WO2022181791A1 - フィルム製造用ドープ、及びアクリル系樹脂フィルム - Google Patents
フィルム製造用ドープ、及びアクリル系樹脂フィルム Download PDFInfo
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- WO2022181791A1 WO2022181791A1 PCT/JP2022/008027 JP2022008027W WO2022181791A1 WO 2022181791 A1 WO2022181791 A1 WO 2022181791A1 JP 2022008027 W JP2022008027 W JP 2022008027W WO 2022181791 A1 WO2022181791 A1 WO 2022181791A1
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- Prior art keywords
- acrylic resin
- dope
- film
- weight
- polymer particles
- Prior art date
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- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 176
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 176
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
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- 239000002904 solvent Substances 0.000 claims abstract description 64
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- -1 oxygen anion Chemical class 0.000 claims description 43
- 229910019142 PO4 Inorganic materials 0.000 claims description 23
- 239000010452 phosphate Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
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- UUNNUENETDBNPB-HKBOAZHASA-N (2s)-2-[[(2s,3r)-3-amino-2-hydroxy-4-(4-phenylmethoxyphenyl)butanoyl]amino]-4-methylpentanoic acid Chemical compound C1=CC(C[C@@H](N)[C@H](O)C(=O)N[C@@H](CC(C)C)C(O)=O)=CC=C1OCC1=CC=CC=C1 UUNNUENETDBNPB-HKBOAZHASA-N 0.000 description 29
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
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- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
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- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 238000009792 diffusion process Methods 0.000 description 4
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- 239000012046 mixed solvent Substances 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
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- 229920003023 plastic Polymers 0.000 description 4
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 3
- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 3
- 125000000686 lactone group Chemical group 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
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- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
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- IUGNCEABJSRDPG-UHFFFAOYSA-N 2,2,2-trichloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(Cl)(Cl)Cl IUGNCEABJSRDPG-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical class C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical class C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical class CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- CNTXYLCDFKRSRI-UHFFFAOYSA-N phosphoric acid;1-tridecoxytridecane Chemical compound OP(O)(O)=O.CCCCCCCCCCCCCOCCCCCCCCCCCCC CNTXYLCDFKRSRI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- 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
Definitions
- the present invention relates to a dope for film production and an acrylic resin film.
- TAC triacetyl cellulose
- polarizer protective films for liquid crystal displays.
- liquid crystal display screens have become larger and higher definition, and the mainstream shipping method is a panel semi-finished product called an open cell, which is not equipped with a backlight module. Under such circumstances, the problem of deterioration in image quality due to warping of panels during transportation due to the high moisture permeability and water absorbency of TAC films has become apparent.
- Acrylic resin film is attracting attention as an alternative film to TAC film because it has excellent optical properties, low moisture permeability, and low water absorption.
- Methods for producing acrylic resin films include a melt extrusion method using a T-die, a solution casting method in which a dope obtained by dissolving a resin in a solvent is cast on the surface of a support, and then the solvent is evaporated to form a film. It has been known.
- the melt extrusion method using a T-die is disadvantageous in that the resulting film tends to have a difference in physical properties between the direction of extrusion and the direction perpendicular to it, and tends to cause residual orientation.
- the solution casting method there is little physical stress applied to the film during film formation, so there is an advantage that polymer orientation is less likely to occur and the strength and optical properties of the film become isotropic.
- the solution casting method has the advantage that the viscosity of the solution can be lowered by adjusting the type of solvent and the concentration of the solid content, and the solution can be filtered with high accuracy.
- the solution casting method has recently been studied as an effective film-forming method, such as obtaining a film containing less foreign matter.
- acrylic resin alone is generally brittle.
- multi-layer structure polymer particles called core-shell rubber are blended with the acrylic resin.
- Patent Document 1 as a dope for a solution casting method, a thermoplastic acrylic resin, a multilayer structure polymer particle having a defined average particle size and a degree of swelling with methyl ethyl ketone, and a specific Hansen solubility parameter It is described that a dope with reduced generation of turbidity (haze) can be provided by containing a solvent having a
- Patent Document 2 describes an acrylic resin film containing an N-substituted maleimide monomer as a film with excellent dimensional stability against humidity changes.
- Patent Document 2 in a film, multi-layer structure polymer particles are added to an acrylic resin in order to improve mechanical strength, and gaps between the acrylic resin and multi-layer structure polymer particles are filled to improve dimensional stability.
- the use of surfactants is exemplified for this purpose.
- the multi-layer structure polymer particles have poor compatibility with the resin solution. If the compatibility between the resin solution and the multilayer structure polymer particles is poor, the multilayer structure polymer particles will aggregate. Aggregation of the particles of the multilayer structure may cause haze during film formation and defects in the appearance of the film. In addition, in the techniques of Patent Documents 1 and 2, even when the multi-layered structure particles are well dispersed in the dope at the time of dope preparation, and the dope has a small haze, the dope is stored over time. The aggregation of the multi-layer structure polymer particles may increase the haze of the film formed using the dope.
- the present inventors found that when preparing a dope containing a thermoplastic acrylic resin having a molecular weight of 500,000 or more and multi-layer structure polymer particles, monoester phosphate having a specific structure
- a system surfactant as a dispersant to the dope and adjusting the solid content concentration of the dope to 3 to 30% by weight
- the acrylic resin film produced by the solution casting method has a multilayer structure.
- the present inventors have found that a film with good appearance and high transparency can be stably obtained without any defect or deterioration of haze caused by aggregation of polymer particles, thereby completing the present invention.
- the present invention (I) A dope for film production, comprising a thermoplastic acrylic resin, multilayer structure polymer particles, and a solvent,
- the film-manufacturing dope contains a phosphate monoester surfactant represented by the following formula (1),
- the solid content concentration of the dope for film production is 3 to 30% by weight
- the thermoplastic acrylic resin has a weight average molecular weight of 500,000 or more
- Dope for film production wherein, R represents a combination of a hydroxy group or an oxygen anion and a monovalent cation.n represents an integer of 1 to 20, and m represents an integer of 1 to 20.
- the phosphoric acid monoester surfactant is 0.01 to 3.0% by weight with respect to the total 100% by weight of the thermoplastic acrylic resin and the multilayer structure polymer particles, (I) The dope according to any one of (III).
- thermoplastic acrylic resin contains 1 to 50% by weight of maleimide units.
- (VII) Any one of (I) to (VI), wherein 10 to 50 parts by weight of the multi-layered polymer particles are contained in a total of 100 parts by weight of the thermoplastic acrylic resin and the multi-layered polymer particles. Dope described in one.
- thermoplastic acrylic resin contains a phosphate monoester surfactant represented by the following formula (1),
- the thermoplastic acrylic resin has a weight average molecular weight of 500,000 or more, An acrylic resin film having a haze of 2% or less.
- R represents a combination of a hydroxy group or an oxygen anion and a monovalent cation.n represents an integer of 1 to 20, and m represents an integer of 1 to 20.
- aggregation of the multi-layer structure polymer particles in the dope over time is suppressed, and even when the dope stored after preparation of the dope is used to form a film, there are no aggregation defects and deterioration of the external haze.
- a dope that can stably produce an acrylic resin film with excellent appearance, and an acrylic resin film that can be produced using the dope and has excellent appearance without cohesive defects and deterioration of external haze. can provide.
- Such an acrylic resin film can be suitably used as an optical film for liquid crystal display members, particularly as a polarizer protective film.
- the dope is prepared by dispersing the multilayer structure polymer particles in the solvent and dissolving the thermoplastic acrylic resin. Dopes are commonly used to produce acrylic resin films using solution casting methods.
- the multilayer structure polymer particles are well dispersed in the state of dispersion.
- a dope state in which a thermoplastic acrylic resin is added and dissolved in a dispersion liquid, the dispersibility of the multilayer structure polymer particles is deteriorated and aggregates over time.
- the haze of the resin film is increased when the dope in which the multi-layer structure polymer particles are aggregated is used to form a film by the solution casting method.
- the present inventors have investigated a method for providing a dope that can suppress the aggregation of multi-layer structure polymer particles even during long-term storage.
- a dope containing multilayer structure polymer particles, a phosphate monoester surfactant having a specific structure, and a solvent and having a solid content concentration of 3 to 30% by weight is obtained, so that the multilayer structure polymer particles during storage of the dope are improved. It was found that aggregation over time was suppressed.
- Multilayer structure polymer particles are generally synthesized by emulsion polymerization, polymerized latex is aggregated with a coagulant (mainly a metal salt of polyvalent cation), and recovered as powder. A washing step then removes excess emulsifier and coagulant. However, not a little emulsifier, coagulant and emulsifier salt remain on the particle surface. The presence of such an emulsifier salt increases the polarity of the multilayer structure polymer particle surface. If the surface polarity of the multilayer structure polymer particles is high, the affinity between the multilayer structure polymer particles and the thermoplastic acrylic resin is low when the thermoplastic acrylic resin is dissolved.
- a coagulant mainly a metal salt of polyvalent cation
- the solvent and co-solvent are determined from the viewpoint of resin dissolution rate, metal releasability, and drying rate. Solvents and co-solvents should be applicable in a wide range of solvent compositions. Also, the viscosity can be adjusted by adjusting the solid content concentration. An excessively high solid content concentration is not preferable because the pressure loss during passage through the polymer filter is large, and defects in appearance such as surface roughness and streaks occur during film formation.
- the phosphoric acid group is adsorbed to the above emulsifier salt, effectively dispersing and solubilizing, thereby suppressing the highly polar state of the particle surface. It is conceivable that.
- the present inventors have found that this action works without greatly affecting the composition and viscosity of the solvent.
- the present inventors have found that when the solid content concentration in the dope is higher than a certain level, the distance between particles becomes small, making it difficult to disperse the dope.
- the dope contains a thermoplastic acrylic resin, multi-layer structure polymer particles, a phosphate monoester surfactant with a specific structure, and a solvent.
- a dope is a dope used to produce films by solution casting.
- the thermoplastic acrylic resin, multi-layer structure polymer particles, and phosphate monoester surfactant are dissolved or dispersed in the solvent. Each component will be described below.
- thermoplastic acrylic resin has a molecular weight of 500,000 or more.
- the thermoplastic acrylic resin may be a resin having a monomer unit containing a (meth)acrylic acid ester as a structural unit.
- a known thermoplastic acrylic resin can be used as the thermoplastic acrylic resin.
- thermoplastic acrylic resins containing structural units derived from methacrylate esters are preferred.
- the thermoplastic acrylic resin preferably contains 30 to 100% by weight of a methacrylic acid alkyl ester unit having 1 to 4 carbon atoms in the alkyl group of the ester moiety. More preferably, it contains up to 100% by weight, more preferably 70 to 100% by weight.
- a methyl methacrylate unit is particularly preferable because of its high heat resistance.
- the amount of other vinyl-based monomer units copolymerizable with methyl methacrylate is preferably 70 to 0% by weight, more preferably 50 to 0% by weight, based on the weight of the thermoplastic acrylic resin. more preferably 30 to 0% by weight.
- a (meth)acrylic acid ester having an alkyl group having 1 to 10 carbon atoms is preferable.
- methyl methacrylate is excluded from the (meth)acrylic acid ester.
- Other vinyl monomers copolymerizable with methyl methacrylate specifically include ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, and methacryl.
- octyl acid glycidyl methacrylate, epoxycyclohexylmethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dicyclopentanyl methacrylate, 2,2,2-trifluoroethyl methacrylate , 2,2,2-trichloroethyl methacrylate, methacrylic acid esters such as isobornyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, glycidyl acrylate , acrylate esters such as epoxycyclohexylmethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate; (meth)acrylamides such as methacrylamide, acrylamide, N-methylol
- methacrylic acid esters other than methyl methacrylate together with methyl methacrylate for the production of thermoplastic acrylic resins.
- methacrylic acid esters include the methacrylic acid esters described above.
- Preferred methacrylates are ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, and octyl methacrylate.
- the amount of methacrylic acid esters other than methyl methacrylate is preferably 1 to 30% by weight of the total monomers. From the viewpoint of solvent drying speed, the amount of methacrylic acid esters is more preferably 2 to 30% by weight, more preferably 3 to 30% by weight, based on the total amount of monomers. From the viewpoint of heat resistance, the amount of methacrylic acid esters is more preferably 1 to 20% by weight, more preferably 1 to 15% by weight or less, and particularly preferably 1 to 10% by weight or less, based on the total amount of monomers. .
- the amount of methacrylic acid esters other than methyl methacrylate is 1 to 30% by weight, 2 to 30% by weight, 3 to 30% by weight, 1 to 20% by weight, and 2 to 20% by weight of the total monomers.
- the thermoplastic acrylic resin preferably contains an N-substituted maleimide monomer unit.
- N-substituted maleimide that gives the N-substituted maleimide monomer unit include N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide and the like.
- the amount of N-substituted maleimide is preferably 1-50% by weight based on the total monomers. From the viewpoint of heat resistance, the amount of the N-substituted maleimide is more preferably 2 to 50% by weight, more preferably 3 to 50% by weight, particularly preferably 4 to 50% by weight, based on the total amount of monomers. Further, from the viewpoint of impact resistance and coloring, the amount of the N-substituted maleimide is more preferably 1 to 40% by weight, more preferably 1 to 30% by weight, particularly 1 to 20% by weight, based on the total amount of monomers. preferable.
- the amount of the N-substituted maleimide in the total monomers is 1 to 50% by weight, 2 to 50% by weight, 3 to 50% by weight, 4 to 50% by weight, 1 to 40% by weight, 2 to 40% by weight.
- the weight average molecular weight of the thermoplastic acrylic resin is not particularly limited as long as it is 500,000 or more.
- the weight average molecular weight of the thermoplastic acrylic resin is preferably 700,000 or more, more preferably 850,000 or more, from the viewpoint of film strength during film handling and particle dispersion in the film. , more preferably 1,000,000 or more, and particularly preferably 1,100,000 or more. From the viewpoint of filtration accuracy and load on the polymer filter, the weight average molecular weight of the thermoplastic acrylic resin is preferably 5,000,000 or less, more preferably 3,000,000 or less.
- the weight average molecular weight of the thermoplastic acrylic resin is 700,000 or more and 5,000,000 or less, 700,000 or more and 3,000,000 or less, 850,000 or more and 5,000,000 or less, 850,000 1,000,000 to 5,000,000, 1,000,000 to 3,000,000, 1,100,000 to 5,000,000, or 1, It is preferably 100,000 or more and 3,000,000 or less.
- the glass transition temperature of the thermoplastic acrylic resin can be set according to the conditions for using the obtained acrylic resin film and the application. For applications that do not require excellent heat resistance, the glass transition temperature may be less than 115°C. From the viewpoint of heat resistance, the glass transition temperature is preferably 90° C. or higher. On the other hand, for applications requiring heat resistance, the glass transition temperature is preferably 115° C. or higher. The glass transition temperature of the thermoplastic acrylic resin is more preferably 118°C or higher, still more preferably 120°C or higher, and most preferably 125°C or higher.
- an acrylic resin composition with excellent heat resistance it is preferable to include an acrylic resin having a ring structure in its main chain.
- ring structures include glutarimide ring structures, lactone ring structures, maleic anhydride-derived structures, maleimide-derived ring structures (including N-substituted maleimide-derived structures), and glutaric anhydride ring structures.
- acrylic resins containing a (meth)acrylic acid structural unit in the molecule are also included.
- maleimide acrylic resins (acrylic resins in which an unsubstituted or N-substituted maleimide compound is copolymerized as a copolymerization component), glutarimide acrylic resins, lactone ring-containing acrylic resins, hydroxyl groups, and/or or partial hydrogenation of aromatic rings of styrene-containing acrylic polymers obtained by polymerizing acrylic resins containing carboxyl groups, methacrylic resins, styrene monomers, and other monomers copolymerizable therewith. partially hydrogenated styrene unit-containing acrylic polymers obtained by the above methods, and acrylic polymers having a cyclic acid anhydride structure such as a glutaric anhydride structure or a maleic anhydride-derived structure.
- thermoplastic acrylic resins lactone ring-containing acrylic resins, maleimide acrylic resins, glutarimide acrylic resins, glutaric anhydride structure-containing acrylic resins, and An acrylic resin containing a maleic anhydride structure, and an acrylic polymer composed of 97 to 100% by weight of methyl methacrylate and 3 to 0% by weight of methyl acrylate are preferred.
- glutarimide acrylic resins and maleimide acrylic resins are particularly preferable in terms of excellent balance between heat resistance and optical properties.
- a glutarimide acrylic resin and a maleimide acrylic resin may be used in combination. Since both resins have excellent compatibility, they can maintain high transparency, have excellent optical properties, have high thermal stability, and can also have solvent resistance.
- the multilayer structure polymer particles are particles having a multilayer structure composed of a plurality of polymer layers.
- a multi-layer structure polymer particle is generally called a core-shell type polymer, and is sometimes called a multi-stage polymer.
- a multistage polymer is a polymer obtained by polymerizing a monomer mixture in the presence of polymer particles.
- a multilayer structure polymer particle is a polymer (core-shell type polymer) having a polymer layer (shell layer) obtained by polymerizing a monomer mixture in the presence of a polymer particle (core layer). Both refer basically to the same polymer.
- the former is a polymer identified mainly by the manufacturing method.
- the latter are polymers characterized primarily by their layered structure. The following description will mainly focus on the latter, but the former viewpoint is equally applicable.
- the average particle size of the core layer is not particularly limited.
- the average particle size of the core layer is preferably 80-400 nm.
- the strength of the produced acrylic resin film can be made excellent.
- the average particle size of the core layer is 400 nm or less, the produced acrylic resin film can have excellent transparency, appearance, and optical properties.
- the average particle size of the core layer of the multilayer structure polymer particles is calculated by measuring light scattering at a wavelength of 546 nm with a spectrophotometer in the state of the polymer latex of the core layer before the shell layer is polymerized. be done.
- the layer structure of the multilayer structure polymer particles is not particularly limited. Since the multi-layer structure particles contain at least a core layer that is a soft crosslinked polymer and a shell layer that is mainly composed of methyl methacrylate, they have excellent compatibility with thermoplastic acrylic resins and have sufficient strength. It can be a multi-layer structure polymer particle to be imparted. Each of the core layer and the shell layer may be composed of one layer, or may be composed of two or more layers. Such multilayer structure polymer particles are not particularly limited, and known multilayer structure particles can be appropriately used.
- the multilayer structure polymer particles can be produced by ordinary emulsion polymerization using a known emulsifier.
- emulsifiers include phosphoric acid ester salts such as sodium polyoxyethylene lauryl ether phosphate, anionic surfactants such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium dioctylsulfosuccinate, sodium lauryl sulfate, and sodium fatty acid. and nonionic surfactants.
- emulsifiers may be used alone or in combination of two or more. From the viewpoint of improving the thermal stability of the acrylic resin film, it is particularly preferable to polymerize using a phosphate ester salt (alkali metal or alkaline earth metal) such as sodium polyoxyethylene lauryl ether phosphate.
- a method of subjecting the liquid containing the resin component to spray drying, or adding a water-soluble electrolyte such as a salt or an acid to the liquid containing the resin component to solidify the resin component, and then subjecting the resin component to heat treatment, followed by Solid or powdery multi-layer structure polymer particles can be obtained by a known method such as separating the resin component and drying the separated resin component. Among them, a method of coagulation using salt is generally used for industrial production.
- the salt is not particularly limited, a divalent salt is preferred. Specific examples of divalent salts include calcium salts such as calcium chloride and calcium acetate, and magnesium salts such as magnesium chloride and magnesium sulfate. Among them, magnesium salts such as magnesium chloride and magnesium sulfate are preferable.
- additives such as an anti-aging agent and an ultraviolet absorber, which are generally added, may be added to the liquid containing the resin component.
- the coagulant salt remaining in the particles is a factor that deteriorates the dispersibility of the multilayer structure polymer particles. Therefore, when spray-dried without using a metal salt as a coagulant, the multilayer structure polymer particles exhibit good dispersibility in the acrylic thermoplastic resin.
- the use of spray-dried multi-layer structure polymer particles is generally not preferred because excessive amounts of emulsifier remain, which adversely affect film quality such as deterioration of water resistance.
- a solvent is added to the polymerized latex, the multi-layered structure polymer particles are taken out into the solvent layer in a loosely aggregated state, and the separated water layer is removed, so that the metal salt is not included and
- a method for obtaining multi-layer structure polymer particles with a small amount of residual emulsifier has the disadvantages of being costly due to the use of a large amount of solvent and having a high environmental impact.
- the multi-layer structure polymer particle latex Before the coagulation operation, it is preferable to filter the multi-layer structure polymer particle latex with a filter, mesh, or the like to remove fine polymerization scales. As a result, it is possible to reduce fisheyes and foreign substances caused by fine polymerization scales, and it is also possible to reduce coarse particles in the dope.
- the mixing ratio of the thermoplastic acrylic resin and the multi-layer structure polymer particles varies depending on the use of the film. It is preferable that the amount of the thermoplastic acrylic resin is 30 to 98 parts by weight and the amount of the multi-layer structure polymer particles is 70 to 2 parts by weight based on the total of 100 parts by weight of the two components.
- the blending amount of the plastic acrylic resin is preferably 50 to 95 parts by weight, the blending amount of the multilayer structure polymer particles is more preferably 50 to 5 parts by weight, and the blending amount of the thermoplastic acrylic resin is 60 to 90 parts by weight.
- the blending amount of the coalesced particles is 40 to 10 parts by weight
- the blending amount of the thermoplastic acrylic resin is particularly preferably 70 to 90 parts by weight
- the blending amount of the multilayer structure polymer particles is particularly preferably 30 to 10 parts by weight.
- the amount of the thermoplastic acrylic resin to be blended is 30 parts by weight or more, the properties of the thermoplastic acrylic resin can be exhibited.
- the blending amount of the thermoplastic acrylic resin is 98 parts by weight or less, the mechanical strength of the thermoplastic acrylic resin can be improved by blending the multilayer structure polymer particles.
- the solvent contained in the dope is not particularly limited as long as it is a solvent capable of dissolving or dispersing the thermoplastic acrylic resin and the multilayer structure polymer particles.
- Specific examples include chlorine-based organic solvents such as methylene chloride and chloroform, and non-chlorine-based organic solvents such as methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, and tetrahydrofuran.
- methyl ethyl ketone, tetrahydrofuran, chloroform, and methylene chloride are preferable, and methylene chloride is more preferable, because they are excellent in solubility of the thermoplastic acrylic resin and have a high volatilization rate.
- the solvent contained in the dope may be a single substance. It is preferable to add an alcohol-based co-solvent in consideration of improvement in film-forming property, film releasability, handling property, etc. during solution casting.
- Alcohol-based co-solvents include methanol, ethanol, isopropanol, butanol, ethylene glycol monoethyl ether, and the like. Among them, methanol and ethanol are preferable because they have high polarity and have the effect of increasing the dispersibility of the multilayer structure polymer particles as described above. These solvents may be used alone or in combination of two or more.
- the amount of co-solvent in the solvent is not particularly limited. Considering the releasability and handleability of the acrylic resin film formed using the dope, the amount of the co-solvent in the solvent is preferably 1 to 30% by weight, and 5 to 30% by weight when the total solvent is 100% by weight. 25% by weight is more preferred, and 8 to 22% by weight is particularly preferred.
- the releasability of the acrylic resin film is, for example, the releasability from a metal roll or the like when producing the film. If the amount of the co-solvent is less than 1% by weight, it is difficult to obtain the effect of improving the releasability of the acrylic resin film formed using the above-mentioned dope. The solubility of the plastic acrylic resin may decrease, and the transparency of the film may deteriorate.
- the dope contains a phosphoric acid monoester surfactant represented by the following formula (1) as a dispersant for improving the temporal dispersibility of the multilayer structure polymer particles.
- a phosphoric acid monoester surfactant represented by the following formula (1) as a dispersant for improving the temporal dispersibility of the multilayer structure polymer particles.
- R represents a combination of a hydroxy group or an oxygen anion and a monovalent cation.n represents an integer of 1 to 20, and m represents an integer of 1 to 20.
- Examples include polyoxyethylene (addition number: 1 to 20) lauryl ether phosphate, polyoxyethylene (addition number: 1 to 20) stearyl ether phosphate, and salts thereof.
- R in formula (1) is preferably a combination of an oxygen anion and a monovalent cation.
- the phosphate monoester surfactant is a salt containing a monovalent cation.
- salts include salts of alkali metals such as sodium, lithium and potassium, and salts of ammonium such as ammonium, methylammonium, dimethylammonium, triethylammonium, monoethanolammonium, diethanolammonium and triethanolammonium. .
- salts such as sodium, potassium, monoethanolammonium, or ammonium are preferable, sodium or monoethanolammonium salts are more preferable, and sodium salts are particularly preferable, from the viewpoint of cost and handling.
- the phosphate monoester surfactant is a salt
- the phosphate monoester surfactant is a salt
- alkali metals such as sodium, lithium, potassium, etc.
- the water solubility of the phosphate monoester surfactant increases, so the film problems such as deterioration of water resistance may occur. It can be applied to a wide range of uses by selecting the form of the salt according to the use or using it in combination.
- the content of the phosphoric acid monoester surfactant is preferably 0.01 to 3.0% by weight, preferably 0.05%, based on the total 100% by weight of the thermoplastic acrylic resin and the multilayer structure polymer particles. ⁇ 2.5 wt% is more preferred, 0.08 to 2.0 wt% is even more preferred, and 0.1 to 1.5 wt% is particularly preferred. Phosphate ester-based surfactants having structures other than those described above are not preferable because they have a small dispersibility-improving effect and need to be added in a large amount, which may deteriorate the water resistance of the film.
- the dope contains the phosphate monoester surfactant. Therefore, the dope is excellent in dispersibility of the multilayer structure polymer particles, and can suppress aggregation of the multilayer structure polymer particles in the dope over time.
- the solid content concentration of the dope can be appropriately set within the range of 3 to 30% by weight depending on the type of thermoplastic acrylic resin and multilayer structure polymer particles used. From the viewpoint of workability during solution casting, film formability, etc., the solid content concentration is preferably 4 to 25% by weight, more preferably 5 to 20% by weight, and particularly preferably 6 to 18% by weight. If the solid content concentration exceeds 30% by weight, the distance between particles in the dope becomes small, making it difficult to maintain dispersion stability.
- the viscosity of the dope is preferably 10 to 1000 poise, more preferably 30 to 500 poise, and particularly preferably 50 to 300 poise.
- the viscosity of the dope is a value measured with a Brookfield viscometer using the dope temperature-controlled to 23°C.
- the above dope has excellent dispersibility of the multilayer structure polymer particles immediately after preparation.
- D50 (Initial) is the median diameter of the multilayer structure polymer particles immediately after preparation of the dope
- D50 (Initial) is preferably 1.0 ⁇ m or less, more preferably 0.9 ⁇ m or less, and further preferably 0.8 ⁇ m or less. 0.7 ⁇ m or less is particularly preferable. From the viewpoint of film strength and the like, D50 (Initial) is preferably 0.03 ⁇ m or more.
- the above dope is excellent not only in dispersibility immediately after preparation but also in stability over time when stored as a dope.
- the ratio of D50 (72 hr) to D50 (Initial), that is, the absolute value of the rate of change is preferably 40% or less.
- the above-mentioned median diameter can be measured using a laser diffraction type particle size distribution diameter.
- the dope may optionally contain light stabilizers, ultraviolet absorbers, heat stabilizers, matting agents, light diffusing agents, colorants, dyes, pigments, antistatic agents, heat ray reflectors, lubricants, plasticizers, ultraviolet absorbers, stabilizing agents, known additives such as agents and fillers, or styrene resins such as acrylonitrile styrene resins and styrene maleic anhydride resins, polycarbonate resins, polyvinyl acetal resins, cellulose acylate resins, polyvinylidene fluoride and polyvinyl fluoride alkyl (meth)acrylates.
- Other resins such as fluorine-based resins such as resins, silicone-based resins, polyolefin-based resins, polyethylene terephthalate resins, and polybutylene terephthalate resins may be contained.
- the dope includes inorganic fine particles having birefringence described in Japanese Patent Nos. 3,648,201 and 4,336,586, and birefringent particles described in Japanese Patent No. 3,696,649.
- a low-molecular-weight compound having a molecular weight of 5,000 or less, preferably 1,000 or less, having a property may be appropriately contained.
- the dope is obtained by dissolving or dispersing a thermoplastic acrylic resin and multilayer structure polymer particles in a solvent.
- a thermoplastic acrylic resin and multilayer structure polymer particles in a solvent.
- primary particles having a core-shell type structure can be aggregated or welded to a size of several microns to several tens of millimeters. For this reason, when preparing the dope, it is preferable to disperse the multilayer structure polymer particles uniformly in the solvent, preferably in a state where the primary particles are dispersed.
- Conventionally known methods can be widely applied as a method for dispersing the multilayer structure polymer particles in the solvent.
- 2) The multi-layer structure polymer particles and the thermoplastic acrylic resin are put into a solvent at the same time, and the multi-layer structure polymer particles in the solvent are stirred while applying appropriate shear and/or heat to form a multi-layer structure polymer in the solvent.
- thermoplastic acrylic resin and the multi-layer structure polymer particles are mixed in advance, preferably heated and melted, and melt-kneaded by applying an appropriate shearing force to disperse the multi-layer structure polymer particles in the thermoplastic acrylic resin.
- a method of preparing a dope by dispersing the resin composition in a solvent after preparing a resin composition are exemplified.
- the method for dispersing the multilayer structure polymer particles in the solvent is not limited to these methods.
- Particularly preferred methods include the following methods. First, while stirring the multi-layer structure polymer particles in the solvent, the multi-layer structure polymer particles are dissolved and dispersed in the solvent. to prepare.
- a dope in which particles are dispersed can be prepared by dissolving a thermoplastic acrylic resin in this particle dispersion liquid, or by mixing a separately prepared dope in which a thermoplastic acrylic resin is dissolved in an arbitrary ratio. According to this method, since the viscosity of the dispersion liquid is low, the dispersion effect by ultrasonic irradiation or the like is high, and foreign matter contained in the multilayer structure polymer particles can be accurately filtered.
- the timing of adding the phosphate monoester surfactant to the dope is not particularly limited.
- adding a predetermined amount of a phosphate monoester surfactant to a solvent and dissolving it in advance allows the surfactant to uniformly and efficiently act on the particle surfaces.
- a predetermined amount of monoester phosphate surfactant may be used during the production of the thermoplastic acrylic resin or the multi-layer structure polymer particles.
- Dopes are commonly used to produce acrylic resin films by solution casting methods. Specifically, the acrylic resin film can be produced by casting the dope on the surface of the support and then evaporating the solvent. A resin film manufactured by a solution casting method in this way is also called a cast film.
- Embodiments of the solution casting method are described below, but are not limited to this.
- pellets containing the thermoplastic acrylic resin, the multilayer structure polymer particles, and optionally the other components are prepared, and then the pellets are mixed with a solvent to prepare a dope in which each component is dissolved and dispersed in the solvent.
- the thermoplastic acrylic resin, the multi-layer structure polymer particles, and optionally the other components are simultaneously or sequentially mixed in a solvent to prepare a dope in which each component is dissolved and dispersed in the solvent.
- the thermoplastic acrylic resin and the multi-layer structure polymer particles can be separately mixed with a solvent to prepare two or more dope preparatory liquids, and the dope can be prepared by mixing these preparatory liquids.
- dissolving steps can be carried out by appropriately adjusting the temperature and pressure.
- a method of preparing pellets containing the thermoplastic acrylic resin, the multilayer structure polymer particles, and optionally the other components and then dissolving and dispersing them in a solvent may be preferable.
- the obtained dope can be filtered or defoamed.
- the dope is sent to a pressurized die by a liquid-sending pump, and cast from the slit of the pressurized die onto the surface (mirror surface) of a support such as an endless belt or drum made of metal or synthetic resin. , forming a doped film.
- the formed dope film is heated on the support to evaporate the solvent and form an acrylic resin film.
- the acrylic resin film thus obtained is peeled off from the surface of the support. After that, the obtained acrylic resin film may be appropriately subjected to a drying process, a heating process, a stretching process, or the like.
- the thickness of the acrylic resin film is not particularly limited.
- the thickness of the acrylic resin film is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the thickness of the acrylic resin film is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
- the thickness of the acrylic resin film is 5 ⁇ m to 300 ⁇ m, 5 ⁇ m to 100 ⁇ m, 5 ⁇ m to 50 ⁇ m, 7 ⁇ m to 300 ⁇ m, 7 ⁇ m to 100 ⁇ m, 7 ⁇ m to 50 ⁇ m, 10 ⁇ m to 300 ⁇ m, 10 ⁇ m to 100 ⁇ m. , or preferably 10 ⁇ m or more and 50 ⁇ m or less.
- the thickness of the film is within the above range, there is an advantage that the film is less likely to be deformed when vacuum forming is performed using the film, and less likely to break at the deep drawn portion. Furthermore, there is also the advantage that a film with uniform optical properties and good transparency can be produced. On the other hand, if the thickness of the film exceeds the upper limit of the above range, the time required for volatilization of the solvent will be increased, resulting in poor productivity and air bubbles being likely to remain in the film. Moreover, when the thickness of the film is less than the lower limit of the above range, it may be difficult to handle the film.
- the total light transmittance measured at a film thickness of 40 ⁇ m of the acrylic resin film is preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more. If the total light transmittance is within the above range, the transparency is high, so the acrylic resin film can be suitably used for optical members, decoration applications, interior applications, and vacuum molding applications that require light transparency.
- the glass transition temperature of the acrylic resin film is preferably 90°C or higher, more preferably 100°C or higher, still more preferably 110°C or higher, and most preferably 120°C or higher. If the glass transition temperature is within the above range, the acrylic resin film will be excellent in heat resistance.
- the haze of the acrylic resin film measured at a film thickness of 40 ⁇ m is preferably 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, and particularly preferably 0.8% or less.
- the internal haze of the film is preferably 1.5% or less, more preferably 1.0% or less, even more preferably 0.5% or less, particularly preferably 0.3% or less, most preferably 0.2% or less. preferable.
- the haze consists of haze inside the film and haze on the surface (outside) of the film, which are referred to as internal haze and external haze, respectively.
- the YI (Yellow Index) of the acrylic resin film measured at a film thickness of 40 ⁇ m is preferably 1.2 or less, more preferably 1.0 or less, further preferably 0.8 or less, and particularly preferably 0.7 or less. .
- an acrylic resin film exhibiting haze, internal haze, and YI within the ranges described above is suitable for optical members, decorative applications, interior applications, and vacuum molding applications that require light transmittance.
- the acrylic resin film can also be used as an optical film.
- the optical anisotropy is small.
- the optical anisotropy not only in the in-plane direction (length direction and width direction) of the film but also in the thickness direction is small. That is, it is preferable that the absolute values of both the in-plane retardation and the thickness direction retardation are small. More specifically, the absolute value of the in-plane retardation is preferably 10 nm or less, more preferably 6 nm or less, even more preferably 5 nm or less, and particularly preferably 3 nm or less.
- the absolute value of the thickness direction retardation is preferably 50 nm or less, more preferably 20 nm or less, even more preferably 15 nm or less, even more preferably 10 nm or less, and 5 nm or less. is most preferred.
- An acrylic resin film having such a retardation can be suitably used as a polarizer protective film provided in a polarizing plate of a liquid crystal display device.
- the absolute value of the in-plane retardation of the acrylic resin film exceeds 10 nm or the absolute value of the thickness direction retardation exceeds 50 nm, when used as a polarizer protective film included in the polarizing plate of a liquid crystal display device, Problems such as a decrease in contrast may occur in the liquid crystal display device.
- the phase difference is an index value calculated based on birefringence.
- nx, ny, and nz are respectively the in-plane extension direction (polymer chain orientation direction) as the X axis, the direction perpendicular to the X axis as the Y axis, and the film thickness direction as the Z axis.
- d represents the thickness of the film
- nx-ny represents the orientation birefringence.
- the MD direction of the film is the X axis, but in the case of a stretched film, the stretching direction is the X axis.
- the acrylic resin film has an orientation birefringence value of preferably ⁇ 2.6 ⁇ 10 ⁇ 4 to 2.6 ⁇ 10 ⁇ 4 , more preferably ⁇ 2.1 ⁇ 10 ⁇ 4 to 2.1 ⁇ 10 ⁇ 4 , more preferably ⁇ 1.7 ⁇ 10 ⁇ 4 to 1.7 ⁇ 10 ⁇ 4 , even more preferably ⁇ 1.6 ⁇ 10 ⁇ 4 to 1.6 ⁇ 10 ⁇ 4 , still more preferably ⁇ 1.5 ⁇ 10 ⁇ 4 to 1.5 ⁇ 10 ⁇ 4 , particularly preferably ⁇ 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 4 , particularly preferably ⁇ 0.5 ⁇ 10 ⁇ 4 to 0.5 ⁇ 10 ⁇ 4 , most preferably ⁇ 0.2 ⁇ 10 ⁇ 4 to 0.2 ⁇ 10 ⁇ 4 . If the orientation birefringence is within the above range, stable optical properties can be obtained without causing birefringence during molding. It is also very suitable as an optical film used in liquid crystal displays and the like.
- the acrylic resin film has high toughness and flexibility even as an unstretched film.
- the acrylic resin film may be further stretched. By stretching the acrylic resin film, it is possible to improve the mechanical strength of the acrylic resin film and improve the accuracy of the film thickness.
- an unstretched film is formed from the dope, and then uniaxially or biaxially stretched.
- a stretched film (uniaxially stretched film or biaxially stretched film) can be produced by doing so, or by appropriately adding a stretching operation along with the progress of film forming and solvent degassing steps during film molding. can. Stretching during film formation and stretching after film formation may be appropriately combined.
- the draw ratio of the stretched film is not particularly limited.
- the draw ratio may be determined according to the mechanical strength, surface properties, thickness accuracy, etc. of the stretched film to be produced. Although it depends on the stretching temperature, the stretching ratio is generally preferably selected in the range of 1.1 times to 5 times, more preferably in the range of 1.3 times to 4 times. It is more preferable to select in the range of 1.5 times to 3 times. If the draw ratio is within the above range, mechanical properties such as film elongation, tear propagation strength, and resistance to rubbing fatigue can be significantly improved.
- the surface gloss of the acrylic resin film can be reduced by a known method, if necessary.
- a method of adding an inorganic filler or crosslinkable polymer particles include a method of adding an inorganic filler or crosslinkable polymer particles.
- embossing the obtained resin film it is possible to form an irregular surface layer with a prism shape, pattern, design, knurling, etc., or to reduce the glossiness of the film surface.
- the acrylic resin film may be laminated with another film using a dry lamination method using an adhesive, an adhesive, etc., and/or a heat lamination method, etc., or a hard coat layer, Functional layers such as an antireflection layer, an antifouling layer, an antistatic layer, a printed decorative layer, a metallic luster layer, a surface uneven layer, and a matte layer can be formed and used.
- Acrylic resin film can be used for various purposes by utilizing properties such as heat resistance, transparency, and flexibility.
- properties such as heat resistance, transparency, and flexibility.
- automobile interiors and exteriors personal computer interiors and exteriors, mobile interiors and exteriors, solar cell interiors and exteriors, solar cell back sheets, cameras, VTRs, shooting lenses for projectors, viewfinders, filters, prisms, Fresnel lenses, lens covers, etc.
- Lens fields such as pickup lenses for optical discs in CD players, DVD players, MD players, etc., optical recording fields for optical discs such as CDs, DVDs, MDs, films for organic EL, light guide plates for liquid crystals, diffusion plates, back sheets, reflection Sheets, polarizer protective films, polarizing films, transparent resin sheets, retardation films, light diffusion films, films for liquid crystal displays such as prism sheets, information equipment fields such as surface protection films, optical fibers, optical switches, optical connectors, etc.
- Communication field such as automobile headlights, tail lamp lenses, inner lenses, instrument covers, sunroofs, etc., eyeglasses, contact lenses, endoscope lenses, medical equipment fields such as medical supplies that require sterilization, road signs, bathrooms Equipment, flooring, road translucent plates, double glazing lenses, daylighting windows, carports, lighting lenses, lighting covers, construction and building materials fields such as sizing for building materials, microwave oven cooking containers (tableware), housings for home appliances , toys, sunglasses, stationery, etc. It can also be used as a substitute for a molded product using a transfer foil sheet.
- the acrylic resin film can be used by laminating it on a base material such as metal or plastic.
- Lamination methods for acrylic resin films include lamination molding, wet lamination in which an adhesive is applied to a metal plate such as a steel plate and then the film is placed on the metal plate, dried, and bonded together, dry lamination, extrusion lamination, and hot lamination. Melt laminate and the like can be mentioned.
- the film is placed in a mold, and the resin is filled by injection molding, such as insert molding, laminate injection press molding, or preforming the film and then inserting it into the mold.
- injection molding such as insert molding, laminate injection press molding, or preforming the film and then inserting it into the mold.
- in-mold molding is performed by arranging and filling resin by injection molding.
- Laminates containing acrylic resin films are used for automobile interior materials, automobile exterior materials, etc., as paint substitutes, window frames, bathroom equipment, wall paper, flooring materials, lighting and light control materials, soundproof walls, road signs, and other civil engineering applications.
- Materials, daily commodities, housings for furniture and electronic and electrical equipment, housings for OA equipment such as facsimiles, laptop computers, and copiers, front panels of liquid crystal screens for mobile phones, smartphones, tablets, and other terminals, lighting lenses, Automotive headlights, optical lenses, optical fibers, optical discs, optical components such as light guide plates for liquid crystals, optical elements, electrical or electronic device parts, medical supplies requiring sterilization, toys or recreational items, fiber reinforced resins It can be used for composite materials and the like.
- acrylic resin films are suitable for optical films because of their excellent heat resistance and optical properties, and can be used for various optical members.
- front panels of liquid crystal screens of terminals such as mobile phones, smartphones, tablets, illumination lenses, automobile headlights, optical lenses, optical fibers, optical discs, light guide plates for liquid crystals, diffusion plates, back sheets, reflective sheets, polarizing films Transparent resin sheets, retardation films, light diffusion films, prism sheets, surface protection films, optically isotropic films, polarizer protection films, transparent conductive films, etc., around liquid crystal display devices, around organic EL devices, optical communication fields, etc. It can be applied to known optical uses.
- thermoplastic acrylic resin The weight average molecular weight (Mw) of the thermoplastic acrylic resin was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). A sample solution prepared by dissolving 5 mg of thermoplastic acrylic resin powder in 2 ml of tetrahydrofuran was analyzed using the following apparatus and conditions.
- Measuring instrument HLC-8220GPC (Tosoh) Detector: RI detector (built into device) Solvent: Tetrahydrofuran Guard Column: TSKguardcolumn SuperHZ-H (4.6 x 35mm ) (Tosoh) Analysis column: TSKgel SuperHZM-H (6.0 x 150 mm) (Tosoh) Measurement temperature: 40°C Standard material: standard polystyrene (Tosoh)
- Dope viscosity The dope viscosity was measured using a B-type viscometer (manufactured by BM Toki Sangyo). The temperature of the measurement sample was adjusted to 23° C. and readings were taken at 6 rpm using a No 3 rotor.
- the multi-layer structure polymer particles swell with an organic solvent. Therefore, the particle size in the dope can be different from the particle size in the latex.
- YI of film The YI of the film produced by the solution casting method was measured according to JIS Z7103 using a spectrophotometric system (SC-P manufactured by Suga Test Instruments Co., Ltd.).
- thermoplastic acrylic resin An 8 liter glass reactor equipped with an H-type stirrer was charged with 200 parts of deionized water and 0.1 parts of disodium hydrogen phosphate, a suspension aid. Next, while stirring the aqueous solution in the reactor at 300 rpm, 85 parts of methyl methacrylate in which 0.3 part of lauroyl peroxide was dissolved, 10 parts of N-phenylmaleimide, and 5 parts of 2-ethylhexyl methacrylate were added to the reactor. A monomer mixture consisting of three parts was added. After that, while replacing the inside of the reactor with nitrogen, the temperature of the liquid in the reactor was raised to 60° C. to initiate polymerization.
- the internal temperature of the polymerization apparatus was set to 80°C. After that, 0.03 part of potassium persulfate was put into the polymerization apparatus as a 2% aqueous solution. Then, 27 parts by weight of a monomer mixture (1-1: 97 parts by weight of methyl methacrylate, 3 parts by weight of butyl acrylate, 0.5 parts by weight of allyl methacrylate) was continuously added into the polymerization apparatus over 81 minutes. By continuing the polymerization for an additional 60 minutes, a polymer (1-1) was obtained. The polymerization conversion rate was 92.3%.
- Surfactant 1 Sf1, phosphate monoester: Plysurf M208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (10) tridecyl ether phosphate monoester monoethanolamine salt)
- Surfactant 2 Sf2, phosphate monoester: Phosphanol RD-510Y (manufactured by Toho Chemical, polyoxyethylene (4) lauryl ether phosphate monoester)
- Surfactant 3 Sf3, phosphate monoester: An excess amount of sodium hydroxide was added to the above aqueous solution of phosphoric acid monoester surfactant 2, and the mixture was heated at 60° C.
- Surfactant 4 (Sf4, sulfonic acid-based): Dioctyl sulfosuccinate sodium salt (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Surfactant 5 (Sf5, phosphate diester) Nikkol DLP-10 (manufactured by Nikko Chemicals, dipolyoxyethylene (10) sodium lauryl ether phosphate)
- Surfactant 6 (Sf6, carboxylic acid-based): Potassium palmitate (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Example 1 Preparation of resin dope containing multilayer structure polymer particles
- 36 g of a mixed solvent composed of 87% by weight of methylene chloride and 13% by weight of ethanol was placed in a screw tube container.
- 0.04 g of phosphate monoester surfactant 1 was prepared and dissolved in the mixed solvent.
- 0.8 g of the multilayer structure polymer particles B1 were added to the mixed solvent and dissolved and dispersed. The resulting particle dispersion was then stirred until uniform.
- the resulting particle dispersion was subjected to an ultrasonic dispersion treatment in an ultrasonic bath (Bransonic 1510J, manufactured by Yamato Scientific Co., Ltd.) for an additional 15 minutes to obtain a dispersion in which multilayer structure polymer particles were monodispersed. While stirring the dispersion, 3.2 g of thermoplastic acrylic resin A1 was added to the dispersion. The dispersion was stirred until the thermoplastic acrylic resin A1 was completely dissolved to prepare a dope having a solid content concentration (SC) of 10%.
- SC solid content concentration
- the dope was cast on a PET film (Cosmoshine A4100 manufactured by Toyobo Co., Ltd.) and applied to form a uniform film with an applicator. The clearance was adjusted so that the thickness after drying was approximately 30 to 50 ⁇ m. After coating, the coating film made of the dope was dried for 5 minutes in a dry atmosphere at 40° C., and then the dried film was peeled off from the PET film. After that, the dried film was fixed to a stainless steel frame and dried in a dry atmosphere of 140° C. for 30 minutes to remove the residual solvent and obtain an acrylic resin film.
- a PET film Cosmoshine A4100 manufactured by Toyobo Co., Ltd.
- Examples 2 to 9, Comparative Examples 1 to 7 An acrylic resin film was produced in the same manner as in Example 1, except that the composition of the solvent and the added surfactant were changed as shown in Tables 1 and 2.
- Tables 1 and 2 show the dispersibility of the dopes obtained in Examples 1 to 9 and Comparative Examples 1 to 7, and the evaluation results of the acrylic resin films obtained from the dopes.
- the dope does not contain a phosphoric acid monoester surfactant, so the D50 (Initial) is large and the dispersibility is not good. Furthermore, D50 (72 hr) also increased, and aggregation over time could not be suppressed. As a result, the haze and YI of the obtained film were large.
- Comparative Examples 13-15 since the dope contains a phosphoric acid monoester surfactant, D50 (Initial) and D50 (72 hr) are improved, but the adhesion of deposits to the wall surface is suppressed, and the film The low haze and the low YI were insufficient. In Comparative Examples 8 and 12, since the molecular weight of the thermoplastic acrylic resin was small, the viscosity of the dope was low, and films could not be produced by the solution casting method.
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Abstract
Description
(I)熱可塑性アクリル系樹脂、多層構造重合体粒子、及び、溶媒を含む、フィルム製造用ドープであって、
前記フィルム製造用ドープが、下記式(1)で表されるリン酸モノエステル系界面活性剤を含み、
前記フィルム製造用ドープの固形分濃度が3~30重量%であり、
前記熱可塑性アクリル系樹脂の重量平均分子量が500,000以上である、
フィルム製造用ドープ。
変化率の絶対値(%)=|D50(72hr)/D50(Initial)×100-100|
前記アクリル系樹脂フィルムが、下記式(1)で表されるリン酸モノエステル系界面活性剤を含み、
前記熱可塑性アクリル系樹脂の重量平均分子量が500,000以上であり、
前記アクリル系樹脂フィルムのヘイズが2%以下である、アクリル系樹脂フィルム。
多層構造重合体粒子は一般に乳化重合で合成され、凝固剤(主に多価カチオンの金属塩)によって重合ラテックスを凝集させ、粉体として回収される。その後、洗浄工程によって余分な乳化剤や凝固剤が除去される。しかし、粒子表面に少なからず乳化剤、凝固剤、及び乳化剤塩が残存する。このような乳化剤塩が存在することにより、多層構造重合体粒子表面の極性が高くなる。多層構造重合体粒子表面の極性が高いと、熱可塑性アクリル系樹脂が溶解した際に、多層構造重合体粒子と熱可塑性アクリル系樹脂との親和性が低い。このことから、多層構造重合体粒子の凝集が誘発されると考えられる。極性の高い溶媒中においては、上記の乳化剤塩が分散液中に可溶化される。このため、多層構造重合体粒子の経時凝集は抑制されると考えられる。また、ドープ粘度が高い場合は、そもそも多層構造重合体粒子の運動が抑制されるため、凝集が起きにくい。
熱可塑性アクリル系樹脂の分子量は、500,000以上である。熱可塑性アクリル系樹脂は、(メタ)アクリル酸エステルを含む単量体単位を構成単位とする樹脂であればよい。熱可塑性アクリル系樹脂としては、公知の熱可塑性アクリル系樹脂を使用できる。
特に、メタクリル酸エステル由来の構成単位を含む熱可塑性アクリル系樹脂が好ましい。
熱可塑性アクリル系樹脂の熱安定性の観点から、熱可塑性アクリル系樹脂は、エステル部のアルキル基の炭素数が1~4のメタクリル酸アルキルエステル単位を30~100重量%含むことが好ましく、50~100重量%含むことがより好ましく、70~100重量%含むことがさらに好ましい。
メタクリル酸アルキルエステル単位としては、耐熱性が高いことからメタクリル酸メチル単位が特に好ましい。また、メタクリル酸メチルと共重合可能な他のビニル系単量体単位の量は、熱可塑性アクリル系樹脂の重量に対して、70~0重量%であることが好ましく、50~0重量%であることがより好ましく、30~0重量%であることがさらに好ましい。
メタクリル酸メチルと共重合可能な他のビニル系単量体としては、具体的には、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸シクロヘキシル、メタクリル酸2-エチルヘキシル、メタクリル酸ベンジル、メタクリル酸オクチル、メタクリル酸グリシジル、メタクリル酸エポキシシクロヘキシルメチル、メタクリル酸ジメチルアミノエチル、メタクリル酸2-ヒドロキシエチル、メタクリル酸2-ヒドロキシプロピル、メタクリル酸ジシクロペンタニル、2,2,2-トリフルオロエチルメタクリレート、2,2,2-トリクロロエチルメタクリレート、メタクリル酸イソボルニル等のメタクリル酸エステル類;アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸2-エチルヘキシル、アクリル酸オクチル、アクリル酸グリシジル、アクリル酸エポキシシクロヘキシルメチル、アクリル酸2-ヒドロキシエチル、アクリル酸2-ヒドロキシプロピル等のアクリル酸エステル類;メタクリルアミド、アクリルアミド、N-メチロ-ルアクリルアミド等の(メタ)アクリルアミド類;メタクリル酸、アクリル酸等のカルボン酸類及びその塩;アクリロニトニル、メタクリロニトリル等のビニルシアン類;スチレン、α-メチルスチレン、モノクロロスチレン、ジクロロスチレン等のビニルアレーン類;N-フェニルマレイミド、N-シクロヘキシルマレイミド、N-メチルマレイミド等のNー置換マレイミド類;マレイン酸、フマル酸及びそれらのエステル等;塩化ビニル、臭化ビニル、クロロプレン等のハロゲン化ビニル類;蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル等のビニルエステル;エチレン、プロピレン、ブチレン、ブタジエン、イソブチレン等のアルケン類;ハロゲン化アルケン類;アリルメタクリレート、ジアリルフタレート、トリアリルシアヌレート、モノエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ジビニルベンゼン等の多官能性単量体が挙げられる。これらのうち、メタクリル酸エステル類やNー置換マレイミド類が好ましい。これらのビニル系単量体は単独で、又は2種類以上を併用して使用することができる。
以上より、メタクリル酸メチル以外のメタクリル酸エステル類の量は、全単量体中、1~30重量%、2~30重量%、3~30重量%、1~20重量%、2~20重量%、3~20重量%、1~15重量%、2~15重量%、3~15重量%、1~10重量%、2~10重量%、又は3~10重量%であるのが好ましい。
以上より、N-置換マレイミドの量は、全単量体中、1~50重量%、2~50重量%、3~50重量%、4~50重量%、1~40重量%、2~40重量%、3~40重量%、4~40重量%、1~30重量%、2~30重量%、3~30重量%、4~30重量%、1~20重量%、2~20重量%、3~20重量%、又は4~20重量%であるのが好ましい。
以上より、熱可塑性アクリル系樹脂の重量平均分子量は、700,000以上5,000,000以下、700,000以上3,000,000以下、850,000以上5,000,000以下、850,000以上3,000,000以下、1,000,000以上5,000,000以下、1,000,000以上3,000,000以下、1,100,000以上5,000,000以下、又は1,100,000以上3,000,000以下であるのが好ましい。
前記多層構造重合体粒子は、複数の重合体層からなる多層構造を有する粒子である。多層構造重合体粒子は、一般に、コアシェル型重合体と呼ばれ、多段重合体と呼ばれる場合もある。多段重合体は、重合体粒子の存在下に、単量体混合物を重合して得られる重合体である。多層構造重合体粒子は、重合体粒子(コア層)の存在下に、単量体混合物を重合して得られる重合体層(シェル層)を有する重合体(コアシェル型重合体)である。両者は基本的に同一の重合体を指す。前者は主に製法によって特定された重合体である。後者は主に層構造によって特定された重合体である。以下の説明は、主に後者について行うが、前者の視点においても同様に適用できる。
熱可塑性アクリル系樹脂の配合量が30重量部以上であると熱可塑性アクリル系樹脂の持つ特性を発揮することができる。熱可塑性アクリル系樹脂の配合量が98重量部以下であると、多層構造重合体粒子の配合によって熱可塑性アクリル系樹脂の機械的強度を改善することができる。
前記ドープに含まれる溶媒は、前記熱可塑性アクリル系樹脂、及び前記多層構造重合体粒子を溶解、又は分散することができる溶媒である限り特に限定されない。具体的に例えば、塩化メチレン、クロロホルム等の塩素系有機溶媒や、酢酸メチル、酢酸エチル、アセトン、メチルエチルケトン、テトラヒドロフラン等の非塩素系有機溶媒を例として挙げることができる。中でも、熱可塑性アクリル系樹脂の溶解性に優れるとともに、揮発速度が速いため、メチルエチルケトン、テトラヒドロフラン、クロロホルム、塩化メチレンが好ましく、塩化メチレンがより好ましい。
前記ドープは、多層構造重合体粒子の経時分散性を向上させるための分散剤として、下記式(1)で示されるリン酸モノエステル系界面活性剤を含む。
リン酸モノエステルと塩を形成する1価のカチオンとしてはリチウムイオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、モノエタノールアンモニウムイオン等が挙げられる。
ドープは、上記リン酸モノエステル系界面活性剤を含んでいる。このため、ドープは、多層構造重合体粒子の分散性に優れており、ドープ中での経時的な多層構造重合体粒子の凝集を抑制できる。ドープの固形分濃度は、3~30重量%の範囲内において、使用する熱可塑性アクリル系樹脂や多層構造重合体粒子の種類によって適宜設定できる。溶液流延時の作業性やフィルムの製膜性等の観点から、固形分濃度が4~25重量%が好ましく、5~20重量%がより好ましく、6~18重量%が特に好ましい。固形分濃度が30重量%を超えるとドープ中における粒子間距離が小さくなるため、分散安定性を保つことが難しくなることがある。
変化率の絶対値(%)=|D50(72hr)/D50(Initial)×100-100|
長期保管時のドープの安定性の観点から変化率の絶対値は30%以下がより好ましく、20%以下がさらに好ましく。10%以下が特に好ましい。なお、上述のメジアン径はレーザー回折式粒度分布径を用いて測定することができる。
ドープは、適宜、光安定剤、紫外線吸収剤、熱安定剤、艶消し剤、光拡散剤、着色剤、染料、顔料、帯電防止剤、熱線反射材、滑剤、可塑剤、紫外線吸収剤、安定剤、フィラー等の公知の添加剤、又は、アクリロニトリルスチレン樹脂やスチレン無水マレイン酸樹脂等のスチレン系樹脂、ポリカーボネート樹脂、ポリビニルアセタール樹脂、セルロースアシレート樹脂、ポリフッ化ビニリデンやポリフッ化アルキル(メタ)アクリレート樹脂等のフッ素系樹脂、シリコーン系樹脂、ポリオレフィン系樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂等その他の樹脂を含有してもよい。
前記ドープは、溶媒中に、熱可塑性アクリル系樹脂、及び多層構造重合体粒子が溶解、又は分散したものである。多層構造重合体粒子においては、コアシェル型構造を有する一次粒子が、数ミクロン~数十ミリメートルの大きさに凝集あるいは溶着し得る。このため、ドープを調製する際には、多層構造重合体粒子を溶媒に均一に、好ましくは一次粒子までばらけた状態で分散させることが好ましい。
例えば、
1)多層構造重合体粒子のパウダーを溶媒に投入し、適宜剪断、及び/又は熱をかけながら溶媒中の多層構造重合体粒子を撹拌し、直接、多層構造重合体粒子を分散させる方法、
2)多層構造重合体粒子と熱可塑性アクリル系樹脂を同時に溶媒に投入して適宜剪断、及び/又は熱をかけながら溶媒中の多層構造重合体粒子を撹拌して、溶媒中の多層構造重合体粒子を分散、又は溶解させ、直接ドープを調製する方法、及び、
3)熱可塑性アクリル系樹脂と多層構造重合体粒子を予め混合し、好ましくは加熱溶融させた上で適宜剪断力を加えて溶融混練し、熱可塑性アクリル系樹脂に多層構造重合体粒子が分散した樹脂組成物(例えば、ペレット状の樹脂組成物)を作製した後に、該樹脂組成物を溶媒に分散させドープを調製する方法等、
が例示される。多層構造重合体粒子の溶媒への分散方法は、これらの方法に限定されない。
この方法によれば、分散液の粘度が低いため超音波照射等による分散効果が高く、多層構造重合体粒子に含まれる異物の濾過を精度良く行うことが可能である。
ドープは、通常、溶液流延法によってアクリル系樹脂フィルムを製造するのに使用される。具体的には、ドープを支持体表面に流延した後、溶媒を蒸発させることによりアクリル系樹脂フィルムを製造することができる。このように溶液流延法によって製造された樹脂フィルムを、キャストフィルムともいう。
アクリル系樹脂フィルムは、通常、前述したドープを用いる溶液流延法により形成される。アクリル系樹脂フィルムの厚みは特に限定されない。アクリル系樹脂フィルムの厚みは、300μm以下が好ましく、100μm以下がより好ましく、50μm以下が特に好ましい。また、アクリル系樹脂フィルムの厚みは、5μm以上が好ましく、7μm以上がより好ましく、10μm以上が特に好ましい。
以上より、アクリル系樹脂フィルムの厚みは、5μm以上300μm以下、5μm以上100μm以下、5μm以上50μm以下、7μm以上300μm以下、7μm以上100μm以下、7μm以上50μm以下、10μm以上300μm以下、10μm以上100μm以下、又は10μm以上50μm以下であるのが好ましい。
さらに、フィルムの内部ヘイズは、1.5%以下が好ましく、1.0%以下がより好ましく、0.5%以下がさらに好ましく、0.3%以下が特に好ましく、0.2%以下が最も好ましい。
なお、ヘイズはフィルム内部とフィルム表面(外部)のヘイズからなり、それぞれを内部ヘイズ、外部ヘイズと表現する。
Re=(nx-ny)×d
Rth=((nx+ny)/2-nz)×d
アクリル系樹脂フィルムは未延伸フィルムとしても靭性が高く柔軟性に富むものである。アクリル系樹脂フィルムは、さらに延伸されてもよい。アクリル系樹脂フィルムを延伸することにより、アクリル系樹脂フィルムの機械的強度の向上、膜厚精度の向上を図ることができる。
アクリル系樹脂フィルムは、必要に応じて、公知の方法によりフィルム表面の光沢を低減させることができる。そのような方法としては、例えば、無機充填剤、又は架橋性高分子粒子を添加する方法が挙げられる。また、得られる樹脂フィルムにエンボス加工を施すことにより、プリズム形状やパターン、意匠、ナーリング等の表面凹凸層を形成したり、フィルム表面の光沢を低減させることも可能である。
熱可塑性アクリル系樹脂の重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)を用いた標準ポリスチレン換算法により算出した。熱可塑性アクリル系樹脂粉末5mgをテトラヒドロフラン2mlに溶解し、調製した試料溶液を下記の装置・条件にて分析を実施した。
測定機器:HLC-8220GPC(東ソー)
検出器 :RI検出器(装置内蔵)
溶媒 :テトラヒドロフラン
ガードカラム:TSKguardcolumn SuperHZ-H(4.6×35mm
)(東ソー)
分析カラム:TSKgel SuperHZM-H(6.0×150mm)(東ソー)
測定温度:40℃
標準物質:標準ポリスチレン(東ソー)
Microtrac UPA150(日機装株式会社製)を使用し、動的光散乱法の原理に基づき、アクリル系重合体の重合ラテックスの体積平均粒子径を求めた。
B型粘度計(BM 東機産業製)を使用し、ドープ粘度を測定した。測定試料の温度を23℃に調整し、No3ローターを使用し、6rpmでの指示値を読み取った。
レーザー回折式粒度分布計(マルバーン社製 マスターサイザー3000)を用いて、ドープ中の粒子の粒度分布を測定した。測定試料の溶媒と同組成の溶媒を分散媒として用いた。溶媒を循環させながら、レーザー散乱強度が0.5~2.0%になるように試料ドープを滴下した。脱泡のため、ドープが加えられた溶媒を2分間循環させた後、粒子径分布の測定を行った。得られた粒度分布から、多層構造重合体粒子の粒子体積の累積が50%となる粒子径(メジアン径 D50)を求めた。粒子径が1μm未満であり、粒度分布が単峰性、かつテーリングが見られない場合、分散していると判断した。
上述のレーザー回折式粒度分布径を用いて、ドープ調製直後、及び調製から23℃で72時間経過した時の多層構造重合体粒子の粒子径を測定した。下記式により算出される、ドープ調製直後の多層構造重合体粒子の粒子径D50(Initial)に対する、ドープ調製から72時間経過後の多層構造重合体粒子の粒子径D50(72hr)の変化率の絶対値が40%以下である場合、経時の凝集が抑制されていると判断した。
変化率の絶対値(%)=|D50(72hr)/D50(Initial)×100-100|
ドープを調製してから72時間経過後にガラス瓶の液面より上の壁面を目視で確認し、ゲル状の付着物の有無を確認した。分散不良が起こっている場合、凝集粒子間に溶媒、及び樹脂を含み、局所的に粘度が上がるため、壁面にゲル状の付着物が見られる。壁面にゲル状の付着物がほとんど見られない状態を○、僅かながらゲル状の付着がある状態を△、ゲル状の付着物が見られる状態を×とした。
溶液キャスト法により作製したフィルムのヘイズを、ヘイズメーター(スガ試験機株式会社製 HZ-V3)を用い、JIS K7105に記載の方法にて測定した。一方、純水を入れた石英セルの中に樹脂フィルムを入れ、水中で測定を行った値を内部ヘイズ値とした。ヘイズ値―内部ヘイズ値=外部ヘイズ値とした。
溶液キャスト法により作製したフィルムのYIを、分光測色系(スガ試験機社製 SC-P)を用いてJIS Z7103に準拠して測定した。
<熱可塑性アクリル系樹脂の製造>
H型撹拌機を備えた8リットルガラス製反応器に、脱イオン水200部、及び懸濁助剤であるリン酸水素2ナトリウム0.1部を仕込んだ。次に、反応器内の水溶液を300rpmで撹拌しながら、反応器内にラウロイルパーオキサイド0.3部を溶解させたメタクリル酸メチル85部、N-フェニルマレイミド10部、及びメタクリル酸2-エチルヘキシル5部からなる単量体混合液を加えた。その後、反応器内を窒素置換しながら、反応器内の液の温度を60℃に上げて重合を開始した。60℃到達後50分間経過時点で、懸濁安定剤としてノニオン系水溶性高分子であるメトローズ60SH-50(株式会社信越化学工業製、ヒドロキシプロピルメチルセルロース)を0.375部反応器内に添加した。その後60℃でさらに単量体を200分間反応させた後、反応器内の液を80℃に昇温した。同温度で、反応液を3時間撹拌し、重合を完結させた。得られた重合体に対して、樹脂量の3倍量の脱イオン水を用いた水洗を4回実施し、乾燥させることで、ビーズ状の懸濁重合体粒子を得た。得られた重合体の重量平均分子量をGPCで確認したところ200万であった。これを熱可塑性アクリル系樹脂(A1)とする。
<多層構造重合体粒子の製造>
撹拌機付き8L重合装置に、以下の物質を仕込んだ。
脱イオン水 175部
ポリオキシエチレンラウリルエーテルリン酸 0.0104部
ホウ酸 0.4725部
炭酸ナトリウム 0.004725部
水酸化ナトリウム 0.00975部
分散安定性を改良するための界面活性剤として下記を使用した。
界面活性剤1(Sf1、リン酸モノエステル系):
プライサーフM208F(第一工業製薬社製 、ポリオキシエチレン(10)トリデシルエーテルリン酸モノエステル モノエタノールアミン塩)
界面活性剤2(Sf2、リン酸モノエステル系):
フォスファノールRD-510Y(東邦化学製 、ポリオキシエチレン(4)ラウリルエーテルリン酸モノエステル)
界面活性剤3(Sf3、リン酸モノエステル系):
上述のリン酸モノエステル系界面活性剤2の水溶液に過剰量の水酸化ナトリウムを添加し、60℃で3時間加熱・鹸化をした。その後、吸引濾過により回収し、ポリオキシエチレンラウリルエーテルリン酸モノエステルのナトリウム塩とした。
界面活性剤4(Sf4、スルホン酸系):
スルホコハク酸ジオクチルナトリウム塩(東京化成工業社製)
界面活性剤5(Sf5、リン酸ジエステル系)
Nikkol DLP-10(日光ケミカルズ社製、ジポリオキシエチレン(10)ラウリルエーテルリン酸ナトリウム)
界面活性剤6(Sf6、カルボン酸系):
パルミチン酸カリウム(東京化成工業社製)
(多層構造重合体粒子を含む樹脂ドープの調製)
スクリュー管容器に塩化メチレン87重量%、エタノール13重量%からなる混合溶媒36gを入れた。次いで、混合溶媒中に、リン酸モノエステル系界面活性剤1を0.04g仕込み溶解させた。その後、界面活性剤を含む混合溶媒を撹拌しながら、混合溶媒中に多層構造重合体粒子B1を0.8g入れ溶解、分散させた。その後、得られた粒子分散液を、均一になるまで撹拌した。得られた粒子分散液を超音波バス(ヤマト科学社製 ブランソニック1510J)でさらに15分間超音波分散処理を行い、多層構造重合体粒子が単分散した分散液を得た。分散液を撹拌しながら、分散液に熱可塑性アクリル系樹脂A1を3.2g添加した。熱可塑性アクリル系樹脂A1が完全に溶解するまで分散液を撹拌して、固形分濃度(SC)10%のドープを調製した。
上記調製から72時間経過したドープを、PETフィルム(東洋紡製 コスモシャインA4100)上に流延し、アプリケーターで均一な膜状に塗布した。乾燥後の厚みがおよそ30~50μmとなるように、クリアランスを調整した。塗工後、40℃の乾燥雰囲気下で、ドープからなる塗布膜を5分間乾燥させた後、乾燥したフィルムをPETフィルムから剥離した。その後、乾燥したフィルムをステンレス製の枠に固定し、140℃の乾燥雰囲気にて30分間乾燥させて残存溶媒を除去し、アクリル系樹脂フィルムを得た。
溶媒の組成、加えた界面活性剤を表1、及び表2の通りに変更した以外は、実施例1と同様に実施し、アクリル系樹脂フィルムを作製した。表1、及び表2に、実施例1~9、比較例1~7で得られたドープの分散性、及びそのドープから得られたアクリル系樹脂フィルムの評価結果を示す。
調製直後のドープを用いたことを除いて、比較例1と同様の組成のドープを用いて製膜した。その結果、得られたフィルムのヘイズの値は0.70、YIの値は0.70であり、比較例1よりも良好なフィルムが得られた。またこの時点のドープは壁面へのゲル状の付着物はなかった。
アクリル系熱可塑性樹脂A2として市販のデルペットPM120N(旭化成製、組成:メタクリル酸メチル/N-フェニルマレイミド/スチレン=81/15/4、重量平均分子量:113,000)を使用し、実施例1と同様に実施し、アクリル系樹脂フィルムを作製した。結果を表3に示す。
Claims (15)
- 下記式により算出される、ドープ調製直後の前記多層構造重合体粒子の粒子径D50(Initial)に対する、ドープ調製から72時間経過後の前記多層構造重合体粒子の粒子径D50(72hr)の変化率の絶対値が40%以下である、請求項1に記載のドープ。
変化率の絶対値(%)=|D50(72hr)/D50(Initial)×100-100| - ドープ調製直後の多層構造重合体粒子の粒子径D50(Initial)が、1.0μm以下である、請求項1、又は2に記載のドープ。
- 前記熱可塑性アクリル系樹脂と前記多層構造重合体粒子の合計100重量%に対して、前記リン酸モノエステル系界面活性剤が0.01~3.0重量%である、請求項1~3のいずれか1項に記載のドープ。
- 前記式(1)において、Rが、酸素アニオンと1価のカチオンとの組み合わせである、請求項1~4のいずれか1項に記載のドープ。
- 前記熱可塑性アクリル系樹脂がマレイミド単位を1~50重量%含む、請求項1~5のいずれか1項に記載のドープ。
- 前記熱可塑性アクリル系樹脂、及び前記多層構造重合体粒子の合計100重量部の内、前記多層構造重合体粒子を10~50重量部含む、請求項1~6のいずれか1項に記載のドープ。
- 前記ドープの23℃における粘度が10~1000ポイズである、請求項1~7のいずれか1項に記載のドープ。
- 前記溶媒100重量%中、メタノール、又はエタノールが1~30重量%である、請求項1~8のいずれか1項に記載のドープ。
- 前記アクリル系樹脂フィルムの内部ヘイズが1.5%以下である、請求項10に記載のアクリル系樹脂フィルム。
- 前記アクリル系樹脂フィルムのYIが1.0以下である、請求項10、又は11に記載のアクリル系樹脂フィルム。
- 前記アクリル系樹脂フィルムが偏光子保護フィルムである、請求項10~12のいずれか1項に記載のアクリル系樹脂フィルム。
- 偏光子と、請求項13に記載のアクリル系樹脂フィルムを積層してなる偏光板。
- 請求項14に記載の偏光板を含む、ディスプレイ装置。
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