KR102649555B1 - Plasticizer for cellulose ester resin, cellulose ester resin composition, optical film, and liquid crystal display device - Google Patents
Plasticizer for cellulose ester resin, cellulose ester resin composition, optical film, and liquid crystal display device Download PDFInfo
- Publication number
- KR102649555B1 KR102649555B1 KR1020207017116A KR20207017116A KR102649555B1 KR 102649555 B1 KR102649555 B1 KR 102649555B1 KR 1020207017116 A KR1020207017116 A KR 1020207017116A KR 20207017116 A KR20207017116 A KR 20207017116A KR 102649555 B1 KR102649555 B1 KR 102649555B1
- Authority
- KR
- South Korea
- Prior art keywords
- ester resin
- residue
- cellulose ester
- acid
- resin composition
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 94
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920002678 cellulose Polymers 0.000 title claims abstract description 45
- 239000012788 optical film Substances 0.000 title claims abstract description 28
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 16
- 239000004014 plasticizer Substances 0.000 title claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 49
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical group CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 5
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical group CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical group OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 53
- 230000035699 permeability Effects 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 7
- 125000004185 ester group Chemical group 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- -1 tert-nonyl alcohol Chemical compound 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 229920002301 cellulose acetate Polymers 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004439 Isononyl alcohol Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000001447 compensatory effect Effects 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- OWVAEQAOZDETGQ-UHFFFAOYSA-N 2,2-bis(benzoyloxymethyl)butyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(COC(=O)C=1C=CC=CC=1)(CC)COC(=O)C1=CC=CC=C1 OWVAEQAOZDETGQ-UHFFFAOYSA-N 0.000 description 1
- YSARLFIXKUULQE-UHFFFAOYSA-N 2,2-diethylpropane-1,3-diol Chemical compound CCC(CC)(CO)CO.CCC(CC)(CO)CO YSARLFIXKUULQE-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- BGIPUMUFMJVJQF-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO.CCCCC(CC)(CO)CO BGIPUMUFMJVJQF-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- OUHCZCFQVONTOC-UHFFFAOYSA-N [3-acetyloxy-2,2-bis(acetyloxymethyl)propyl] acetate Chemical compound CC(=O)OCC(COC(C)=O)(COC(C)=O)COC(C)=O OUHCZCFQVONTOC-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N cyclohexene-1,2-dicarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000011899 heat drying method Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 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
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/16—Esters of inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
필름상으로 가공했을 때의 내투습성을 향상시킬 수 있으며, 또한 습열 환경 하에서도 보존안정성이 우수한, 셀룰로오스에스테르 수지에 대해서 가소화제로서 호적하게 사용할 수 있는 에스테르 수지, 이것을 포함하는 수지 조성물과, 당해 수지 조성물을 사용해서 얻어지는 광학 필름 및 이것을 사용한 액정 표시 장치를 제공하는 것을 목적으로 해서, 식
B-(A-G)n-A-B
〔B는 지방족 모노알코올 잔기, G는 알킬렌글리콜 잔기, 옥시알킬렌글리콜 잔기 또는 아릴글리콜 잔기, A는 알킬렌디카르복시산 잔기(A1) 또는 아릴디카르복시산 잔기(A2)이며, (A1)과 (A2)의 합계(A1+A2)에 있어서의 (A2)의 함유율이 70∼100몰%이고, n은 반복수〕
으로 표시되는 에스테르 수지이고, 수 평균 분자량이 350∼1000인 에스테르 수지, 이것을 포함하는 셀룰로오스에스테르 수지 조성물, 당해 조성물을 포함하는 광학 필름 및 액정 표시 장치를 제공한다.An ester resin that can be suitably used as a plasticizer for cellulose ester resin, which can improve moisture permeability resistance when processed into a film and has excellent storage stability even in a moist heat environment, a resin composition containing the same, and the resin For the purpose of providing an optical film obtained using the composition and a liquid crystal display device using the same,
B-(AG) n -AB
[B is an aliphatic monoalcohol residue, G is an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue, A is an alkylenedicarboxylic acid residue (A1) or aryldicarboxylic acid residue (A2), (A1) and (A2) ) The content rate of (A2) in the total (A1 + A2) is 70 to 100 mol%, and n is the number of repetitions]
It is an ester resin represented by and has a number average molecular weight of 350 to 1000, a cellulose ester resin composition containing the same, an optical film and a liquid crystal display device containing the composition.
Description
본 발명은, 셀룰로오스에스테르 수지의 가소화제로서 호적한 에스테르 수지, 및 이것을 포함하는 셀룰로오스에스테르 수지 조성물과, 당해 수지 조성물을 사용해서 얻어지는 광학 필름 및 이것을 사용한 액정 표시 장치에 관한 것이다.The present invention relates to an ester resin suitable as a plasticizer for cellulose ester resin, a cellulose ester resin composition containing the same, an optical film obtained by using the resin composition, and a liquid crystal display device using the same.
최근, 액정 디스플레이는 박막화가 진행되고 있고, 편광판 보호 필름도 종래의 80㎛로부터 40㎛∼20㎛로 박막화가 진행되고 있다. 편광판의 보호 필름에는 편광자와의 맞붙임이 용이한 관점에서, 종래 트리아세틸셀룰로오스 수지(이하, TAC)가 많이 사용되어 왔다.Recently, liquid crystal displays are becoming thinner, and polarizing plate protective films are also becoming thinner from the conventional 80㎛ to 40㎛ to 20㎛. Conventionally, triacetylcellulose resin (hereinafter referred to as TAC) has been widely used as a protective film for a polarizing plate from the viewpoint of ease of bonding with a polarizer.
그러나 TAC는 투습성이 높고, 흡습에 의한 치수 변화, 습열 조건 하에서의 가수 분해가 일어나기 쉽기 때문에, 첨가제에 의해 흡습을 억제할 필요가 있어, 각종 첨가제가 제공되어 왔다(예를 들면, 특허문헌 1, 2 참조).However, TAC has high moisture permeability and is prone to dimensional changes due to moisture absorption and hydrolysis under moist heat conditions, so it is necessary to suppress moisture absorption with additives, and various additives have been provided (e.g., Patent Documents 1 and 2 reference).
그러나, 특히 에스테르계의 첨가제의 경우는, 첨가제 자신이 가수 분해함에 의해, 수지 조성물 또는 이것을 성형해서 이루어지는 필름의 보존안정성의 면에서, 추가적인 개량이 필요하게 되어 있다.However, especially in the case of ester-based additives, the additive itself is hydrolyzed, so further improvement is required in terms of storage stability of the resin composition or the film formed by molding it.
상기 실정에 감안해서, 본 발명이 해결하려고 하는 과제는, 특히 필름상으로 가공했을 때의 내투습성을 향상시킬 수 있으며, 또한 습열 환경 하에서도 보존안정성이 우수한, 셀룰로오스에스테르 수지에 대해서 가소화제로서 호적하게 사용할 수 있는 에스테르 수지, 이것을 포함하는 수지 조성물과, 당해 수지 조성물을 사용해서 얻어지는 광학 필름 및 이것을 사용한 액정 표시 장치를 제공하는 것에 있다.In view of the above circumstances, the problem that the present invention aims to solve is to improve the moisture permeability resistance, especially when processed into a film, and to improve the cellulose ester resin, which has excellent storage stability even in a moist heat environment, and is suitable as a plasticizer. The object is to provide an ester resin that can be easily used, a resin composition containing the same, an optical film obtained by using the resin composition, and a liquid crystal display device using the same.
본 발명자들은 예의 검토를 행한 결과, 에스테르 수지에 있어서의 원료 성분을 특정한 것으로 함에 의해, 상기 과제를 해결할 수 있는 것을 알아내어, 본 발명을 완성하는데 이르렀다.As a result of intensive studies, the present inventors have found that the above-described problem can be solved by specifying the raw material components of the ester resin, and have completed the present invention.
즉, 본 발명은, 하기 일반식(1)That is, the present invention has the following general formula (1)
B-(A-G)n-A-B (1)B-(AG) n -AB (1)
〔식(1) 중, B는 탄소 원자수 4∼20의 지방족 모노알코올 잔기이고, G는 알킬렌글리콜 잔기, 옥시알킬렌글리콜 잔기 또는 아릴글리콜 잔기이고, A는 알킬렌디카르복시산 잔기(A1) 또는 아릴디카르복시산 잔기(A2)이며, 알킬렌디카르복시산 잔기(A1)와 아릴디카르복시산 잔기(A2)의 합계(A1+A2)에 있어서의 아릴디카르복시산 잔기(A2)의 함유율이 70∼100몰%이고, n은 반복수이고, 반복할 때마다 G, A는 동일해도 되며 달라도 되고, 또한 복수 있는 A, B는 동일해도 되며 달라도 된다〕[In formula (1), B is an aliphatic monoalcohol residue having 4 to 20 carbon atoms, G is an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue, and A is an alkylenedicarboxylic acid residue (A1) or It is an aryldicarboxylic acid residue (A2), and the content of the aryldicarboxylic acid residue (A2) in the total of the alkylenedicarboxylic acid residue (A1) and the aryldicarboxylic acid residue (A2) (A1+A2) is 70 to 100 mol%, , n is the number of repetitions, and for each repetition, G and A may be the same or different, and plural A and B may be the same or different]
으로 표시되는 에스테르 수지이고, 수 평균 분자량이 350∼1000인 것을 특징으로 하는 에스테르 수지를 제공하는 것이다.It is an ester resin represented by , and an ester resin characterized by having a number average molecular weight of 350 to 1000 is provided.
본 발명에 따르면, 필름상으로 가공했을 때의 내투습성을 향상시킬 수 있으며, 또한 습열 환경 하에서도 보존안정성이 우수한, 셀룰로오스에스테르 수지에 대해서 가소화제로서 호적하게 사용할 수 있는 에스테르 수지, 이것을 포함하는 수지 조성물과, 당해 수지 조성물을 사용해서 얻어지는 광학 필름 및 이것을 사용한 액정 표시 장치를 제공할 수 있다.According to the present invention, an ester resin can be suitably used as a plasticizer for cellulose ester resin, which can improve moisture permeability resistance when processed into a film and has excellent storage stability even in a moist heat environment, and a resin containing the same. A composition, an optical film obtained using the resin composition, and a liquid crystal display device using the same can be provided.
본 발명의 에스테르 수지는, 하기 일반식(1)The ester resin of the present invention has the following general formula (1)
B-(A-G)n-A-B (1)B-(AG) n -AB (1)
〔식(1) 중, B는 탄소 원자수 4∼20의 지방족 모노알코올 잔기이고, G는 알킬렌글리콜 잔기, 옥시알킬렌글리콜 잔기 또는 아릴글리콜 잔기이고, A는 알킬렌디카르복시산 잔기(A1) 또는 아릴디카르복시산 잔기(A2)이며, 알킬렌디카르복시산 잔기(A1)와 아릴디카르복시산 잔기(A2)의 합계(A1+A2)에 있어서의 아릴디카르복시산 잔기(A2)의 함유율이 70∼100몰%이고, n은 반복수이고, 반복할 때마다 G, A는 동일해도 되며 달라도 되고, 또한 복수 있는 A, B는 동일해도 되며 달라도 된다〕[In formula (1), B is an aliphatic monoalcohol residue having 4 to 20 carbon atoms, G is an alkylene glycol residue, oxyalkylene glycol residue or aryl glycol residue, and A is an alkylenedicarboxylic acid residue (A1) or It is an aryldicarboxylic acid residue (A2), and the content of the aryldicarboxylic acid residue (A2) in the total of the alkylenedicarboxylic acid residue (A1) and the aryldicarboxylic acid residue (A2) (A1+A2) is 70 to 100 mol%, , n is the number of repetitions, and G and A may be the same or different for each repetition, and plural A and B may be the same or different]
으로 표시되는 에스테르 수지이고, 수 평균 분자량이 350∼1000인 것을 특징으로 하는 에스테르 수지인 것을 특징으로 한다.It is an ester resin represented by , and is characterized in that it is an ester resin characterized by a number average molecular weight of 350 to 1000.
상기 일반식(1) 중의 B는, 탄소 원자수 4∼20의 지방족 모노알코올 잔기이다. 여기에서, 모노알코올 잔기란, 수산기로부터 수소 원자를 제거한 후의 기를 나타낸다. 상기 지방족은, 분기 구조를 갖는 것이어도 되고, 직쇄상의 것이어도 되며, 예를 들면, 1-부탄올, 2-부탄올, 이소부탄올, t-부탄올, 1-펜탄올, 이소펜틸알코올, tert-펜틸알코올, 시클로펜탄올, 1-헥산올, 시클로헥산올, 1-헵탄올, 1-옥탄올, 2-에틸-1-헥산올, 이소노닐알코올, 1-노닐알코올, tert-노닐알코올, 데칸올, 도데칸올, 도데카헥산올, 도데카옥탄올, 알릴알코올, 올레일알코올 등의 잔기를 들 수 있고, 일반식(1) 중의 B가 동일한 것으로 이루어지는 수지여도 되고 서로 다른 것의 혼합물로 이루어져 있어도 된다.B in the general formula (1) is an aliphatic monoalcohol residue having 4 to 20 carbon atoms. Here, the monoalcohol residue represents the group after removing the hydrogen atom from the hydroxyl group. The aliphatic may have a branched structure or may be linear, for example, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl. Alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, tert-nonyl alcohol, decanol , dodecanol, dodecahexanol, dodecaoctanol, allyl alcohol, oleyl alcohol, etc., and may be a resin in which B in General Formula (1) is the same or a mixture of different substances. .
이들 중에서도, 셀룰로오스에스테르 수지와의 상용성이 양호하고, 수지 조성물로서의 보존안정성, 및 필름으로서의 보존안정성이 보다 우수한 관점에서, 탄소 원자수 6∼12의 지방족 모노알코올 잔기인 것이 바람직하고, 탄소 원자수 9∼12의 지방족 모노알코올 잔기인 것이 더 바람직하고, 노닐알코올 잔기 또는 이소노닐알코올 잔기인 것이 특히 바람직하다.Among these, from the viewpoint of good compatibility with cellulose ester resin and superior storage stability as a resin composition and as a film, an aliphatic monoalcohol residue having 6 to 12 carbon atoms is preferable, and the number of carbon atoms is It is more preferable that it is a 9-12 aliphatic monoalcohol residue, and it is especially preferable that it is a nonyl alcohol residue or an isononyl alcohol residue.
상기 일반식(1) 중의 G는 알킬렌글리콜 잔기, 옥시알킬렌글리콜 잔기 또는 아릴글리콜 잔기이다. 글리콜 잔기란, 수산기로부터 수소 원자를 제거한 후의 기를 나타낸다.G in the general formula (1) is an alkylene glycol residue, an oxyalkylene glycol residue, or an aryl glycol residue. The glycol residue represents the group after removing the hydrogen atom from the hydroxyl group.
상기 알킬렌글리콜 잔기로서는, 탄소 원자수 2∼12의 알킬렌글리콜 잔기인 것이, 본 발명의 효과를 보다 발현하기 쉬운 관점에서 바람직하며, 예를 들면, 에틸렌글리콜, 1,2-프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 2-메틸-1,3-프로판디올, 1,4-부탄디올, 1,5-펜탄디올, 2,2-디메틸-1,3-프로판디올(네오펜틸글리콜), 2,2-디에틸-1,3-프로판디올(3,3-디메틸올펜탄), 2-n-부틸-2-에틸-1,3-프로판디올(3,3-디메틸올헵탄), 3-메틸-1,5-펜탄디올, 1,6-헥산디올, 2,2,4-트리메틸1,3-펜탄디올, 2-에틸-1,3-헥산디올, 2-메틸-1,8-옥탄디올, 1,9-노난디올, 1,10-데칸디올, 1,12-도데칸디올 등의 잔기를 들 수 있고, 단독이어도 되고 2종 이상을 병유하고 있어도 된다. 이들 중에서도, 후술하는 셀룰로오스에스테르 수지와 혼합했을 때의 상용성이 보다 우수한 에스테르 수지인 관점에서, OH기 간의 분기를 포함하지 않는 탄소 원자수가 3 이하인 것이 바람직하고, 그 중에서도 에틸렌글리콜, 1,2-프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 2-메틸-1,3-프로판디올, 네오펜틸글리콜의 잔기인 것이 바람직하고, 에틸렌글리콜, 1,2-프로필렌글리콜의 잔기인 것이 보다 바람직하다.As the alkylene glycol residue, an alkylene glycol residue having 2 to 12 carbon atoms is preferable from the viewpoint of easier expression of the effects of the present invention, for example, ethylene glycol, 1,2-propylene glycol, 1 ,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1, 3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol ( 3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl1,3-pentanediol, 2-ethyl-1,3-hexane Residues such as diol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol may be used alone or in combination of two or more types. You can do it. Among these, from the viewpoint of being an ester resin with better compatibility when mixed with the cellulose ester resin described later, those having a carbon atom number of 3 or less not including branching between OH groups are preferable, and among them, ethylene glycol, 1,2- It is preferable that it is a residue of propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, and ethylene glycol, 1,2- It is more preferable that it is a residue of propylene glycol.
상기 옥시알킬렌글리콜 잔기로서는, 탄소 원자수 4∼12의 옥시알킬렌글리콜 잔기인 것이, 본 발명의 효과를 보다 발현하기 쉬운 관점에서 바람직하며, 예를 들면, 디에틸렌글리콜, 트리에틸렌글리콜, 테트라에틸렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜 등의 잔기를 들 수 있고, 단독이어도 되고, 2종 이상을 병유하고 있어도 된다.As the oxyalkylene glycol residue, an oxyalkylene glycol residue having 4 to 12 carbon atoms is preferable from the viewpoint of easier expression of the effect of the present invention, for example, diethylene glycol, triethylene glycol, tetra Residues such as ethylene glycol, dipropylene glycol, and tripropylene glycol may be mentioned, and may be used alone or in combination of two or more types.
상기 아릴글리콜 잔기로서는, 탄소수 6∼18의 아릴글리콜 잔기인 것이, 본 발명의 효과를 보다 발현하기 쉬운 관점에서 바람직하며, 예를 들면, 하이드로퀴논, 레조르신, 비스페놀A, 비스페놀A의 알킬렌옥사이드 부가물, 비스페놀F, 비스페놀F의 알킬렌옥사이드 부가물, 비페놀, 비페놀의 알킬렌옥사이드 부가물 등의 잔기를 들 수 있고, 단독이어도 되고, 2종 이상을 병유하고 있어도 된다.As the aryl glycol residue, an aryl glycol residue having 6 to 18 carbon atoms is preferable from the viewpoint of easier expression of the effect of the present invention, for example, hydroquinone, resorcinol, bisphenol A, alkylene oxide of bisphenol A. Residues such as adducts, bisphenol F, alkylene oxide adducts of bisphenol F, biphenol, and alkylene oxide adducts of biphenol may be mentioned, and may be used alone or in combination of two or more types.
또한, 상기 일반식(1) 중의 A는 알킬렌디카르복시산 잔기(A1) 또는 아릴디카르복시산 잔기(A2)이다. 여기에서, 디카르복시산 잔기란, 카르복시기 중의 -OH를 제외한 기를 말한다.In addition, A in the general formula (1) is an alkylenedicarboxylic acid residue (A1) or an aryldicarboxylic acid residue (A2). Here, the dicarboxylic acid residue refers to a group excluding -OH in the carboxyl group.
상기 알킬렌디카르복시산 잔기(A1)로서는, 탄소 원자수 2∼12의 알킬렌디카르복시산 잔기인 것이, 본 발명의 효과를 보다 발현하기 쉬운 관점에서 바람직하며, 예를 들면, 옥살산, 말론산, 숙신산, 글루타르산, 아디프산, 말레산, 푸마르산, 1,2-디카르복시시클로헥산, 1,2-디카르복시시클로헥센 등의 잔기를 들 수 있고, 단독이어도 되고, 2종 이상을 병유하고 있어도 된다. 이들 중에서도, 보다 내투습성이 우수한 광학 필름이 얻어지므로, 숙신산, 아디프산, 1,2-디카르복시시클로헥산의 잔기인 것이 바람직하고, 아디프산의 잔기가 가장 바람직하다.As the alkylenedicarboxylic acid residue (A1), an alkylenedicarboxylic acid residue having 2 to 12 carbon atoms is preferable from the viewpoint of easier expression of the effect of the present invention, for example, oxalic acid, malonic acid, succinic acid, and glucurate. Residues such as taric acid, adipic acid, maleic acid, fumaric acid, 1,2-dicarboxycyclohexane, and 1,2-dicarboxycyclohexene may be mentioned, and may be used alone or in combination of two or more types. Among these, since an optical film with more excellent moisture permeability resistance is obtained, the residues of succinic acid, adipic acid, and 1,2-dicarboxycyclohexane are preferable, and the residues of adipic acid are most preferable.
상기 아릴디카르복시산 잔기(A2)로서는, 예를 들면, 프탈산, 테레프탈산, 이소프탈산, 1,4-나프탈렌디카르복시산, 2,3-나프탈렌디카르복시산, 2,6-나프탈렌디카르복시산, 2,7-나프탈렌디카르복시산, 1,8-나프탈렌디카르복시산 등의 잔기를 들 수 있고, 단독이어도 되고, 2종 이상을 병유하고 있어도 된다. 이들 중에서도, 보다 강도가 높은 광학 필름이 얻어지므로, 프탈산, 테레프탈산, 이소프탈산의 잔기인 것이 바람직하고, 프탈산의 잔기가 가장 바람직하다.Examples of the aryldicarboxylic acid residue (A2) include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalene. Residues such as dicarboxylic acid and 1,8-naphthalene dicarboxylic acid may be mentioned, and may be used alone or in combination of two or more types. Among these, since an optical film with higher strength can be obtained, residues of phthalic acid, terephthalic acid, and isophthalic acid are preferable, and residues of phthalic acid are most preferable.
상기 일반식(1) 중의 A에 있어서의 알킬렌디카르복시산 잔기(A1)와 아릴디카르복시산 잔기(A2)의 합계 몰수(A1+A2)에 있어서의 아릴디카르복시산 잔기(A2)의 함유율은, 본 발명의 효과인 내투습성과 보존안정성의 양립을 위해서는, 70∼100몰%인 것을 필수로 하고, 75∼100몰%의 범위인 것이 바람직하고, 90∼100몰%인 것이 가장 바람직하다.The content of the aryldicarboxylic acid residue (A2) in the total molar number (A1+A2) of the alkylenedicarboxylic acid residue (A1) and the aryldicarboxylic acid residue (A2) in A in the general formula (1) is defined as the content of the aryldicarboxylic acid residue (A2) according to the present invention. In order to achieve both moisture permeability resistance and storage stability, which are the effects of , it is essential that it is 70 to 100 mol%, preferably in the range of 75 to 100 mol%, and most preferably 90 to 100 mol%.
본 발명에서는, 상기 일반식(1)으로 표시되는 에스테르 수지로서, B, G, A가 동일한 것으로 이루어지고, n, 즉 반복수만이 서로 다른 화합물의 혼합물이어도 되고, 혹은, 일반식(1) 중의 B, G, A 및 n이 각각 서로 다른 화합물의 혼합물이어도 된다.In the present invention, the ester resin represented by the general formula (1) may be a mixture of compounds in which B, G, and A are the same and only n, that is, the number of repetitions, is different from each other, or it may be a mixture of compounds in the general formula (1). B, G, A and n may each be a mixture of different compounds.
또, 본 발명에서의 GPC 측정은 하기 조건에서 실시한 것이다.In addition, the GPC measurement in the present invention was conducted under the following conditions.
[GPC 측정 조건][GPC measurement conditions]
측정 장치 : 도소가부시키가이샤제 고속 GPC 장치 「HLC-8320GPC」Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation.
칼럼 : 도소가부시키가이샤제 「TSK GURDCOLUMN SuperHZ-L」+도소가부시키가이샤제 「TSK gel SuperHZM-M」+도소가부시키가이샤제 「TSK gel SuperHZM-M」+도소가부시키가이샤제 「TSK gel SuperHZ-2000」+도소가부시키가이샤제 「TSK gel SuperHZ-2000」Column: “TSK GURDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation “TSK gel SuperHZ-2000” + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation
검출기 : RI(시차 굴절계)Detector: RI (differential refractometer)
데이터 처리 : 도소가부시키가이샤제 「EcoSEC Data Analysis 버전1.07」Data processing: “EcoSEC Data Analysis version 1.07” manufactured by Tosoh Corporation.
칼럼 온도 : 40℃Column temperature: 40℃
전개 용매 : 테트라히드로퓨란Development solvent: tetrahydrofuran
유속 : 0.35mL/분Flow rate: 0.35mL/min
측정 시료 : 시료 7.5mg을 10ml의 테트라히드로퓨란에 용해하여, 얻어진 용액을 마이크로 필터로 여과한 것을 측정 시료로 했다.Measurement sample: 7.5 mg of sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to serve as a measurement sample.
시료 주입량 : 20μlSample injection volume: 20μl
표준 시료 : 상기 「HLC-8320GPC」의 측정 매뉴얼에 준거해서, 분자량이 기지인 하기의 단분산 폴리스티렌을 사용했다.Standard sample: In accordance with the measurement manual of “HLC-8320GPC” above, the following monodisperse polystyrene with a known molecular weight was used.
(단분산 폴리스티렌)(Monodisperse polystyrene)
도소가부시키가이샤제 「A-300」“A-300” made by Tosoh Corporation
도소가부시키가이샤제 「A-500」“A-500” made by Tosoh Corporation
도소가부시키가이샤제 「A-1000」“A-1000” made by Tosoh Corporation
도소가부시키가이샤제 「A-2500」“A-2500” made by Tosoh Corporation
도소가부시키가이샤제 「A-5000」“A-5000” made by Tosoh Corporation
도소가부시키가이샤제 「F-1」“F-1” made by Tosoh Corporation
도소가부시키가이샤제 「F-2」“F-2” made by Tosoh Corporation
도소가부시키가이샤제 「F-4」“F-4” made by Tosoh Corporation
도소가부시키가이샤제 「F-10」“F-10” made by Tosoh Corporation
도소가부시키가이샤제 「F-20」“F-20” made by Tosoh Kabushiki Kaisha.
도소가부시키가이샤제 「F-40」“F-40” made by Tosoh Corporation
도소가부시키가이샤제 「F-80」“F-80” made by Tosoh Corporation
도소가부시키가이샤제 「F-128」“F-128” made by Tosoh Corporation
도소가부시키가이샤제 「F-288」“F-288” manufactured by Tosoh Corporation
본 발명의 효과가 한층 더 발현되는 관점에서, 일반식(1)에 있어서, B가 탄소 원자수 6∼12의 지방족 모노알코올 잔기이고, G가 탄소 원자수 2∼12의 알킬렌글리콜 잔기, 탄소 원자수 4∼12의 옥시알킬렌글리콜 잔기 또는 탄소수 6∼18의 아릴글리콜 잔기이고, A에 있어서의 알킬렌디카르복시산 잔기(A1)가 탄소 원자수 2∼12의 알킬렌디카르복시산 잔기이고, A에 있어서의 아릴디카르복시산 잔기(A2)가 탄소 원자수 6∼12의 아릴디카르복시산 잔기인 것이 바람직하고, 특히, B가 노닐알코올 잔기 또는 이소노닐알코올 잔기이고, G가 에틸렌글리콜, 1,2-프로필렌글리콜의 잔기이고, A1이 아디프산 잔기이고, A2가 프탈산의 잔기인 것이 가장 바람직하다.From the viewpoint of further realizing the effect of the present invention, in general formula (1), B is an aliphatic monoalcohol residue having 6 to 12 carbon atoms, and G is an alkylene glycol residue having 2 to 12 carbon atoms, carbon is an oxyalkylene glycol residue having 4 to 12 atoms or an aryl glycol residue having 6 to 18 carbon atoms, and the alkylenedicarboxylic acid residue (A1) in A is an alkylenedicarboxylic acid residue having 2 to 12 carbon atoms, and in A It is preferable that the aryldicarboxylic acid residue (A2) of is an aryldicarboxylic acid residue having 6 to 12 carbon atoms, and in particular, B is a nonyl alcohol residue or isononyl alcohol residue, and G is ethylene glycol or 1,2-propylene glycol. It is most preferable that A1 is the residue of adipic acid, and A2 is the residue of phthalic acid.
또한 본 발명의 에스테르 수지로서는, 그 수 평균 분자량은 상용성과 필름 물성을 양립시키는 관점에서, 350∼1000의 범위이고, 400∼800의 범위인 것이 특히 바람직하다. 또한, 상기 일반식(1) 중의 반복수 n의 평균값으로서는, 마찬가지로 상용성과 필름 물성을 양립시키는 관점에서, 0.2∼3의 범위인 것이 바람직하다. 또, 이 수 평균 분자량 및 n의 평균값도 상기 GPC 측정으로 측정한 값이다.Moreover, as for the ester resin of this invention, its number average molecular weight is in the range of 350-1000, and it is especially preferable that it is in the range of 400-800 from a viewpoint of achieving both compatibility and film physical properties. Additionally, the average value of the repetition number n in the general formula (1) is preferably in the range of 0.2 to 3 from the viewpoint of achieving both compatibility and film properties. In addition, the number average molecular weight and the average value of n are also values measured by the GPC measurement.
또한 본 발명의 에스테르 수지의 산가로서는, 셀룰로오스에스테르 수지와의 상용성이 보다 양호한 관점에서 5 이하인 것이 바람직하고, 1 이하가 보다 바람직하다. 또한, 마찬가지의 관점에서, 에스테르 수지의 수산기가는 50 이하인 것이 바람직하고, 20 이하인 것이 보다 바람직하다.Furthermore, the acid value of the ester resin of the present invention is preferably 5 or less, and more preferably 1 or less from the viewpoint of better compatibility with the cellulose ester resin. Moreover, from the same viewpoint, the hydroxyl value of the ester resin is preferably 50 or less, and more preferably 20 or less.
본 발명의 에스테르 수지는, 예를 들면, 상기한 원료를, 필요에 따라서 에스테르화 촉매의 존재 하에서, 예를 들면, 180∼250℃의 온도 범위 내에서 10∼25시간, 에스테르화 반응시킴에 의해 제조할 수 있다. 또, 에스테르화 반응의 온도, 시간 등의 조건은 특히 한정하지 않으며, 적의(適宜) 설정해도 된다. 디카르복시산에 대해서는, 원료로서 산 그대로를 사용해도 되고, 혹은, 그 에스테르화물, 산염화물, 무수물 등을 원료로 해도 된다.The ester resin of the present invention is produced by, for example, subjecting the above-mentioned raw materials to an esterification reaction, if necessary, in the presence of an esterification catalyst, for example, within a temperature range of 180 to 250°C for 10 to 25 hours. It can be manufactured. Additionally, conditions such as temperature and time for the esterification reaction are not particularly limited and may be set appropriately. As for dicarboxylic acid, the acid itself may be used as a raw material, or its ester, acid chloride, anhydride, etc. may be used as a raw material.
상기 에스테르화 촉매로서는, 예를 들면, 테트라이소프로필티타네이트, 테트라부틸티타네이트 등의 티타늄계 촉매; 디부틸주석옥사이드 등의 주석계 촉매; p-톨루엔설폰산 등의 유기 설폰산계 촉매 등을 들 수 있다.Examples of the esterification catalyst include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; Tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.
상기 에스테르화 촉매의 사용량은, 적의 설정하면 되지만, 통상적으로, 원료의 전량 100질량부에 대해서, 0.001∼0.1질량부의 범위에서 사용하는 것이 바람직하다.The amount of the esterification catalyst to be used may be appropriately set, but it is usually preferably used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of raw materials.
본 발명의 에스테르 수지의 성상은, 그 수 평균 분자량이나 원료의 조합 등의 요인에 따라 서로 다르지만, 통상적으로, 상온에서 액체, 고체, 페이스트상 등이다.The properties of the ester resin of the present invention vary depending on factors such as its number average molecular weight and the combination of raw materials, but are usually liquid, solid, paste-like, etc. at room temperature.
보다 구체적인 에스테르 수지의 제조 방법으로서는, 상술의 알킬렌글리콜, 옥시알킬렌글리콜 또는 아릴글리콜과, 디카르복시산을 사용해서 얻어지는 말단에 카르복시기를 갖는 화합물과, 지방족 모노알코올을 반응시키는 방법을 들 수 있다. 여기에서, 상기 알킬렌글리콜, 옥시알킬렌글리콜 또는 아릴글리콜과 디카르복시산과 모노알코올은 일괄로 반응계에 투입하고, 이들을 반응시켜도 되고, 혹은, 알킬렌글리콜, 옥시알킬렌글리콜 또는 아릴글리콜과 디카르복시산을 사용해서 얻어지는 말단에 카르복시기를 갖는 화합물을 얻은 후, 추가로, 모노알코올을 반응계에 투입하는, 축차 반응이어도 된다.A more specific method for producing an ester resin includes a method of reacting the above-mentioned alkylene glycol, oxyalkylene glycol or aryl glycol with a compound having a carboxyl group at the terminal obtained by using a dicarboxylic acid and an aliphatic monoalcohol. Here, the alkylene glycol, oxyalkylene glycol, or aryl glycol, dicarboxylic acid, and monoalcohol may be added to the reaction system in batches and reacted, or alkylene glycol, oxyalkylene glycol, or aryl glycol, and dicarboxylic acid. After obtaining a compound having a carboxyl group at the terminal obtained using , a sequential reaction may be performed in which monoalcohol is further added to the reaction system.
상기에서 얻어진 에스테르 수지를 그대로 본 발명의 에스테르 수지로서 사용해도 되고, 혹은, 예를 들면, 박막 증류 장치에 의한 증류 제거법, 칼럼 흡착법, 용매 분리 추출법 등의 방법에 의해, n=0 성분의 함유율, 고분자량 성분의 함유율을 조정해도 된다.The ester resin obtained above may be used as is as the ester resin of the present invention, or, for example, by methods such as distillation using a thin film distillation device, column adsorption, or solvent separation and extraction, the n = 0 component content, You may adjust the content rate of the high molecular weight component.
이와 같은 방법 등으로 얻어지는 본 발명의 에스테르 수지는, 이것을 셀룰로오스에스테르 수지에 배합함에 의해, 얻어지는 필름의 내투습성과 보존안정성의 밸런스가 우수한 것으로 할 수 있고, 소위 가소화제로서 사용할 수 있는 것이며, 특히 광학 필름으로서 호적하게 사용할 수 있다.The ester resin of the present invention obtained by such a method can be used as a so-called plasticizer, and can be used as a so-called plasticizer, by mixing it with a cellulose ester resin, the resulting film can be excellent in moisture permeability resistance and storage stability. It can be suitably used as a film.
셀룰로오스에스테르 수지에 대한 본 발명의 에스테르 수지의 배합량은, 목적으로 하는 성능(내투습성, 보존안정성, 투명성 등)에 따라서 결정하면 되며, 예를 들면, 셀룰로오스에스테르 수지 100질량부에 대해서 0.1∼50질량부의 범위이고, 1∼30질량부의 범위인 것이 바람직하고, 특히 5∼20질량부의 범위인 것이 보다 바람직하다.The mixing amount of the ester resin of the present invention relative to the cellulose ester resin may be determined depending on the desired performance (moisture permeability resistance, storage stability, transparency, etc.), for example, 0.1 to 50 parts by mass per 100 parts by mass of the cellulose ester resin. It is a negative range, preferably in the range of 1 to 30 parts by mass, and especially more preferably in the range of 5 to 20 parts by mass.
상기 셀룰로오스에스테르 수지로서는, 예를 들면, 면화 린터, 목재 펄프, 케나프 등으로부터 얻어지는 셀룰로오스가 갖는 수산기의 일부 또는 전부가 에스테르화된 것 등을 예시할 수 있다.Examples of the cellulose ester resin include those in which part or all of the hydroxyl groups of cellulose obtained from cotton linter, wood pulp, kenaf, etc. are esterified.
상기 셀룰로오스에스테르 수지로서는, 예를 들면, 셀룰로오스아세테이트, 셀룰로오스아세테이트프로피오네이트, 셀룰로오스아세테이트부티레이트, 셀룰로오스아세테이트프탈레이트, 질산셀룰로오스 등을 들 수 있고, 편광판용 보호 필름으로서 사용하는 경우에는, 셀룰로오스아세테이트를 사용하는 것이, 기계적 물성 및 투명성이 우수한 필름을 얻을 수 있으므로, 바람직하다. 이들 셀룰로오스에스테르 수지는, 단독이어도 되고 2종 이상을 병용해도 된다.Examples of the cellulose ester resin include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate. When used as a protective film for a polarizing plate, cellulose acetate is used. This is preferable because a film with excellent mechanical properties and transparency can be obtained. These cellulose ester resins may be used individually or in combination of two or more types.
상기 셀룰로오스아세테이트로서는, 중합도가 250∼400의 범위인 것이 바람직하며, 또한, 아세트화도가 54.0∼62.5질량%의 범위인 것이 바람직하고, 58.0∼62.5질량%의 범위인 것이 보다 바람직하다. 상기 셀룰로오스아세테이트의 중합도와 아세트화도가 이러한 범위이면, 우수한 기계적 물성을 갖는 필름을 얻을 수 있다. 본 발명에서는, 소위 셀룰로오스트리아세테이트를 사용하는 것이 보다 바람직하다. 또, 본 발명에서 말하는 아세트화도란, 셀룰로오스아세테이트의 전량에 대한, 당해 셀룰로오스아세테이트를 비누화함에 의해서 생성하는 아세트산의 질량 비율이다.As for the cellulose acetate, the degree of polymerization is preferably in the range of 250 to 400, and the degree of acetylation is preferably in the range of 54.0 to 62.5 mass%, and more preferably 58.0 to 62.5 mass%. If the degree of polymerization and acetylation of the cellulose acetate are within this range, a film with excellent mechanical properties can be obtained. In the present invention, it is more preferable to use so-called cellulose triacetate. In addition, the degree of acetylation referred to in the present invention is the mass ratio of acetic acid produced by saponifying the cellulose acetate to the total amount of cellulose acetate.
상기 셀룰로오스아세테이트의 수 평균 분자량은, 70,000∼300,000의 범위인 것이 바람직하고, 80,000∼200,000의 범위인 것이 보다 바람직하다. 상기 셀룰로오스아세테이트의 수 평균 분자량이 이 범위이면, 우수한 기계적 물성을 갖는 필름을 용이하게 얻을 수 있다.The number average molecular weight of the cellulose acetate is preferably in the range of 70,000 to 300,000, and more preferably in the range of 80,000 to 200,000. If the number average molecular weight of the cellulose acetate is within this range, a film with excellent mechanical properties can be easily obtained.
본 발명에 있어서의 광학 필름은, 본 발명의 에스테르 수지와 셀룰로오스에스테르 수지를 포함하는 셀룰로오스에스테르 수지 조성물을 사용하는 것이고, 필요에 따라서 그 밖의 각종 첨가제 등을 함유해서 이루어지는 수지 조성물을 사용해도 된다.The optical film in the present invention uses a cellulose ester resin composition containing the ester resin of the present invention and a cellulose ester resin, and a resin composition containing various other additives, etc. may be used as needed.
본 발명의 광학 필름을 얻기 위해서는, 예를 들면, 압출 성형, 캐스트 성형 등의 방법이 사용된다. 구체적으로는, 예를 들면, T 다이, 원형 다이 등이 장착된 압출기 등을 사용해서, 미연신 상태의 광학 필름을 압출 성형할 수 있다. 압출 성형에 의해 본 발명의 광학 필름을 얻는 경우는, 사전에 상기 에스테르 수지, 셀룰로오스에스테르 수지, 그 외 첨가제 등을 용융 혼련(混練)해서 얻어지는 수지 조성물을 사용할 수도 있으며, 압출 성형 시에 용융 혼련하고, 그대로 압출 성형할 수도 있다.To obtain the optical film of the present invention, methods such as extrusion molding and cast molding are used, for example. Specifically, for example, an unstretched optical film can be extruded using an extruder equipped with a T die, a circular die, etc. When obtaining the optical film of the present invention by extrusion molding, a resin composition obtained by melt-kneading the above-mentioned ester resin, cellulose ester resin, other additives, etc. in advance may be used, and melt-kneading during extrusion molding , it can also be extruded as is.
상기 첨가제로서는, 예를 들면, 본 발명의 에스테르 수지 이외의 그 밖의 개질제, 열가소성 수지, 자외선 흡수제, 매트제, 열화방지제(예를 들면, 산화방지제, 과산화물 분해제, 라디칼금지제, 금속 불활성화제, 산포획제 등), 염료 등을 들 수 있다.The additives include, for example, other modifiers other than the ester resin of the present invention, thermoplastic resins, ultraviolet absorbers, matting agents, anti-deterioration agents (e.g., antioxidants, peroxide decomposition agents, radical inhibitors, metal deactivators, acid capture agents, etc.), dyes, etc.
상기 그 밖의 개질제로서는, 본 발명에서 규정하는 에스테르 수지 이외의 에스테르 수지나, 트리페닐포스페이트(TPP), 트리크레질포스페이트, 크레질디페닐포스페이트 등의 인산에스테르, 디메틸프탈레이트, 디에틸프탈레이트, 디부틸프탈레이트, 디-2-에틸헥실프탈레이트 등의 프탈산에스테르, 에틸프타릴에틸글리콜레이트, 부틸프타릴부틸글리콜레이트, 트리메틸올프로판트리벤조에이트, 펜타에리트리톨테트라아세테이트, 아세틸시트르산트리부틸 등을, 본 발명의 효과를 손상시키지 않는 범위에서 사용할 수 있다. Examples of the other modifiers include ester resins other than those specified in the present invention, phosphoric acid esters such as triphenyl phosphate (TPP), tricresyl phosphate, and creasyl diphenyl phosphate, dimethyl phthalate, diethyl phthalate, and dibutyl phthalate. , phthalic acid esters such as di-2-ethylhexyl phthalate, ethyl phtharyl ethyl glycolate, butyl phtharyl butyl glycolate, trimethylol propane tribenzoate, pentaerythritol tetraacetate, tributyl acetyl citrate, etc. of the present invention. It can be used within the range that does not impair the effect.
상기 열가소성 수지로서는, 특히 한정하지 않지만, 예를 들면, 본 발명의 에스테르 수지 이외의 폴리에스테르 수지, 폴리에스테르에테르 수지, 아크릴 수지, 우레탄 수지, 에폭시 수지, 톨루엔설폰아미드 수지 등을 들 수 있다.The thermoplastic resin is not particularly limited, but examples include polyester resins other than the ester resin of the present invention, polyester ether resin, acrylic resin, urethane resin, epoxy resin, and toluenesulfonamide resin.
상기 자외선 흡수제로서는, 특히 한정하지 않지만, 예를 들면, 옥시벤조페논계 화합물, 벤조트리아졸계 화합물, 살리실산에스테르계 화합물, 벤조페논 화합물, 시아노아크릴레이트계 화합물, 니켈 착염계 화합물 등을 들 수 있다. 상기 자외선 흡수제는, 상기 셀룰로오스에스테르 수지 100질량부에 대해서, 0.01∼2질량부의 범위에서 사용하는 것이 바람직하다.The ultraviolet absorber is not particularly limited, but examples include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone compounds, cyanoacrylate-based compounds, and nickel complex salt-based compounds. . The ultraviolet absorber is preferably used in the range of 0.01 to 2 parts by mass with respect to 100 parts by mass of the cellulose ester resin.
상기 매트제로서는, 예를 들면, 산화규소, 산화티타늄, 산화알루미늄, 탄산칼슘, 규산칼슘, 규산알루미늄, 규산마그네슘, 인산칼슘, 카올린, 탈크 등을 들 수 있다. 상기 매트제는, 상기 셀룰로오스에스테르 수지 100질량부에 대해서, 0.1∼0.3질량부의 범위에서 사용하는 것이 바람직하다.Examples of the matting agent include silicon oxide, titanium oxide, aluminum oxide, calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, kaolin, and talc. The matting agent is preferably used in the range of 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the cellulose ester resin.
상기 염료로서는, 본 발명의 목적을 저해하지 않는 범위이면, 종류나 배합량 등 특히 한정하지 않는다.There is no particular limitation on the type or mixing amount of the dye as long as it does not impair the purpose of the present invention.
또한, 상기 광학 필름은, 상기 성형 방법 외에, 예를 들면, 상기 셀룰로오스에스테르 수지 조성물을 유기 용제 중에 용해해서 얻어지는 수지 용액을, 금속 지지체 상에 유연(流延)시키고, 다음으로, 상기 유기 용제를 증류 제거하여 건조시키는, 소위 용액 유연법(솔벤트 캐스트법)으로 성형함에 의해서 얻을 수도 있다.In addition to the above molding method, the optical film is, for example, prepared by dissolving the cellulose ester resin composition in an organic solvent, casting a resin solution obtained by dissolving the above-mentioned cellulose ester resin composition in an organic solvent, onto a metal support, and then mixing the organic solvent. It can also be obtained by molding using the so-called solution casting method (solvent casting method), which involves distilling and drying.
상기 용액 유연법에 따르면, 성형 도중의 필름 중에 있어서의 상기 셀룰로오스에스테르 수지의 배향을 억제할 수 있기 때문에, 얻어지는 필름은 실질적으로 등방성을 나타낼 수 있다. 상기 광학 등방성을 나타내는 필름은, 예를 들면 액정 디스플레이 등의 광학 재료에 사용할 수 있고, 그 중에서도 편광판용 보호 필름에 유용하다. 또한, 상기 방법에 의해서 얻어진 필름은, 그 표면에 요철이 형성되기 어렵고, 표면평활성도 우수하다.According to the solution casting method, the orientation of the cellulose ester resin in the film during molding can be suppressed, so the resulting film can be substantially isotropic. The film showing the optical isotropy can be used for optical materials such as liquid crystal displays, and is especially useful for protective films for polarizing plates. In addition, the film obtained by the above method is unlikely to form irregularities on the surface and has excellent surface smoothness.
상기 용액 유연법은, 일반적으로, 상기 셀룰로오스에스테르 수지 조성물을 유기 용제 중에 용해시켜서, 얻어진 수지 용액을 금속 지지체 상에 유연시키는 제1 공정과, 유연시킨 상기 수지 용액 중에 포함되는 유기 용제를 증류 제거하여 건조시켜서 필름을 형성하는 제2 공정, 그것에 이어지는, 금속 지지체 상에 형성된 필름을 금속 지지체로부터 박리하고 가열 건조시키는 제3 공정으로 이루어진다.The solution softening method generally includes a first step of dissolving the cellulose ester resin composition in an organic solvent and softening the obtained resin solution on a metal support, and distilling off the organic solvent contained in the softened resin solution. It consists of a second step of drying to form a film, followed by a third step of peeling the film formed on the metal support from the metal support and heating and drying it.
상기 제1 공정에서 사용하는 금속 지지체로서는, 무단(無端) 벨트상 또는 드럼상의 금속제의 것 등을 예시할 수 있으며, 예를 들면, 스테인리스제이고 그 표면이 경면(鏡面) 마감이 실시된 것을 사용할 수 있다.Examples of the metal support used in the first step include endless belt-shaped or drum-shaped metal supports, for example, those made of stainless steel and whose surface is mirror-finished can be used. You can.
상기 금속 지지체 상에 수지 용액을 유연시켰을 때에는, 얻어지는 필름에 이물이 혼입하는 것을 방지하기 위하여, 필터로 여과한 수지 용액을 사용하는 것이 바람직하다.When the resin solution is cast on the metal support, it is preferable to use a filter-filtered resin solution to prevent foreign substances from entering the resulting film.
상기 제2 공정의 건조 방법으로서는, 특히 한정하지 않지만, 예를 들면 30∼50℃의 온도 범위의 바람을 상기 금속 지지체의 상면 및/또는 하면에 맞힘으로써, 유연한 상기 수지 용액 중에 포함되는 유기 용제의 50∼80질량%를 증발시켜서, 상기 금속 지지체 상에 필름을 형성시키는 방법을 들 수 있다.The drying method in the second step is not particularly limited, but, for example, by blowing wind in a temperature range of 30 to 50°C on the upper and/or lower surfaces of the metal support, the organic solvent contained in the flexible resin solution is dried. A method of forming a film on the metal support by evaporating 50 to 80% by mass is included.
다음으로, 상기 제3 공정은, 상기 제2 공정에서 형성된 필름을 금속 지지체 상으로부터 박리하고, 상기 제2 공정보다도 높은 온도 조건 하에서 가열 건조시키는 공정이다. 상기 가열 건조 방법으로서는, 예를 들면 100∼160℃의 온도 조건에서 단계적으로 온도를 상승시키는 방법이, 양호한 치수안정성을 얻을 수 있기 때문에, 바람직하다. 상기 온도 조건에서 가열 건조함에 의해, 상기 제2 공정 후의 필름 중에 잔존하는 유기 용제를 거의 완전하게 제거할 수 있다.Next, the third step is a step of peeling the film formed in the second step from the metal support and heating and drying it under higher temperature conditions than the second step. As the heat drying method, for example, a method of gradually increasing the temperature under temperature conditions of 100 to 160°C is preferable because good dimensional stability can be obtained. By heating and drying under the above temperature conditions, the organic solvent remaining in the film after the second step can be almost completely removed.
또, 상기 제1 공정∼제3 공정에서, 유기 용매는 회수하여 재사용하는 것도 가능하다.Additionally, in the first to third steps, the organic solvent can be recovered and reused.
상기 수지 조성물을 유기 용제에 혼합시켜서 용해할 때에 사용할 수 있는 유기 용제로서는, 그들을 용해 가능한 것이면 특히 한정하지 않지만, 예를 들면 셀룰로오스에스테르로서 셀룰로오스아세테이트를 사용하는 경우는, 양용매(良溶媒)로서, 예를 들면 메틸렌클로라이드 등의 유기 할로겐 화합물이나 디옥솔란류를 사용하는 것이 바람직하다.The organic solvent that can be used when mixing and dissolving the resin composition in an organic solvent is not particularly limited as long as it is capable of dissolving them. For example, when cellulose acetate is used as a cellulose ester, as a good solvent, For example, it is preferable to use organic halogen compounds such as methylene chloride or dioxolanes.
또한, 상기 양용매와 함께, 예를 들면 메탄올, 에탄올, 2-프로판올, n-부탄올, 시클로헥산, 시클로헥산온 등의 빈용매(貧溶媒)를 병용하는 것이, 필름의 생산 효율을 향상시키는데 바람직하다.In addition, it is preferable to use poor solvents such as methanol, ethanol, 2-propanol, n-butanol, cyclohexane, and cyclohexanone together with the above-mentioned good solvent to improve film production efficiency. do.
상기 양용매와 빈용매와의 혼합 비율은, 양용매/빈용매=75/25∼95/5질량비의 범위인 것이 바람직하다.The mixing ratio of the good solvent and the poor solvent is preferably in the range of good solvent/poor solvent = 75/25 to 95/5 mass ratio.
상기 수지 용액 중의 셀룰로오스에스테르 수지의 농도는, 10∼50질량%가 바람직하고, 15∼35질량%가 보다 바람직하다.The concentration of the cellulose ester resin in the resin solution is preferably 10 to 50 mass%, and more preferably 15 to 35 mass%.
본 발명에 있어서는, 예를 들면, 상기한 방법으로 얻어지는 미연신 상태의 광학 필름을 필요에 따라서, 기계적 흐름 방향으로 종일축 연신, 기계적 흐름 방향에 직교하는 방향으로 횡일축 연신함으로써 연신된 광학 필름을 얻을 수 있다. 또한, 롤 연신과 텐터 연신의 축차 2축 연신법, 텐터 연신에 의한 동시 2축 연신법, 튜블러 연신에 의한 2축 연신법 등에 의해서 연신함에 의해 2축 연신된 연신 필름을 얻을 수 있다. 연신 배율은 적어도 어느 일방향으로 0.1% 이상 1000% 이하인 것이 바람직하고, 0.2% 이상 600% 이하인 것이 더 바람직하고, 0.3% 이상 300% 이하인 것이 특히 바람직하다. 이 범위로 설계함에 의해, 복굴절, 내열성, 강도의 관점에서 바람직한 연신된 광학 필름이 얻어진다.In the present invention, for example, the unstretched optical film obtained by the above-mentioned method is stretched longitudinally in the mechanical flow direction or transversely uniaxially stretched in the direction orthogonal to the mechanical flow direction, as needed, to produce a stretched optical film. You can get it. In addition, a biaxially stretched stretched film can be obtained by stretching using a sequential biaxial stretching method of roll stretching and tenter stretching, a simultaneous biaxial stretching method using tenter stretching, and a biaxial stretching method using tubular stretching. The draw ratio is preferably 0.1% to 1000% in at least one direction, more preferably 0.2% to 600%, and especially preferably 0.3% to 300%. By designing within this range, a stretched optical film that is desirable in terms of birefringence, heat resistance, and strength is obtained.
본 발명의 광학 필름은, 내투습성, 투명성이 우수하며, 또한 보존안정성이 우수하므로, 예를 들면, 액정 표시 장치의 광학 필름에 사용할 수 있다. 상기 액정 표시 장치의 광학 필름으로서는, 예를 들면, 편광판용 보호 필름, 위상차 필름, 반사 필름, 시야각 향상 필름, 방현 필름, 무반사 필름, 대전 방지 필름, 컬러 필터 등을 들 수 있고, 그들 중에서도, 편광판용 보호 필름으로서 바람직하게 사용할 수 있다.The optical film of the present invention is excellent in moisture permeability resistance and transparency, and is also excellent in storage stability, so it can be used, for example, as an optical film for a liquid crystal display device. Examples of the optical film of the liquid crystal display device include protective films for polarizing plates, retardation films, reflective films, viewing angle improvement films, anti-glare films, anti-reflective films, anti-static films, color filters, etc., among them, polarizing plates. It can be preferably used as a protective film.
상기 광학 필름의 막두께는, 20∼120㎛의 범위인 것이 바람직하고, 25∼100㎛의 범위인 것이 보다 바람직하고, 25∼80㎛의 범위인 것이 특히 바람직하다. 상기 광학 필름을 편광판용 보호 필름으로서 사용하는 경우에는, 막두께가 25∼80㎛의 범위이면, 액정 표시 장치의 박형화를 도모할 때에 호적하며, 또한 충분한 필름 강도, Rth안정성, 내투습성 등의 우수한 성능을 유지할 수 있다.The thickness of the optical film is preferably in the range of 20 to 120 μm, more preferably in the range of 25 to 100 μm, and particularly preferably in the range of 25 to 80 μm. When using the optical film as a protective film for a polarizing plate, if the film thickness is in the range of 25 to 80 ㎛, it is suitable for reducing the thickness of the liquid crystal display device, and has excellent film strength, Rth stability, moisture permeability resistance, etc. Performance can be maintained.
본 발명의 광학 필름은, 그 보존안정성이 에스테르 수지를 배합하지 않는 경우보다도 양호하게 되는 것을 특징으로 한다. 일반적으로 셀룰로오스에스테르 수지는, 습열 환경 하에서 가수 분해가 진행되는 것이 알려져 있다. 이것을 억제하기 위해서는, 내투습성을 높이기 위한 첨가제를 사용하게 되지만, 본 발명의 에스테르 수지 이외의 에스테르 수지에서는, 당해 에스테르 수지 자체가, 가수 분해하는 경우가 있고, 그때 발생하는 아세트산 등의 카르복시산이, 셀룰로오스에스테르 수지의 가수 분해를 촉진하는 경우가 있다. 따라서, 첨가제로서 사용하는 에스테르 수지의 내가수분해성을 억제하는 것이, 나아가서는, 얻어지는 셀룰로오스에스테르 필름에 있어서의 보존안정성을 향상시키는 것으로 연결된다.The optical film of the present invention is characterized by better storage stability than when no ester resin is added. In general, it is known that hydrolysis of cellulose ester resin progresses in a moist heat environment. In order to suppress this, an additive for increasing moisture permeability resistance is used. However, in the case of ester resins other than the ester resin of the present invention, the ester resin itself may be hydrolyzed, and the carboxylic acid such as acetic acid generated at that time may be converted to cellulose. In some cases, it promotes hydrolysis of ester resin. Therefore, suppressing the hydrolysis resistance of the ester resin used as an additive leads to further improving the storage stability in the resulting cellulose ester film.
또한, 상기 광학 필름은, 고온 다습 하에서의 블리드를 발생시키지 않고, 원하는 Rth로 조정하는 것도 가능하므로, 용도에 따라서 다양한 액정 표시 방식에 광범위로 사용할 수 있다.In addition, the optical film does not bleed under high temperature and humidity and can be adjusted to a desired Rth, so it can be widely used in various liquid crystal display systems depending on the application.
상기 액정 표시 방식으로서는, 예를 들면 IPS(인-플레인 스위칭 : In-Plane Switching), TN(트위스티드 네마틱 : Twisted Nematic), VA(버티컬리 얼라인드 : Vertically Aligned), OCB(옵티컬리 컴펜세이터리 벤드 : Optically Compensatory Bend) 등을 예시할 수 있다.Examples of the liquid crystal display methods include IPS (In-Plane Switching), TN (Twisted Nematic), VA (Vertically Aligned), and OCB (Optically Compensatory). Bend: Optically Compensatory Bend).
본 발명에 따른 광학 필름은, 광학 재료로서, 액정 표시 장치, 플라스마 디스플레이, 유기 EL 디스플레이, 필드 에미션 디스플레이, 리어 프로젝션 텔레비전 등의 디스플레이에 사용되는 편광판 보호 필름, 1/4 파장판, 1/2 파장판, 시야각 제어 필름, 액정 광학 보상 필름 등의 위상차 필름, 디스플레이 전면판 등에 호적하게 사용할 수 있다. 또한, 본 발명의 수지 조성물은, 그 외에도, 광통신 시스템, 광교환 시스템, 광계측 시스템의 분야에 있어서, 도파로, 렌즈, 광파이버, 광파이버의 기재, 피복 재료, LED의 렌즈, 렌즈 커버 등에도 사용할 수 있다.The optical film according to the present invention is an optical material that is used in displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, and rear projection televisions, such as a polarizer protective film, a quarter wave plate, and a half wave plate. It can be suitably used for wave plates, viewing angle control films, retardation films such as liquid crystal optical compensation films, and display front panels. In addition, the resin composition of the present invention can be used for waveguides, lenses, optical fibers, optical fiber substrates, coating materials, LED lenses, lens covers, etc. in the fields of optical communication systems, optical exchange systems, and optical measurement systems. there is.
(실시예)(Example)
이하, 본 발명을 실시예에 의거해서 더 구체적으로 설명한다. 예 중의 부 및 %는 한정하지 않는 한 질량 기준이다.Hereinafter, the present invention will be described in more detail based on examples. Parts and percentages in examples are based on mass unless otherwise specified.
실시예 1Example 1
2리터 3구 플라스크에, 글리콜 성분으로서 90% 네오펜틸글리콜(이하 「NPG」로 약기한다) 158g, 디카르복시산 성분으로서 무수프탈산(이하 「PA」로 약기한다) 422g, 알코올 성분으로서 이소노닐알코올(이하 「INA」로 약기한다) 410g 및 촉매인 테트라이소프로필티타네이트(이하 「TIPT」로 약기한다) 0.056g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 8시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 200℃에서 과잉의 글리콜을 제거함으로써 본 발명의 에스테르 수지(1)를 얻었다. 얻어진 에스테르 수지(1)는, 상온에서 담황색 액체이고, 산가가 0.2, 수 평균 분자량은 520이었다.In a 2-liter three-necked flask, 158 g of 90% neopentyl glycol (hereinafter abbreviated as “NPG”) as the glycol component, 422 g of phthalic anhydride (hereinafter abbreviated as “PA”) as the dicarboxylic acid component, and isononyl alcohol (hereinafter abbreviated as “PA”) as the alcohol component. 410 g of tetraisopropyl titanate (hereinafter abbreviated as “INA”) and 0.056 g of tetraisopropyl titanate (hereinafter abbreviated as “TIPT”) as a catalyst were added, and the temperature was gradually raised to 220°C under a nitrogen stream from a nitrogen introduction tube. A condensation reaction was conducted at 220°C for 8 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (1) of the present invention was obtained by removing excess glycol at 200°C under reduced pressure. The obtained ester resin (1) was a light yellow liquid at room temperature, had an acid value of 0.2, and a number average molecular weight of 520.
실시예 2Example 2
2리터 3구 플라스크에, 글리콜 성분으로서 프로필렌글리콜(이하 「PG」로 약기한다) 107.6g, 디카르복시산 성분으로서 PA 362g, 알코올 성분으로서 INA 412g 및 촉매인 TIPT 0.062g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 8시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 200℃에서 과잉의 글리콜을 제거함으로써 본 발명의 에스테르 수지(2)를 얻었다. 얻어진 에스테르 수지(2)는, 상온에서 담황색 액체이고, 산가가 0.2, 수 평균 분자량은 560이었다.Into a 2-liter three-necked flask, 107.6 g of propylene glycol (hereinafter abbreviated as “PG”) as a glycol component, 362 g of PA as a dicarboxylic acid component, 412 g of INA as an alcohol component, and 0.062 g of TIPT as a catalyst were added, and Under a nitrogen stream, the temperature was gradually raised to 220°C. A condensation reaction was conducted at 220°C for 8 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (2) of the present invention was obtained by removing excess glycol at 200°C under reduced pressure. The obtained ester resin (2) was a light yellow liquid at room temperature, had an acid value of 0.2, and a number average molecular weight of 560.
비교대조용 에스테르 수지의 합성예 1Synthesis example 1 of ester resin for comparison and control
2리터 3구 플라스크에, 글리콜 성분으로서 PG 383g, 디카르복시산 성분으로서 아디프산(이하 AA로 약기한다) 381g, PA 129g, 및 TIPT 0.054g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 13시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 140℃에서 과잉의 글리콜을 제거함으로써 비교대조용 에스테르 수지(1')를 얻었다. 얻어진 에스테르 수지(1')는, 상온에서 담황색 액체이고, 산가가 0.3이고, 수 평균 분자량은 760이었다.Into a 2-liter three-necked flask, 383 g of PG as a glycol component, 381 g of adipic acid (hereinafter abbreviated as AA), 129 g of PA, and 0.054 g of TIPT as dicarboxylic acid components were added, and then gradually introduced from a nitrogen introduction tube under a nitrogen stream. The temperature was raised to 220°C. A condensation reaction was conducted at 220°C for 13 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (1') for comparison and control was obtained by removing excess glycol at 140°C under reduced pressure. The obtained ester resin (1') was a light yellow liquid at room temperature, had an acid value of 0.3, and a number average molecular weight of 760.
비교대조용 에스테르 수지의 합성예 2Synthesis example 2 of ester resin for comparison and control
2리터 3구 플라스크에, 글리콜 성분으로서 PG 390g, 디카르복시산 성분으로서 AA 658g, PA 222g, 알코올 성분으로서 n-부탄올(이하 nBuOH로 약기한다) 253g 및 TIPT 0.091g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 13시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 200℃에서 과잉의 글리콜을 제거함으로써 비교대조용 에스테르 수지(2')를 얻었다. 얻어진 에스테르 수지(2')는, 상온에서 담황색 액체이고, 산가가 0.2이고, 수 평균 분자량은 1230이었다.Into a 2-liter three-necked flask, 390 g of PG as a glycol component, 658 g of AA and 222 g of PA as dicarboxylic acid components, and 253 g of n-butanol (hereinafter abbreviated as nBuOH) and 0.091 g of TIPT as alcohol components were added, and nitrogen was introduced from a nitrogen introduction tube. Under airflow, the temperature was gradually raised to 220°C. A condensation reaction was conducted at 220°C for 13 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (2') for comparison and control was obtained by removing excess glycol at 200°C under reduced pressure. The obtained ester resin (2') was a light yellow liquid at room temperature, had an acid value of 0.2, and a number average molecular weight of 1230.
비교대조용 에스테르 수지의 합성예 3Synthesis Example 3 of ester resin for comparison and control
2리터 3구 플라스크에, 글리콜 성분으로서 에틸렌글리콜(이하 「EG」로 약기한다) 448g, 디카르복시산 성분으로서 AA 812g, 및 TIPT 0.038g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 13시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 200℃에서 과잉의 글리콜을 제거함으로써 비교대조용 에스테르 수지(3')를 얻었다. 얻어진 에스테르 수지(3')는, 상온에서 담황색 액체이고, 산가가 0.2이고, 수 평균 분자량은 1320이었다.Into a 2-liter three-necked flask, 448 g of ethylene glycol (hereinafter abbreviated as “EG”) as a glycol component, 812 g of AA, and 0.038 g of TIPT as a dicarboxylic acid component were added, and the temperature was gradually heated to 220°C under a nitrogen stream from a nitrogen inlet tube. The temperature was raised to A condensation reaction was conducted at 220°C for 13 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (3') for comparison and control was obtained by removing excess glycol at 200°C under reduced pressure. The obtained ester resin (3') was a light yellow liquid at room temperature, had an acid value of 0.2, and a number average molecular weight of 1320.
비교대조용 에스테르 수지의 합성예 4Synthesis Example 4 of ester resin for comparison and control
2리터 3구 플라스크에, 글리콜 성분으로서 EG 93g, PG 114g, 디카르복시산 성분으로서 아디프산(이하 AA로 약기한다) 601g, 알코올 성분으로서 INA 415g 및 TIPT 0.061g을 투입하고, 질소 도입관으로부터 질소 기류 하, 단계적으로 220℃까지 승온했다. 220℃에서 13시간 축합 반응시키고, 산가가 1.0 이하로 된 것을 확인했다. 감압 하, 200℃에서 과잉의 글리콜을 제거함으로써 비교대조용 에스테르 수지(4')를 얻었다. 얻어진 에스테르 수지(4')는, 상온에서 담황색 액체이고, 산가가 0.3이고, 수 평균 분자량은 1190이었다.Into a 2-liter three-necked flask, 93 g of EG and 114 g of PG as glycol components, 601 g of adipic acid (hereinafter abbreviated as AA) as dicarboxylic acid components, and 415 g of INA and 0.061 g of TIPT as alcohol components were added, and nitrogen was introduced from the nitrogen introduction tube. Under airflow, the temperature was gradually raised to 220°C. A condensation reaction was conducted at 220°C for 13 hours, and it was confirmed that the acid value was 1.0 or less. Ester resin (4') for comparison and control was obtained by removing excess glycol at 200°C under reduced pressure. The obtained ester resin (4') was a light yellow liquid at room temperature, had an acid value of 0.3, and a number average molecular weight of 1190.
<셀룰로오스에스테르 광학 필름의 조정><Adjustment of cellulose ester optical film>
트리아세틸셀룰로오스 수지(가부시키가이샤다이셀제 「LT-35」) 100부, 에스테르 수지 10부를, 메틸렌클로라이드 810부 및 메탄올 90부로 이루어지는 혼합 용제에 더하고 용해하여, 도프액을 조제했다. 이 도프액을 유리판 상에 두께 0.8㎜로 되도록 유연하고, 실온에서 16시간 건조시킨 후, 50℃에서 30분, 120℃에서 30분 더 건조시킴으로써 필름을 얻었다. 또, 비교예 1은 에스테르 수지를 첨가하지 않고, 비교예 2에서는 에스테르 수지 대신에 트리페닐포스페이트를 동량 사용해서 필름을 제조했다. 비교예 3은 시판 트리아세틸셀룰로오스 필름 4UY(코니카미놀타제)이다.100 parts of triacetylcellulose resin (“LT-35” manufactured by Daicel Corporation) and 10 parts of ester resin were added and dissolved in a mixed solvent consisting of 810 parts of methylene chloride and 90 parts of methanol to prepare a dope liquid. This dope was softened on a glass plate to a thickness of 0.8 mm, dried at room temperature for 16 hours, and then dried at 50°C for 30 minutes and 120°C for 30 minutes to obtain a film. In addition, in Comparative Example 1, an ester resin was not added, and in Comparative Example 2, the same amount of triphenyl phosphate was used instead of the ester resin to produce a film. Comparative Example 3 is a commercially available triacetylcellulose film 4UY (made by Konica Minolta).
<투습도 측정><Water permeability measurement>
JIS Z 0208에 기재된 방법에 따라, 측정했다. 측정 조건은, 온도 40℃, 상대 습도 90%에서 행했다. 얻어지는 값이 작을수록, 내투습성이 우수한 것을 나타낸다. 단위 : g/㎡·24h It was measured according to the method described in JIS Z 0208. The measurement conditions were performed at a temperature of 40°C and a relative humidity of 90%. The smaller the value obtained, the more excellent the moisture permeability resistance is. Unit: g/㎡·24h
<습열 시험><Moist heat test>
필름을 85℃, 상대 습도 90%의 환경 하(습열 환경 하)에 120시간 노출했다.The film was exposed to an environment of 85°C and 90% relative humidity (under a moist heat environment) for 120 hours.
<HAZE><HAZE>
HAZE값은, 탁도계(니혼덴쇼쿠고교가부시키가이샤제 「NDH 5000」)를 사용해서, JIS K 7105에 준거해서 측정했다. 얻어지는 값이 0%에 가까울수록, 투명한 것을 나타낸다.The HAZE value was measured based on JIS K 7105 using a turbidity meter (“NDH 5000” manufactured by Nippon Denshoku Kogyo Co., Ltd.). The closer the obtained value is to 0%, the more transparent it is.
<습열 감량><Moist heat loss>
4㎝×4㎝ 사방의 필름으로 상술의 습열 시험을 행하고, 시험 전후의 질량을 측정함으로써, 시험 후의 질량 감소율(%)을 구했다.The above-mentioned moist heat test was performed on a 4 cm x 4 cm square film, and the mass before and after the test was measured to determine the mass reduction rate (%) after the test.
<셀룰로오스에스테르 수지 필름의 보존안정성 평가><Evaluation of storage stability of cellulose ester resin film>
필름 1.2g을, 30ml의 샘플병에 넣고, 85℃×습도 90%의 조건 하에 1000시간 존재시켰을 때에 가수 분해에 의해 발생하는 아세트산량을 검지관(기타가와식 가스 검지관 아세트산용)으로 측정했다. 발생하는 아세트산량이 적을수록, 보존안정성이 우수한 것을 나타낸다.1.2 g of film was placed in a 30 ml sample bottle and left for 1000 hours under the conditions of 85°C did. The smaller the amount of acetic acid generated, the better the storage stability.
[표 1][Table 1]
실시예에서는, 셀룰로오스에스테르 수지 조성물로부터 얻어지는 필름의 아세트산 발생량이 비교예보다도 대폭으로 억제되어 있고, 필름의 보존안정성이 향상되어 있는 것을 확인했다. 또한, 습열 시험 후의 질량 감소%가 작고, 셀룰로오스에스테르 수지에 대한 상용성도 높은 것을 알 수 있다. 투습도도 비교예보다도 낮게 억제되어 있어, 편광판으로서의 안정성 향상을 기대할 수 있다.In the examples, it was confirmed that the amount of acetic acid generated in the film obtained from the cellulose ester resin composition was significantly suppressed compared to the comparative example, and the storage stability of the film was improved. In addition, it can be seen that the mass loss percentage after the wet heat test is small, and the compatibility with cellulose ester resin is high. The moisture permeability is also suppressed to a lower level than that of the comparative example, and improved stability as a polarizing plate can be expected.
Claims (9)
상기 셀룰로오스에스테르 수지의 가소화제가, 하기 일반식(1)으로 표시되는 에스테르 수지이고, 수 평균 분자량이 350∼1000인, 셀룰로오스에스테르 수지 조성물.
B-(A-G)n-A-B (1)
〔식(1) 중, B는 탄소 원자수 4∼20의 지방족 모노알코올 잔기이고, G는 탄소 원자수 2∼12의 알킬렌글리콜 잔기, 탄소 원자수 4∼12의 옥시알킬렌글리콜 잔기 또는 탄소 원자수 6∼18의 아릴글리콜 잔기이고, A는 탄소 원자수 2∼12의 알킬렌디카르복시산 잔기(A1) 또는 탄소 원자수 6∼12의 아릴디카르복시산 잔기(A2)이며, 알킬렌디카르복시산 잔기(A1)와 아릴디카르복시산 잔기(A2)의 합계(A1+A2)에 있어서의 아릴디카르복시산 잔기(A2)의 함유율이 70∼100몰%이고, n은 반복수이고, n의 평균값이 0.2∼3이며, 반복할 때마다 G, A는 동일해도 되며 달라도 되고, 또한 복수 있는 A, B는 동일해도 되며 달라도 된다〕 A cellulose ester resin composition comprising a cellulose ester resin plasticizer and a cellulose ester resin,
A cellulose ester resin composition in which the plasticizer of the cellulose ester resin is an ester resin represented by the following general formula (1) and has a number average molecular weight of 350 to 1000.
B-(AG) n -AB (1)
[In formula (1), B is an aliphatic monoalcohol residue having 4 to 20 carbon atoms, G is an alkylene glycol residue having 2 to 12 carbon atoms, an oxyalkylene glycol residue having 4 to 12 carbon atoms, or carbon A is an aryl glycol residue having 6 to 18 atoms, and A is an alkylenedicarboxylic acid residue (A1) having 2 to 12 carbon atoms or an aryldicarboxylic acid residue (A2) having 6 to 12 carbon atoms, and A is an alkylenedicarboxylic acid residue (A1). ) and the aryldicarboxylic acid residue (A2), the content of the aryldicarboxylic acid residue (A2) in the total (A1+A2) is 70 to 100 mol%, n is the number of repetitions, and the average value of n is 0.2 to 3. , each time it is repeated, G and A may be the same or different, and plural A and B may be the same or different]
상기 일반식(1) 중의 B가, 탄소 원자수 6∼12의 지방족 모노알코올 잔기인, 셀룰로오스에스테르 수지 조성물.According to paragraph 1,
A cellulose ester resin composition wherein B in the general formula (1) is an aliphatic monoalcohol residue having 6 to 12 carbon atoms.
상기 일반식(1) 중의 B가 노닐알코올 잔기 또는 이소노닐알코올 잔기이고, G가 에틸렌글리콜, 1,2-프로필렌글리콜, 1,3-프로판디올, 1,2-부탄디올, 1,3-부탄디올, 2-메틸-1,3-프로판디올, 및 네오펜틸글리콜로 이루어지는 군에서 선택되는 1종 이상의 잔기이고, A1이 숙신산, 아디프산 및 디카르복시시클로헥산으로 이루어지는 군에서 선택되는 1종 이상의 잔기이고, A2가 프탈산, 테레프탈산 및 이소프탈산으로 이루어지는 군에서 선택되는 1종 이상의 잔기인, 셀룰로오스에스테르 수지 조성물.According to claim 1 or 2,
In the general formula (1), B is a nonyl alcohol residue or an isononyl alcohol residue, G is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, is one or more residues selected from the group consisting of 2-methyl-1,3-propanediol, and neopentyl glycol, and A1 is one or more residues selected from the group consisting of succinic acid, adipic acid, and dicarboxycyclohexane, , A cellulose ester resin composition wherein A2 is one or more residues selected from the group consisting of phthalic acid, terephthalic acid, and isophthalic acid.
상기 일반식(1) 중의 A에 있어서의 알킬렌디카르복시산 잔기(A1)와 아릴디카르복시산 잔기(A2)의 합계 몰수(A1+A2)에 있어서의 아릴디카르복시산 잔기(A2)의 함유율이 75∼100몰%인, 셀룰로오스에스테르 수지 조성물.According to claim 1 or 2,
The content of the aryldicarboxylic acid residue (A2) in the total number of moles (A1+A2) of the alkylenedicarboxylic acid residue (A1) and the aryldicarboxylic acid residue (A2) in A in the general formula (1) is 75 to 100. Mol%, cellulose ester resin composition.
편광판 보호용인 광학 필름.According to clause 6,
Optical film used to protect polarizers.
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| JP2005200602A (en) * | 2004-01-19 | 2005-07-28 | Dainippon Ink & Chem Inc | (meth)acrylic resin composition for molding and molded article by using the same |
| JP2006071876A (en) | 2004-09-01 | 2006-03-16 | Konica Minolta Opto Inc | Cellulose ester film, optical compensation film, polarizing plate and liquid crystal display apparatus |
| CN1824688A (en) | 2006-04-01 | 2006-08-30 | 江南大学 | O-phthalic acid polyester plasticizer and its preparation method |
| JP2008081632A (en) | 2006-09-28 | 2008-04-10 | Kawasaki Kasei Chem Ltd | Antistatic agent and resin composition |
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