 3.
In particular, A represents and L represents ~R3 . ~R9 Preference is given to the group of symmetrical compounds of the formula - -Y1-N=N ~ H=CH ~ N=N-Y
~ 503H Ho35 in which Y~ is Y.
Le A 26 394 - 11 -2t)~ 7 A further preferred group of compounds conforms to the formula OH
Y-N=N ~ H=CH ~ N= ~
A further preferred group of compounds conforms to the formula Y-N=N ~ H=CH ~ =N ~ ~
sO3H 503H R5 H035 18 A further preferred group of compounds conforms to the formula Rl- ~ N=N ~ H=C ~ N=N-Y
503H sO3H
Dyestuffs I can be prepared in analogy to processes known from the literature.
H2N~CH= C1~3NH2 503H H035 (VI) which can be tetrazotized and coupled onto coupling components serves as starting material. Free amino groups of the coupled products obtained can be diazotized and Le A 26 394 - 12 -coupled again.
The compound 02~ ~ H=C ~ .NH2 S03H H035 (VII) can be used for preparing unsymmetrical dyestuffs. To this end, VII is diazotized and coupled onto suitable coupling components. Free amino groups of the coupled products obtained can be diazotized and coupled again.
The nitro group of the dyestuffs obtained can be reduced, and the amino compound obtained can be diazotized and coupled onto suitable coupling components. This makes the unsymmetrical compounds of the formula I accessible.
The monoamino compound VII can be converted according to Sandmeyer to the corresponding halogen, CN or OH com-pounds etc. (cf. S.Y. Zherdeva et al., J. Org. Chem~ ~SSR
16 (1980) 383) or, for example, to various derivatives (triazoles, pyrazoles etc.). After reduction of the nitro group, the monoamino compounds obtained can be coupled, after diazotization, to give azo dyestuffs.
Compound VII can furthermore be acylated at the amino group in a known manner (acetylated, benzoylated);
subsequent reduction of the nitro group gives amino-containing intermediates, for example Le A 26 394 - 13 -C~3 C,~ ~CH=CH~ ; .2 (VIII) which like VII are suitable for the preparation of unsymmetrical dyestuffs. In particular, they can be diazotized and coupled onto suitable coupling components.
After elimination of the acyl group, the dyestuffs obtained can be diazotized and coupled again. Compound VIII like VII can be converted according to Sandmeyer to derivatives which, after elimination of the acyl group, can be diazotized and coupled to give azo dyestuffs.
In particular, the invention relates to light-polarizing films (sheets) which contain an organic polymer and one or more compounds of the formula I.
The organic polymer is preferably an oriented polymer which forms transparent films and is compatible with dyestuffs which contain acidic groups. Examples of such a polymer are: polyamides, cellulose (acetate), vinyl alcohol homopolymers and copolymers and vinyl acetate homopolymers and copolymers, where the comonomers present can be, for example, ethylene, propylene, crotonic acid, (meth)acrylic acid, maleic acid. Polyvinyl alcohols which have been prepared by complete or partial hydrolysis of polyvinyl acetate, in particular those types which have a viscosity of > 4 mPa.sec2, preferably 20 to 70 mPa.sec2, at 20C in 4% strength agueous solution and a hydrolysis degree of > 80 mole %, preferably 85 to 100 mole %, are preferably used.
Le A 26 394 - 14 -The films preferably have a thickness of 10 to 150 ~.
The films preferably contain 0.01 to 10 % by weight, particularly preferably 0.5 to 6 % by weight, relative to the weight of the film, of the dyestuff.
The films are coloured in the usual manner, for example by colouring the polymer which is dissolved (in water).
The film is prepared from the solution in a manner known per se.
It is recommended to free the dyestuffs or dyestuff salts before use of foreign salts, for example by recrystal-lization, extraction and/or dialysis.
Preferably, these sheets are used which have been stretched at elevated temperature, preferably at 80-160C, by 200 to 1000%
If desired, the dyestuff-containing films can also be subjected to an aftertreatment, for example with aqueous boric acid solution, in order to improve the light permeability or the polarization coefficient. The condi-tions under which this aftertreatment is carried out can vary, depending on the film material and dyestuff.
Preferably, a 1-15 % strength by weight, particularly preferably a 5-10 % strength by weight, boric acid solution is used at 30-80C, particularly preferably at 50-80C. Preferably, surfactants and, if desired, in-Le A 26 394 - 15 -t~ .7 organic salts are added to the boric acid solution. The surfactants can be nonionic, cationic or anionic; prefer-ably, they are nonionic.
Examples of nonionic surfactan~s are: addition products of ethylene oxide with higher alcohols or addition products of ethylene oxide with nonylphenol. Preferably, 0.005-0.5 % by weight, particularly preferably 0.02-0.2 % by weight, of surfactant is used, relative to the water.
Suitable inorganic salts are preferably sodium sulphate and furthermore potassium sulphate, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate.
Relative to the water, preferably 0.1-5 % by weight, particularly preferably 0.3-3 % by weight, of inorganic salts are used. If desired, this can be followed by a fixation treatment with an aqueous solution of a high-molecular-weight cationic compound.
The light-polarizing films or sheets can be compounded or laminated with other materials in a manner known p~r se.
Examples of suitable protective coatings are sheets made of a tetrafluoroethylene/hexafluoroethylene copolymer or another fluorohydrocarbon resin, a polyester, polyolefine or polyamide resin,a polycarbonate or cellulose ester, preferably cellulose (tri)acetate, cellulose (tri)propionate, cellulose (tri)butyrate.
The dichroism of the system can be considerably enhanced Le A 26 394 - 16 -~2~
by addition of lower mono- or polyhydric alcohols, such as methanol, ethanol or glycol, glycerol, trimethol-ethane, trimethylolpropane, pentaerythritol, sorbitol, their ethers, such as glycol monomethyl ether, glycol monoethyl ether, glycol dimethyl ether, diglycol diethyl ether, lower amines such as propylamine, hydroxy amines, such as propanolamine or amides, such as DMF, N-methyl-pyrrolidone, pyrrolidone, ~-caprolactam, to the casting solution. The additives can be used alone or, more advantageously, in mixtures, in which lower monohydric alcohols, for example methanol, ethanol, i-propanol, can also be present as components of the mixture. The addi-tives are preferably added to the casting solution in amounts of 5-50 % by weight, relative to the casting solution.
Besides being used in light-polarizing films, the dye-stuffs of the formula I can be used alone or in mixtures for rendering ordered structures visible in the analysis of polymers and in biological materials.
Example 1 a) Svnthesis of the dvestuff:
R-N ~ H=CH ~ ~N-~
~y ~ 503H
R = ~ 0-~H ~ 03H
Le A 26 394 - 17 -~i5''~7 37 g (0.1 M) of 4,4~-diaminostilbene-2,2~-disulphonic acid are suspended in 1 1 of water. 83 ml of concentrated hydrochloric acid are added and 51 ml (0.22 M) of sodium nitrite solution (as an approximately 30 ~ strength solution) are added dropwise slowly at room temperature.
The suspension is stirred overnight. After this time, it should be possible to detect a nitrite excess which is destroyed by the addition of sulphamic acid solution.
This tetrazonium salt solution is slowly added dropwise at room temperature, while controlling the pH, to a solution of 69 g (0.2 M) of l-hydroxy-6-benzoylamino-naphthalene-3-sulphonic acid in 0.5 1 of water, the pH
being maintained between 6.5 and 7 by dropwise addition of 10 per cent strength sodium hydroxide solution. After stirring overnight, the precipitated dyestuff is filtered off with suction and washed several times with small portions of water. The dyestuff is then dissolved in water and subjected to dialysis, to separate off salts;
the dyestuff solution obtained is then evaporated, and the residue is dried. Yield: 98.7 g.
b) Manufacture of the sheet 9.9 g of ~MOWIOL 28-99 (hydrolyzed polyvinyl acetate;
degree of hydrolysis 99.4 + 0.4 mole %; viscosity of the 4 % strength agueous solution at 20C:28 i 2.0 mPa.sec2;
from Hoechst AG) and 0.1 g of the dye of Example la are dissolved in 190 ml of water by heating the mixture at Le A 26 394 - 18 -90C for 2 hours with stirring. 5 g of methanol and 2.5 g of glycerol are added to 92.5 g of the 1 %
strength, relative to the polymer, dyestuff solution obtained. By means of a knife, 500 ~ thick layers are applied from this solution to a clean glassplate, and the layers thus obtained are dried in air at room temperature on a support in an exactly horizontal position. The resulting dry sheets are peeled off from the glassplate;
they have a violet colour and are about 40-50 ~ thick.
c) Stretching of the sheets To produce dichroic properties, the sheets are stretched.
To this end, they are heated in a drying cabinet at a constant temperature of 130C for 15 minutes and then stretched at a speed of about 10 cm/min to about 700 % of their original length. The stretched sheets have a dichroic ratio of about 28 at the absorption maximum (557 nm), measured with polarized light; losses due to reflection were not taken into account in the measure-ment.
d) Sheet manufacture on the castin~ machine 0.2 g of the dyestuff of Example la is dissolved in 100 g of hot water. 10 g of glycerol are added, and 19.8 g of ~OWIOL 28-99 are stirred into the cooled solution. After stirring at room temperature for 1 hour, the mixture is heated to 90C, and stirring is continued at this temperature until, after about 3 hours, a homoge-Le A 26 394 - 19 -~ 7'~7 nous solution has been formed. At 50C, 5 g of methanol are then stirred in. The warm solution is filtered through a filter press, while injecting air, and is then degassed by evacuation. The casting solution is pourable and stable at 30C.
To produce a sheet, the casting solution is applied continuously by means of 250 ~ knife to the casting wheel (wheel diameter 25 cm, rotating speed about 7.5 min per revolution) which has been preheated to about 50C. The layer is dried by passing heated air over it, and the solidified sheet is continuously peeled off the wheel and additionally dried. The sheet obtained is about 40 ~
- thick. It is stretched as described above in c), leading to similar results.
e) Exactly analogously as in Example la, analogous dyestuffs are obtained by using the coupling components mentioned, which are incorporated into sheets according to lb. Stretching according to lc gives dichroic sheets.
~ I H . . ..
.~ ~~, .
c~ ~.,~-C'3-G'l OH
OH
!
c3s~5~3H
!~H 2 OH
~.' 5~3H
Le A 26 394 - 20 -- Z~ 27 Further dyestuffs are prepared analogously to Example la from the following coupling components:
OH H;C-CO-NH OH
~35 503.~ ~ ~
H~ <~3-Co-HH OH
CH3-CO-h'H ~ 503H H2N ~
. 503H
NH ~ H035 CO-NH ~ NC-CH2-CH2-N ~ 3 OH OH OH
CH3-CO-N ~
303H ~ 03H ~ 303H
NH-CO
Le A 26 394 - 21 .
.
2~64Z7 OH ~2N O.Y
~CO-N~ ~
503H ~503H
~C ~503 H C O - N~503H
~0 NH R
OH
~N~503H C~3 503H
,~ NH2 OH
CH3 - O~N~So3H
;' C~, ~503H
OH
Le A 26 394 - 22 -~3C-CO~ OH COCH
H35~o3H OH 503 O~O_NH OH
HO~} H03S~
<~ H035 The products obtained from the coupling onto phenols can be ''sealedll by subsequent alkylation (methylation, ethylation, benzylation).
Exam~le 2 a) 17.3 q (0.1 mol) of 4-aminobenzenesulphonic acid are dissolved in 200 ml of water together with about 7 ml of sodium hydroxide solution (45 ~ strength), : and 28 ml of concentrated hydrochloric acid are then added all at once. The freshly precipitated suspen-sion is diazotized at 5-10C with 7 g of sodium nitrite in 15 ml of water. After 15 minutes, the product is filtered off with suction and washed on the filter with icewater. The moist product is Le A 26 394 - 23 -~ 7 immediately stirred into 100 ml of water (caution:
the dry product is explosive). To the suspension of the diazonium salt thus obtained is added dropwise, with vigorous stirring, a cold solution of 34.1 g (0.1 mol) of 8-amino-1-hydroxy-naphthalene-3,6-disulphonic acid monosodium salt and 5.5 g of sodium carbonate in 100 ml of water over a period of 45 minutes. The mixture is stirred for 12 hours while warming to room temperature, the product is filtered off with suction and washed neutral. This gives a dyestuff paste of the formula:
H03S ~ = ~
b) The dyestuff paste from a) is dissolved together with 40 g of sodium carbonate in about 500 ml of water, if necessary with heating, and then cooled to below 10CC. The tetrazonium salt solution from 18.5 g (0.05 mol) of 4,4~-diaminostilbene-2,2'-disulphonic acid prepared according to Example la is added dropwise to the suspension obtained over a period of 30 minutes, while maintaining the pH at 6.5 to 7 by metering in 10% strength sodium hydroxide solution. The mixture is stirred over-night, the dyestuff is filtered off with suction, washed neutral with water and then dissolved in water and dialyzed, to separate off salts. The Le A 26 394 - 24 -dyestuff solution is evaporated and the residue is dried. The dyestuff obtained has the structure:
HO 3S~
R-N'N~H=C~l~N=N-R
503~
13035~3H .
c) The following coupling components which can be prepared analogously to 2a) can also be used:
H035 ~ N= ~
: NH2 OH
H035 ~ N=N ~ N= ~ S
H35~N.~o3H
.; S03~
H035 ~ Ns ~ S03H
OH
Le A 26 394 - 25 -Zl[)0~427 OH
H03S ~ N=N ~ 503H
H035 ~ '~`
0}~
H03S ~ ' ~ 503H
d) Exactly analogously, the dyestuff of the structure:
R-N=N ~ H=CH ~ =N-R
R = H035 ~ H03 ~ 03H
is obtained by coupling the tetrazonium salt solu-tion of Example la first at a pH of 4.5-5.5 onto 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid and then coupling the diazonium compound from 4-amino-benzenesulphonic acid prepared according to Example 2a twice onto the product at a pH of 7-7.5.
The other components mentioned in c) can also be reacted in reverse order to give analogous dye-Le A 26 394 - 26 -20~42~7 stuffs.
Example 3 a) At a maximum temperature of 10C, a solution of 30.6 g (0.2 mol) of 2,5-dimethoxyaniline in 500 ml of water (to which concentrated hydrochloric acid is added until a clear solution is formed) is added dropwise to the tetrazonium salt solution prepared according to Example la, with stirring, while maintaining a pH of 3 to 4.5 by simultaneous meter-ing in of sodium hydroxide solution. After stirring overnight and warming to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water. The dyestuff obtained after drying weighs 52.4 g and has the formula:
R-N=N ~ H=CH ~ N=N-R
R - H2N ~
. .
Instead of 2,5-dimethoxyaniline, it is also possible to use 2-methoxy-5-methylaniline, 2,5-dimethyl-aniline, 3-methylaniline, 3-acetylaminoaniline, Le A 26 394 - 27 -2~ i427 1-naphthylamine, 1-amino-2-ethoxy-naphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.
b) The intermediate product obtained in a) is tetrazot-ized in aqueous hydrochloric acid with sodium nitrite while letting it stand overnight at room temperature, and the tetrazonium salt solution obtained, after destruction of the nitrite excess, is coupled onto l-hydroxy-6-benzoylamino-naph-thalene-3-sulphonic acid at a pH of 6.5 to 8. The dyestuff obtained has the formula:
R-N=N ~ H=CH ~ =N-R
R CH3-CO-NHJ~03H OCH !
c) The other compounds mentioned in Example le and 2c can also be used as components of the final coupling reaction, preferably benzoyl I acid, acetyl gamma-acid or acetyl K acid; phenolic coupling components can subsequently be ~sealed~ by alkylation. The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.
Le A 26 394 - 28 -Example 4 a) 9.6 g (0.01 mol) of the dyestuff from Example le formed by coupling of the tetrazonium salt from la onto l-hydroxy-6-acetylaminonaphthalene-3-sulphonic acid are stirred in 200 ml of 2N sodium hydroxide solution at 80CC until the acetyl groups have been completely cleaved off (monitoring of the reaction by thin-layer chromatography). The reaction mixture is neutralized, cooled, and is filtered off with suction and the residue washed neutral.
b) The dyestuff formed according to a) is dissolved in 100 ml of IN sodium hydroxide solution, 1.8 g of sodium nitrite are added to the solution, and the solution is then run into excess hydrochloric acid.
After standing overnight at room temperature, the tetrazonium salt solution has been formed; excess nitrite is destroyed by means of sulphamic acid, 2 g of phenol dissolved in sodium hydroxide solution are then added dropwise, and the pH is brought to about 9 with sodium hydroxide solution. After stirring for 3 hours, the coupling reaction is completed. The product i5 filtered off with suction and washed neutral.
c) The dyestuff formed according to b) is dissolved in 100 ml of lN sodium hydroxide solution, and 4 g of dimethyl sulphate are added to the solution with Le A 26 394 - 29 -stirring. Afer about 1 hour, the methylation is completed. The producted is filtered off with suction, washed neutral and dried. The dyestuff obtained has the formula:
R-N=N ~ H=C ~ N=N-R
OH
CH3{~N=N~C03H
Instead of dimethyl sulphate, it is also possible to convert the phenolic groups with diethyl sulphate or benzyl bromide to the ethers.
Instead of phenol in 4b), it is also possible to use the other coupling components listed in ~ables le and 2c as end groups.
Example S
a) The tetrazonium salt solution from Example la is added dropwise at about lO~C to the solution of 68.4 g (0.2 mol) of 1-hydroxy-8-acetylaminonaph-thalene-3,6-disulphonic acid (monosodium salt) in 0.8 1 of water, during which the pH is maintained at 6.5-7.5 by dropwise addition of 2N sodium hydroxide Le A 26 394 - 30 -:
'' 4~7 solution. The coupling reaction is then allowed to go to completion overni.ght, while heating to room temperature. The product is filtered off with suction, washed neutral with water and dried. Yield:
62.5 g of a blue-violet soluble dyestuff.
b) 20 g of the dyestuff from 5a) are heated in 200 ml of 2N sodium hydroxide solution at about 80C, until the acetyl groups have been cleaved off. The mixture is then acidified with hydrochloric acid, the pro-duct is filtered off with suction, washed neutral and dried. This gives 15.3 g of a dyestuff which, in the form of the free acid, has the following formula: HO3S
R-N=N ~ H=CH ~ =N-R
R = HO35 ~ O3H
An analogous dyestuff is also obtained from l-hydroxy-8-acetylaminonaphthalene-3,5-disulphonic acid, followed by cleavage.
The dyestuffs can be incorporated according to Example lb into a sheet and stretched according to lc.
"Unsvmmetrical" dyestuffs A suitable intermediate for the preparation of "un-symmetrical'- compounds is 4-amino-4'-nitrostilbene-2,2'-Le A 26 394 - 31 -2C~ 27 disulphonic acid.
Example 6 21.2 g(0.05 mol) of 4-amino-4'-nitrostilbene-2,2'-disul-phonic acid are suspended in 400 ml of water, and 40 ml of concentrated hydrochloric acid are added. Diazotiza-tion is carried out by dropwise addition of 12.8 ml of 30% strength sodium nitrite solution (0.05 mol + 10 %) at a maximum temperature of 10C, and stirring is then continued at about 20C overnight. The nitrite excess is then destroyed by addition of sulphamic acid.
The diazonium salt solution obtained is added dropwise to a solution of 17.2 g (0.05 mol) of 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid in 160 ml of water at about 20C, during which the pH is kept in the range from 7 to 8 by dropwise addition of sodium hydroxide solution.
After stirring overnight, the precipitated dyestuff is filtered off with suction, washed neutral with a small amount of water and dried. Yield: 28.5 g (75 %). This gives a dyestuff of the structure:
02N~H=CH~N=~
-S03H HO3S ~ NH-C ~
Exactly analogously as described above, an analogous Le A 26 394 - 32 -2~ i42~
dyestuff is obtained by replacing 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid by 1-hydroxy-6-anilino-naphthalene-3-sulphonic acid.
b) Further suitable coupling components are the ones mentioned in the Table of Examples le and 2c, preferably acetyl I acid, acetyl gamma-acid, R acid, acetyl R acid, benzoyl R acid, acetyl H acid, benzoyl H acid, Chicago SS acid, benzoyloxy C acid or phenol. The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
In addition, they can be reduced as described in 9a) to the amino compounds, which are diazotized and then coupled onto suitable coupling components, for example those the Tables of Examples le and 2c. -Example 7 a) 4-Benzoylamino-4'-nitrostilbene-2,2'-disulphonic acid:
200 g (0.5 mol) of 4-amino-4~-nitrostilbene-2,2'-disul-phonic acid are suspended in l l of water, and the mixture is brought to a pH of 9 with 40% strength sodium hydroxide solution. At about 10C, 77 g (0.5 mol + 10%) of benzoyl chloride are added dropwise with vigorous stir-Le A 26 394 - 33 -42~
ring, during which the pH is maintained at 9 by dropwise addition of sodium hydroxide solution. As soon as the pH
remains stable, stirring at room temperature is continued for 1 hour, the product is filtered off with suction, washed neutral and dried. This gives 233 g.
b) 4-Amino-4'-benzoylaminostilbene-2,2~-disulphonic acid:
151 g (0.3 mol) of the product from a) are suspended in 2.5 1 of water, 100 g of 45~ strength sodium hydroxide solution and 200 g of sodium sulphide trihydrate are added, and the mixture is slowly heated to 80C until the starting material has disappeared (TLC). 200 g of sodium chloride are added to the hot solution. After cooling, the product is filtered off with suction and washed carefully neutral with water. The dry product weighs 113 g.
c) Diazotization of 4-amino-4'-benzoylaminostilbene-2,2'-disulphonic acid in accordance with the pro-cedure of Example 6a, destruction of the nitrite excess with sulphamic acid, and coupling of the product onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of 7-8, gives a dyestuff of the structure:
. .
Le A 26 394 - 34 -~(.) H OH
~3 C O - NH~ H = C 1~ ~ - C o~3 The corresponding dyestuff which has an acetylamino group on the stilbene radical is obtained analogously.
Further suitable coupling components are the ones men-tioned in Examples le and 2c, preferably phenyl I acid, acetyl R acid, benzoyl K acid, acetyl gamma-acid, acetyl H acid, benzoyl H acid, Chicago SS acid and phenol (followed by methylation). The dyestuffs obtained can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
ExamPle 8 a) At a maximum temperature of 1ODC, a solution of 7.8 g (0.05 mol) of 2,5-dimethoxyaniline in 125 ml of water (dissolved with the concentrated hydro-chloric acid addition until a clear solution is formed) is added dropwise to the diazonium salt solution prepared according to Example 6a, with stirring, while maintaining a p~ of 3 to 4.5 by metering in sodium hydroxide solution. After stirring overnight, during which the temperature is allowed to rise to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water.
Le A 26 394 ~ 35 ~
Instead of 2,5-dimethoxyaniline, it is also possible touse2-methoxy-5-methylaniline, 2,5-dimethylanili-ne, 3-methylaniline, 3-acetylaminoaniline, l-naph-thylamine, 1-amino-2-ethoxynaphthalene-6-sulphonic acid etc.
b) The intermediate obtained in a) is diazotized in the form of a paste in aqueous hydrochloric acid with sodium nitrite, the diazotization being allowed to go to completion by standing overnight and warming to room temperature. Excess nitrite is destroyed by means of sulphamic acid.
The diazonium salt solution is coupled onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid at pH
6.5 to 7.5. The dyestuff obtained has the formula:
S ~ OC~3 R-CH-C ~ N=N ~ N=N-R
It is also possible to USQ the other compounds mentioned in Examples le and 2c as components of the end coupling.
c) Exactly analogously as described in 8a and b, the Le A 26 394 - 36 -4~;D7 dyestuff of the formula R-CH=CH ~ = ~ =N-R~
R = ~ ONH ~
H03S ~ NH ~
is obtained by using the diazonium salt from Example 7c.
It is also possible to use the other compounds mentioned in Examples le and 2c as components of the S end coupling.
If benzoyl chloride in Example 7a is replaced by other active acid derivatives, for example acetic anhydride, propionic anhydride, 4-methylbenzoyl chloride etc., and the procedure according to 7b and then according to 7c and 8c is repeated, analogous dyestuffs in which the benzoyl group is replaced correspondingly are obtained.
. . .
Example 9 a) The dyestuff of Example 6a which still contains a Le A 26 394 - 37 -Z~ 27 nitro group is reduced in an ethanol/water mixture with sodium sulphide or analogously to the procedure in DOS ~German Patent Specification) 3,805,513, Exzmple 3, to the amino compound. Another possible reduction is that using iron powder in weakly acidic aqueous medium according to Bechamp.
Exactly analogously, the corresponding nitro-con-taining dyestuffs of Example 6b can be reduced to the amino compounds.
b) 18.1 g (0.025 mol) of the dyestuff obtained in a) are suspended in 300 ml of water, 20 ml of con-centrated hydrochloric acid are added, and the mixture is diazotized by dropwise addition of 6.4 ml of 30% strength sodium nitrite solution (0.025 M
+ 10%) at a maximum temperature of 10C, and stir-ring is allowed to continue overnight at room temperature. The nitrite excess is then destroyed by addition of sulphamic acid.
The diazonium salt solution obtained is added - 20 dropwise to a solution of 8 g ~0.025 mol) of 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid in 80 ml of water at about 20C, while maintaining the pH at about 7. After stirrinq overnight, the precip-itated dyestuff is filtered off with suction, washed with a small amount of water and dried. The dyestuff obtained has the structure:
Le A 26 394 - 38 -SO H
'"'''2 OH ~-CH~N=N-R' ? ~ ;S~ S03H
OH
SO~H
H O 3 S~NI~ - C C~3 It is also possible to use the other compounds mentioned in Examples le and 2c as coupling components.
The same reaction sequence 9a, b can also be carried out with the dyestuff from Example 8b and its analogues. This dyestuff is also obtained by deacylating the dyestuff from Example 8c with 2N hydrochloric acid or 2N sodium hydroxide solution at about 80C and diazotizing and coupling the intermediate thus obtained as described in 9b.
Example 10 a) 5 g (about 0.05 mol) of phenol are dissolved in 100 ml of water with the addition of sodium hydroxide solution, until a clear solution has been obtained, and the diazonium salt solution obtained in Example 6a is then added dropwise at about 10C, during which a pH of about 9 is maintained by addition of sodium hydroxide solution. After stirring overnight, the mixture is neutralized, the precipitate filtered off with suction and washed.
Le A 26 394 - 39 _ ~r~;~7 The moist paste is reacted analogously to the procedure in Example 4c in a~leous alkaline solution with dimethyl sulphate, until complete methylation has taken place. This gives a dyestuff of the structure:
N02{~CH=CH~N=N{~_CH3 Likewise, other (substituted) phenols can also be used instead of phenol.
If dimethyl sulphate is replaced by benzyl bromide, the corresponding benzylated compound is obtained;
other alkylating agents, for example diethyl sul-phate, are also suitable.
b) The dyestuff obtained in a) is reduced with sodium sulphide in ethanol and water or with iron powder in weakly acidic medium to the amine. This amine is diazotized analogously to Example 6a with sodium nitrite, and excess nitrite is then destroyed by means of sulphamic acid.
The diazonium salt solution obtained is coupled in accordance with the further procedure in Example 6a onto 1-hydroxy-6-henzoylaminonaphthalene-3-sulphonic acid at a pH between 7 and 8, which gi~es a dyestuff of the formula below:
Le A 26 394 _ 40 -R-l~'=N~H=CH~N=N-R ' 0~
R = }~ 3C ~3 H0 3 5~NH - C G~) It is also possible to use the other compounds mentioned in Examples le and 2c as components of the end coupling, preferably acetyl I acid, N-phenyl I acid and acetyl H
acid.
The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.
The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
Exam~le 11 (Condensation dyestuffs) The condensation reaction for the preparation of azo dyestuffs is described in Houben-Weyl, Methoden der Organischen Chemie (Methods of organic chemistry), Vol.
10/3, Part 3, p. 339-346.
5 a) The preparation of the following dyestuff is de-scribed there on page 343:
Le A 26 394 - 41 -2~4Z7 2-N=N ~ N=N ~ H=CH ~ N=N ~ N=N-R
R = H035 ~
b) The following dyestuffs are prepared by suitable modification of the procedure given there:
H3C- ~ N:N ~ H=CH ~
N
H3C- ~ s ~ H=CH
N - N ~ HrCH ~ =N ~
H035 ~ NS03H S03H CH
CH
Nl Nl ~
H03S ~ N S03H
~ .' Exam~ 2 a) The compound 2~-C~l Le A 26 394 - 42 -is prepared by the procedure in J. Org. Chem. USSR 16 ~1980) 388.
Exactly analogously, it is also possible to prepare the corresponding bromine compound or the cyanide instead of the chlorine compound.
b) The compound of Example 12a is reduced analogously to the procedure in Example 7b, 10b or in J. Org.
Chem., USSR 16 (1980) 386, 389 to the amino com-pound. This compound is converted into the corres-ponding diazonium salt, for example as described in 6a, and then as also described in 6a, coupled onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of about 7-8. This gives the dyestuff of the structure:
Cl ~ H=CH ~ N=
503H HO35 ~ NH-C ~
Further suitable coupling components are those mentioned in Tables le and 2c.
c) If the procedure of Example 8 is repeated and the diazonium salt solution prepared in 12b is used instead of that used in 8a, and the product is first coupled onto 3-methylaniline and then onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid, a Le A 26 394 _ 43 _ dyestuff of the structure:
R-HC=CH ~ =N ~ =N-R
R Cl { ~ R~ . ~`NH~
is obtained.
Further suitable coupling components are those mentioned in Tables le and 2c.
Instead of 3-methylaniline, it is also possible to use2,5-dimethoxyaniline,2-methoxy-5-methylaniline, 2,5-dimethylaniline, 3-acetylaminoaniline, 1-naph-thylamine, l-amino-2-ethoxynaphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.
d) If the corresponding bromine or cyano compound is used in 12b and c) instead of the chlorine compound from 12a, analogous dyestuffs are obtained.
Example 1~
The known compound of the following formula obtained by Le A 26 394 _ 44 _ 2~)~64'~;7 coupling of diazotized 4-amino-4'-nitrostilbene-2,2'-disulphonic acid onto l-aminonaphthalene-4-sulphonic acid analogously to the procedures in Houben-Weyl, Methoden der Organischen Chemie (Nethods of Organic Chemistry), Vol. 10/3, Part 3, p. 428, 429:
02N{~CH = CI~N~>~
S03H 503H ~
is reduced analogously to the procedure of Examples 7b, lOb or 12b to the amino compound.
The compound which is an isomer with respect to the position of the sulpho group is obtained analogously by coupling onto 2-aminonaphthalene-6-sulphonic acid, followed by reduction to the amino compound.
b) The amino compound prepared in a) is diazotized according to the procedure in Example 6a, and the product is coupled as described there onto l-hydroxy-6-anilinonaphthalene-3-sulphonic acid. This gives a dyestuff of the structure:
Le A 26 394 _ 45 _ zf )~ 7 R-N~N ~ H=C ~ ' OH
R = ~ R' = -N
Analogously, the use of 2-aminonaphthalene-6-sulphonic acid in 12a, reduction, diazotization and coupling onto phenyl I acid gi~es the isomeric dyestuff:
R-N=N ~ H=CH ~ ' OH
R =H ~ R~ = _ ~ S03H
. .
~e A 26 394 - 46 -
Films based on polyvinyl alcohol (PVA) containing iodine or dichroic dyestuffs as polarizing agents are known.
Until now, it has been very predominantly the iodine-containing polarizers which have found industrial appli-cations, for example in passive liquid crystal displays for the visualization of information. In the absence of moisture, these polarizers are characterized by excellent light fastness and outstanding dichroic properties in the long-wave region of the visible spectrum. The active agent of these films is the iodine/PVA complex (M.M.
Zwick. J. Appl. Polym. Sci. 9, 2393-2424 ~1965)), which admittedly absorbs a wide band of the daylight spectrum, but not all of it. In the short-wave region, a ~hole", i.e. a region of diminished extinction, is present, which is the reason that the sheets have a characteristic blue .. . .. . . . ..
colour.
This has disadvantageous consequences, if it is desired to produce white light. The light transmitted in unpolar-ized form diminishes the dichroism and thus the polariza-tion performance in this region. To increase it again, it is necessary to increase the concentration of iodine complex. However, this correction in the short-wave region results in excessive extinction in the long-wave Le A 26 394 - 1 -~ 7 region. This leads to a significant decrease of the transmitted light in the transmission setting in combina-tion with a decrease in the brightness of the display which is equipped with this sheet. To achieve acceptable degrees of brightness, compromises must be made.
An important critical parameter of a display is its readability under various illumination conditions; it is usually stated as ~perceived contrast ratio" (PCR =
Tl/TIl); this ratio should be as large as possible. From this follows that the transmission on the one hand has to made as small as possible in the blocked setting (T¦¦) (readability in the dark) and, on the other hand as large as possible in the transmission setting (Tl) (readability in the light). This requires a very uniform polarizing performance of the filter over the entire spectral range, which can usually not be achieved by means of the iodine sheet.
There has not been a lack of attempts to replace iodine by dyestuff triples of dichroic dyestuffs to produce a neutral grey colour having a uniform dichroism. However, this requires a range of high-performance dyestuffs. In addition to good light and weather fastness, they must have a high extinction and a high dichroism in the matrix; in addition, they must not have secondary den-sities which have lower dichroism. ~hus, preferablypolyazo dyestuffs have been proposed, for example based on 4 nitro-4' stilbenedisulfonic acid (JA 59/145,255, JA
60/156,759, JA 60/168,743) or of substituted benzidine.
Le A 26 394 - 2 -2~ 2~7 In addition, numerous individual dyestuffs have been mentioned, for example Direct Red 2, 31, 81, Direct Orange 26, 107, Direct Green 85, Direct Blue 1, 106, 107, 109, 190, 202, Direct Black 17, 19, Direct Yellow 12,44 etc. (JA 60/230,606, JA 60~159,705, EP 182, 632). How-ever, although dichroism is a wide-spread property with dyestuffs (cf. W. Hanle, H. Scherer, Zeitschr. Natur-forsch. 6a, 437-439 (1951)), it has sofar not been possible to achieve or surpass the spectral properties of the iodine sheet. This can be attributed, on the one hand, to the lack of good blue shades, and, on the other hand, to the requirement of high dichroism of the system dyestuff/ matrix.
Surprisingly, it has now been found that certain novel stilbene dyestuffs have excellent dichroic properties and are highly suitable for the production of light-polariz-ing films or sheets.
(In what follows, a definition of a radical or index once given is maintained in the further text).
... . . .. . ... . ... ... . .
The invention relates to light-polarizing films or sheets containing dyestuffs which, in the form of their free acid, conform to the formula X ~ H=CH ~ =N-Y
~~ SO~H HO~S
Le A 26 394 - 3 -;7 in which X signifies -CN, -CF3, halogen, -NH2, -NHRl~ -NRlR2~
RlCONH-, -COOH, -CONH2, -CONHRl, -CONR~R2, -COORl, -OH, -OR1, -O-CO-R1, -N=N-Y1, or a substituted or S unsubstituted heterocyclic radical, Rl, R2 signify alkyl, cycloalkyl, aryl or aralkyl, which may be interrupted by O and/or S, and Yr Ylsignify a substituted or unsubstituted aryl or heterocyclic radical, in particular ~ R3 ~6 in which R3 signifies H, -OH, -ORl, -NH2, -NHRl, -NRlR2, -NH-COR1, -O-COR', -N=N=R1l, a heterocyclic radical, R4, R5, R7, R8, R9, RlD s ignify H, halogen, -OH, -ORl, -NH2, -NHRl, -NRlR2, -Rl, -S03H, -NH-CO-Rl, -O-CO-Rl, -SO2-NH2, -SO2-NHRl, -SO2-NRlR2, R6 - ~~ signifies H, -N=N=Rll, heterocyclic radical and Rll signifies a substituted or unsubstituted aryl radical, preferably a substituted or unsubstitut-ed phenyl or naphthyl radical or a substituted or unsubstituted heterocyclic radical containing a maximum of eight azobridges.
Preferred radicals y, yl and Rll of the benzene series are as follows:
Le A 26 394 _ 4 _ . . .... . - :
In particular, suitable radicals are those which are derived from phenol and aniline and its substitution products, if appropriate subsequently alkylated or acylated. Examples are:
H , ~ CH3 ~ ~ C2H5 -CH2-CH2-OH , ~ H , ~ H
H2 ' ~ `CH3 ~ `CH2-CH2-OH
,CH3 ~ ,CH3 `c}l2-cH2-ocH3 `CH2-CH2-CN
.
~1~ . --~3N5N_Rl 1 ~=N-Rl 1 , Le A 26 394 - 5 -=N-RIl ~ =N-Rll ~ =N-Rl _Ri 1 ~N_Rl 1 , ~
OCH3 HN~ 503H
COCH~
Preferred radicals y, yl and Rll of the naphthalene series are listed below:
~ R9 Rl2 = -OH, -NH2 _ ~ ~4 . . ~ . . .
R8~R9 Rl3 i8 H, if Rl~ = -N=N-Rll or H, and is -N=N-Rl1, if R14 = -OH, -NH2, R14 is -OH, -NH2, -N=N-R , Le A 26 394 - 6 -.... _ . _ .. .. ... . . . . . . .
R 15 R ~ 5 6 ' ~R14 R15)~R16 Rl5, Rl6 are H, -OH, -ORl, -O-CORl, -NH2, -NH-R1, -NR1R2, -NH-CO-Rl, -S03H, Rl7 is H, -SO3H.
In particular, the following radicals y, yl and R11 of the naphthalene series are preferred:
~ 18 ~ R17 Rl8 is H, OH, NH2, -NH-CO-Rl, -NH-Rl, -N=N-Rl1, -S03H, R2 R2 1 R2 o - ~ 3H
R1~ is H, -N=N-R11, R20, R2l are OH, NH2, -O-CO-R1, -NH-CO-Rl, Le A 26 394 ~ 7 ~
D~:27 OH OH R20 OH Rl 7 \~ ' ~ ' ~ 18 Preferably, Y, Y~ and Rll are derived from the (sub-stituted) I acid:
OH
HO ~5 ~R
R is -NH-Rl, -NH-CO-Rl, -N=N-Rll Halogen preferably represents F, Cl, Br, I.
Alkyl (Rl, R2) preferably represents Cl-C6-alkyl (methyl, ethyl).
Cycloalkyl (Rl, R2) preferably represents C3-C7-cvcloalkyl (cyclopentyl, cyclohexyl).
Aryl (Rl, R2) preferably represents phenyl and naphthyl.
Aralkyl (Rl, R2) preferably represents phenyl-C,-C4-alkyl (benzyl, phenethyl).
Suitable substituents for the alkyl and cycloalkyl radicals (Rl, RZ) are, for example, halogen (Cl, Br, F), -OH, -CN, Cl-C4-alkoxy and the like.
Suitable substituents for the aryl and aralkyl radicals (Rl, R2) are, for example, halogen (Cl, Br, F), -OH~ Cl-C4-Le A 26 394 - 8 -.. , _ . .... ..
alkoxy (methoxy), Cl-C4-alkyl (methyl), CF3, NO2, CN.
Preferred radicals X, R3 and R6 of the heterocyclic series have the formula:
; ~ R
-X jz ; in which . 5 X is a C or an N atom, where the free valence of ; carbon has been saturated by a double bound, and Z represents the remaining members of a preferably 5- or 6-membered monocyclic or bicyclic or tricyclic ring 10 which can contain 1 to 3 heteroatoms from the series con-sisting of N, O, S and is substituted or unsubstituted.
In particular, they are derived from the following heterocyclic systems:
triazole, pyrazole, benzotriazole, naphthotriazole, oxazole, imidazole, thiazole, oxadiazole.
Preferred radicals y, yl and Rll of the heterocyclic series have the formula ~'Rl 9 -C z in which Z represents the remaining members of a preferably Le A 26 394 - 9 -..
2~ 27 5- or 6-membered monocyclic or bicyclic or tricyclic ring, which can contain 1 to 3 heteroatoms from the series con-sisting of N, 0, S and is substituted or unsubstituted, S the free valence of carbon being saturated by a double bond.
In particular, Y, Y~ and R11 are derived from the follow-ing heterocyclic systems:
thiophene, triazole, pyrazole, pyridine, benzotriazole, pyridone, naphthotriazole.
In addition, R11 is derived from the following hetero-cyclic systems:
thiadiazole, thiazole, benzothiazole.
Suitable heterocyclic radicals (Y, Y~ and R11) are in particular a substituted 5-amino- or 5-hydroxypyrazole radical, for example R2 2~T=N
~N_R23 in which R12 R22 is H, C~-C4-alkyl (methyl), -COOH, R23 is ~ 503H ~ 503H, ~ =N ~ S03H
Further preferred radicals Y, Y~ and R~1 are those of the Le A 26 394 - 10 -formula:
~ A-N=N ~ L
in which A is a substituted or unsubstituted phenylene or naphthalene radical, L is a substituted or unsubstituted phenyl or naphthyl radical and p is 1, 2, 3.
In particular, A represents and L represents ~R3 . ~R9 Preference is given to the group of symmetrical compounds of the formula - -Y1-N=N ~ H=CH ~ N=N-Y
~ 503H Ho35 in which Y~ is Y.
Le A 26 394 - 11 -2t)~ 7 A further preferred group of compounds conforms to the formula OH
Y-N=N ~ H=CH ~ N= ~
A further preferred group of compounds conforms to the formula Y-N=N ~ H=CH ~ =N ~ ~
sO3H 503H R5 H035 18 A further preferred group of compounds conforms to the formula Rl- ~ N=N ~ H=C ~ N=N-Y
503H sO3H
Dyestuffs I can be prepared in analogy to processes known from the literature.
H2N~CH= C1~3NH2 503H H035 (VI) which can be tetrazotized and coupled onto coupling components serves as starting material. Free amino groups of the coupled products obtained can be diazotized and Le A 26 394 - 12 -coupled again.
The compound 02~ ~ H=C ~ .NH2 S03H H035 (VII) can be used for preparing unsymmetrical dyestuffs. To this end, VII is diazotized and coupled onto suitable coupling components. Free amino groups of the coupled products obtained can be diazotized and coupled again.
The nitro group of the dyestuffs obtained can be reduced, and the amino compound obtained can be diazotized and coupled onto suitable coupling components. This makes the unsymmetrical compounds of the formula I accessible.
The monoamino compound VII can be converted according to Sandmeyer to the corresponding halogen, CN or OH com-pounds etc. (cf. S.Y. Zherdeva et al., J. Org. Chem~ ~SSR
16 (1980) 383) or, for example, to various derivatives (triazoles, pyrazoles etc.). After reduction of the nitro group, the monoamino compounds obtained can be coupled, after diazotization, to give azo dyestuffs.
Compound VII can furthermore be acylated at the amino group in a known manner (acetylated, benzoylated);
subsequent reduction of the nitro group gives amino-containing intermediates, for example Le A 26 394 - 13 -C~3 C,~ ~CH=CH~ ; .2 (VIII) which like VII are suitable for the preparation of unsymmetrical dyestuffs. In particular, they can be diazotized and coupled onto suitable coupling components.
After elimination of the acyl group, the dyestuffs obtained can be diazotized and coupled again. Compound VIII like VII can be converted according to Sandmeyer to derivatives which, after elimination of the acyl group, can be diazotized and coupled to give azo dyestuffs.
In particular, the invention relates to light-polarizing films (sheets) which contain an organic polymer and one or more compounds of the formula I.
The organic polymer is preferably an oriented polymer which forms transparent films and is compatible with dyestuffs which contain acidic groups. Examples of such a polymer are: polyamides, cellulose (acetate), vinyl alcohol homopolymers and copolymers and vinyl acetate homopolymers and copolymers, where the comonomers present can be, for example, ethylene, propylene, crotonic acid, (meth)acrylic acid, maleic acid. Polyvinyl alcohols which have been prepared by complete or partial hydrolysis of polyvinyl acetate, in particular those types which have a viscosity of > 4 mPa.sec2, preferably 20 to 70 mPa.sec2, at 20C in 4% strength agueous solution and a hydrolysis degree of > 80 mole %, preferably 85 to 100 mole %, are preferably used.
Le A 26 394 - 14 -The films preferably have a thickness of 10 to 150 ~.
The films preferably contain 0.01 to 10 % by weight, particularly preferably 0.5 to 6 % by weight, relative to the weight of the film, of the dyestuff.
The films are coloured in the usual manner, for example by colouring the polymer which is dissolved (in water).
The film is prepared from the solution in a manner known per se.
It is recommended to free the dyestuffs or dyestuff salts before use of foreign salts, for example by recrystal-lization, extraction and/or dialysis.
Preferably, these sheets are used which have been stretched at elevated temperature, preferably at 80-160C, by 200 to 1000%
If desired, the dyestuff-containing films can also be subjected to an aftertreatment, for example with aqueous boric acid solution, in order to improve the light permeability or the polarization coefficient. The condi-tions under which this aftertreatment is carried out can vary, depending on the film material and dyestuff.
Preferably, a 1-15 % strength by weight, particularly preferably a 5-10 % strength by weight, boric acid solution is used at 30-80C, particularly preferably at 50-80C. Preferably, surfactants and, if desired, in-Le A 26 394 - 15 -t~ .7 organic salts are added to the boric acid solution. The surfactants can be nonionic, cationic or anionic; prefer-ably, they are nonionic.
Examples of nonionic surfactan~s are: addition products of ethylene oxide with higher alcohols or addition products of ethylene oxide with nonylphenol. Preferably, 0.005-0.5 % by weight, particularly preferably 0.02-0.2 % by weight, of surfactant is used, relative to the water.
Suitable inorganic salts are preferably sodium sulphate and furthermore potassium sulphate, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate.
Relative to the water, preferably 0.1-5 % by weight, particularly preferably 0.3-3 % by weight, of inorganic salts are used. If desired, this can be followed by a fixation treatment with an aqueous solution of a high-molecular-weight cationic compound.
The light-polarizing films or sheets can be compounded or laminated with other materials in a manner known p~r se.
Examples of suitable protective coatings are sheets made of a tetrafluoroethylene/hexafluoroethylene copolymer or another fluorohydrocarbon resin, a polyester, polyolefine or polyamide resin,a polycarbonate or cellulose ester, preferably cellulose (tri)acetate, cellulose (tri)propionate, cellulose (tri)butyrate.
The dichroism of the system can be considerably enhanced Le A 26 394 - 16 -~2~
by addition of lower mono- or polyhydric alcohols, such as methanol, ethanol or glycol, glycerol, trimethol-ethane, trimethylolpropane, pentaerythritol, sorbitol, their ethers, such as glycol monomethyl ether, glycol monoethyl ether, glycol dimethyl ether, diglycol diethyl ether, lower amines such as propylamine, hydroxy amines, such as propanolamine or amides, such as DMF, N-methyl-pyrrolidone, pyrrolidone, ~-caprolactam, to the casting solution. The additives can be used alone or, more advantageously, in mixtures, in which lower monohydric alcohols, for example methanol, ethanol, i-propanol, can also be present as components of the mixture. The addi-tives are preferably added to the casting solution in amounts of 5-50 % by weight, relative to the casting solution.
Besides being used in light-polarizing films, the dye-stuffs of the formula I can be used alone or in mixtures for rendering ordered structures visible in the analysis of polymers and in biological materials.
Example 1 a) Svnthesis of the dvestuff:
R-N ~ H=CH ~ ~N-~
~y ~ 503H
R = ~ 0-~H ~ 03H
Le A 26 394 - 17 -~i5''~7 37 g (0.1 M) of 4,4~-diaminostilbene-2,2~-disulphonic acid are suspended in 1 1 of water. 83 ml of concentrated hydrochloric acid are added and 51 ml (0.22 M) of sodium nitrite solution (as an approximately 30 ~ strength solution) are added dropwise slowly at room temperature.
The suspension is stirred overnight. After this time, it should be possible to detect a nitrite excess which is destroyed by the addition of sulphamic acid solution.
This tetrazonium salt solution is slowly added dropwise at room temperature, while controlling the pH, to a solution of 69 g (0.2 M) of l-hydroxy-6-benzoylamino-naphthalene-3-sulphonic acid in 0.5 1 of water, the pH
being maintained between 6.5 and 7 by dropwise addition of 10 per cent strength sodium hydroxide solution. After stirring overnight, the precipitated dyestuff is filtered off with suction and washed several times with small portions of water. The dyestuff is then dissolved in water and subjected to dialysis, to separate off salts;
the dyestuff solution obtained is then evaporated, and the residue is dried. Yield: 98.7 g.
b) Manufacture of the sheet 9.9 g of ~MOWIOL 28-99 (hydrolyzed polyvinyl acetate;
degree of hydrolysis 99.4 + 0.4 mole %; viscosity of the 4 % strength agueous solution at 20C:28 i 2.0 mPa.sec2;
from Hoechst AG) and 0.1 g of the dye of Example la are dissolved in 190 ml of water by heating the mixture at Le A 26 394 - 18 -90C for 2 hours with stirring. 5 g of methanol and 2.5 g of glycerol are added to 92.5 g of the 1 %
strength, relative to the polymer, dyestuff solution obtained. By means of a knife, 500 ~ thick layers are applied from this solution to a clean glassplate, and the layers thus obtained are dried in air at room temperature on a support in an exactly horizontal position. The resulting dry sheets are peeled off from the glassplate;
they have a violet colour and are about 40-50 ~ thick.
c) Stretching of the sheets To produce dichroic properties, the sheets are stretched.
To this end, they are heated in a drying cabinet at a constant temperature of 130C for 15 minutes and then stretched at a speed of about 10 cm/min to about 700 % of their original length. The stretched sheets have a dichroic ratio of about 28 at the absorption maximum (557 nm), measured with polarized light; losses due to reflection were not taken into account in the measure-ment.
d) Sheet manufacture on the castin~ machine 0.2 g of the dyestuff of Example la is dissolved in 100 g of hot water. 10 g of glycerol are added, and 19.8 g of ~OWIOL 28-99 are stirred into the cooled solution. After stirring at room temperature for 1 hour, the mixture is heated to 90C, and stirring is continued at this temperature until, after about 3 hours, a homoge-Le A 26 394 - 19 -~ 7'~7 nous solution has been formed. At 50C, 5 g of methanol are then stirred in. The warm solution is filtered through a filter press, while injecting air, and is then degassed by evacuation. The casting solution is pourable and stable at 30C.
To produce a sheet, the casting solution is applied continuously by means of 250 ~ knife to the casting wheel (wheel diameter 25 cm, rotating speed about 7.5 min per revolution) which has been preheated to about 50C. The layer is dried by passing heated air over it, and the solidified sheet is continuously peeled off the wheel and additionally dried. The sheet obtained is about 40 ~
- thick. It is stretched as described above in c), leading to similar results.
e) Exactly analogously as in Example la, analogous dyestuffs are obtained by using the coupling components mentioned, which are incorporated into sheets according to lb. Stretching according to lc gives dichroic sheets.
~ I H . . ..
.~ ~~, .
c~ ~.,~-C'3-G'l OH
OH
!
c3s~5~3H
!~H 2 OH
~.' 5~3H
Le A 26 394 - 20 -- Z~ 27 Further dyestuffs are prepared analogously to Example la from the following coupling components:
OH H;C-CO-NH OH
~35 503.~ ~ ~
H~ <~3-Co-HH OH
CH3-CO-h'H ~ 503H H2N ~
. 503H
NH ~ H035 CO-NH ~ NC-CH2-CH2-N ~ 3 OH OH OH
CH3-CO-N ~
303H ~ 03H ~ 303H
NH-CO
Le A 26 394 - 21 .
.
2~64Z7 OH ~2N O.Y
~CO-N~ ~
503H ~503H
~C ~503 H C O - N~503H
~0 NH R
OH
~N~503H C~3 503H
,~ NH2 OH
CH3 - O~N~So3H
;' C~, ~503H
OH
Le A 26 394 - 22 -~3C-CO~ OH COCH
H35~o3H OH 503 O~O_NH OH
HO~} H03S~
<~ H035 The products obtained from the coupling onto phenols can be ''sealedll by subsequent alkylation (methylation, ethylation, benzylation).
Exam~le 2 a) 17.3 q (0.1 mol) of 4-aminobenzenesulphonic acid are dissolved in 200 ml of water together with about 7 ml of sodium hydroxide solution (45 ~ strength), : and 28 ml of concentrated hydrochloric acid are then added all at once. The freshly precipitated suspen-sion is diazotized at 5-10C with 7 g of sodium nitrite in 15 ml of water. After 15 minutes, the product is filtered off with suction and washed on the filter with icewater. The moist product is Le A 26 394 - 23 -~ 7 immediately stirred into 100 ml of water (caution:
the dry product is explosive). To the suspension of the diazonium salt thus obtained is added dropwise, with vigorous stirring, a cold solution of 34.1 g (0.1 mol) of 8-amino-1-hydroxy-naphthalene-3,6-disulphonic acid monosodium salt and 5.5 g of sodium carbonate in 100 ml of water over a period of 45 minutes. The mixture is stirred for 12 hours while warming to room temperature, the product is filtered off with suction and washed neutral. This gives a dyestuff paste of the formula:
H03S ~ = ~
b) The dyestuff paste from a) is dissolved together with 40 g of sodium carbonate in about 500 ml of water, if necessary with heating, and then cooled to below 10CC. The tetrazonium salt solution from 18.5 g (0.05 mol) of 4,4~-diaminostilbene-2,2'-disulphonic acid prepared according to Example la is added dropwise to the suspension obtained over a period of 30 minutes, while maintaining the pH at 6.5 to 7 by metering in 10% strength sodium hydroxide solution. The mixture is stirred over-night, the dyestuff is filtered off with suction, washed neutral with water and then dissolved in water and dialyzed, to separate off salts. The Le A 26 394 - 24 -dyestuff solution is evaporated and the residue is dried. The dyestuff obtained has the structure:
HO 3S~
R-N'N~H=C~l~N=N-R
503~
13035~3H .
c) The following coupling components which can be prepared analogously to 2a) can also be used:
H035 ~ N= ~
: NH2 OH
H035 ~ N=N ~ N= ~ S
H35~N.~o3H
.; S03~
H035 ~ Ns ~ S03H
OH
Le A 26 394 - 25 -Zl[)0~427 OH
H03S ~ N=N ~ 503H
H035 ~ '~`
0}~
H03S ~ ' ~ 503H
d) Exactly analogously, the dyestuff of the structure:
R-N=N ~ H=CH ~ =N-R
R = H035 ~ H03 ~ 03H
is obtained by coupling the tetrazonium salt solu-tion of Example la first at a pH of 4.5-5.5 onto 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid and then coupling the diazonium compound from 4-amino-benzenesulphonic acid prepared according to Example 2a twice onto the product at a pH of 7-7.5.
The other components mentioned in c) can also be reacted in reverse order to give analogous dye-Le A 26 394 - 26 -20~42~7 stuffs.
Example 3 a) At a maximum temperature of 10C, a solution of 30.6 g (0.2 mol) of 2,5-dimethoxyaniline in 500 ml of water (to which concentrated hydrochloric acid is added until a clear solution is formed) is added dropwise to the tetrazonium salt solution prepared according to Example la, with stirring, while maintaining a pH of 3 to 4.5 by simultaneous meter-ing in of sodium hydroxide solution. After stirring overnight and warming to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water. The dyestuff obtained after drying weighs 52.4 g and has the formula:
R-N=N ~ H=CH ~ N=N-R
R - H2N ~
. .
Instead of 2,5-dimethoxyaniline, it is also possible to use 2-methoxy-5-methylaniline, 2,5-dimethyl-aniline, 3-methylaniline, 3-acetylaminoaniline, Le A 26 394 - 27 -2~ i427 1-naphthylamine, 1-amino-2-ethoxy-naphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.
b) The intermediate product obtained in a) is tetrazot-ized in aqueous hydrochloric acid with sodium nitrite while letting it stand overnight at room temperature, and the tetrazonium salt solution obtained, after destruction of the nitrite excess, is coupled onto l-hydroxy-6-benzoylamino-naph-thalene-3-sulphonic acid at a pH of 6.5 to 8. The dyestuff obtained has the formula:
R-N=N ~ H=CH ~ =N-R
R CH3-CO-NHJ~03H OCH !
c) The other compounds mentioned in Example le and 2c can also be used as components of the final coupling reaction, preferably benzoyl I acid, acetyl gamma-acid or acetyl K acid; phenolic coupling components can subsequently be ~sealed~ by alkylation. The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.
Le A 26 394 - 28 -Example 4 a) 9.6 g (0.01 mol) of the dyestuff from Example le formed by coupling of the tetrazonium salt from la onto l-hydroxy-6-acetylaminonaphthalene-3-sulphonic acid are stirred in 200 ml of 2N sodium hydroxide solution at 80CC until the acetyl groups have been completely cleaved off (monitoring of the reaction by thin-layer chromatography). The reaction mixture is neutralized, cooled, and is filtered off with suction and the residue washed neutral.
b) The dyestuff formed according to a) is dissolved in 100 ml of IN sodium hydroxide solution, 1.8 g of sodium nitrite are added to the solution, and the solution is then run into excess hydrochloric acid.
After standing overnight at room temperature, the tetrazonium salt solution has been formed; excess nitrite is destroyed by means of sulphamic acid, 2 g of phenol dissolved in sodium hydroxide solution are then added dropwise, and the pH is brought to about 9 with sodium hydroxide solution. After stirring for 3 hours, the coupling reaction is completed. The product i5 filtered off with suction and washed neutral.
c) The dyestuff formed according to b) is dissolved in 100 ml of lN sodium hydroxide solution, and 4 g of dimethyl sulphate are added to the solution with Le A 26 394 - 29 -stirring. Afer about 1 hour, the methylation is completed. The producted is filtered off with suction, washed neutral and dried. The dyestuff obtained has the formula:
R-N=N ~ H=C ~ N=N-R
OH
CH3{~N=N~C03H
Instead of dimethyl sulphate, it is also possible to convert the phenolic groups with diethyl sulphate or benzyl bromide to the ethers.
Instead of phenol in 4b), it is also possible to use the other coupling components listed in ~ables le and 2c as end groups.
Example S
a) The tetrazonium salt solution from Example la is added dropwise at about lO~C to the solution of 68.4 g (0.2 mol) of 1-hydroxy-8-acetylaminonaph-thalene-3,6-disulphonic acid (monosodium salt) in 0.8 1 of water, during which the pH is maintained at 6.5-7.5 by dropwise addition of 2N sodium hydroxide Le A 26 394 - 30 -:
'' 4~7 solution. The coupling reaction is then allowed to go to completion overni.ght, while heating to room temperature. The product is filtered off with suction, washed neutral with water and dried. Yield:
62.5 g of a blue-violet soluble dyestuff.
b) 20 g of the dyestuff from 5a) are heated in 200 ml of 2N sodium hydroxide solution at about 80C, until the acetyl groups have been cleaved off. The mixture is then acidified with hydrochloric acid, the pro-duct is filtered off with suction, washed neutral and dried. This gives 15.3 g of a dyestuff which, in the form of the free acid, has the following formula: HO3S
R-N=N ~ H=CH ~ =N-R
R = HO35 ~ O3H
An analogous dyestuff is also obtained from l-hydroxy-8-acetylaminonaphthalene-3,5-disulphonic acid, followed by cleavage.
The dyestuffs can be incorporated according to Example lb into a sheet and stretched according to lc.
"Unsvmmetrical" dyestuffs A suitable intermediate for the preparation of "un-symmetrical'- compounds is 4-amino-4'-nitrostilbene-2,2'-Le A 26 394 - 31 -2C~ 27 disulphonic acid.
Example 6 21.2 g(0.05 mol) of 4-amino-4'-nitrostilbene-2,2'-disul-phonic acid are suspended in 400 ml of water, and 40 ml of concentrated hydrochloric acid are added. Diazotiza-tion is carried out by dropwise addition of 12.8 ml of 30% strength sodium nitrite solution (0.05 mol + 10 %) at a maximum temperature of 10C, and stirring is then continued at about 20C overnight. The nitrite excess is then destroyed by addition of sulphamic acid.
The diazonium salt solution obtained is added dropwise to a solution of 17.2 g (0.05 mol) of 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid in 160 ml of water at about 20C, during which the pH is kept in the range from 7 to 8 by dropwise addition of sodium hydroxide solution.
After stirring overnight, the precipitated dyestuff is filtered off with suction, washed neutral with a small amount of water and dried. Yield: 28.5 g (75 %). This gives a dyestuff of the structure:
02N~H=CH~N=~
-S03H HO3S ~ NH-C ~
Exactly analogously as described above, an analogous Le A 26 394 - 32 -2~ i42~
dyestuff is obtained by replacing 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid by 1-hydroxy-6-anilino-naphthalene-3-sulphonic acid.
b) Further suitable coupling components are the ones mentioned in the Table of Examples le and 2c, preferably acetyl I acid, acetyl gamma-acid, R acid, acetyl R acid, benzoyl R acid, acetyl H acid, benzoyl H acid, Chicago SS acid, benzoyloxy C acid or phenol. The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
In addition, they can be reduced as described in 9a) to the amino compounds, which are diazotized and then coupled onto suitable coupling components, for example those the Tables of Examples le and 2c. -Example 7 a) 4-Benzoylamino-4'-nitrostilbene-2,2'-disulphonic acid:
200 g (0.5 mol) of 4-amino-4~-nitrostilbene-2,2'-disul-phonic acid are suspended in l l of water, and the mixture is brought to a pH of 9 with 40% strength sodium hydroxide solution. At about 10C, 77 g (0.5 mol + 10%) of benzoyl chloride are added dropwise with vigorous stir-Le A 26 394 - 33 -42~
ring, during which the pH is maintained at 9 by dropwise addition of sodium hydroxide solution. As soon as the pH
remains stable, stirring at room temperature is continued for 1 hour, the product is filtered off with suction, washed neutral and dried. This gives 233 g.
b) 4-Amino-4'-benzoylaminostilbene-2,2~-disulphonic acid:
151 g (0.3 mol) of the product from a) are suspended in 2.5 1 of water, 100 g of 45~ strength sodium hydroxide solution and 200 g of sodium sulphide trihydrate are added, and the mixture is slowly heated to 80C until the starting material has disappeared (TLC). 200 g of sodium chloride are added to the hot solution. After cooling, the product is filtered off with suction and washed carefully neutral with water. The dry product weighs 113 g.
c) Diazotization of 4-amino-4'-benzoylaminostilbene-2,2'-disulphonic acid in accordance with the pro-cedure of Example 6a, destruction of the nitrite excess with sulphamic acid, and coupling of the product onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of 7-8, gives a dyestuff of the structure:
. .
Le A 26 394 - 34 -~(.) H OH
~3 C O - NH~ H = C 1~ ~ - C o~3 The corresponding dyestuff which has an acetylamino group on the stilbene radical is obtained analogously.
Further suitable coupling components are the ones men-tioned in Examples le and 2c, preferably phenyl I acid, acetyl R acid, benzoyl K acid, acetyl gamma-acid, acetyl H acid, benzoyl H acid, Chicago SS acid and phenol (followed by methylation). The dyestuffs obtained can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
ExamPle 8 a) At a maximum temperature of 1ODC, a solution of 7.8 g (0.05 mol) of 2,5-dimethoxyaniline in 125 ml of water (dissolved with the concentrated hydro-chloric acid addition until a clear solution is formed) is added dropwise to the diazonium salt solution prepared according to Example 6a, with stirring, while maintaining a p~ of 3 to 4.5 by metering in sodium hydroxide solution. After stirring overnight, during which the temperature is allowed to rise to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water.
Le A 26 394 ~ 35 ~
Instead of 2,5-dimethoxyaniline, it is also possible touse2-methoxy-5-methylaniline, 2,5-dimethylanili-ne, 3-methylaniline, 3-acetylaminoaniline, l-naph-thylamine, 1-amino-2-ethoxynaphthalene-6-sulphonic acid etc.
b) The intermediate obtained in a) is diazotized in the form of a paste in aqueous hydrochloric acid with sodium nitrite, the diazotization being allowed to go to completion by standing overnight and warming to room temperature. Excess nitrite is destroyed by means of sulphamic acid.
The diazonium salt solution is coupled onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid at pH
6.5 to 7.5. The dyestuff obtained has the formula:
S ~ OC~3 R-CH-C ~ N=N ~ N=N-R
It is also possible to USQ the other compounds mentioned in Examples le and 2c as components of the end coupling.
c) Exactly analogously as described in 8a and b, the Le A 26 394 - 36 -4~;D7 dyestuff of the formula R-CH=CH ~ = ~ =N-R~
R = ~ ONH ~
H03S ~ NH ~
is obtained by using the diazonium salt from Example 7c.
It is also possible to use the other compounds mentioned in Examples le and 2c as components of the S end coupling.
If benzoyl chloride in Example 7a is replaced by other active acid derivatives, for example acetic anhydride, propionic anhydride, 4-methylbenzoyl chloride etc., and the procedure according to 7b and then according to 7c and 8c is repeated, analogous dyestuffs in which the benzoyl group is replaced correspondingly are obtained.
. . .
Example 9 a) The dyestuff of Example 6a which still contains a Le A 26 394 - 37 -Z~ 27 nitro group is reduced in an ethanol/water mixture with sodium sulphide or analogously to the procedure in DOS ~German Patent Specification) 3,805,513, Exzmple 3, to the amino compound. Another possible reduction is that using iron powder in weakly acidic aqueous medium according to Bechamp.
Exactly analogously, the corresponding nitro-con-taining dyestuffs of Example 6b can be reduced to the amino compounds.
b) 18.1 g (0.025 mol) of the dyestuff obtained in a) are suspended in 300 ml of water, 20 ml of con-centrated hydrochloric acid are added, and the mixture is diazotized by dropwise addition of 6.4 ml of 30% strength sodium nitrite solution (0.025 M
+ 10%) at a maximum temperature of 10C, and stir-ring is allowed to continue overnight at room temperature. The nitrite excess is then destroyed by addition of sulphamic acid.
The diazonium salt solution obtained is added - 20 dropwise to a solution of 8 g ~0.025 mol) of 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid in 80 ml of water at about 20C, while maintaining the pH at about 7. After stirrinq overnight, the precip-itated dyestuff is filtered off with suction, washed with a small amount of water and dried. The dyestuff obtained has the structure:
Le A 26 394 - 38 -SO H
'"'''2 OH ~-CH~N=N-R' ? ~ ;S~ S03H
OH
SO~H
H O 3 S~NI~ - C C~3 It is also possible to use the other compounds mentioned in Examples le and 2c as coupling components.
The same reaction sequence 9a, b can also be carried out with the dyestuff from Example 8b and its analogues. This dyestuff is also obtained by deacylating the dyestuff from Example 8c with 2N hydrochloric acid or 2N sodium hydroxide solution at about 80C and diazotizing and coupling the intermediate thus obtained as described in 9b.
Example 10 a) 5 g (about 0.05 mol) of phenol are dissolved in 100 ml of water with the addition of sodium hydroxide solution, until a clear solution has been obtained, and the diazonium salt solution obtained in Example 6a is then added dropwise at about 10C, during which a pH of about 9 is maintained by addition of sodium hydroxide solution. After stirring overnight, the mixture is neutralized, the precipitate filtered off with suction and washed.
Le A 26 394 - 39 _ ~r~;~7 The moist paste is reacted analogously to the procedure in Example 4c in a~leous alkaline solution with dimethyl sulphate, until complete methylation has taken place. This gives a dyestuff of the structure:
N02{~CH=CH~N=N{~_CH3 Likewise, other (substituted) phenols can also be used instead of phenol.
If dimethyl sulphate is replaced by benzyl bromide, the corresponding benzylated compound is obtained;
other alkylating agents, for example diethyl sul-phate, are also suitable.
b) The dyestuff obtained in a) is reduced with sodium sulphide in ethanol and water or with iron powder in weakly acidic medium to the amine. This amine is diazotized analogously to Example 6a with sodium nitrite, and excess nitrite is then destroyed by means of sulphamic acid.
The diazonium salt solution obtained is coupled in accordance with the further procedure in Example 6a onto 1-hydroxy-6-henzoylaminonaphthalene-3-sulphonic acid at a pH between 7 and 8, which gi~es a dyestuff of the formula below:
Le A 26 394 _ 40 -R-l~'=N~H=CH~N=N-R ' 0~
R = }~ 3C ~3 H0 3 5~NH - C G~) It is also possible to use the other compounds mentioned in Examples le and 2c as components of the end coupling, preferably acetyl I acid, N-phenyl I acid and acetyl H
acid.
The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.
The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.
Exam~le 11 (Condensation dyestuffs) The condensation reaction for the preparation of azo dyestuffs is described in Houben-Weyl, Methoden der Organischen Chemie (Methods of organic chemistry), Vol.
10/3, Part 3, p. 339-346.
5 a) The preparation of the following dyestuff is de-scribed there on page 343:
Le A 26 394 - 41 -2~4Z7 2-N=N ~ N=N ~ H=CH ~ N=N ~ N=N-R
R = H035 ~
b) The following dyestuffs are prepared by suitable modification of the procedure given there:
H3C- ~ N:N ~ H=CH ~
N
H3C- ~ s ~ H=CH
N - N ~ HrCH ~ =N ~
H035 ~ NS03H S03H CH
CH
Nl Nl ~
H03S ~ N S03H
~ .' Exam~ 2 a) The compound 2~-C~l Le A 26 394 - 42 -is prepared by the procedure in J. Org. Chem. USSR 16 ~1980) 388.
Exactly analogously, it is also possible to prepare the corresponding bromine compound or the cyanide instead of the chlorine compound.
b) The compound of Example 12a is reduced analogously to the procedure in Example 7b, 10b or in J. Org.
Chem., USSR 16 (1980) 386, 389 to the amino com-pound. This compound is converted into the corres-ponding diazonium salt, for example as described in 6a, and then as also described in 6a, coupled onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of about 7-8. This gives the dyestuff of the structure:
Cl ~ H=CH ~ N=
503H HO35 ~ NH-C ~
Further suitable coupling components are those mentioned in Tables le and 2c.
c) If the procedure of Example 8 is repeated and the diazonium salt solution prepared in 12b is used instead of that used in 8a, and the product is first coupled onto 3-methylaniline and then onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid, a Le A 26 394 _ 43 _ dyestuff of the structure:
R-HC=CH ~ =N ~ =N-R
R Cl { ~ R~ . ~`NH~
is obtained.
Further suitable coupling components are those mentioned in Tables le and 2c.
Instead of 3-methylaniline, it is also possible to use2,5-dimethoxyaniline,2-methoxy-5-methylaniline, 2,5-dimethylaniline, 3-acetylaminoaniline, 1-naph-thylamine, l-amino-2-ethoxynaphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.
d) If the corresponding bromine or cyano compound is used in 12b and c) instead of the chlorine compound from 12a, analogous dyestuffs are obtained.
Example 1~
The known compound of the following formula obtained by Le A 26 394 _ 44 _ 2~)~64'~;7 coupling of diazotized 4-amino-4'-nitrostilbene-2,2'-disulphonic acid onto l-aminonaphthalene-4-sulphonic acid analogously to the procedures in Houben-Weyl, Methoden der Organischen Chemie (Nethods of Organic Chemistry), Vol. 10/3, Part 3, p. 428, 429:
02N{~CH = CI~N~>~
S03H 503H ~
is reduced analogously to the procedure of Examples 7b, lOb or 12b to the amino compound.
The compound which is an isomer with respect to the position of the sulpho group is obtained analogously by coupling onto 2-aminonaphthalene-6-sulphonic acid, followed by reduction to the amino compound.
b) The amino compound prepared in a) is diazotized according to the procedure in Example 6a, and the product is coupled as described there onto l-hydroxy-6-anilinonaphthalene-3-sulphonic acid. This gives a dyestuff of the structure:
Le A 26 394 _ 45 _ zf )~ 7 R-N~N ~ H=C ~ ' OH
R = ~ R' = -N
Analogously, the use of 2-aminonaphthalene-6-sulphonic acid in 12a, reduction, diazotization and coupling onto phenyl I acid gi~es the isomeric dyestuff:
R-N=N ~ H=CH ~ ' OH
R =H ~ R~ = _ ~ S03H
. .
~e A 26 394 - 46 -
Claims (6)
1. Light-polarizing films or sheets containing dye-stuffs which, in the form of the free acid, conform to the formula in which X signifies -CN, -CF3, halogen, -NH2, -NHR1, -NR1R2, R1CONH-, -COOH, -CONH2, -CONHR1, -CONR1R2, -COOR1, -OH, -OR1, -O-CO-R1, -N=N-Y1, or a substituted or unsubstituted heterocyclic radical, R1, R2 signify alkyl, cycloalkyl, aryl or aralkyl, which may be interrupted by O and/or S, and Y, Y1 signify a substituted or unsubstituted aryl or heterocyclic radical.
2. Light-polarizing films or sheets containing dye-stuffs of Claim 1 in which y, y1 are in which A is a substituted or unsubstituted phenylene or naphthalene radical, L is a substituted or unsubstituted phenyl or naphthyl radical and p is 1, 2, 3.
Le A 26 394
Le A 26 394
3. Light-polarizing films or sheets containing dye-stuffs of Claim 1 where y, y1 are , in which R3 signifies H, -OH, -OR1, -NH2, -NHR1, -NR1R2, -NH-COR1, -O-COR1, -N=N=R11, a heterocyclic radical, R4, R5, R7, R8, R9, R10 signify H, halogen, -OH, -OR1, -NH2, -NHR1, -NR1R2, -R1, -SO3H, -NH-CO-R1, -O-CO-R1, -SO2-NH2, -SO2-NHR1, -SO2-NR1R2, R6 signifies H, -N=N=R11, a heterocyclic radical and R11 signifies a substituted or unsubstituted aryl radical, preferably a substituted or unsubstitut-ed phenyl or naphthyl radical or a substituted or unsubstituted heterocyclic radical containing a maximum of 8 azobridges.
4. Light-polarizing films or sheets containing dye-stuffs of Claims 1 and 3 in which y, y1 and R11 are radicals from the benzene series of the formula , Le A 26 394 or radicals from the naphthalene series of the formulae in which R12 = -OH, -NH2 , R13 is H, if R14 = -N=N-R11 or H, and is -N=N-R11, if R14 = -OH, -NH2, R14 is -OH, -NH2, -N=N-R11, , R15, R16 are H, -OH, -OR1, -O-COR1, -NH2, -NH-R1, -NHR1R2, -NH-CO-R1, -SO3H, R17 is H, -SO3H.
in particular of the formulae Le A 26 394 - 49 - , , in which R18 denotes H, OH, NH2, -NH-CO-R1, -NH-R1, -N=N-R11, -SO3H, , in which R19 denotes H, -N=N-R11, R20, R21 denote OH, NH2, -O-CO-R1, -NH-CO-R1, , , and in which R is NH-R1, -NH-CO-R1, -N=N-R11.
in particular of the formulae Le A 26 394 - 49 - , , in which R18 denotes H, OH, NH2, -NH-CO-R1, -NH-R1, -N=N-R11, -SO3H, , in which R19 denotes H, -N=N-R11, R20, R21 denote OH, NH2, -O-CO-R1, -NH-CO-R1, , , and in which R is NH-R1, -NH-CO-R1, -N=N-R11.
5. Light-polarizing films or sheets according to Claims 1 and 4 containing dyestuffs of the formula (II) where y1 is Y.
Le A 26 394 - 50-
Le A 26 394 - 50-
6. Films and sheets according to Claims 1-5 containing dyestuffs of the formula or Le A 26 394 - 51 -
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3843411 | 1988-12-23 | ||
DEP3843417.2 | 1988-12-23 | ||
DEP3821669.1 | 1989-07-01 | ||
DE3921669A DE3921669A1 (en) | 1988-12-23 | 1989-07-01 | LIGHT-POLARIZING FILMS OR FILMS CONTAINING STYLE DYES |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2006427A1 true CA2006427A1 (en) | 1990-06-23 |
Family
ID=25875521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002006427A Abandoned CA2006427A1 (en) | 1988-12-23 | 1989-12-21 | Light-polarizing films or sheets containing stilbene dyestuffs |
Country Status (4)
Country | Link |
---|---|
US (1) | US5007942A (en) |
EP (1) | EP0374655B1 (en) |
JP (1) | JPH02269136A (en) |
CA (1) | CA2006427A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5785718A (en) * | 1996-05-31 | 1998-07-28 | Bayer Aktiengesellschaft | Substantive stilbene-azo dyestuffs |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0296102A (en) * | 1987-11-02 | 1990-04-06 | Sumitomo Chem Co Ltd | Polarizing film consisting of dye system |
ATE118621T1 (en) * | 1988-03-08 | 1995-03-15 | Toray Industries | POLARIZATION FILTER. |
US5272259A (en) * | 1988-12-23 | 1993-12-21 | Bayer Aktiengesellschaft | Stilbene dyestuffs and light-polarizing films or sheets containing stilbene |
DE4019309A1 (en) * | 1990-06-16 | 1991-12-19 | Bayer Ag | NEW LIGHT-POLARIZING FILMS OR FILMS AND DYES FOR THEIR PRODUCTION |
US5286420A (en) * | 1990-08-25 | 1994-02-15 | Bayer Aktiengesellschaft | Production of light polarizing films |
DE4227591A1 (en) * | 1992-08-20 | 1994-02-24 | Basf Ag | Use of liquid dye preparations containing a disazo dye in the ink-jet process and disazo dye |
US5423100A (en) * | 1992-08-26 | 1995-06-13 | Mitsui Toatsu Chemicals, Inc. | Water-soluble azo compounds and polarizing films using the compounds |
RU2047643C1 (en) * | 1993-05-21 | 1995-11-10 | Хан Ир Гвон | Material for polarizing coating |
JP3680323B2 (en) * | 1993-10-14 | 2005-08-10 | 住友化学株式会社 | Dye-type polarizing film |
EP1150142B1 (en) * | 1998-12-18 | 2005-06-01 | Nippon Kayaku Kabushiki Kaisha | Color polarizer with support for liquid crystal projector and color liquid crystal projector |
US6522468B2 (en) | 1999-03-18 | 2003-02-18 | Sumitomo Chemical Company, Limited | Light-polarizing film |
RU2178900C2 (en) | 2000-02-25 | 2002-01-27 | ОПТИВА, Инк. | Dichroic polarizer and material for its manufacture |
US7015990B2 (en) * | 2000-04-24 | 2006-03-21 | Nitto Denko Corporation | Liquid crystal display including O-type and E-type polarizer |
ES2269490T3 (en) * | 2000-12-28 | 2007-04-01 | Ciba Specialty Chemicals Holding Inc. | DISCOUNT COLORS AND COPPER COMPLEX, FOR PAPER STAINING. |
RU2207603C2 (en) * | 2001-06-04 | 2003-06-27 | Хан Ир Гвон | Optical device for production and/or transformation of polarized electromagnetic radiation and optical device in the form of liquid crystalline display |
US7113337B2 (en) | 2001-07-10 | 2006-09-26 | Nitto Denko Corporation | Multilayer optical coating |
US7053970B2 (en) * | 2001-07-26 | 2006-05-30 | Nitto Denko Corporation | Liquid crystal display and the method of its fabrication |
RU2226708C2 (en) * | 2001-09-21 | 2004-04-10 | ОПТИВА, Инк. | Liquid-crystal display with reflection polarizer |
US7931702B2 (en) * | 2006-06-01 | 2011-04-26 | Nippon Kayaku Kabushiki Kaisha | Azo compound and salt thereof, and dye-containing polarizing film comprising the compound or salt |
US8389122B2 (en) * | 2006-06-13 | 2013-03-05 | Nippon Kayaku Kabushiki Kaisha | Azo compound and dye polarizing film containing the same |
CN101479347B (en) | 2006-06-22 | 2013-08-07 | 日本化药株式会社 | Azo compound and dye polarizing film containing the same |
KR20100028525A (en) * | 2007-07-09 | 2010-03-12 | 미쓰비시 가가꾸 가부시키가이샤 | Compound for anisotropic film |
TWI406907B (en) * | 2007-11-02 | 2013-09-01 | Nippon Kayaku Kk | Azo compounds and dye-containing polarizing films containing the same |
KR101672555B1 (en) * | 2008-05-20 | 2016-11-03 | 니폰 가야꾸 가부시끼가이샤 | Azo compounds, and dye-based polarizing films and polarizing plates comprising the same |
TWI444438B (en) * | 2008-06-17 | 2014-07-11 | Nippon Kayaku Kk | Azo compound and salt thereof, and dye containing polarizing film and polarizing plate containing the same |
CN110945083B (en) * | 2017-07-28 | 2022-07-01 | 日本化药株式会社 | Styrene compound or salt thereof, polarizing film, polarizing plate and display device |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
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US3981558A (en) * | 1973-11-12 | 1976-09-21 | Timex Corporation | Liquid crystal electro-optical display |
US4007077A (en) * | 1973-12-27 | 1977-02-08 | Dai Nippon Toryo Kabushiki Kaisha | Liquid crystal cells |
JPS566430A (en) * | 1979-06-27 | 1981-01-23 | Fujitsu Ltd | Manufacture of semiconductor device |
US4396646A (en) * | 1981-07-20 | 1983-08-02 | Polaroid Corporation | Method of making patterned polarizers |
JPS59145255A (en) * | 1983-02-07 | 1984-08-20 | Nippon Kayaku Co Ltd | Water-soluble disazo compound |
GB2144760B (en) * | 1983-08-04 | 1987-07-22 | Photophysics Research Limited | Light-polarsing material |
JPS60156759A (en) * | 1984-01-25 | 1985-08-16 | Nippon Kayaku Co Ltd | Water-soluble disazo compound |
JPS60159705A (en) * | 1984-01-30 | 1985-08-21 | Sekisui Chem Co Ltd | Polarizing plate |
JPS60168743A (en) * | 1984-02-14 | 1985-09-02 | Nippon Kayaku Co Ltd | Colored polyvinyl alcohol film |
US4514559A (en) * | 1984-04-27 | 1985-04-30 | Nippon Kayaku Kabushiki Kaisha | Water soluble disazo compound, copper salt thereof, and sheet or film colored therewith |
JPS60230606A (en) * | 1984-04-30 | 1985-11-16 | Kuraray Co Ltd | Polarizing film |
CA1269555A (en) * | 1984-11-16 | 1990-05-29 | Sumitomo Chemical Company, Limited | Light-polarizing film |
JPS6289907A (en) * | 1985-06-19 | 1987-04-24 | Sumitomo Bakelite Co Ltd | Transparent conductive film united with polarizing film |
JPH0653012B2 (en) * | 1985-06-27 | 1994-07-20 | 功 皆川 | Fertilizer spraying equipment |
JP2668784B2 (en) * | 1987-09-11 | 1997-10-27 | 日本化薬株式会社 | Manufacturing method of polarizing film |
JP2510873B2 (en) * | 1988-01-18 | 1996-06-26 | 日本化薬株式会社 | Polarizer |
-
1989
- 1989-12-09 EP EP89122773A patent/EP0374655B1/en not_active Expired - Lifetime
- 1989-12-14 US US07/450,757 patent/US5007942A/en not_active Expired - Fee Related
- 1989-12-21 CA CA002006427A patent/CA2006427A1/en not_active Abandoned
- 1989-12-23 JP JP1334630A patent/JPH02269136A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5785718A (en) * | 1996-05-31 | 1998-07-28 | Bayer Aktiengesellschaft | Substantive stilbene-azo dyestuffs |
Also Published As
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EP0374655B1 (en) | 1993-09-15 |
JPH02269136A (en) | 1990-11-02 |
EP0374655A1 (en) | 1990-06-27 |
US5007942A (en) | 1991-04-16 |
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