JPH08337601A - Cellulose acetate having excellent moldability and its production - Google Patents
Cellulose acetate having excellent moldability and its productionInfo
- Publication number
- JPH08337601A JPH08337601A JP6260296A JP6260296A JPH08337601A JP H08337601 A JPH08337601 A JP H08337601A JP 6260296 A JP6260296 A JP 6260296A JP 6260296 A JP6260296 A JP 6260296A JP H08337601 A JPH08337601 A JP H08337601A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose acetate
- solvent
- viscosity
- molecular weight
- cellulose
- 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.)
- Granted
Links
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002904 solvent Substances 0.000 claims abstract description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- 230000021736 acetylation Effects 0.000 claims abstract description 31
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000001913 cellulose Substances 0.000 claims abstract description 9
- 150000002170 ethers Chemical class 0.000 claims abstract description 9
- 235000005985 organic acids Nutrition 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002284 Cellulose triacetate Polymers 0.000 claims abstract 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 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 abstract description 3
- 239000011654 magnesium acetate Substances 0.000 abstract description 3
- 229940069446 magnesium acetate Drugs 0.000 abstract description 3
- 235000011285 magnesium acetate Nutrition 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 235000011054 acetic acid Nutrition 0.000 description 16
- 239000000523 sample Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000007796 conventional method Methods 0.000 description 8
- -1 aliphatic organic acid Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000003811 acetone extraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- AWKXKNCCQLNZDB-UHFFFAOYSA-N 2-[2-(2-propanoyloxyethoxy)ethoxy]ethyl propanoate Chemical compound CCC(=O)OCCOCCOCCOC(=O)CC AWKXKNCCQLNZDB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000623 Cellulose acetate phthalate Polymers 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229940081734 cellulose acetate phthalate Drugs 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 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
- 239000004922 lacquer Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フィルムなどへの
成形性の高い酢酸セルロース（特に三酢酸セルロース）
及びその製造方法に関する。TECHNICAL FIELD The present invention relates to cellulose acetate (especially cellulose triacetate) which has high moldability for a film or the like.
And its manufacturing method.
【０００２】[0002]
【従来の技術】一般的に酢酸セルロースは、セルロース
を出発原料にして、無水酢酸を用いてエステル化されて
得られる半合成高分子である。現在、市販されている酢
酸セルロースは主に酢化度によって大きく２つのものに
分けられる。１つは酢化度が59％以上の三酢酸セルロー
ス（以下ＣＴＡ）、もう１つは二酢酸セルロースである
が、その範囲は広く、酢化度で50〜59％ぐらいのものを
二酢酸セルロース（ＣＤＡ）と称している。それは、一
方ではアセトンに可溶な酢酸セルロースという言い方も
できる。2. Description of the Related Art Cellulose acetate is generally a semi-synthetic polymer obtained by esterifying cellulose with acetic anhydride as a starting material. Currently, commercially available cellulose acetate is mainly classified into two types according to the degree of acetylation. One is cellulose triacetate (hereinafter CTA) with an acetylation degree of 59% or more, and the other is cellulose diacetate, but the range is wide, and the degree of acetylation is about 50-59%. (CDA). On the one hand, it can be said that it is cellulose acetate which is soluble in acetone.
【０００３】酢酸セルロース、特にＣＴＡは、優れた物
性、特に易加工性と高い光学的性質を有しているため、
プラスチック、繊維、フィルム（例えば、写真用フィル
ムなど）などの分野において長年にわたり利用されてい
る。また、酢酸セルロースは生分解性などを有するた
め、近年では、地球環境の観点からも脚光を浴びてい
る。Cellulose acetate, especially CTA, has excellent physical properties, particularly easy workability and high optical properties,
It has been used for many years in fields such as plastics, fibers, and films (for example, photographic films). Further, since cellulose acetate has biodegradability and the like, it has recently been in the spotlight from the viewpoint of global environment.
【０００４】ＣＴＡなどの酢酸セルロース成形品は、通
常、溶媒に溶解した酢酸セルロース溶液を、所望の形態
に流動させた後、溶媒を蒸発などにより除去することに
より得られる（特公昭45-9074 号公報、特公昭49-4554
号公報、特公昭49-5614 号公報等）。Cellulose acetate molded articles such as CTA are usually obtained by allowing a cellulose acetate solution dissolved in a solvent to flow into a desired form and then removing the solvent by evaporation or the like (Japanese Patent Publication No. Sho 45-9074). Bulletin, Japanese Patent Publication No. 49-4554
Gazette, Japanese Patent Publication No. 49-5614, etc.).
【０００５】一方、酢酸セルロースの用途の拡大に伴っ
て、加工技術の高速化が要求されているとともに、高速
成形、高速紡糸、成形品の高速処理が試みられている。
例えば、フィルムの製造においては、酢酸セルロース溶
液を高速で流延し、フィルム成形することが検討されて
いる。このような高速化に対応して成形性を向上させる
ためには、酢酸セルロースの濃厚な溶液粘度を小さくす
ることが考えられる。濃厚溶液の粘度を低下させるため
には、一般に、酢酸セルロースの平均重合度を低下させ
ることが行われている。しかし、重合度の小さな酢酸セ
ルロースを用いると、成形品の力学強度が低下する
（「糸の物理機械的性質に対するＣＴＡの重合度の影
響」， Krim Volokna, 1985, No.3, p46〜47など）。）
特に、酢化度の高い酢酸セルロース、中でもＣＴＡにお
いては、高い重合度を維持しつつ、溶液粘度を低下させ
ることが困難である。On the other hand, with the expansion of applications of cellulose acetate, higher processing techniques are required, and high-speed molding, high-speed spinning, and high-speed processing of molded products have been attempted.
For example, in the production of a film, it has been considered to cast a cellulose acetate solution at a high speed to form a film. In order to improve the moldability in response to such speeding up, it is conceivable to reduce the concentrated solution viscosity of cellulose acetate. In order to reduce the viscosity of concentrated solutions, it is common practice to reduce the average degree of polymerization of cellulose acetate. However, when cellulose acetate with a low degree of polymerization is used, the mechanical strength of the molded article decreases (“Influence of the degree of polymerization of CTA on the physico-mechanical properties of yarn”, Krim Volokna, 1985, No.3, p46-47, etc. ). )
Particularly, in the case of cellulose acetate having a high degree of acetylation, especially CTA, it is difficult to reduce the solution viscosity while maintaining a high degree of polymerization.
【０００６】さらに、一般に酢酸セルロースの成形品は
堅く、脆いということがあり、それは酢化度が高くなれ
ばなるほど顕著になる。一高分子材料の物性はその結晶
性に依存するところが大きい。すなわち、結晶性の高い
ものは、強度は出るが、柔らかさ、具体的には伸度が低
くなり脆くなる。ＣＴＡも例外ではなく、その構造の均
一性に起因して結晶性が高い。すなわち酢酸セルロース
の場合、その酢化度が高くなれば結晶性は高くなる。ま
た、一般に分子量の小さいものが核となって結晶を形成
する。そこでＣＴＡ、ＣＤＡを用いる場合には可塑剤を
添加して成形品にやわらかさを付与する処置がなされる
のが一般的である。たとえば、ドライバーの柄などに用
いられるアセテートプラスチックなどには、ジエチルフ
タレートなどフタル酸系の可塑剤を用いることが多い。
また、酢酸セルロース、特にＣＴＡの場合、その優れた
透明性から各種フィルム素材としての用途があるが、フ
ィルムが堅く、脆いという欠点があり、その物性的な欠
点を補うため、やはりここでも可塑剤が用いられること
が多い。可塑剤等の成分を添加することは、成形時のブ
リードアウトによる完成品の収率悪化を伴うだけでな
く、経済的にも不利である。そこで、ＣＴＡの性能を有
しつつ、可塑剤を少量使用することにより、優れた物性
を有するフィルムが得られる素材の開発が望まれてい
た。Furthermore, in general, a molded article of cellulose acetate is sometimes hard and brittle, which becomes more remarkable as the degree of acetylation increases. The physical properties of one polymeric material largely depend on its crystallinity. That is, a material having high crystallinity has high strength but softness, specifically, low elongation and becomes brittle. CTA is no exception and has high crystallinity due to its structural homogeneity. That is, in the case of cellulose acetate, the higher the degree of acetylation, the higher the crystallinity. Further, generally, a substance having a small molecular weight serves as a nucleus to form a crystal. Therefore, when using CTA or CDA, it is general to add a plasticizer to give the molded article softness. For example, a phthalic acid-based plasticizer such as diethyl phthalate is often used for acetate plastics used for driver's handle.
In addition, cellulose acetate, especially CTA, has applications as various film materials because of its excellent transparency, but it has the drawback that the film is rigid and brittle. Is often used. Adding components such as a plasticizer is not only economically disadvantageous in addition to the deterioration of the yield of the finished product due to bleed-out during molding. Therefore, it has been desired to develop a material that can obtain a film having excellent physical properties by using a small amount of a plasticizer while having the performance of CTA.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明の目的
は、分子量及び重合度が高いにも拘らず、溶液粘度の小
さな成形性に優れる酢酸セルロースを提供することにあ
る。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a cellulose acetate having a small solution viscosity and excellent moldability in spite of having a high molecular weight and a high degree of polymerization.
【０００８】本発明の他の目的は、平均重合度及び平均
置換度が高いにも拘らず、溶媒に対する溶解性及び成形
性の高い酢酸セルロースを提供することにある。Another object of the present invention is to provide a cellulose acetate having high solubility in a solvent and high moldability in spite of having a high average degree of polymerization and a high degree of substitution.
【０００９】本発明のさらに他の目的は、溶液粘度が小
さな酢酸セルロース溶液を用い、加工速度が大きな成形
法により、耐湿性、寸法精度の高い成形品を得る上で有
用な酢酸セルロースを提供することにある。Still another object of the present invention is to provide a cellulose acetate useful for obtaining a molded article having high moisture resistance and high dimensional accuracy by a molding method using a cellulose acetate solution having a small solution viscosity and a high processing speed. Especially.
【００１０】本発明の別の目的は、前記の如き優れた特
性を有する酢酸セルロースの製造方法を提供することに
ある。Another object of the present invention is to provide a method for producing cellulose acetate having the above-mentioned excellent properties.
【００１１】[0011]
【課題を解決するための手段】本発明者らは前記目的を
達成するため鋭意検討の結果、（１）ＣＴＡなどの酢酸
セルロースを溶媒で処理し、低分子量成分を溶出する
と、酢酸セルロースの分子量分布の指標Ｍｗ／Ｍｎが狭
くなること、（２）低分子量成分の除去により、分子量
が高いにも拘らず、Ｍｗ／Ｍｎが特定の範囲では、濃厚
溶液の粘度が有意に小さくなり、成形性を改良できるこ
と、（３）素材の結晶性を低くすること、すなわち、結
晶形成の核となる低分子量物を取り除くことにより、成
形品の物性、特にフィルム強度が向上し、しなやかさが
増すことを見いだし、本発明を完成した。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that (1) when cellulose acetate such as CTA is treated with a solvent and low molecular weight components are eluted, the molecular weight of cellulose acetate is Due to the narrow distribution index Mw / Mn, and (2) the removal of low molecular weight components, the viscosity of the concentrated solution becomes significantly small within a certain range of Mw / Mn, even though the molecular weight is high. That (3) lowering the crystallinity of the material, that is, removing the low molecular weight material that is the nucleus of crystal formation, improves the physical properties of the molded product, especially film strength, and increases flexibility. Found and completed the present invention.
【００１２】すなわち、本発明の酢酸セルロースは、ゲ
ルパーミエーションクロマトグラフィーによる分子量分
布Ｍｗ／Ｍｎ１〜1.7 を有しており、成形性が高い。こ
のような酢酸セルロースには、例えば、平均酢化度が52
〜62.5％であり、分子量分布Ｍｗ／Ｍｎが1.2 〜1.7 程
度の酢酸セルロース、さらには、アセトン抽出分が５％
以下で、粘度平均重合度（DP）が 290以上であり、かつ
粘度平均重合度（DP）に対する落球粘度法による濃厚溶
液粘度（η）が下記の式(1) で表されることを特徴とす
る酢酸セルロース、特にＣＴＡが含まれる。 2.814×ln(DP)-11.753 ≦ln（η）≦7.28×ln(DP)-37.059 (1) このような酢酸セルロースは、酢酸セルロースの低分子
量成分を溶出する溶媒を用いて、酢酸セルロースを洗浄
することにより得ることができる。洗浄溶媒には、酢酸
セルロースを膨潤又は部分的に溶解する溶媒、例えば、
温度25℃、固形分濃度５重量％で酢酸セルロースを分散
させたとき、酢酸セルロースの 0.1〜30重量％を溶解す
る溶媒などが含まれる。洗浄溶媒としては、ケトン類、
エーテル類、有機酸及びエステル類などが例示できる。
このような溶媒の溶解度パラメーターδは７〜12.5程度
である場合が多い。That is, the cellulose acetate of the present invention has a molecular weight distribution Mw / Mn of 1 to 1.7 according to gel permeation chromatography and has high moldability. Such cellulose acetate has, for example, an average acetylation degree of 52.
~ 62.5%, cellulose acetate with a molecular weight distribution Mw / Mn of about 1.2 to 1.7, and 5% acetone extracted
In the following, the viscosity average degree of polymerization (DP) is 290 or more, and the concentrated solution viscosity (η) by the falling ball viscosity method with respect to the viscosity average degree of polymerization (DP) is represented by the following formula (1). Cellulose acetate, especially CTA. 2.814 × ln (DP) -11.753 ≦ ln (η) ≦ 7.28 × ln (DP) -37.059 (1) Such cellulose acetate is washed with a solvent that elutes low molecular weight components of cellulose acetate. It can be obtained by The washing solvent, a solvent that swells or partially dissolves cellulose acetate, for example,
When the cellulose acetate is dispersed at a temperature of 25 ° C. and a solid content concentration of 5% by weight, a solvent that dissolves 0.1 to 30% by weight of the cellulose acetate is included. As the cleaning solvent, ketones,
Examples thereof include ethers, organic acids and esters.
The solubility parameter δ of such a solvent is often about 7 to 12.5.
【００１３】[0013]
【発明の実施の形態】以下に、本発明を詳細に説明す
る。酢酸セルロースは、セルロースの酢酸エステル（酢
酸セルロース）であるのが好ましいものの、酢酸エステ
ルを主成分とする限り、他の有機酸との混酸エステル
〔例えば、炭素数３又は４程度の脂肪族有機酸とのエス
テル（例えば、酢酸セルロースプロピオネート、酢酸セ
ルロースブチレートなど）、酢酸セルロースフタレート
など〕、無機酸との混酸エステル（例えば、硝酸酢酸セ
ルロースなど）であってもよい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. Cellulose acetate is preferably an acetic acid ester of cellulose (cellulose acetate), but as long as it contains acetic acid ester as a main component, it is a mixed acid ester with another organic acid [for example, an aliphatic organic acid having about 3 or 4 carbon atoms]. Ester (eg, cellulose acetate propionate, cellulose acetate butyrate, etc.), cellulose acetate phthalate, etc.], and a mixed acid ester with an inorganic acid (eg, cellulose nitrate acetate etc.).
【００１４】本発明の酢酸セルロースは、ゲルパーミエ
ーションクロマトグラフィーによる分子量分布Ｍｗ／Ｍ
ｎ（Ｍｗは重量平均分子量、Ｍｎは数平均分子量を示
す）が狭いという特色がある。すなわち、本発明の酢酸
セルロースのＭｗ／Ｍｎは、１〜1.7(例えば、 1.2〜1.
7)、好ましくは 1.3〜1.65、さらに好ましくは 1.4〜1.
65程度であり、 1.3〜1.6 程度である場合が多い。分子
量分布Ｍｗ／Ｍｎが前記範囲の上限を外れると、酢酸セ
ルロース溶液の粘度が大きくなり、流延法などによる成
形性（特に、高速での成形加工性）が低下する。Ｍｗ／
Ｍｎの下限が1.0に近づく程溶液粘度は低下するもの
の、成形品の強度を損なうためＭｗ／Ｍｎは１を超える
範囲が好ましい。The cellulose acetate of the present invention has a molecular weight distribution Mw / M by gel permeation chromatography.
It has a characteristic that n (Mw is a weight average molecular weight and Mn is a number average molecular weight) is narrow. That is, Mw / Mn of the cellulose acetate of the present invention is 1 to 1.7 (for example, 1.2 to 1.
7), preferably 1.3-1.65, more preferably 1.4-1.
It is about 65 and often 1.3 to 1.6. When the molecular weight distribution Mw / Mn deviates from the upper limit of the above range, the viscosity of the cellulose acetate solution increases, and the moldability by the casting method or the like (particularly, the moldability at high speed) decreases. Mw /
Although the solution viscosity decreases as the lower limit of Mn approaches 1.0, Mw / Mn is preferably in the range of more than 1 because the strength of the molded product is impaired.
【００１５】酢酸セルロースの重量平均分子量は、特に
制限されず、用途に応じて選択でき、例えば、１×104
〜 100×104 、好ましくは５×104 〜75×104 、さらに
好ましくは10×104 〜50×104 程度である。The weight average molecular weight of cellulose acetate is not particularly limited and can be selected according to the intended use. For example, 1 × 10 4
It is about 100 × 10 4 , preferably 5 × 10 4 to 75 × 10 4 , and more preferably about 10 × 10 4 to 50 × 10 4 .
【００１６】さらに、本発明の酢酸セルロースは、低分
子量成分が除去されているため、従来の酢酸セルロース
に比べて、分子量及び重合度が高くても、濃厚溶液の粘
度が小さいという特色がある。この理由は定かではない
が、高分子の溶液における見掛け粘度は、高分子量物が
支配的に働くことが考えられ、本発明の場合、平均分子
量は高くなるが、高分子量物の量は変化しないことによ
るものと推定できる。そのため、酢酸セルロースの平均
重合度は成形品の機械的特性などを損なわない範囲で選
択でき、酢酸セルロース（特にＣＴＡ）の粘度平均重合
度（DP）は、例えば、好ましくは 290以上（例えば、 2
90〜400)、さらに好ましくは 250〜350(例えば、 300〜
350)程度であるのが好ましい。酢酸セルロースの粘度平
均重合度が 100未満であると成形品の力学的特性が低下
し易い。Further, since the low molecular weight component is removed from the cellulose acetate of the present invention, it has a feature that the viscosity of the concentrated solution is small as compared with the conventional cellulose acetate even if the molecular weight and the degree of polymerization are high. The reason for this is not clear, but it is considered that the apparent viscosity of the polymer in the solution is predominantly the high molecular weight substance. In the case of the present invention, the average molecular weight increases, but the amount of the high molecular weight substance does not change. It can be presumed that this is due to the fact. Therefore, the average degree of polymerization of cellulose acetate can be selected within a range that does not impair the mechanical properties of the molded product, and the viscosity average degree of polymerization (DP) of cellulose acetate (particularly CTA) is, for example, preferably 290 or more (eg, 2
90-400), more preferably 250-350 (e.g., 300-
It is preferably about 350). If the viscosity average degree of polymerization of cellulose acetate is less than 100, the mechanical properties of the molded product are likely to deteriorate.
【００１７】酢酸セルロースの酢化度（結合酢酸％）
は、52〜62.5％の範囲から選択できる。好ましい酢酸セ
ルロースの酢化度は、59％以上（例えば、59.0〜62.5
％）、特に59〜62％（例えば、60〜61.5％) 程度であ
る。なお、酢化度が小さい場合には、吸湿性が増大し、
寸法安定性が低下しやすい。そのため、特に好ましい酢
酸セルロースには、酢化度の高い酢酸セルロース、例え
ば、ＣＤＡ及びＣＴＡ、特にＣＴＡが含まれる。Degree of acetylation of cellulose acetate (% bound acetic acid)
Can be selected from the range of 52 to 62.5%. The preferred degree of acetylation of cellulose acetate is 59% or more (for example, 59.0 to 62.5
%), Especially about 59 to 62% (for example, 60 to 61.5%). When the degree of acetylation is small, the hygroscopicity increases,
Dimensional stability tends to decrease. Thus, particularly preferred cellulose acetates include cellulose acetates with a high degree of acetylation, such as CDA and CTA, especially CTA.
【００１８】このような酢酸セルロースのうち、下記の
特性を有するＣＴＡは、耐湿性及び寸法安定性が高いと
ともに、酢化度が高いにも拘らず、溶媒に対する溶解性
が高く、溶液の低粘度化が可能であるため、成形性が高
い。 分子量分布（Ｍｗ／Ｍｎ）： 1.3〜1.65、特に 1.4〜1.
65 重量平均分子量（Ｍｗ，×104)：５〜100 、特に10〜50 酢化度：59.0〜62.5％、特に59〜62％（例えば60〜62
％）。Among such cellulose acetates, CTA having the following characteristics has high humidity resistance and dimensional stability, and has high solubility in a solvent despite having a high degree of acetylation, and a low viscosity of the solution. Since it can be made into a resin, it has high moldability. Molecular weight distribution (Mw / Mn): 1.3-1.65, especially 1.4-1.
65 Weight average molecular weight (Mw, × 10 4 ): 5 to 100, especially 10 to 50 Degree of acetylation: 59.0 to 62.5%, especially 59 to 62% (for example, 60 to 62)
%).
【００１９】前記のように本発明の酢酸セルロースは、
酢化度が高くても溶媒に対する溶解性が高いため、溶液
中の酢酸セルロース含有量、酢酸セルロース溶液の粘度
は、用途に応じて選択できる。なお、酢酸セルロースの
溶液粘度は、高速成形性、特に流延法や紡糸法における
高速成形性の尺度となり得る。すなわち、溶液粘度の低
い酢酸セルロースは、高速での流延塗布や紡糸を可能に
するとともに、表面が短時間内に平滑化する（すなわ
ち、レベリング性が高い）ので、高速で成形しても成形
性が高く、成形品の生産性を向上できる。酢酸セルロー
スの溶液粘度は、高速での成形性を損なわない範囲で選
択でき、例えば、酢酸セルロース13重量％及びトリフェ
ニルフォスフェート２重量％を含む15％溶液粘度は、下
記の落球粘度法１により、20〜70秒、好ましくは30〜65
秒程度である。As described above, the cellulose acetate of the present invention is
Since the solubility in a solvent is high even if the degree of acetylation is high, the content of cellulose acetate in the solution and the viscosity of the cellulose acetate solution can be selected according to the application. The solution viscosity of cellulose acetate can be a measure of high-speed moldability, particularly in the casting method and spinning method. That is, since cellulose acetate having a low solution viscosity enables casting coating and spinning at high speed, and the surface is smoothed within a short time (that is, high leveling property), it can be molded even at high speed. Highly productive and can improve the productivity of molded products. The solution viscosity of cellulose acetate can be selected within a range that does not impair the moldability at high speed. For example, a 15% solution viscosity containing 13% by weight of cellulose acetate and 2% by weight of triphenyl phosphate can be determined by the falling ball viscosity method 1 described below. , 20-70 seconds, preferably 30-65
It is about a second.
【００２０】落球粘度法１ ＣＴＡなどの酢酸セルロース42.7重量部を、可塑剤とし
てのトリフェニルフォスフェート 6.8重量部（酢酸セル
ロースに対して16重量％）と、混合溶媒〔ｎ−ブタノー
ル／メタノール／ジクロロメタン＝３／15／82（重量
比）〕280.5 重量部に溶解し、トリフェニルフォスフェ
ートを含めた固形分15重量％の酢酸セルロース溶液を調
製する。この溶液をガラス管（直径2.53cm、長さ31.9c
m、標線間距離9.93cm) に注入し、25℃で溶液中に所定
の鋼球（直径3.20mm、ステンレス製、比重7.87ｇ／cm
3(23℃））を落下させ、ガラス管の標線間を鋼球が通過
する秒数を粘度の指標とする。Falling ball viscosity method 1 42.7 parts by weight of cellulose acetate such as CTA and 6.8 parts by weight of triphenyl phosphate as a plasticizer (16% by weight based on cellulose acetate) and a mixed solvent [n-butanol / methanol / dichloromethane] = 3/15/82 (weight ratio)] dissolved in 280.5 parts by weight to prepare a cellulose acetate solution containing triphenyl phosphate and having a solid content of 15% by weight. Add this solution to a glass tube (diameter 2.53 cm, length 31.9c
m, the distance between the marked lines is 9.93 cm), and the specified steel balls (diameter 3.20 mm, stainless steel, specific gravity 7.87 g / cm) in the solution at 25 ° C
3 (23 ℃)), and the number of seconds the steel ball passes between the marked lines of the glass tube is used as an index of viscosity.
【００２１】さらに、本発明の酢酸セルロースは、アセ
トン抽出分が５％以下で、粘度平均重合度（DP）が 290
以上であり、且つ粘度平均重合度（DP）に対する落球粘
度法２による濃厚溶液粘度（η）が下記の式(1) で表さ
れることを特徴とする。 2.814×ln(DP)-11.753 ≦ln（η）≦7.28×ln(DP)-37.059 (1) 本発明における上記の式(1) は、本発明者等が行った実
験から得たものである。粘度平均重合度 290以上の酢酸
セルロースにおいては、一般的に重合度が高くなると濃
厚溶液の粘度が指数的に増加していくのに対し、本発明
の酢酸セルロースは、それとは異なる挙動を示す。そこ
で、粘度平均重合度と濃厚溶液粘度のプロットから、式
(1) を算出した。尚、下記の式(2) を満たすことが特に
好ましい。 2.814×ln(DP)-11.753 ≦ln（η）≦6.29×ln(DP)-31.469 (2) 落球粘度法２による濃厚溶液粘度（η）の測定方法は以
下の通りである。 落球粘度法２ 酢酸セルロースを15重量％になるように、メチレンクロ
ライド：メタノール＝８：２（重量比）に溶解し、溶液
を内径 2.6cmの粘度管に注入し、25℃に調温後、溶液中
に所定の鋼球、直径3.15mm、 0.135ｇを落下させて、間
隔10cmの標線間を通過する秒数を粘度とした。Further, the cellulose acetate of the present invention has an acetone extractable content of 5% or less and a viscosity average degree of polymerization (DP) of 290.
It is characterized in that the concentrated solution viscosity (η) according to the falling ball viscosity method 2 with respect to the viscosity average degree of polymerization (DP) is represented by the following formula (1). 2.814 × ln (DP) -11.753 ≦ ln (η) ≦ 7.28 × ln (DP) -37.059 (1) The above formula (1) in the present invention is obtained from an experiment conducted by the present inventors. . In the case of cellulose acetate having a viscosity average degree of polymerization of 290 or more, the viscosity of the concentrated solution generally increases exponentially as the degree of polymerization increases, whereas the cellulose acetate of the present invention behaves differently. Therefore, from the plot of viscosity average polymerization degree and concentrated solution viscosity,
(1) was calculated. It is particularly preferable that the following formula (2) is satisfied. 2.814 × ln (DP) -11.753 ≦ ln (η) ≦ 6.29 × ln (DP) -31.469 (2) The method for measuring the concentrated solution viscosity (η) by falling ball viscosity method 2 is as follows. Falling ball viscosity method 2 Cellulose acetate was dissolved in methylene chloride: methanol = 8: 2 (weight ratio) so as to be 15% by weight, the solution was poured into a viscous tube having an inner diameter of 2.6 cm, and the temperature was adjusted to 25 ° C. A predetermined steel ball, having a diameter of 3.15 mm and 0.135 g, was dropped into the solution, and the viscosity was defined as the number of seconds that passed between the marked lines at intervals of 10 cm.
【００２２】本発明においては、常法により得られたＣ
ＴＡを、ケトン類、酢酸エステル類、セロソルブ類など
で洗浄し、低分子量物を除去することにより、結晶化を
抑制し、物性的に優れたフィルムを提供する素材とな
る。In the present invention, C obtained by a conventional method is used.
By washing TA with ketones, acetic acid esters, cellosolves and the like to remove low molecular weight substances, crystallization is suppressed, and it becomes a material that provides a film with excellent physical properties.
【００２３】この洗浄により得られるＣＴＡの特徴とし
ては、常法により得られるＣＴＡを一回洗浄を行うと、
洗浄液中に存在する低分子量ＣＴＡの量が10〜15％程度
存在するが、洗浄後の酢酸セルロースは再度洗浄抽出を
しても５％以下になる。言い換えると、洗浄抽出によ
り、再度抽出しても、低分子量ＣＴＡが５％以下になる
ように洗浄抽出する必要がある。The characteristic of the CTA obtained by this washing is that if the CTA obtained by a conventional method is washed once,
The amount of low molecular weight CTA present in the washing solution is about 10 to 15%, but the cellulose acetate after washing is 5% or less even if washed and extracted again. In other words, it is necessary to carry out the washing extraction so that the low molecular weight CTA becomes 5% or less even if the extraction is performed again by the washing extraction.
【００２４】フィルム等の物性が向上した理由として
は、洗浄除去することにより、製品中の低分子量物が除
去されることにより、成形時に無用の結晶を形成せず、
その結果、フィルム中に非結晶部分が増えることによ
り、フィルムにしなやかさとさらなる透明性を付与でき
るものと考えられる。The reason why the physical properties of the film and the like are improved is that the low molecular weight substances in the product are removed by washing and removal, so that unnecessary crystals are not formed during molding,
As a result, it is considered that the amorphous portion is increased in the film, so that the film can be imparted with flexibility and further transparency.
【００２５】酢酸セルロースは、慣用の方法、例えば、
硫酸触媒法、酢酸法、メチレンクロライド法などの方法
で製造できる。酢酸セルロースは、通常、セルロースを
酢酸などにより活性化処理した後、硫酸触媒を用いて無
水酢酸によりトリアセテートを調製し、ケン化（加水分
解）により酢化度を調整する場合が多い。このような方
法で得られる酢酸セルロースのＭｗ／Ｍｎは、通常、
1.8〜3.0 程度である。Cellulose acetate can be prepared by conventional methods, eg,
It can be produced by a method such as a sulfuric acid catalyst method, an acetic acid method or a methylene chloride method. Cellulose acetate is often activated by acetic acid or the like, then triacetate is prepared with acetic anhydride using a sulfuric acid catalyst, and the degree of acetylation is adjusted by saponification (hydrolysis). The Mw / Mn of cellulose acetate obtained by such a method is usually
It is about 1.8 to 3.0.
【００２６】本発明の方法では、酢酸セルロースを溶媒
で洗浄処理することにより、分子量分布幅の狭い酢酸セ
ルロースを製造する。前記溶媒としては、酢酸セルロー
スを完全に溶解することなく、膨潤又は部分的に溶解す
る溶媒が使用できる。酢酸セルロースを膨潤又は一部溶
解する溶媒は、低分子量成分を溶解・溶出可能な溶媒で
あればよく、高分子量成分を分画できる限り、溶媒によ
る酢酸セルロースの溶解成分の割合は特に制限されな
い。酢酸セルロースの低分子量成分を除去し、高分子量
成分を効率よく得るためには、常温（25℃）、固形分濃
度５重量％で酢酸セルロースを分散させたとき、酢酸セ
ルロースの 0.1〜30重量％、好ましくは１〜25重量％、
さらに好ましくは５〜15重量％を溶解する溶媒を用いる
のが好ましい。低分子量成分を溶出可能な溶媒は、通
常、酢酸セルロースの１〜20重量％程度を溶解する溶媒
である場合が多い。溶媒による酢酸セルロースの溶解成
分が0.1 重量％未満であると、繰り返し洗浄しても低分
子量成分を溶出できず、30重量％を超えると経済的でな
く工業的に効率よく酢酸セルロースを製造することが困
難となる。In the method of the present invention, cellulose acetate is washed with a solvent to produce cellulose acetate having a narrow molecular weight distribution range. As the solvent, a solvent that can swell or partially dissolve cellulose acetate without completely dissolving it can be used. The solvent that swells or partially dissolves the cellulose acetate may be any solvent that can dissolve and elute the low molecular weight component, and the ratio of the soluble component of the cellulose acetate to the solvent is not particularly limited as long as the high molecular weight component can be fractionated. In order to remove low molecular weight components of cellulose acetate and efficiently obtain high molecular weight components, when cellulose acetate is dispersed at room temperature (25 ° C) at a solid concentration of 5% by weight, 0.1 to 30% by weight of cellulose acetate is obtained. , Preferably 1 to 25% by weight,
It is more preferable to use a solvent that dissolves 5 to 15% by weight. The solvent capable of eluting the low molecular weight component is usually a solvent which dissolves approximately 1 to 20% by weight of cellulose acetate. If the content of dissolved cellulose acetate in the solvent is less than 0.1% by weight, low molecular weight components cannot be eluted even after repeated washing. If it exceeds 30% by weight, it is not economical and industrially efficient production of cellulose acetate is possible. Will be difficult.
【００２７】このような洗浄溶媒は、酢酸セルロースの
種類に応じて選択できる。洗浄溶媒の選択に際しては、
溶解度パラメーターδを参照できる（例えば、H. Burre
ll；Off. Dig.,29, 1069(1957)) 。この溶解性パラメー
ターδは、例えば、J.H. Hildebrand, R.L. Scott; "So
lubility of Non-electrolytes" Chap.20, Rein hold(1
950)に記載されているように、下記式に従って求めるこ
とができる。 δ＝（Ｅ／Ｖ）0.5 〔式中、Ｅはモル蒸発熱(cal) を示し、Ｖは分子容(cc)
を示す〕。Such a washing solvent can be selected according to the type of cellulose acetate. When selecting the washing solvent,
Reference may be made to the solubility parameter δ (eg H. Burre
ll; Off. Dig., 29 , 1069 (1957)). This solubility parameter δ is calculated, for example, by JH Hildebrand, RL Scott; "So
lubility of Non-electrolytes "Chap.20, Rein hold (1
950), it can be determined according to the following formula. δ = (E / V) 0.5 [In the formula, E indicates the heat of molar evaporation (cal), V is the molecular volume (cc)
]].
【００２８】洗浄溶媒としては、例えば、アセトン（1
0.0、以下、単に溶解度パラメーターδの値を括弧内に
示す）、メチルエチルケトン(9.3) 、ジエチルケトン
(8.8) 、メチルイソブチルケトン(8.4) 、ジイソプロピ
ルケトン(8.0) 、ジイソブチルケトン(7.8) などのケト
ン類；ジブチルエーテル(7.1) 、ジオキサン(9.9) 、テ
トラヒドロフラン(10.2)などのエーテル類；ギ酸、酢
酸、プロピオン酸、酪酸、乳酸などの有機酸；酢酸メチ
ル(9.6) 、酢酸エチル(9.1) 、酢酸イソプロピル(8.4)
、酢酸ブチル(8.5) 、酢酸アミル(8.5) 、酢酸セロソ
ルブ(8.7) 、プロピオン酸メチル、プロピオン酸エチ
ル、乳酸エチルなどのエステル類；メチルセロソルブ
(9.9) 、エチルセロソルブ、イソプロピルセロソルブ、
プロピルセロソルブ、ブチルセロソルブ(8.9) 、メチル
セロソルブアセテート、セロソルブアセテートなどのセ
ロソルブ類；メチルカルビトール、エチルカルビトール
(9.6) 、プロピルカルビトール、ブチルカルビトール
(8.9) などのカルビトール類；クロロホルム(9.3) 、ジ
クロロメタン(10.2)、ジクロロエタン(9.5) 、四塩化炭
素などのハロゲン化炭化水素類；ニトロメタン(12.7)、
ニトロエタン(11.1)、ニトロプロパンなどのニトロ化合
物；アセトニトリル(11.9)、Ｎ，Ｎ−ジメチルホルムア
ミド(12.1)、Ｎ，Ｎ−ジエチルホルムアミド(10.6)、ジ
メチルアセトアミド(10.8)、ジエチルアセトアミド(9.
9) 、ジメチルスルホキシドなどの非プロトン性極性溶
媒；及びこれらの混合溶媒などが例示できる。As the washing solvent, for example, acetone (1
0.0, below, the value of solubility parameter δ is simply shown in parentheses), methyl ethyl ketone (9.3), diethyl ketone
(8.8), methyl isobutyl ketone (8.4), diisopropyl ketone (8.0), diisobutyl ketone (7.8) and other ketones; dibutyl ether (7.1), dioxane (9.9), tetrahydrofuran (10.2) and other ethers; formic acid, acetic acid , Organic acids such as propionic acid, butyric acid, lactic acid; methyl acetate (9.6), ethyl acetate (9.1), isopropyl acetate (8.4)
, Butyl acetate (8.5), amyl acetate (8.5), cellosolve acetate (8.7), methyl propionate, ethyl propionate, ethyl lactate and other esters; methyl cellosolve
(9.9), ethyl cellosolve, isopropyl cellosolve,
Cellosolves such as propyl cellosolve, butyl cellosolve (8.9), methyl cellosolve acetate, cellosolve acetate; methyl carbitol, ethyl carbitol
(9.6), propyl carbitol, butyl carbitol
Carbitols such as (8.9); chloroform (9.3), dichloromethane (10.2), dichloroethane (9.5), halogenated hydrocarbons such as carbon tetrachloride; nitromethane (12.7),
Nitro compounds such as nitroethane (11.1) and nitropropane; acetonitrile (11.9), N, N-dimethylformamide (12.1), N, N-diethylformamide (10.6), dimethylacetamide (10.8), diethylacetamide (9.
9), an aprotic polar solvent such as dimethyl sulfoxide; and a mixed solvent thereof.
【００２９】さらに、前記溶媒は、酢酸セルロースに対
する溶解性を調整するため、他の溶媒、例えば、水、メ
タノール(14.5)、エタノール(12.7)、ｎ−プロパノール
(11.9)、イソプロパノール、ｎ−ブタノール(11.4)、イ
ソブタノール、ジアセトンアルコール、シクロヘキサノ
ール(11.4)などのアルコール類；ペンタン(7.0) 、ヘキ
サン(7.3) 、ヘプタン(7.4) 、オクタン(7.2) などの脂
肪族炭化水素類；シクロヘキサン(8.2) 、メチルシクロ
ヘキサン(7.8) などの脂環族炭化水素類；ベンゼン(9.
2) 、トルエン(8.9) 、キシレン(8.8) 、エチルベンゼ
ン(8.8) などの芳香族炭化水素類などとの混合溶媒とし
て使用してもよい。なお、ジクロロメタン単独やジクロ
ロメタンとエタノールとを重量比９：１で混合した混合
溶媒は、殆ど酢酸セルロースに対する良溶媒であり、溶
解性が高い。このような良溶媒では、混合溶媒の成分の
割合、他の溶媒の添加により、酢酸セルロースに対する
溶解度を調整することができる。また、前記溶媒のうち
水は、通常、親水性溶媒、特にアセトン、酢酸などの水
溶性溶媒とともに用いられる。Further, the solvent is used in order to adjust the solubility in cellulose acetate, for example, other solvents such as water, methanol (14.5), ethanol (12.7), n-propanol.
(11.9), isopropanol, n-butanol (11.4), isobutanol, diacetone alcohol, cyclohexanol (11.4) and other alcohols; pentane (7.0), hexane (7.3), heptane (7.4), octane (7.2), etc. Aliphatic hydrocarbons; cyclohexane (8.2), alicyclic hydrocarbons such as methylcyclohexane (7.8); benzene (9.
2), toluene (8.9), xylene (8.8), ethylbenzene (8.8) and the like may be used as a mixed solvent with aromatic hydrocarbons and the like. It should be noted that dichloromethane alone or a mixed solvent obtained by mixing dichloromethane and ethanol at a weight ratio of 9: 1 is a good solvent for cellulose acetate and has a high solubility. In such a good solvent, the solubility in cellulose acetate can be adjusted by the ratio of the components of the mixed solvent and the addition of another solvent. Further, of the above solvents, water is usually used together with a hydrophilic solvent, particularly a water-soluble solvent such as acetone or acetic acid.
【００３０】好ましい洗浄溶媒には、溶解度パラメータ
ーδが７〜12.5、好ましくは８〜12（例えば、 8.5〜1
1.5) 、さらに好ましくは９〜11（例えば、９〜10.5)
程度の溶媒が含まれる。低分子量成分を効率よく溶出す
るためには、ハロゲン化炭化水素類を除く極性溶媒、例
えば、ケトン類、エーテル類、有機酸、エステル類、セ
ロソルブ類、カルビトール類などから選択された少なく
とも一種の溶媒を用いる場合が多い。特に、低分子量成
分の溶出効率を高めるためには、前記溶解度パラメータ
ーの如何に拘らず、例えば、アセトンなどのケトン類、
テトラヒドロフランなどのエーテル類、酢酸などの有機
酸、酢酸メチルなどのエステル類などが好ましい。特に
好ましい溶媒には、ケトン類、エーテル類、有機酸及び
エステル類から選択され、かつ溶解度パラメーターが
8.5〜11.5（好ましくは９〜11）程度の溶媒が含まれ
る。Preferred washing solvents have a solubility parameter δ of 7 to 12.5, preferably 8 to 12 (eg 8.5 to 1
1.5), more preferably 9-11 (eg 9-10.5)
Some solvent is included. In order to efficiently elute low molecular weight components, polar solvents other than halogenated hydrocarbons, for example, at least one selected from ketones, ethers, organic acids, esters, cellosolves, carbitols, etc. Often a solvent is used. In particular, in order to enhance the elution efficiency of low molecular weight components, regardless of the solubility parameter, for example, ketones such as acetone,
Ethers such as tetrahydrofuran, organic acids such as acetic acid, esters such as methyl acetate are preferable. Particularly preferred solvents are selected from ketones, ethers, organic acids and esters and have solubility parameters
A solvent of about 8.5 to 11.5 (preferably 9 to 11) is included.
【００３１】酢酸セルロースが酢化度の高いＣＤＡやＣ
ＴＡ、特にＣＴＡである場合、洗浄溶媒としては、ケト
ン類（アセトンなど）、エステル類（酢酸メチルな
ど）、炭素数２〜４の有機酸（酢酸など）、エーテル類
（テトラヒドロフランなど）などが好ましい。Cellulose acetate is CDA or C having a high degree of acetylation.
In the case of TA, especially CTA, as the washing solvent, ketones (acetone etc.), esters (methyl acetate etc.), organic acids having 2 to 4 carbon atoms (acetic acid etc.), ethers (tetrahydrofuran etc.) and the like are preferable. .
【００３２】なお、洗浄溶媒として貧溶媒（例えば、水
及び／又はアルコール類など）を含む混合溶媒を用いる
場合、貧溶媒の割合が多くなると、低分子量成分の溶出
効率が損なわれる。そのため、低分子量成分に対して貧
溶媒の割合は、酢酸セルロースの低分子量成分を溶出可
能な範囲で選択でき、例えば、洗浄溶媒全体の40重量％
以下（例えば、５〜35重量％）、好ましくは30重量％以
下（例えば、10〜30重量％）程度である。When a mixed solvent containing a poor solvent (for example, water and / or alcohols) is used as the washing solvent, if the proportion of the poor solvent is large, the elution efficiency of the low molecular weight component is impaired. Therefore, the ratio of the poor solvent to the low molecular weight component can be selected within a range in which the low molecular weight component of cellulose acetate can be eluted, for example, 40% by weight of the entire washing solvent.
It is below (for example, 5 to 35% by weight), preferably below 30% by weight (for example, 10 to 30% by weight).
【００３３】酢酸セルロースの洗浄処理に際して、酢酸
セルロースは、種々の形態、例えば、粉末状、粒状、繊
維状、フレーク状などのいずれであってもよい。酢酸セ
ルロースの洗浄処理は、慣用の方法、例えば、前記溶媒
中に酢酸セルロースを浸漬又は分散させる方法、前記溶
媒を酢酸セルロースに湿潤又は含浸させた後、必要に応
じて溶媒を追加し、溶媒を遠心分離などにより分離する
方法などが挙げられる。洗浄処理は、必要に応じて、低
分子量成分の溶出効率を高めるため、加温又は加熱下、
例えば、30℃〜溶媒の沸点の範囲（例えば、40〜90℃程
度）で行ってもよい。洗浄処理に際して、酢酸セルロー
スの１〜50重量％、好ましくは３〜30重量％、さらに好
ましくは５〜20重量％（例えば、５〜15重量％）程度を
洗い出す場合が多い。In the washing treatment of the cellulose acetate, the cellulose acetate may be in any of various forms, for example, powder, granules, fibers and flakes. Washing treatment of cellulose acetate is a conventional method, for example, a method of dipping or dispersing cellulose acetate in the solvent, after wetting or impregnating the solvent to the cellulose acetate, if necessary add a solvent, the solvent Examples include a method of separating by centrifugation or the like. The washing treatment is, if necessary, under heating or heating in order to enhance the elution efficiency of low molecular weight components,
For example, it may be carried out in the range of 30 ° C to the boiling point of the solvent (for example, about 40 to 90 ° C). In the washing treatment, 1 to 50% by weight, preferably 3 to 30% by weight, and more preferably 5 to 20% by weight (for example, 5 to 15% by weight) of cellulose acetate is often washed out.
【００３４】前記溶媒の使用量は、特に制限されず、広
い範囲から選択でき、例えば、酢酸セルロース 100重量
部に対して、50〜5000重量部、好ましくは 100〜2500重
量部程度である場合が多い。溶媒による洗浄処理に供さ
れた酢酸セルロースは、通常、濾過、遠心分離などによ
り分離され、乾燥される。The amount of the solvent used is not particularly limited and can be selected from a wide range, for example, 50 to 5000 parts by weight, preferably 100 to 2500 parts by weight, relative to 100 parts by weight of cellulose acetate. Many. Cellulose acetate that has been subjected to a washing treatment with a solvent is usually separated by filtration, centrifugation or the like and dried.
【００３５】このようにして得られた酢酸セルロースを
成形材料として用いると、成形品の強度に影響を及ぼす
平均分子量を低下させることなく、成形品の生産性を高
めることができる。本発明の酢酸セルロースは、成形法
の種類に応じた種々の形態（例えば、粉末状、ペレット
状など）で成形に供してもよいが、溶媒に対する高い溶
解性を維持しているとともに、溶液粘度が小さいので、
通常、酢酸セルロース溶液（ドープ）として使用され
る。酢酸セルロース溶液を用いた代表的な成形法として
は、例えば、スピン法なども含む流延法によるフィルム
やシート（写真用フィルムなど）の製造、紡糸法による
繊維の製造などが挙げられる。さらに、本発明の酢酸セ
ルロースは、溶液粘度が小さいので、他の用途、例え
ば、プラスチック、塗料のラッカー、電気絶縁材などの
用途にも利用できる。なお、酢酸セルロース溶液は、酢
酸セルロースの種類に応じて、良溶媒を用いることによ
り調製でき、良溶媒は、前記例示の溶媒（例えば、ジク
ロロメタンなどのハロゲン化炭化水素など）などから適
当に選択できる。When the cellulose acetate thus obtained is used as a molding material, the productivity of the molded product can be improved without lowering the average molecular weight which affects the strength of the molded product. The cellulose acetate of the present invention may be subjected to molding in various forms depending on the type of molding method (for example, powder form, pellet form, etc.), while maintaining high solubility in a solvent and solution viscosity. Is small,
Usually, it is used as a cellulose acetate solution (dope). Typical molding methods using a cellulose acetate solution include, for example, production of films and sheets (such as photographic films) by a casting method including a spin method, production of fibers by a spinning method, and the like. Furthermore, since the cellulose acetate of the present invention has a low solution viscosity, it can be used in other applications such as plastics, paint lacquers, and electrical insulating materials. The cellulose acetate solution can be prepared by using a good solvent according to the type of cellulose acetate, and the good solvent can be appropriately selected from the solvents exemplified above (for example, halogenated hydrocarbons such as dichloromethane). .
【００３６】本発明の酢酸セルロースの成形に際して
は、他のセルロースエステル（例えば、セルロースプロ
ピオネート、セルロースブチレートなどの有機酸エステ
ル、硝酸セルロース、硫酸セルロース、リン酸セルロー
スなどの無機酸エステル）などを併用してもよい。ま
た、酢酸セルロースには、必要に応じて、前記溶媒に加
えて、種々の添加剤、例えば、エステル系可塑剤（例え
ば、トリアセチン、トリエチレングリコールジアセテー
ト、トリエチレングリコールジプロピオネート、ジブチ
ルフタレート、ジメトキシエチルフタレート、クエン酸
トリエチルエステルなど）、無機粉体（例えば、カオリ
ン、タルク、ケイソウ土、石英、炭酸カルシウム、硫酸
バリウム、酸化チタン、アルミナなど）、熱安定化剤
（例えば、カルシウム、マグネシウムなどのアルカリ土
類金属の塩など）、着色剤などを添加してもよい。In molding the cellulose acetate of the present invention, other cellulose esters (eg, organic acid esters such as cellulose propionate and cellulose butyrate, inorganic acid esters such as cellulose nitrate, cellulose sulfate, and cellulose phosphate), etc. You may use together. Further, cellulose acetate, if necessary, in addition to the solvent, various additives, for example, ester plasticizers (e.g., triacetin, triethylene glycol diacetate, triethylene glycol dipropionate, dibutyl phthalate, Dimethoxyethyl phthalate, citric acid triethyl ester etc.), inorganic powder (eg kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, alumina etc.), heat stabilizer (eg calcium, magnesium etc.) Alkaline earth metal salts, etc.), colorants and the like may be added.
【００３７】[0037]
【発明の効果】本発明の酢酸セルロースは、分子量分布
Ｍｗ／Ｍｎが小さく、低分子量成分が除去されているの
で、重合度を低下させることなく、溶液粘度を低下で
き、成形性を高めることができる。また、酢酸セルロー
スは平均重合度及び平均置換度が高いにも拘らず、溶媒
に対する溶解性及び成形性が高い。そのため、溶液粘度
が小さな酢酸セルロース溶液を用い、加工速度が大きな
成形法により、耐湿性、寸法精度の高い成形品を得る上
で有用である。本発明の方法では、溶媒による洗浄処理
という簡単な操作で、前記の如き優れた特性を有する酢
酸セルロースを製造できる。INDUSTRIAL APPLICABILITY The cellulose acetate of the present invention has a small molecular weight distribution Mw / Mn and has a low molecular weight component removed, so that the solution viscosity can be lowered and the moldability can be enhanced without lowering the polymerization degree. it can. In addition, although cellulose acetate has a high average degree of polymerization and a high degree of substitution, it has high solubility and moldability in a solvent. Therefore, it is useful for obtaining a molded article with high moisture resistance and dimensional accuracy by using a cellulose acetate solution having a small solution viscosity and a molding method having a high processing speed. According to the method of the present invention, cellulose acetate having excellent properties as described above can be produced by a simple operation of washing with a solvent.
【００３８】[0038]
【実施例】以下に、実施例及び比較例に基づいて本発明
をより詳細に説明する。なお、実施例及び比較例におい
て、濃厚溶液の粘度は、前記「落球粘度法」に従って測
定した。また、分子量、分子量分布、酢化度、粘度平均
重合度、フィルムの力学物性、アセトン抽出分は次のよ
うにして測定した。EXAMPLES The present invention will be described in more detail below based on examples and comparative examples. In the examples and comparative examples, the viscosity of the concentrated solution was measured according to the “falling ball viscosity method”. Further, the molecular weight, the molecular weight distribution, the degree of acetylation, the viscosity average degree of polymerization, the mechanical properties of the film, and the acetone extracted content were measured as follows.
【００３９】（１）分子量及び分量分布 ゲル濾過カラムに、屈折率、光散乱を検出する検出器を
接続した高速液体クロマトグラフィーシステム「GPC-LA
LLS 」を用いて測定した。測定条件は、以下の通りであ
る。 溶媒：メチレンクロラロイド カラム：ＧＭＨｘ１（東ソー（株）製） 試料濃度：0.1 ％(w/v) 流量：１ml／分 試料注入量：300 μl 標準試料：ポリメタクリル酸メチル（Ｍｗ＝188,200) 温度：23℃。(1) Molecular weight and molecular weight distribution A high performance liquid chromatography system "GPC-LA" in which a detector for detecting refractive index and light scattering is connected to a gel filtration column.
LLS ”. The measurement conditions are as follows. Solvent: Methylenechloroid Column: GMHx1 (manufactured by Tosoh Corporation) Sample concentration: 0.1% (w / v) Flow rate: 1 ml / min Sample injection amount: 300 μl Standard sample: Polymethylmethacrylate (Mw = 188,200) Temperature: 23 ° C.
【００４０】（２）酢化度（％） 酢化度はケン化法により測定できる。すなわち、乾燥し
たＣＴＡなどの酢酸セルロースを精秤し、アセトンとジ
メチルスルホキシドとの混合溶媒（容量比４：１）に溶
解した後、所定量の１Ｎ−水酸化ナトリウム水溶液を添
加し、25℃で２時間ケン化する。フェノールフタレイン
を指示薬として添加し、１Ｎ−硫酸（濃度ファクター：
Ｆ）で過剰の水酸化ナトリウムを滴定する。また、上記
と同様の方法により、ブランクテストを行う。そして、
下記式に従って酢化度を算出する。 酢化度（％）＝(6.005×（Ｂ−Ａ）×Ｆ）／Ｗ （式中、Ａは試料の滴定に要した１Ｎ−硫酸のml数、Ｂ
はブランクテストの滴定に要した１Ｎ−硫酸のml数、Ｆ
は１Ｎ−硫酸の濃度ファクター、Ｗは試料重量を示
す）。(2) Acetylation degree (%) The acetylation degree can be measured by a saponification method. That is, dry cellulose acetate such as CTA is precisely weighed and dissolved in a mixed solvent of acetone and dimethyl sulfoxide (volume ratio 4: 1), and then a predetermined amount of 1N-sodium hydroxide aqueous solution is added, and the mixture is added at 25 ° C. Saponify for 2 hours. Phenolphthalein was added as an indicator, and 1N-sulfuric acid (concentration factor:
Excess sodium hydroxide is titrated in F). In addition, a blank test is performed by the same method as above. And
The acetylation degree is calculated according to the following formula. Acetification degree (%) = (6.005 × (B−A) × F) / W (where A is the number of ml of 1N-sulfuric acid required for titration of the sample, B
Is the number of ml of 1N-sulfuric acid required for titration in the blank test, F
Is the concentration factor of 1N-sulfuric acid, and W is the sample weight).
【００４１】（３）粘度平均重合度（DP）の測定方法、
及び算出方法 絶乾した酢酸セルロース約 0.2ｇ（精秤）を、メチレン
クロライド：エタノール＝９：１の溶液 100mlに溶解す
る。これをオストワルド粘度計にて25℃で溶液の落下秒
数を測定する。重合度を以下の式によって求める。 ηrel ＝ T／T0 T ：測定試料溶液の落下秒数 〔η〕＝（lnηrel ）／c T0 ：溶剤単独の落下秒数 DP＝〔η〕／km c ：濃度（ｇ／ｌ） km ：６×10-4。(3) Method of measuring viscosity average degree of polymerization (DP),
And calculation method About 0.2 g (exact balance) of absolutely dried cellulose acetate is dissolved in 100 ml of a solution of methylene chloride: ethanol = 9: 1. This is measured at 25 ° C. with an Ostwald viscometer for the number of seconds that the solution falls. The degree of polymerization is calculated by the following formula. η rel = T / T 0 T: Falling seconds of measurement sample solution [η] = (ln η rel ) / c T 0 : Falling seconds of solvent alone DP = [η] / km c: Concentration (g / l) km: 6 × 10 -4 .
【００４２】（４）フィルム調製方法 力学強度の測定に供するフィルムは、所定量の酢酸セル
ロース、可塑剤を溶媒に溶解し、濾過した後、ガラス板
上でクリアランスおよび流延速度が一定になるように流
延し、乾燥することにより調整した。(4) Film preparation method The film to be used for the measurement of mechanical strength was prepared by dissolving a predetermined amount of cellulose acetate and a plasticizer in a solvent, filtering the solution, and keeping the clearance and the casting rate constant on the glass plate. It was adjusted by casting it in a plate and drying it.
【００４３】（５）フィルムの力学物性 フィルムの力学強度は引張強度、耐折強度、引裂
強度、引張伸度の４種の試験を行った。それぞれの評
価方法を以下に示す。 引張強度の測定 10cmに切り出したフィルムをISO1184-1983の規格に従
い、初期試料長５cm引張速度20mm／分で引っ張り、切断
時の荷重から求めた。 耐折強度の測定 12cmの長さに切り出したフィルムをISO8776-1988の規格
に従って、折り曲げによって切断するまでの往復回数を
測定した。 引裂強度の測定 ５×6.4cm に切り出したフィルムをISO6383/2-1983の規
格に従って、引裂に要した引裂荷重を求めた。 引張伸度の測定 10cmに切り出したフィルムをISO1184-1983の規格に従
い、初期試料長５cm引張速度20mm／分で引っ張り、切断
時のフィルム伸度から求めた。(5) Mechanical Properties of Film The mechanical strength of the film was subjected to four tests of tensile strength, folding endurance, tear strength and tensile elongation. The respective evaluation methods are shown below. Measurement of Tensile Strength A film cut into 10 cm was pulled according to the standard of ISO1184-1983 at an initial sample length of 5 cm and a pulling speed of 20 mm / min, and was determined from the load during cutting. Measurement of folding endurance The film cut into a length of 12 cm was measured for the number of reciprocations until the film was cut by bending according to the ISO8776-1988 standard. Measurement of Tear Strength A film cut to a size of 5 × 6.4 cm was subjected to a tear load required for tearing in accordance with the standard of ISO6383 / 2-1983. Measurement of Tensile Elongation A film cut into 10 cm was pulled according to the standard of ISO1184-1983 at an initial sample length of 5 cm and a pulling speed of 20 mm / min, and the film elongation at the time of cutting was determined.
【００４４】（６）アセトン抽出分の測定方法 酢酸セルロース２ｇをソックスレー抽出装置を用いてア
セトンを溶媒として、８時間抽出を行う。抽出残分を絶
乾し、その重量を測定することによって、アセトン抽出
分を算出した。(6) Method for Measuring Acetone Extraction Content 2 g of cellulose acetate is extracted for 8 hours using acetone as a solvent using a Soxhlet extractor. The extraction residue was completely dried, and the weight thereof was measured to calculate the acetone extraction content.
【００４５】実施例１〜４ セルロース 100重量部（水分５％含む）を酢酸36重量部
で前処理活性化した後、硫酸 7.8重量部、無水酢酸 260
重量部及び酢酸 400重量部を用いて36℃で 120分エステ
ル化した。酢酸マグネシウムで中和した後、63℃で30分
ケン化熟成することにより、ＣＴＡを得た。得られたＣ
ＴＡを４等分し、各ＣＴＡに対して、それぞれ10重量倍
の酢酸メチル（実施例１）、アセトン（実施例２）、テ
トラヒドロフラン（実施例３）、及び80％酢酸水溶液
（実施例４）を添加し、室温で 120分攪拌した後、濾
過、乾燥させることにより、精製ＣＴＡを得た。なお、
ＣＴＡの洗い出し量は、酢酸メチル（実施例１）におい
て25重量％、アセトン（実施例２）において15重量％、
テトラヒドロフラン（実施例３）において８重量％、酢
酸水溶液（実施例４）において12重量％であった。Examples 1 to 4 100 parts by weight of cellulose (containing 5% of water content) was pretreated with 36 parts by weight of acetic acid and activated, and then 7.8 parts by weight of sulfuric acid and 260 parts of acetic anhydride.
Esterification was carried out for 120 minutes at 36 ° C. using 400 parts by weight of acetic acid and 400 parts by weight of acetic acid. After neutralizing with magnesium acetate, saponification and aging for 30 minutes at 63 ° C. to obtain CTA. C obtained
TA is divided into four equal parts, and 10 times by weight of each CTA is methyl acetate (Example 1), acetone (Example 2), tetrahydrofuran (Example 3), and 80% acetic acid aqueous solution (Example 4). Was added, and the mixture was stirred at room temperature for 120 minutes, filtered, and dried to obtain purified CTA. In addition,
The amount of CTA washed out was 25% by weight with methyl acetate (Example 1) and 15% by weight with acetone (Example 2).
It was 8% by weight in tetrahydrofuran (Example 3) and 12% by weight in an aqueous acetic acid solution (Example 4).
【００４６】比較例１〜４ エステル化条件及びケン化条件を変える従来の方法によ
り、４種類の異なる分子量を持つ酢酸セルロースを作製
した。すなわち、セルロース 100重量部（水分５％含
む）を酢酸36重量部で前処理活性化した後、硫酸 7.8重
量部、無水酢酸 260重量部及び酢酸 400重量部を用いて
36〜40℃で 100〜110 分エステル化し、酢酸マグネシウ
ムで中和した後、60〜63℃で20〜40分間ケン化熟成する
ことにより、４種類の酢酸セルロースを作製した。Comparative Examples 1 to 4 Cellulose acetate having four different molecular weights was prepared by a conventional method in which esterification conditions and saponification conditions were changed. That is, 100 parts by weight of cellulose (containing 5% of water content) was pretreated with 36 parts by weight of acetic acid, and then 7.8 parts by weight of sulfuric acid, 260 parts by weight of acetic anhydride and 400 parts by weight of acetic acid were used.
Four kinds of cellulose acetate were prepared by esterification at 36-40 ° C for 100-110 minutes, neutralization with magnesium acetate, and saponification aging at 60-63 ° C for 20-40 minutes.
【００４７】比較例５ 実施例１で得られたＣＴＡを、低分子量成分に対する貧
溶媒を用いて洗浄処理した。すなわち、実施例１で得ら
れたＣＴＡに対して、10重量倍の酢酸水溶液（酢酸／水
＝５／５（重量比））を用い、実施例１と同様にして洗
浄処理し、濾過、乾燥することにより酢酸セルロースを
得た。Comparative Example 5 The CTA obtained in Example 1 was washed with a poor solvent for low molecular weight components. That is, with respect to the CTA obtained in Example 1, 10 times by weight aqueous acetic acid solution (acetic acid / water = 5/5 (weight ratio)) was used, washed in the same manner as in Example 1, filtered, and dried. By doing so, cellulose acetate was obtained.
【００４８】前記実施例及び比較例で得られた酢酸セル
ロースの酢化度、分子量（Ｍｎ，Ｍｗ）、分子量分布及
び濃厚溶液の粘度（落球粘度法１）を表１に、アセトン
抽出分、粘度平均重合度（DP）、粘度平均重合度と濃厚
溶液落球粘度（落球粘度法２）の関係、フィルム物性を
表２に示す。また、重量平均分子量と落球粘度（落球粘
度法１）との関係を図１に示す。The degree of acetylation, the molecular weight (Mn, Mw), the molecular weight distribution and the viscosity of the concentrated solution (falling ball viscosity method 1) of the cellulose acetates obtained in the above Examples and Comparative Examples are shown in Table 1, and the acetone extracted content and the viscosity are shown. Table 2 shows the relationship between the average degree of polymerization (DP) and the viscosity average degree of polymerization and the falling solution viscosity of the concentrated solution (falling ball viscosity method 2) and the film physical properties. The relationship between the weight average molecular weight and falling ball viscosity (falling ball viscosity method 1) is shown in FIG.
【００４９】[0049]
【表１】 [Table 1]
【００５０】[0050]
【表２】 [Table 2]
【００５１】表１、表２及び図１からも明らかなよう
に、実施例で得られた酢酸セルロースは、同じ分子量で
比較すると、比較例の酢酸セルロースよりも、溶液粘度
が低い。As is clear from Tables 1 and 2 and FIG. 1, the cellulose acetates obtained in Examples have lower solution viscosities than the cellulose acetates of Comparative Examples when compared with the same molecular weight.
【００５２】実施例５ 常法により得られた酢酸セルロース（酢化度60.9％、粘
度平均重合度299)を10重量倍のアセトン中、室温で30分
攪拌し、脱液、乾燥させて、アセトン可溶分 0.4％の酢
酸セルロースを得た。その性状は、平均酢化度60.9％、
粘度平均重合度322、分子量分布1.59であった。一方、
アセトン中に抽出除去された成分は、原料重量に対して
12重量％存在し、その性状は、酢化度60.9％、粘度平均
重合度196 であった。得られた低重合度物除去試料のフ
ィルム物性を表３に示す。また、この試料の粘度平均重
合度と濃厚溶液落球粘度の関係は、ln（η）＝4.66で4.
50＜ln（η）＜4.85＜4.98となり、式(1) 及び式(2) を
満たすものであった。Example 5 Cellulose acetate obtained by a conventional method (acetylation degree 60.9%, viscosity average degree of polymerization 299) was stirred in 10 times by weight of acetone at room temperature for 30 minutes, deliquored and dried to give acetone. Cellulose acetate having a soluble content of 0.4% was obtained. The property is that the average degree of acetylation is 60.9%,
The viscosity average degree of polymerization was 322 and the molecular weight distribution was 1.59. on the other hand,
The components extracted and removed in acetone are
It was present in an amount of 12% by weight, and its properties were an acetylation degree of 60.9% and a viscosity average degree of polymerization of 196. Table 3 shows the film physical properties of the obtained sample with a low degree of polymerization removed. The relationship between the viscosity-average degree of polymerization of this sample and the viscosity of the concentrated solution falling ball is ln (η) = 4.66.
50 <ln (η) <4.85 <4.98, which satisfies the formulas (1) and (2).
【００５３】比較例６ 実施例１で合成したアセトン洗浄前の酢酸セルロース
（アセトン可溶分12％）を用いた。この試料の粘度平均
重合度と濃厚溶液落球粘度との関係は、ln（η）＝4.31
で4.29＜ln（η）＜4.39＜4.44となり、式(1) 及び式
(2) を満たすものであった。また、分子量分布は、2.20
であった。そのフィルム性状を表１に示す。Comparative Example 6 Cellulose acetate (acetone-soluble matter 12%) synthesized in Example 1 before washing with acetone was used. The relationship between the viscosity average degree of polymerization of this sample and the viscosity of the concentrated solution falling ball is ln (η) = 4.31
4.29 <ln (η) <4.39 <4.44, and the formula (1) and the formula
(2) was satisfied. The molecular weight distribution is 2.20.
Met. The film properties are shown in Table 1.
【００５４】比較例７ 常法により平均酢化度60.8、粘度平均重合度 314の酢酸
セルロースを得た。この試料はアセトン可溶分13％を含
んでいる。この試料の粘度平均重合度と濃厚溶液落球粘
度との関係は、ln（η）＝4.74であり、4.43＜4.69＜ln
（η）＜4.80となり式(1) は満たすものの、式(2) を満
たすものではなかった。また、分子量分布は、2.07であ
った。このもののフィルム物性を表１に示す。Comparative Example 7 Cellulose acetate having an average degree of acetylation of 60.8 and a viscosity average degree of polymerization of 314 was obtained by a conventional method. This sample contains 13% acetone solubles. The relationship between the viscosity average degree of polymerization of this sample and the viscosity of the concentrated solution falling ball is ln (η) = 4.74, and 4.43 <4.69 <ln
(Η) <4.80, which satisfies the expression (1), but does not satisfy the expression (2). The molecular weight distribution was 2.07. The physical properties of the film of this product are shown in Table 1.
【００５５】比較例８ 常法により平均酢化度61.7％、粘度平均重合度 291の酢
酸セルロースを得た。この試料はアセトン可溶分12％を
含んでいる。この試料の粘度平均重合度と濃厚溶液落球
粘度との関係は、ln（η）＝4.68であり、4.21＜4.22＜
4.24＜ln（η）となり式(1) 及び式(2) を満たすもので
はなかった。また、分子量分布は、２．１１であった。
このもののフィルム物性を表１に示す。Comparative Example 8 Cellulose acetate having an average degree of acetylation of 61.7% and a viscosity average degree of polymerization of 291 was obtained by a conventional method. This sample contains 12% acetone solubles. The relationship between the viscosity average degree of polymerization of this sample and the viscosity of the concentrated solution falling ball is ln (η) = 4.68, 4.21 <4.22 <
4.24 <ln (η) was obtained, which did not satisfy the formulas (1) and (2). The molecular weight distribution was 2.11.
The physical properties of the film of this product are shown in Table 1.
【００５６】[0056]
【表３】 [Table 3]
【図１】図１は、実施例１〜４及び比較例１〜５で得ら
れた酢酸セルロースの重量平均分子量と落球粘度との関
係を示すグラフである。FIG. 1 is a graph showing the relationship between the weight average molecular weight of cellulose acetate obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and falling ball viscosity.
Claims (15)
ーによる分子量分布Ｍｗ／Ｍｎが１〜1.7 である成形性
の高い酢酸セルロース。1. A cellulose acetate having a high moldability, which has a molecular weight distribution Mw / Mn of 1 to 1.7 by gel permeation chromatography.
分布Ｍｗ／Ｍｎが1.2 〜1.7 である請求項１記載の酢酸
セルロース。2. The cellulose acetate according to claim 1, which has an average acetylation degree of 52 to 62.5% and a molecular weight distribution Mw / Mn of 1.2 to 1.7.
量分布Ｍｗ／Ｍｎが1.4 〜1.65である請求項１記載の酢
酸セルロース。3. The cellulose acetate according to claim 1, which has an average acetylation degree of 59.0 to 62.5% and a molecular weight distribution Mw / Mn of 1.4 to 1.65.
重合度（DP）が 290以上であり、かつ粘度平均重合度
（DP）に対する落球粘度法による濃厚溶液粘度（η）が
下記の式(1) で表されることを特徴とする請求項１〜３
のいずれか１項に記載の酢酸セルロース。 2.814×ln(DP)-11.753 ≦ln（η）≦7.28×ln(DP)-37.059 (1) 4. The acetone-extracted content is 5% or less, the viscosity-average degree of polymerization (DP) is 290 or more, and the viscosity of the concentrated solution (η) according to the falling-ball viscosity method is the following formula. It is represented by (1), Claims 1-3 characterized by the above-mentioned.
The cellulose acetate according to any one of 1. 2.814 x ln (DP) -11.753 ≤ ln (η) ≤ 7.28 x ln (DP) -37.059 (1)
法による濃厚溶液粘度（η）が下記の式(2) で表される
ことを特徴とする請求項４記載の酢酸セルロース。 2.814×ln(DP)-11.753 ≦ln（η）≦6.29×ln(DP)-31.469 (2) 5. The cellulose acetate according to claim 4, wherein the concentrated solution viscosity (η) by the falling ball viscosity method with respect to the viscosity average degree of polymerization (DP) is represented by the following formula (2). 2.814 x ln (DP) -11.753 ≤ ln (η) ≤ 6.29 x ln (DP) -31.469 (2)
る請求項４又は５記載の酢酸セルロース。6. The cellulose acetate according to claim 4, which has a viscosity average degree of polymerization (DP) of 290 to 400.
る溶媒を用いて、酢酸セルロースを洗浄し、請求項１〜
６の何れか１項に記載の酢酸セルロースを製造する方
法。7. The cellulose acetate is washed with a solvent that elutes the low molecular weight component of the cellulose acetate,
7. The method for producing the cellulose acetate according to any one of 6 above.
部分的に溶解する溶媒である請求項７記載の酢酸セルロ
ースの製造方法。8. The method for producing cellulose acetate according to claim 7, wherein the washing solvent is a solvent that swells or partially dissolves cellulose acetate.
量％で酢酸セルロースを分散させたとき、酢酸セルロー
スの 0.1〜30重量％を溶解する溶媒である請求項７又は
８記載の酢酸セルロースの製造方法。9. The acetic acid according to claim 7, wherein the washing solvent is a solvent that dissolves 0.1 to 30% by weight of cellulose acetate when the cellulose acetate is dispersed at a temperature of 25 ° C. and a solid content concentration of 5% by weight. Method for producing cellulose.
重量％を洗い出す請求項７〜９のいずれかの項に記載の
酢酸セルロースの製造方法。10. By washing, 1 to 50 of cellulose acetate is obtained.
The method for producing cellulose acetate according to claim 7, wherein the weight% is washed out.
ーδが７〜12.5である溶媒で洗浄する請求項７記載の酢
酸セルロースの製造方法。11. The method for producing cellulose acetate according to claim 7, wherein the cellulose acetate is washed with a solvent having a solubility parameter δ of 7 to 12.5.
有機酸及びエステル類から選択された少なくとも一種の
溶媒である請求項７〜11のいずれか１項に記載の酢酸セ
ルロースの製造方法。12. The washing solvent comprises ketones, ethers,
The method for producing cellulose acetate according to any one of claims 7 to 11, which is at least one solvent selected from organic acids and esters.
である請求項12記載の酢酸セルロースの製造方法。13. The method for producing cellulose acetate according to claim 12, wherein the washing solvent is acetone or methyl acetate.
ルロースを、ケトン類、エーテル類、有機酸及びエステ
ル類から選択され、かつ溶解度パラメーターが 8.5〜1
1.5の溶媒で洗浄処理する請求項７記載の酢酸セルロー
スの製造方法。14. Cellulose triacetate having an average acetylation degree of 59.0 to 62.5% is selected from ketones, ethers, organic acids and esters, and has a solubility parameter of 8.5 to 1
The method for producing cellulose acetate according to claim 7, wherein the cellulose acetate is washed with a solvent of 1.5.
に、酢酸セルロースの低分子量成分を溶出可能な洗浄溶
媒を用いる請求項14記載の酢酸セルロースの製造方法。15. The method for producing cellulose acetate according to claim 14, which further comprises water or alcohol and uses a washing solvent capable of eluting low-molecular weight components of cellulose acetate.
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|---|---|---|---|
| JP06260296A JP3942668B2 (en) | 1995-03-31 | 1996-03-19 | Highly moldable cellulose acetate and process for producing the same |
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|---|---|---|---|
| JP10071195 | 1995-03-31 | ||
| JP7-100711 | 1995-03-31 | ||
| JP8555095 | 1995-04-11 | ||
| JP7-85550 | 1995-04-11 | ||
| JP06260296A JP3942668B2 (en) | 1995-03-31 | 1996-03-19 | Highly moldable cellulose acetate and process for producing the same |
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| JP3942668B2 JP3942668B2 (en) | 2007-07-11 |
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ID=27297892
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|---|---|---|---|
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