WO2018062378A1 - アクリル系樹脂フィルムおよびそれの製造方法 - Google Patents
アクリル系樹脂フィルムおよびそれの製造方法 Download PDFInfo
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- WO2018062378A1 WO2018062378A1 PCT/JP2017/035197 JP2017035197W WO2018062378A1 WO 2018062378 A1 WO2018062378 A1 WO 2018062378A1 JP 2017035197 W JP2017035197 W JP 2017035197W WO 2018062378 A1 WO2018062378 A1 WO 2018062378A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- mass
- acrylic polymer
- resin film
- acrylic
- Prior art date
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- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 63
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 31
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- 239000011347 resin Substances 0.000 claims abstract description 126
- 229920005989 resin Polymers 0.000 claims abstract description 126
- 239000004816 latex Substances 0.000 claims abstract description 60
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- 238000000034 method Methods 0.000 claims abstract description 39
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- 238000002844 melting Methods 0.000 claims abstract description 21
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- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 16
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- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 39
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 22
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229920001169 thermoplastic Polymers 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 238000006116 polymerization reaction Methods 0.000 description 46
- 230000002087 whitening effect Effects 0.000 description 39
- 239000000178 monomer Substances 0.000 description 28
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- 238000009835 boiling Methods 0.000 description 18
- -1 n-butyl methyl Chemical group 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 238000000149 argon plasma sintering Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
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- 239000007788 liquid Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 241001093575 Alma Species 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
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- 238000000465 moulding Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- JHCAASGQBQNAKN-UHFFFAOYSA-N 1-bicyclo[2.2.1]hept-2-enyl prop-2-enoate Chemical compound C(C=C)(=O)OC12C=CC(CC1)C2 JHCAASGQBQNAKN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- PCVSIMQAFWRUEC-UHFFFAOYSA-N N2-[1-[methyl-(phenylmethyl)amino]-3-(2-naphthalenyl)-1-oxopropan-2-yl]-N1-(2-nitrophenyl)pyrrolidine-1,2-dicarboxamide Chemical compound C=1C=C2C=CC=CC2=CC=1CC(NC(=O)C1N(CCC1)C(=O)NC=1C(=CC=CC=1)[N+]([O-])=O)C(=O)N(C)CC1=CC=CC=C1 PCVSIMQAFWRUEC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- OXOPJTLVRHRSDJ-SNAWJCMRSA-N [(e)-but-2-enyl] 2-methylprop-2-enoate Chemical compound C\C=C\COC(=O)C(C)=C OXOPJTLVRHRSDJ-SNAWJCMRSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 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
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 150000002019 disulfides Chemical class 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- ZWEDFBKLJILTMC-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-hydroxybutanoate Chemical compound CCOC(=O)CC(O)C(F)(F)F ZWEDFBKLJILTMC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- ZZMDMGNQUXYKQX-UHFFFAOYSA-L sodium;1-nonyl-2-(2-nonylphenoxy)benzene;sulfate Chemical compound [Na+].[O-]S([O-])(=O)=O.CCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1CCCCCCCCC ZZMDMGNQUXYKQX-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
Definitions
- the present invention relates to a resin film and a method for producing the same. More specifically, the present invention relates to a resin film excellent in transparency, warm water resistance (80 ° C.) whitening resistance, boiling water (100 ° C.) whitening resistance, stress whitening resistance, film forming property, and heat shrink resistance, and production thereof. Regarding the method.
- the acrylic resin film Since the acrylic resin film is excellent in transparency, design properties, weather resistance, etc., its use as a film material for the outermost surface layer of the wall material is known (see, for example, Patent Document 1). Wall materials used in garages, bathrooms, toilets, and washrooms often come in contact with hot water. However, the acrylic resin film may be whitened when it comes into direct contact with warm water (about 80 ° C.).
- Patent Document 2 is an acrylic resin in which rubber particles are dispersed in a methacrylic resin, and has a water-soluble substance content of 200 ppm or less, and warm water at 80 ° C. for 1 hour.
- An acrylic resin film having a haze value of 5% or less after immersion and a thickness of 50 ⁇ m or more and 600 ⁇ m or less is disclosed.
- Patent Document 3 discloses an acrylic resin film which is a film formed by molding an acrylic resin composition, and the number of microvoids whose major axis is less than 500 nm is 30/400 ⁇ m 2 or less. Yes.
- Patent Document 4 describes that methacrylic resin (A) 60 to 98% by mass and multilayer structure polymer particles (B) 40 to 2% by mass are intended to improve impact resistance, slipperiness and matte properties. %, And a film made of a methacrylic resin composition comprising 100 to 5 parts by mass of the silicone fine particles (C) and 0.1 to 5 parts by mass.
- Patent Document 5 contains acrylic rubber particles (A) having an acid value of 0.2 mmol / g or more, and the acid value of the entire resin constituting the film is 0, as an improvement in adhesion to metal.
- the (meth) acrylic-type resin film which is .15 mmol / g or more and 1.5 mmol / g or less is disclosed.
- An object of the present invention is to provide a resin film excellent in transparency, weather resistance, warm water (80 ° C.) whitening, boiling water (100 ° C.) whitening, stress whitening resistance, film-forming property, and heat shrink resistance, and its It is to provide a manufacturing method.
- the multilayer structure acrylic polymer contains the polymer (a), the polymer (b), and the polymer (c).
- the polymer (a) comprises 40 to 99.99 mass% of structural units derived from methyl methacrylate, 1 to 60 mass% of structural units derived from alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, A polymer comprising 0.01 to 1% by mass of structural units derived from 0% and 0.5% by mass of structural units derived from a crosslinking agent;
- the polymer (b) comprises 70 to 99.5% by mass of a structural unit derived from an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 0 to 30% by mass of a structural unit derived from methyl methacrylate, A polymer comprising 0.5 to 5 mass% of structural units derived from and 0 to 5 mass% of structural units derived from a crosslinking agent; and the polymer (c) is a structural unit of 80 to 99 derived from methyl methacrylate
- the resin film according to [1] which is a polymer having a glass transition temperature of 80 ° C. or more, comprising 1% by mass to 20% by mass and a structural unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group.
- Emulsion polymerization is performed to obtain a latex containing a multilayer structure acrylic polymer,
- the latex is coagulated to obtain a slurry, Washing and dewatering the slurry;
- the dehydrated slurry is dried to obtain a multilayer structure acrylic polymer,
- methyl methacrylate 40 to 99.99% by mass, alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 1 to 60% by mass, grafting agent 0.01 to 1% by mass, and A latex (I) containing the polymer (a) is obtained by polymerizing 0 to 0.5% by mass of a crosslinking agent;
- latex (I) an alkyl acrylate having an alkyl group with 1 to 8 carbon atoms of 70 to 99.5% by mass, methyl methacrylate of 0 to 30% by mass, grafting agent of 0.5 to 5% by mass, and
- a latex (II) containing a polymer (a) and a polymer (b) is obtained by polymerizing 0 to 5% by mass of a crosslinking agent;
- latex (II) 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass of alkyl acrylate having 1 to 8
- thermoplastic polymers are polycarbonate polymers, vinyl chloride polymers, vinylidene fluoride polymers, vinyl acetate polymers, maleic acid copolymers, methacrylic resins, ABS resins, AES resins.
- laminate according to [11] which is at least one selected from AS resin.
- the resin film of the present invention is excellent in transparency, warm water (80 ° C.) whitening resistance, boiling water (100 ° C.) whitening resistance, stress whitening resistance, film-forming property, and heat shrinkage resistance.
- a resin film excellent in transparency, warm water resistance (80 ° C.) whitening resistance, boiling water resistance (100 ° C.) whitening resistance, stress whitening resistance, film-forming property, and heat shrink resistance is produced. be able to.
- the resin film of the present invention has a small residual amount of water-soluble substances such as an emulsifier and a polymerization initiator used during polymerization. In the method of the present invention, the amount of heat to be applied is suppressed because the process of undergoing a relatively high temperature state such as drying and extrusion molding is performed for a short time and at a low temperature.
- the acid value of acetone-insoluble matter is 0.018 mmol / g or less, preferably 0.015 mmol / g or less, more preferably 0.012 mmol / g or less.
- the lower limit of the acid value of the acetone-insoluble component of the film of the present invention is preferably 0.001 mmol / g. As the acid value of the acetone-insoluble component of the film is lower, the warm water resistance or boiling water whitening resistance of the film tends to be improved.
- the resin film of the present invention has an acid value of acetone-soluble component of 0.012 mmol / g or less, preferably 0.009 mmol / g or less, more preferably 0.007 mmol / g or less.
- the lower limit of the acid value of the acetone-soluble component of the film of the present invention is preferably 0.001 mmol / g. As the acid value of the acetone-soluble portion of the film is lower, the hot water resistance or the boiling water whitening resistance of the film tends to be improved.
- the glass transition temperature of the resin film of the present invention is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher. As the glass transition temperature of the film is higher, the warm water resistance or boiling water whitening resistance of the film tends to be improved.
- the thickness of the resin film of the present invention is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 15 to 100 ⁇ m.
- the resin film of a preferred embodiment of the present invention has a haze (H 0 ) of preferably 1.5% or less, more preferably 1% or less, and even more preferably 0.5% or less in a room temperature storage state.
- the haze is measured with a test piece having an optical path length of 50 ⁇ m in accordance with JIS K 7136.
- the resin film of a preferred embodiment of the present invention has a haze change width ( ⁇ H 80 ) before and after a hot water whitening test using 80 ° C. water, preferably 10% or less, more preferably 7% or less, and even more preferably 5 % Or less.
- the resin film of a preferred embodiment of the present invention has a haze change width ( ⁇ H 100 ) before and after a boiling water whitening test using 100 ° C. water (boiling water), preferably 10% or less, more preferably 7% or less. Preferably it is 5% or less.
- the resin film of the present invention contains a multilayer structure acrylic polymer.
- Examples of the layer structure of the multilayer structure acrylic polymer include a core-shell multilayer structure, a sea-island multilayer structure, and a mosaic multilayer structure. Of these, a core-shell multilayer structure is preferred.
- the core-shell multilayer structure acrylic polymer can be obtained, for example, by melt-kneading a three-layer granular material composed of a core, an inner shell, and an outer shell.
- the core and the inner shell, and the inner shell and the outer shell are made of different polymers. It is preferable that there is no gap between the core and the inner shell and between the inner shell and the outer shell.
- the polymer constituting the inner shell is preferably softer than the polymer constituting the core and the polymer constituting the outer shell.
- the polymer constituting the inner shell and the polymer constituting the core are preferably insoluble in acetone.
- the polymer constituting the outer shell is preferably soluble in acetone.
- the polymer constituting the outer shell can be a matrix of a two-layer granule composed of a core and an inner shell by fusing all or part of the outer shell by melting and kneading the three-layer granule.
- the lower limit of the average particle diameter of the three-layer granule contained in the core-shell multilayer structure acrylic polymer is preferably 0.01 ⁇ m, more preferably 0.04 ⁇ m, still more preferably 0.05 ⁇ m, still more preferably 0.1 ⁇ m.
- the upper limit of the average particle diameter is preferably 0.35 ⁇ m, more preferably 0.3 ⁇ m, still more preferably 0.2 ⁇ m, and still more preferably 0.15 ⁇ m.
- the stress whitening resistance of the film tends to decrease as the average particle size of the granular material increases.
- the average particle diameter of the three-layer granule is a value obtained by a light scattering method.
- the multilayer structure acrylic polymer preferably contains a polymer (a), a polymer (b), and a polymer (c) and forms a layer structure with them.
- the polymer (a) constitutes the core
- the polymer (b) constitutes the inner shell
- the polymer (c) constitutes the outer shell.
- the amount of the polymer (a) contained in the multilayer structure acrylic polymer is preferably 5 to 30% by mass, more preferably 10 to 20% by mass with respect to the mass of the multilayer structure acrylic polymer.
- the amount of the polymer (b) contained in the multilayer structure acrylic polymer is preferably 20 to 45% by mass, more preferably 30 to 40% by mass, based on the mass of the multilayer structure acrylic polymer. There exists a tendency for the thermal stability and productivity of a multilayer structure acrylic polymer to fall, so that there is little quantity of a polymer (b).
- the amount of the polymer (c) contained in the multilayer structure acrylic polymer is preferably 50 to 75 mass%, more preferably 50 to 60 mass%, based on the mass of the multilayer structure acrylic polymer.
- the fluidity liquidity of a multilayer structure acrylic polymer and the moldability of a film to fall, so that the quantity of a polymer (c) is small.
- the amount of the polymer (c) increases, the impact resistance and stress whitening resistance of the film tend to decrease.
- the polymer (a) is a polymer comprising a structural unit derived from methyl methacrylate, a structural unit derived from an alkyl acrylate, a structural unit derived from a grafting agent, and a structural unit derived from a crosslinking agent as necessary. is there.
- the amount of the structural unit derived from methyl methacrylate in the polymer (a) is preferably 40 to 98.9% by mass, more preferably 90 to 96.9% by mass, based on all the structural units of the polymer (a). More preferably, it is 90 to 96.5% by mass.
- the weather resistance of the film tends to decrease as the amount of structural units derived from methyl methacrylate decreases, and the impact resistance of the film tends to decrease as the amount of structural units derived from methyl methacrylate increases.
- the amount of the structural unit derived from the alkyl acrylate in the polymer (a) is preferably 1 to 59.99% by mass, more preferably 2.6 to 9.99, based on all the structural units of the polymer (a). % By mass, more preferably 3 to 9.9% by mass.
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of the structural unit derived from the alkyl acrylate, the lower the thermal decomposition resistance of the multi-layered acrylic polymer. The larger the amount of the structural unit derived from the alkyl acrylate, the more resistant the film to warm water or boiling water resistance Tends to decrease.
- the amount of the structural unit derived from the grafting agent in the polymer (a) is preferably 0.01 to 1% by mass, more preferably 0.1 to 0.00%, based on the total structural units of the polymer (a). 5% by mass.
- the larger the amount of the structural unit derived from the grafting agent There is a tendency for impact resistance to decrease.
- the amount of the structural unit derived from the crosslinking agent in the polymer (a) is preferably 0 to 0.5% by mass, more preferably 0 to 0.2% by mass, based on all the structural units of the polymer (a). It is. As the amount of the structural unit derived from the cross-linking agent increases, the impact resistance of the film tends to decrease.
- the polymer (b) is a polymer composed of a structural unit derived from an alkyl acrylate, a structural unit derived from a grafting agent, and a structural unit derived from methyl methacrylate and a structural unit derived from a crosslinking agent, if necessary. It is.
- the amount of the structural unit derived from the alkyl acrylate in the polymer (b) is preferably 70 to 99.5% by mass, more preferably 80 to 99% by mass, based on all the structural units of the polymer (b). .
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the impact resistance of the film, and the larger the amount of structural units derived from alkyl acrylate, the lower the stress whitening resistance and transparency of the film. is there.
- the amount of the structural unit derived from the grafting agent in the polymer (b) is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass with respect to the total structural units of the polymer (b). is there.
- the amount of the structural unit derived from methyl methacrylate in the polymer (b) is preferably 0 to 29.5% by mass, more preferably 0 to 19% by mass, based on all the structural units of the polymer (b). .
- the amount of the structural unit derived from the crosslinking agent in the polymer (b) is preferably 0 to 5% by mass, more preferably 0 to 2% by mass with respect to the total structural units of the polymer (b). As the amount of the structural unit derived from the cross-linking agent increases, the impact resistance of the film tends to decrease.
- the polymer (c) is a polymer composed of a structural unit derived from methyl methacrylate and a structural unit derived from alkyl acrylate.
- the amount of the structural unit derived from methyl methacrylate in the polymer (c) is preferably 80 to 99% by mass, more preferably 95 to 98% by mass, based on all the structural units of the polymer (c).
- the amount of the structural unit derived from the alkyl acrylate in the polymer (c) is preferably 1 to 20% by mass, more preferably 2 to 5% by mass with respect to all the structural units of the polymer (c).
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of the structural unit derived from the alkyl acrylate, the lower the thermal decomposition resistance of the multilayer acrylic polymer. The larger the amount of the structural unit derived from the alkyl acrylate, the lower the stress whitening resistance of the film. Tend.
- the polymer (c) has a glass transition temperature of preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 100 ° C. or higher. As the glass transition temperature of the polymer (c) is higher, the warm water resistance or boiling water whitening resistance of the film tends to be improved.
- alkyl acrylate used in the polymer (a), the polymer (b) and the polymer (c) examples include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, t- Examples thereof include butyl acrylate, n-butyl methyl acrylate, n-heptyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These alkyl acrylates can be used alone or in combination of two or more. Of these, methyl acrylate and / or n-butyl acrylate are preferable.
- the grafting agent used for the polymer (a) and the polymer (b) chemically bonds the polymer (a) and the polymer (b), and the polymer (b) and the polymer (c). It is a monomer that mainly has a role and is considered to have a role of assisting the formation of a crosslinked structure in the polymer (a) or the polymer (b).
- the grafting agent in the present invention is a monomer having two or more different polymerizable groups. Examples of the grafting agent in the present invention include allyl methacrylate, allyl acrylate, mono- or di-allyl maleate, mono- or di-allyl fumarate, crotyl acrylate, crotyl methacrylate and the like.
- grafting agents can be used alone or in combination of two or more.
- allyl methacrylate improves the bonding ability between the polymer (a) and the polymer (b) or between the polymer (b) and the polymer (c), and the stress resistance of the film. Since it is excellent in the effect
- the crosslinking agent used in the polymer (a) and the polymer (b) is a monomer that is considered to mainly have a role of forming a crosslinked structure in the polymer (a) or the polymer (b).
- the cross-linking agent in the present invention is a monomer having two or more of the same type of polymerizable group, and examples thereof include a diacryl compound, a dimethacryl compound, a diallyl compound, a divinyl compound, a diene compound, and a trivinyl compound.
- crosslinking agent in the present invention examples include ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, trivinylbenzene, ethylene Examples thereof include glycol diallyl ether, propylene glycol diallyl ether, and butadiene. These crosslinking agents can be used singly or in combination of two or more.
- the multilayer acrylic polymer used in the present invention has a melt flow rate under a load of 230 ° C. and a load of 3.8 kg, preferably 0.5 to 20 g / 10 minutes, more preferably 0.8 to 10 g / 10 minutes.
- the lower the melt flow rate of the multilayer structure acrylic polymer the lower the fluidity of the multilayer structure acrylic polymer and the moldability of the film.
- the multilayer structure acrylic polymer used in the present invention has an acid value of acetone insolubles of preferably 0.008 mmol / g or less, more preferably 0.006 mmol / g or less, and further preferably 0.004 mmol / g or less. is there.
- the lower limit of the acid value of the acetone-insoluble part of the multilayer acrylic polymer is preferably 0.001 mmol / g. The lower the acid value of the acetone-insoluble component of the multi-layer structure acrylic polymer, the better the warm water resistance or boiling water whitening resistance of the film.
- the multilayer structure acrylic polymer used in the present invention has an acid value of acetone-soluble content of preferably 0.012 mmol / g or less, more preferably 0.009 mmol / g or less, and further preferably 0.007 mmol / g or less. It is.
- the lower limit of the acid value of the acetone-soluble component of the multilayer acrylic polymer is preferably 0.001 mmol / g. As the acid value of the multilayer acrylic polymer is lower, the warm water resistance or boiling water whitening resistance of the film tends to be improved.
- the polymer (a), the polymer (b), and the polymer chain of the polymer (c) grafted to the polymer chain of the polymer (b) are detected as acetone-insoluble matter.
- the polymer chain of the polymer (c) that is not grafted to the polymer chain of the polymer (b) is detected as an acetone-soluble component.
- the multilayer structure acrylic polymer is not particularly limited depending on the production method.
- the polymer (a), the polymer (b), and the polymer (c) can be sequentially formed by a seed emulsion polymerization method to obtain an acrylic polymer having a core-shell multilayer structure.
- the resin film of the present invention may contain other thermoplastic resins in addition to the multilayer structure acrylic polymer.
- Other thermoplastic resins include polycarbonate polymers, vinyl chloride polymers, vinylidene fluoride polymers, vinyl acetate polymers, maleic acid copolymers, acrylic resins, ABS resins, AES resins, AS resins. And so on.
- the mass ratio of the other thermoplastic resin / multilayer structure acrylic polymer is preferably 0/100 to 35/65, more preferably 0/100 to 20/80.
- a preferred method for producing the resin film of the present invention is to obtain a latex containing a multilayer acrylic polymer by emulsion polymerization of an acrylic monomer; and coagulate a latex containing a multilayer acrylic polymer to obtain a slurry.
- the slurry is washed and dewatered;
- the dehydrated slurry is dried to obtain a multilayer structure acrylic polymer;
- a more preferable production method of the resin film of the present invention is that methyl methacrylate is 40 to 99.99 mass%, more preferably 90 to 96.9 mass%, and the alkyl group has 1 to 8 carbon atoms in the presence of an emulsifier.
- Alkyl acrylate 1 to 60% by mass, more preferably 3 to 10% by mass, grafting agent 0.01 to 1% by mass, more preferably 0.1 to 0.5% by mass and cross-linking agent 0 to 0.5% by mass More preferably, 0 to 0.2 mass% is polymerized (1st polymerization) to obtain latex (I) containing polymer (a); in the presence of latex (I), the alkyl group has 1 carbon atom.
- a latex (II) containing a polymer (a) and a polymer (b) by polymerizing (2nd polymerization) 1 to 3% by mass and a crosslinking agent 0 to 5% by mass, more preferably 0 to 2% by mass.
- methyl methacrylate is 80 to 99% by mass, more preferably 95 to 98% by mass, and alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, 1 to 20% by mass, and more Preferably 2 to 5% by mass is polymerized (3rd polymerization) to obtain latex (III) containing polymer (a), polymer (b) and polymer (c); Solidified to obtain a slurry; ⁇ The slurry is washed and dewatered; The dehydrated slurry is dried to contain a polymer (a), a polymer (b), and a polymer (c). A polymer is obtained; 0-35% by mass of acrylic resin and multilayer structure It is intended to include extruding melted the mixture of the acrylic polymer 65-100% by weight.
- Polymerization can be performed by a known method. Among the polymerizations carried out in the presence of latex, seed emulsion polymerization is preferably used for obtaining a core-shell multilayer acrylic polymer. Since emulsion polymerization or seed polymerization is a method well known in the art, details are left to the literature on polymerization techniques.
- the rate at which the monomers used in each polymerization, specifically, a mixture of methyl methacrylate, alkyl acrylate, grafting agent and cross-linking agent in the proportions described above, is supplied to the reaction system depends on each polymerization. Is preferably 0.05 to 3% by mass / min, more preferably 0.1 to 1% by mass / min, and still more preferably 0.2 to 0% with respect to 100% by mass of the total amount of monomers used in 8% by mass / min.
- the polymerization initiator used in each polymerization is not particularly limited.
- examples of polymerization initiators include, for example, water-soluble inorganic initiators such as potassium persulfate and ammonium persulfate; redox initiators formed by using sulfites or thiosulfates in combination with inorganic initiators; organic peroxides The redox initiator etc. which combine ferrous salt or sodium sulfoxylate etc. can be mentioned.
- the polymerization initiator may be added to the reaction system all together at the start of the polymerization, or may be added to the reaction system separately at the start of polymerization and during the polymerization in consideration of the reaction rate.
- the amount of the polymerization initiator used can be appropriately set so that, for example, the average particle diameter of the granular material contained in the core-shell multilayer acrylic polymer is within the above-mentioned range.
- the emulsifier used in each polymerization is not particularly limited.
- the emulsifier include anionic emulsifiers such as long-chain alkyl sulfonates, sulfosuccinic acid alkyl ester salts, and alkyl benzene sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene nonylphenyl ethers; Polyoxyethylene nonylphenyl ether sulfate such as sodium nonylphenyl ether sulfate, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene alkyl ether sulfate, alkyl ether carboxylate such as sodium polyoxyethylene tridecyl ether acetate, etc.
- Nonionic and anionic emulsifiers can be mentioned.
- the amount of the emulsifier used can be appropriately set so that, for example, the average particle diameter of the granular material contained in the core-shell multilayer acrylic polymer falls within the above-mentioned range.
- the 1st polymerization, the 2nd polymerization, and the 3rd polymerization may be sequentially performed in one polymerization tank, or may be sequentially performed by changing the polymerization tank for each of the 1st polymerization, the 2nd polymerization, and the 3rd polymerization. In the present invention, it is preferable to perform each polymerization sequentially in one polymerization tank. Further, the temperature of the reaction system during the polymerization is preferably 30 to 120 ° C., more preferably 50 to 100 ° C.
- a reactive ultraviolet absorber such as 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-1, 2,3-benzotriazole and the like can be added.
- a reactive ultraviolet absorber is introduced into the molecular chain of the multilayer acrylic polymer, and the ultraviolet resistance of the multilayer acrylic polymer is improved.
- the addition amount of the reactive ultraviolet absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used for the polymerization.
- Chain transfer agents can be used in each polymerization to control molecular weight.
- the chain flow agent is added to the reaction system to adjust the molecular weight of the polymer (c), whereby the melt flow rate of the multilayer structure acrylic polymer can be within the aforementioned range.
- the chain transfer agent used for each polymerization is not particularly limited.
- Examples of the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan; xanthogen disulfides such as dimethylxanthogen disulfide and diethylxanthogen disulfide; And thiuram disulfides such as halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide.
- the amount of the chain transfer agent used can be appropriately set within a range in which the polymer can be adjusted to a predetermined molecular weight in each polymerization.
- the amount of chain transfer agent used in the 3rd polymerization is an amount that can bring the value of the melt flow rate into the above-mentioned range.
- the amount of chain transfer agent used in 3rd polymerization varies depending on the amount of polymerization initiator used in 3rd polymerization, etc., but the monomers used in 3rd polymerization, specifically the total of methyl methacrylate and alkyl acrylate
- the amount is preferably 0.05 to 2 parts by mass, more preferably 0.08 to 1 part by mass with respect to 100 parts by mass.
- the latex can be coagulated by a known method.
- the coagulation method include a freeze coagulation method, a salting out coagulation method, and an acid precipitation coagulation method.
- the freeze-coagulation method is preferred because it does not require the addition of a coagulant as an impurity for the multilayer structure acrylic polymer.
- the washing and dehydration of the slurry obtained by coagulation is preferably sufficiently performed so that the acid value of the multilayer acrylic polymer is in the above-mentioned range.
- water-soluble components such as emulsifiers and catalysts can be removed from the slurry.
- the slurry can be washed and dehydrated by, for example, a filter press, a belt press, a gina centrifuge, a screw decanter centrifuge, or the like. From the viewpoint of productivity and washing efficiency, it is preferable to use a screw decanter centrifuge.
- the slurry is preferably washed and dehydrated at least twice. As the number of washing and dehydration increases, the remaining amount of water-soluble components decreases. However, from the viewpoint of productivity, the number of washing and dehydration is preferably 3 times or less.
- the slurry is dried so that the moisture content is preferably less than 0.2% by mass, more preferably less than 0.1% by mass.
- the higher the moisture content the more the ester hydrolysis reaction occurs in the multilayer acrylic polymer during melt extrusion molding, and the carboxyl group tends to be generated in the molecular chain.
- the resin film of the present invention can be obtained, for example, by extruding a multilayer structure acrylic polymer.
- the resin film of the present invention may be obtained by mixing a multilayer structure acrylic polymer and an acrylic resin and extruding the mixture.
- the mass ratio of the acrylic resin / multilayer structure acrylic polymer is preferably 0/100 to 35/65, more preferably 0/100 to 30/70, and further preferably 5/95 to 20/80. If it is this range, film forming property will become favorable.
- An acrylic resin that can be used as necessary in extrusion molding is a resin having a structural unit derived from methyl methacrylate and, if necessary, a structural unit derived from an acrylate ester.
- the amount of the structural unit derived from methyl methacrylate in the acrylic resin is preferably 85 to 100% by mass, more preferably 92 to 100% by mass, based on the mass of all structural units of the acrylic resin.
- the amount of the structural unit derived from the acrylate ester in the acrylic resin is preferably 0 to 15% by mass, more preferably 0 to 8% by mass, based on the mass of all structural units of the acrylic resin.
- Acrylic esters in acrylic resins include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, n- Hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate Glycidyl acrylate, allyl acrylate, phenyl acrylate, etc. Can. Of these, alkyl acrylates having 1 to 6 carbon atom
- the acrylic resin used as necessary for extrusion molding has a glass transition temperature of preferably 95 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 105 ° C. or higher.
- the acrylic resin has a melt flow rate at 230 ° C. under a load of 3.8 kg, preferably 0.5 to 20 g / 10 minutes, more preferably 0.8 to 10 g / 10 minutes.
- the acrylic resin is not particularly limited by the manufacturing method.
- it can be produced by a known polymerization method such as a radical polymerization method or an anionic polymerization method.
- Adjustments to the above-mentioned characteristic values of acrylic resins can be made by adjusting the polymerization conditions, specifically the polymerization temperature, polymerization time, type and amount of chain transfer agent, type and amount of polymerization initiator, etc. Can be done. Adjustment of resin characteristics by adjusting polymerization conditions is a technique well known to those skilled in the art.
- the multilayer structure acrylic polymer and acrylic resin are preferably pelletized in order to facilitate transportation, storage, molding, and the like. It is preferable that the extruder used when pelletizing the multilayer acrylic polymer is provided with a vent.
- the vent is preferably a vacuum vent or an open vent. It is preferable to provide at least one vent on the downstream side of the resin melting start portion.
- the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, further preferably 9 Torr or less, and most preferably 6 Torr or less. If the pressure in the vacuum vent is within the above range, the devolatilization efficiency is good and the residual moisture and monomer can be reduced.
- the extruder used for pelletization is preferably a single screw type.
- a single screw extruder has a small shearing energy applied to a multilayer acrylic polymer or the like, and can suppress thermal decomposition of the polymer.
- the screw configuration is preferably full flight.
- the cylinder heating temperature of the extruder used for pelletization is preferably 210 to 270 ° C, more preferably 220 to 260 ° C, and further preferably 230 to 250 ° C.
- the residence time in the extruder is preferably 7 minutes or less, more preferably 5 minutes or less, and even more preferably 3 minutes or less. The higher the cylinder heating temperature or the longer the residence time, the greater the shear energy given to the multilayer acrylic polymer and the like, the more likely the thermal decomposition of the polymer proceeds, and the hot water whitening resistance of the film tends to decrease.
- the moisture content of the multilayered acrylic polymer and acrylic resin before being subjected to extrusion molding is preferably less than 0.2% by mass, more preferably less than 0.1% by mass. The higher the moisture content, the more likely to cause silver streak and decrease in resistance to warm water whitening.
- the additive for resin may be contained.
- the total content of the additive for resin is preferably 20% by mass or less with respect to 100% by mass of the total amount of the multilayer structure acrylic polymer and the acrylic resin.
- the additive for resin may be added to, for example, the multilayered acrylic polymer and acrylic resin melted in the film forming machine, or may be added to the pelletized multilayered acrylic polymer or acrylic resin. They may be blended or added when pelletizing the multilayer structure acrylic polymer or acrylic resin (masterbatch method).
- the multilayer structure acrylic polymer and acrylic resin preferably contain an ultraviolet absorber.
- the ultraviolet absorber examples include reactive ultraviolet absorbers such as 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-1,2,3-benzotriazole.
- the content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the multilayer structure acrylic polymer and the acrylic resin.
- the extruder used for film formation preferably has a vent.
- the vent is preferably a vacuum vent or an open vent. It is preferable to provide at least one vent on the downstream side of the resin melting start portion.
- the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, further preferably 9 Torr or less, and most preferably 6 Torr or less.
- the extruder used for film formation is preferably a single screw type or a co-rotating twin screw type.
- the cylinder heating temperature of the extruder used for film formation is preferably 220 to 300 ° C, more preferably 230 to 290 ° C, and further preferably 240 to 280 ° C.
- the residence time in the extruder used for film formation is preferably 7 minutes or less, more preferably 5 minutes or less, and even more preferably 3 minutes or less.
- the extrusion molding for film formation is preferably carried out with a residence time in the extruder of 5 minutes or less and a resin temperature of 280 ° C. or less.
- the resin film of the present invention can be obtained by the production method as described above.
- the resin film of the present invention is excellent in impact resistance and stress whitening resistance, and does not cause whitening even when bent, and has excellent hot water whitening resistance and boiling water whitening resistance, and is exposed to hot water and boiling water. No whitening occurs.
- the resin film of the present invention is excellent in adhesiveness to other polymers, particularly thermoplastic polymers.
- the laminate of the present invention has at least one layer made of the resin film of the present invention and at least one layer made of another thermoplastic polymer molded article.
- the other thermoplastic polymer used in the laminate of the present invention is not particularly limited.
- Other thermo-plastic polymers include polycarbonate polymers, vinyl chloride polymers, vinylidene fluoride polymers, vinyl acetate polymers, maleic acid copolymers, methacrylic resins, ABS resins, AES resins, or AS resin is preferable because it has good adhesion to the resin film of the present invention.
- the thermoplastic polymer molded product may be a planar molded product such as a film, a sheet, or a plate, a linear molded product such as a tube or a rod, a lens, a prism, a container, or the like.
- the molded product may have various shapes such as
- the laminate of the present invention is not particularly limited by its production method.
- the laminate of the present invention is obtained by, for example, co-extrusion molding the above-mentioned multilayer structure acrylic polymer and another thermoplastic polymer, so that the multilayer structure acrylic system is formed on the other thermoplastic polymer molded article.
- the resin of the present invention is formed by coating and extruding the resin, placing another thermoplastic polymer molded article in a desired mold, melting the multilayer structure acrylic polymer, and injecting or injecting it into the mold. By placing the film in the desired mold, melting the other thermoplastic polymer, and injecting or injecting it into the mold, the above-mentioned multilayer structure acrylic resin is placed on the other thermoplastic polymer molded article and pressed.
- the resin film of the present invention can be obtained by heat-sealing or bonding to other thermoplastic polymer molded articles.
- part represents a mass part.
- the latex of the multilayer structure acrylic polymer was collected, and the average particle size was determined by a light scattering method using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 manufactured by Horiba.
- melt flow rate (Melt flow rate) According to ASTM-D1238, the melt flow rate (hereinafter referred to as “MFR”) at 230 ° C. under a load of 3.8 kg was measured.
- Glass-transition temperature In accordance with JIS K7121, using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation), the temperature was raised once to 250 ° C., then cooled to room temperature, and then from room temperature to 230 ° C. at 20 ° C./min. The DSC curve was measured under the condition of raising the temperature at. The midpoint glass transition temperature obtained from the DSC curve was defined as the glass transition temperature in the present invention (hereinafter referred to as “Tg”).
- methyl methacrylate is abbreviated as MMA, n-butyl acrylate as nBA, methyl acrylate as MA, allyl methacrylate as ALMA, and n-octyl mercaptan (chain transfer agent) as nOM.
- a monomer mixture was prepared by putting 92 parts of purified MMA and 8 parts of MA in an autoclave equipped with a stirrer and a sampling tube.
- a polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction capacity: 1%, 1 hour half-life temperature: 83 ° C.
- 0.15 part of nOM was dissolved to obtain a raw material liquid.
- the oxygen gas in the production apparatus was purged with nitrogen gas.
- the raw material liquid is supplied from an autoclave to a continuous flow tank reactor controlled at a temperature of 140 ° C.
- the liquid discharged from the tank reactor is heated to 240 ° C., and supplied to a twin-screw extruder having an open vent and a vacuum vent controlled at 250 ° C. at a constant flow rate.
- Adiabatic flash evaporation Components volatilized by adiabatic flash evaporation (monomer, dimer, trimer, etc.) were discharged from the open vent.
- Components (such as monomers) volatilized by melt kneading with a twin screw were discharged from a vacuum vent reduced to 6 Torr provided downstream from the extruder supply port.
- the resin component from which volatile components were substantially removed was extruded with a biaxial screw to obtain a strand.
- the strand was cut with a pelletizer to pelletize the acrylic resin [B1].
- the acrylic resin [B1] had a Tg of 110 ° C. and an MFR of 2 g / 10 min.
- a monomer mixture was prepared by placing 94 parts of purified MMA and 6 parts of MA in an autoclave equipped with a stirrer and a sampling tube.
- a polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction ability: 1%, 1 hour half-life temperature: 83 ° C.
- 0.35 part of nOM was dissolved to obtain a raw material liquid.
- the oxygen gas in the production apparatus was purged with nitrogen gas.
- the raw material liquid is supplied from an autoclave to a continuous flow tank reactor controlled at a temperature of 140 ° C.
- the liquid discharged from the tank reactor is heated to 240 ° C., and supplied to a twin-screw extruder having an open vent and a vacuum vent controlled at 250 ° C. at a constant flow rate.
- Adiabatic flash evaporation Components volatilized by adiabatic flash evaporation (monomer, dimer, trimer, etc.) were discharged from the open vent.
- Components (such as monomers) volatilized by melt kneading with a twin screw were discharged from a vacuum vent reduced to 6 Torr provided downstream from the extruder supply port.
- the resin component from which volatile components were substantially removed was extruded with a biaxial screw to obtain a strand.
- the strand was cut with a pelletizer to pelletize the acrylic resin [B2].
- the acrylic resin [B2] had a Tg of 112 ° C. and an MFR of 10 g / 10 min.
- Example 1 (Process 1) In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube and reflux condenser, 150 parts of ion-exchanged water, 1.3 parts of sodium dodecylbenzenesulfonate and 0.05 parts of sodium carbonate And the inside of the container was sufficiently replaced with nitrogen gas to make it substantially free from the influence of oxygen. Thereafter, the temperature in the reaction vessel was set to 80 ° C. Into the reaction vessel, 0.015 part of potassium persulfate was added and stirred for 5 minutes.
- a monomer mixture composed of 4 parts of MMA, 4 parts of nBA and 0.02 part of ALMA was continuously added dropwise over 20 minutes to carry out emulsion polymerization. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, and emulsion polymerization was carried out so that the conversion rate was 98% or more to obtain a latex containing the polymer (a).
- a reactor containing a latex containing the polymer (a) 0.030 part of potassium persulfate was added and stirred for 5 minutes.
- a monomer mixture consisting of 4 parts of MMA, 26 parts of nBA and 0.9 part of ALMA was continuously added dropwise over 40 minutes to perform seed emulsion polymerization.
- the mixture was further stirred for 30 minutes, and seed emulsion polymerization was carried out so that the conversion rate was 98% or more to obtain a latex containing the polymer (a) and the polymer (b).
- seed emulsion polymerization was carried out so that the conversion rate was 98% or more to obtain a latex containing the polymer (a) and the polymer (b).
- 0.055 part of potassium persulfate was added and stirred for 5 minutes. Thereafter, a monomer mixture consisting of 56 parts of MMA, 6 parts of nBA and 0.2 part of nOM was continuously added dropwise over 100 minutes to perform seed polymerization.
- the mixture is further stirred for 60 minutes, and the seed emulsion polymerization is carried out so that the conversion is 98% or more, and the latex containing the polymer (a), the polymer (b) and the polymer (c) , Expressed as latex [1].).
- the average particle size of latex [1] determined by the light scattering method was 0.09 ⁇ m. Table 1 shows the monomer unit composition ratio and average particle size of latex [1].
- Latex [1] was frozen in an atmosphere of ⁇ 20 ° C. for 4 hours.
- the obtained frozen material was poured into 3 times amount of 80 ° C. water and melted to obtain a slurry.
- the slurry was washed and dewatered with a centrifugal force of 2100 G using a screw decanter centrifuge.
- ion-exchanged water was added so that the slurry concentration became 10%, and washing and dehydration were performed again with a screw decanter centrifuge. Thereafter, the dehydrated slurry was dried with a continuous fluidized bed dryer set at 80 ° C. to obtain a core-shell multilayer acrylic polymer (hereinafter referred to as acrylic polymer [A1]).
- the acrylic polymer [A1] was supplied to a single screw extruder with a vent and pelletized under the conditions of a vent vacuum pressure of 5 Torr and a melt extrusion temperature of 245 ° C. The residence time in the extruder was 2.5 minutes.
- the pelletized acrylic polymer [A1] was dried at 80 ° C.
- the dried acrylic polymer [A1] has a moisture content of 0.06% by mass, an MFR of 2.0 g / 10 min, a Tg of 93 ° C., an acid value of acetone insolubles of 0.004 mmol / g, and acetone.
- the acid value of the solute was 0.009 mmol / g.
- Table 2 shows the characteristic values of the acrylic polymer [A1].
- the obtained resin film had a Tg of 100 ° C., an acid value of acetone-insoluble component of 0.012 mmol / g, and an acid value of acetone-soluble component of 0.008 mmol / g.
- the resin film is 0.4% haze at room temperature, [Delta] H 80 is 2.4%, [Delta] H 100 was 2.3%. It can be seen that the hot water whitening resistance and the boiling water whitening resistance are excellent. The results are shown in Table 3.
- Example 2 The amount of acrylic polymer [A1] and acrylic resin [B1] in step 3 was changed to 90 parts and 10 parts, respectively, and the residence time in the single screw extruder with a vent in step 3 was changed to 3.0 minutes. And the resin film was obtained by the same method as Example 1 except having changed the film thickness into 55 micrometers. Table 3 shows the properties and the like of the obtained resin film.
- Example 3 The amount of acrylic polymer [A1] and acrylic resin [B1] in step 3 was changed to 80 parts and 20 parts, respectively, and the melting temperature in the single screw extruder with a vent in step 3 was changed to 270 ° C. Obtained the resin film by the same method as Example 1. Table 3 shows the properties and the like of the obtained resin film.
- Example 4 Change the acrylic resin [B1] in step 3 to the acrylic resin [B2], change the melting temperature in the vented single screw extruder in step 3 to 260 ° C, the residence time to 3.0 minutes, and the film thickness A resin film was obtained in the same manner as in Example 1 except that the thickness was changed to 60 ⁇ m. Table 3 shows the properties and the like of the obtained resin film.
- Example 5 The amounts of the acrylic polymer [A1] and the acrylic resin [B1] were changed to 100 parts and 0 parts, respectively, the melting temperature in the single screw extruder with a vent in Step 3 was 270 ° C., and the residence time was 4. A resin film was obtained in the same manner as in Example 1 except that the time was changed to 0 minutes. Table 3 shows the properties and the like of the obtained resin film.
- Example 6 Latex [2] was obtained in the same manner as in Step 1 of Example 1 except that the monomer mixture in Step 1 was changed to that shown in Table 1.
- the average particle size of the latex [2] determined by the light scattering method was 0.09 ⁇ m.
- a core-shell multilayer acrylic polymer (hereinafter referred to as acrylic polymer [A4]) is obtained in the same manner as in Step 2 of Example 1, except that latex [2] is used instead of latex [1]. It was.
- Table 2 shows properties of the acrylic polymer [A4]. 70 parts of acrylic polymer [A1] and 30 parts of acrylic resin [B1] were changed to 90 parts of acrylic polymer [A4] and 10 parts of acrylic resin [B1].
- a resin film was obtained in the same manner as in Example 1 except that the melting temperature was changed to 270 ° C. and the residence time was changed to 5.0 minutes.
- Table 3 shows the properties and the like of the obtained resin film.
- Example 7 A core-shell multilayered acrylic polymer (hereinafter referred to as acrylic polymer [A5]) was obtained in the same manner as in Step 2 of Example 6 except that the number of washing and dehydration was changed to 3.
- Table 2 shows properties of the acrylic polymer [A5]. Change 90 parts of acrylic polymer [A4] and 10 parts of acrylic resin [B1] to 100 parts of acrylic polymer [A5], and change the residence time in vented single screw extruder in step 3 to 4.0 minutes.
- a resin film was obtained in the same manner as in Example 6 except that. Table 3 shows the properties and the like of the obtained resin film.
- Example 8 Latex [3] was obtained in the same manner as in Step 1 of Example 1, except that the monomer mixture in Step 1 of Example 1 was changed to that shown in Table 1.
- the average particle size of latex [3] determined by the light scattering method was 0.09 ⁇ m.
- a core-shell multilayer acrylic polymer (hereinafter referred to as an acrylic polymer [hereinafter referred to as an acrylic polymer]) was used in the same manner as in Step 2 of Example 1 except that the latex [3] was used instead of the latex [1] and the melt extrusion temperature was changed to 250 ° C. A8] is obtained.
- Table 2 shows properties of the acrylic polymer [A8].
- Example 9 100 parts of the acrylic polymer [A8] is changed to 70 parts of the acrylic polymer [A8] and 30 parts of the acrylic resin [B2], the melting temperature in the single screw extruder with a vent in step 3 is set to 265 ° C., and the residence time
- the resin film was obtained by the same method as Example 8 except having changed for 2.5 minutes.
- Table 4 shows the characteristics and the like of the obtained resin film.
- Example 10 A core-shell multilayered acrylic polymer (hereinafter referred to as acrylic polymer [A2]) was obtained in the same manner as in step 2 of Example 1 except that drying at 80 ° C. in step 2 was not performed.
- the properties of the acrylic polymer [A2] are shown in Table 2. 70 parts of the acrylic polymer [A1] and 30 parts of the acrylic resin [B1] are changed to 100 parts of the acrylic polymer [A2], the melting temperature in the single screw extruder with a vent in step 3 is set to 260 ° C., and the residence time
- the resin film was obtained by the same method as Example 1 except having changed to 2.0 minutes. Table 4 shows the characteristics and the like of the obtained resin film.
- Example 11 Latex [4] was obtained in the same manner as in Step 1 of Example 1, except that the monomer mixture in Step 1 of Example 1 was changed to that shown in Table 1.
- the average particle size of latex [4] determined by the light scattering method was 0.09 ⁇ m.
- a core-shell multilayered acrylic polymer (hereinafter referred to as acrylic polymer [A9]) is obtained in the same manner as in Step 2 of Example 1, except that latex [4] is used instead of latex [1]. It was.
- the properties and the like of the acrylic polymer [A9] are shown in Table 2.
- Table 4 shows the characteristics and the like of the obtained resin film.
- Example 12 Latex [5] was obtained in the same manner as in Step 1 of Example 1, except that the monomer mixture in Step 1 of Example 1 was changed to that shown in Table 1.
- the average particle size of the latex [5] determined by the light scattering method was 0.09 ⁇ m.
- a core-shell multilayer acrylic polymer (hereinafter referred to as an acrylic polymer [hereinafter referred to as an acrylic polymer [hereinafter referred to as an acrylic polymer]) is used in the same manner as in Step 2 of Example 1 except that the latex [5] is used instead of the latex [1] and the melt extrusion temperature is changed to 250 ° C. A10] is obtained.
- Table 2 shows the characteristics of the acrylic polymer [A10].
- Example 13 90 parts of acrylic polymer [A1], 10 parts of acrylic resin [B1] and 2 parts of UV absorber, 85 parts of acrylic polymer [A10], 15 parts of acrylic resin [B2] and 3 parts of UV absorber
- the resin film was obtained by the same method as Example 2 except having changed into.
- Table 4 shows the characteristics and the like of the obtained resin film.
- Example 14 Latex [6] was obtained in the same manner as in Step 1 of Example 1, except that the monomer mixture in Step 1 of Example 1 was changed to that shown in Table 1.
- the average particle size of latex [6] determined by the light scattering method was 0.09 ⁇ m.
- a core-shell multilayer acrylic polymer (hereinafter referred to as an acrylic polymer [hereinafter referred to as an acrylic polymer]) was used in the same manner as in Step 2 of Example 1, except that latex [6] was used instead of latex [1] and the melt extrusion temperature was changed to 250 ° C. A11].) was obtained.
- Table 2 shows properties of the acrylic polymer [A11].
- Example 15 A core-shell multilayer acrylic polymer was prepared in the same manner as in Step 2 of Example 1 except that latex [6] was used instead of latex [1], the melt extrusion temperature was changed to 250 ° C., and drying at 80 ° C. was not performed. (Hereinafter referred to as acrylic polymer [A12]).
- Table 2 shows properties of the acrylic polymer [A12].
- a resin film was obtained in the same manner as in Example 10 except that 100 parts of the acrylic polymer [A2] was changed to 100 parts of the acrylic polymer [A12] and the residence time was changed to 2.5 minutes.
- Table 4 shows the characteristics and the like of the obtained resin film.
- Comparative Example 1 A resin film was obtained in the same manner as in Example 1 except that the residence time in the extruder in Step 3 of Example 1 was changed to 18 minutes. Table 5 shows the characteristics of the resin film.
- acrylic polymer [A3] A core-shell multilayered acrylic polymer (hereinafter referred to as acrylic polymer [A3]) is obtained in the same manner as in step 2 of Example 1, except that the number of washing and dehydration in step 2 is changed to 1. It was.
- the properties of the acrylic polymer [A3] are shown in Table 2. Change 70 parts of acrylic polymer [A1], 30 parts of acrylic resin [B1] and 2 parts of UV absorber to 100 parts of acrylic polymer [A3], and change the residence time in the single screw extruder with vent in step 3 A resin film was obtained in the same manner as in Example 1 except that the time was changed to 6.0 minutes. Table 5 shows the properties and the like of the obtained resin film.
- Comparative Example 3 Change 70 parts of acrylic polymer [A1], 30 parts of acrylic resin [B1] and 2 parts of UV absorber to 100 parts of acrylic polymer [A1] and change the melting temperature in the single screw extruder with vent in step 3 A resin film was obtained in the same manner as in Example 1 except that the residence time was changed to 290 ° C. and 4.0 minutes. Table 5 shows the properties and the like of the obtained resin film.
- Comparative Example 4 A core-shell multilayer structure acrylic polymer (hereinafter referred to as acrylic polymer [A6]) was obtained in the same manner as in Step 2 of Example 6 except that drying at 80 ° C. in Step 2 was not performed. Table 2 shows properties of the acrylic polymer [A6]. The same method as in Example 6 except that 90 parts of the acrylic polymer [A4] was changed to 90 parts of the acrylic polymer [A6] and the residence time in the vented single screw extruder in Step 3 was changed to 10.0 minutes. A resin film was obtained. Table 5 shows the properties and the like of the obtained resin film.
- Comparative Example 5 A core-shell multilayered acrylic polymer (hereinafter referred to as acrylic polymer [A7]) was obtained in the same manner as in Step 2 of Example 6 except that the drying at 80 ° C. in Step 2 was changed to natural drying. .
- Table 2 shows properties of the acrylic polymer [A7].
- a resin film was obtained.
- Table 5 shows the properties and the like of the obtained resin film.
- Comparative Example 6 Comparison except that the amount of acrylic polymer [A6] and acrylic resin [B1] in Step 3 of Comparative Example 4 was changed to 80 parts and 20 parts, respectively, and the residence time in the extruder was changed to 5 minutes. A resin film was obtained in the same manner as in Example 4. Table 5 shows the characteristics of the resin film.
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Abstract
Description
特許文献3は、アクリル系樹脂組成物を成形してなるフィルムであって、フィルム中に含有される長軸が500nm未満であるミクロボイドが30個/400μm2以下であるアクリル樹脂フィルムを開示している。
特許文献5は、金属との密着性の改良を図ったものとして、酸価が0.2mmol/g以上のアクリル系ゴム粒子(A)を含有し、フィルムを構成する樹脂全体の酸価が0.15mmol/g以上1.5mmol/g以下である、(メタ)アクリル系樹脂フィルムを開示している。
アセトン不溶分の酸価が0.018mmol/g以下で、アセトン可溶分の酸価が0.012mmol/g以下で、ガラス転移温度が80℃以上で、且つ厚さが5~300μmである樹脂フィルム。
重合体(a)は、メチルメタクリレートに由来する構造単位40~98.99質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~60質量%、グラフト化剤に由来する構造単位0.01~1質量%、および架橋剤に由来する構造単位0~0.5質量%からなる重合体であり;
重合体(b)は、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位70~99.5質量%、メチルメタクリレートに由来する構造単位0~30質量%、グラフト化剤に由来する構造単位0.5~5質量%、および架橋剤に由来する構造単位0~5質量%からなる重合体であり;且つ
重合体(c)は、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%からなるガラス転移温度80℃以上の重合体である、〔1〕に記載の樹脂フィルム。
該ラテックスを凝固させてスラリーを得、
該スラリーを洗浄および脱水し、
脱水されたスラリーを乾燥させて多層構造アクリル系重合体を得、
アクリル系樹脂0~35質量%と前記で得られた多層構造アクリル系重合体65~100質量%との混合物を溶融させ押出成形することを含む、〔1〕または〔2〕に記載の樹脂フィルムの製造方法。
〔4〕 前記脱水されたスラリーを乾燥させて多層構造アクリル系重合体を得た後、
該多層構造アクリル系重合体を押出機に供給してペレット化し、
該ペレット化した多層構造アクリル系重合体を乾燥して、前記混合物の製造に用いることを含む、〔3〕に記載の樹脂フィルムの製造方法。
ラテックス(I)の存在下に、アルキル基の炭素数が1~8であるアルキルアクリレート70~99.5質量%、メチルメタクリレート0~30質量%、グラフト化剤0.5~5質量%、および架橋剤0~5質量%を重合して重合体(a)と重合体(b)とを含有するラテックス(II)を得;
ラテックス(II)の存在下に、メチルメタクリレート80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレート1~20質量%を重合して重合体(a)と重合体(b)と重合体(c)とを含有してなるラテックス(III)を得、
該ラテックス(III)を凝固させてスラリーを得、
該スラリーを洗浄および脱水し、
脱水されたスラリーを乾燥させて重合体(a)と重合体(b)と重合体(c)とを含有してなる多層構造アクリル系重合体を得、
アクリル系樹脂0~35質量%と前記で得られた多層構造アクリル系重合体65~100質量%との混合物を溶融させ押出成形することを含む、〔2〕に記載の樹脂フィルムの製造方法。
〔6〕 前記脱水されたスラリーを乾燥させて重合体(a)と重合体(b)と重合体(c)とを含有してなる多層構造アクリル系重合体を得た後、
該多層構造アクリル系重合体を押出機に供給してペレット化し、
該ペレット化した多層構造アクリル系重合体を乾燥して、前記混合物の製造に用いることを含む、〔5〕に記載の樹脂フィルムの製造方法。
〔8〕 スラリーの乾燥またはペレット化した多層構造アクリル系重合体の乾燥は、水分率が0.1質量%未満になるように行う、〔3〕~〔7〕のいずれかひとつに記載の樹脂フィルムの製造方法。
〔9〕 スラリーの洗浄および脱水は、アセトン不溶分の酸価が0.008mmol/g以下で且つアセトン可溶分の酸価が0.012mmol/g以下である多層構造アクリル系重合体が得られるように、繰り返し行う、〔3〕~〔8〕のいずれかひとつに記載の樹脂フィルムの製造方法。
〔10〕 押出成形は、押出機を用い、且つ押出機での滞留時間を5分間以下および樹脂温度を280℃以下にして行う、〔3〕~〔9〕のいずれかひとつに記載の樹脂フィルムの製造方法。
〔12〕 他の熱可塑性重合体が、ポリカーボネート系重合体、塩化ビニル系重合体、フッ化ビニリデン系重合体、酢酸ビニル系重合体、マレイン酸系共重合体、メタクリル樹脂、ABS樹脂、AES樹脂およびAS樹脂から選ばれる少なくともひとつである、〔11〕に記載の積層体。
本発明の方法によれば、透明性、耐温水(80℃)白化性、耐沸水(100℃)白化性、耐応力白化性、製膜性、および耐熱収縮性に優れた樹脂フィルムを製造することができる。
また、本発明の樹脂フィルムは、重合時に使用した乳化剤や重合開始剤などの水溶性物質の残存量が少ない。本発明の方法は、乾燥、押出成形などの比較的に高温となりやすい状態を経る過程を短時間且つ低温度にしているので被る熱量が抑えられている。
本発明の好ましい態様の樹脂フィルムは、80℃の水を用いた耐温水白化試験前後でのヘイズ変化幅(ΔH80)が、好ましくは10%以下、より好ましくは7%以下、さらに好ましくは5%以下である。本発明の好ましい態様の樹脂フィルムは、100℃の水(沸水)を用いた耐沸水白化試験前後でのヘイズ変化幅(ΔH100)が、好ましくは10%以下、より好ましくは7%以下、さらに好ましくは5%以下である。
多層構造アクリル系重合体に含有される重合体(b)の量は、多層構造アクリル系重合体の質量に対して、好ましくは20~45質量%、より好ましくは30~40質量%である。重合体(b)の量が少ないほど多層構造アクリル系重合体の熱安定性および生産性が低下する傾向がある。重合体(b)の量が多いほどフィルムの耐衝撃性および柔軟性が向上する傾向がある。
多層構造アクリル系重合体に含有される重合体(c)の量は、多層構造アクリル系重合体の質量に対して、好ましくは50~75質量%、より好ましくは50~60質量%である。重合体(c)の量が少ないほど多層構造アクリル系重合体の流動性およびフィルムの成形性が低下する傾向がある。重合体(c)の量が多いほどフィルムの耐衝撃性および耐応力白化性が低下する傾向がある。
本発明におけるグラフト化剤は、異種の重合性基を2個以上有する単量体である。本発明におけるグラフト化剤としては、例えば、アリルメタクリレート、アリルアクリレート、モノ-またはジ-アリルマレエート、モノ-またはジ-アリルフマレート、クロチルアクリレート、クロチルメタクリレートなどを挙げることができる。これらグラフト化剤は、1種単独でまたは2種以上を組み合わせて用いることができる。これらのうちでも、アリルメタクリレートが、重合体(a)と重合体(b)との間、若しくは重合体(b)と重合体(c)との間の結合能を向上させ、フィルムの耐応力白化性および透明性を向上させる作用に優れるので、好ましく用いられる。
本発明における架橋剤は、同種の重合性基を2個以上有する単量体であり、例えば、ジアクリル化合物、ジメタクリル化合物、ジアリル化合物、ジビニル化合物、ジエン化合物、トリビニル化合物などである。本発明における架橋剤としては、例えば、エチレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ジビニルベンゼン、トリビニルベンゼン、エチレングリコールジアリルエーテル、プロピレングリコールジアリルエーテル、ブタジエンなどを挙げることができる。これら架橋剤は、1種単独でまたは2種以上を組み合わせて用いることができる。
アクリル系樹脂におけるメチルメタクリレートに由来する構造単位の量は、アクリル系樹脂の全構造単位の質量に対して、好ましくは85~100質量%、より好ましくは92~100質量%である。アクリル系樹脂におけるアクリル酸エステルに由来する構造単位の量は、アクリル系樹脂の全構造単位の質量に対して、好ましくは0~15質量%、より好ましくは0~8質量%である。
多層構造アクリル系重合体およびアクリル系樹脂には、紫外線吸収剤を含有させることが好ましい。紫外線吸収剤としては、例えば2-[2-ヒドロキシ-5-(2-メタクリロイルオキシエチル)フェニル]-2H-1,2,3-ベンゾトリアゾールなどの反応性紫外線吸収剤を挙げることができる。紫外線吸収剤の含有量は、多層構造アクリル系重合体およびアクリル系樹脂の合計量100質量部に対して、好ましくは0.05~5質量部である。
本発明の樹脂フィルムは、耐衝撃性に優れ、しかも耐応力白化性に優れていて折り曲げても白化が生じず、耐温水白化性および耐沸水白化性に優れていて温水および沸水に曝されても白化が生じない。本発明の樹脂フィルムは、他の重合体、特に熱可塑性重合体との接着性にも優れている。
本発明の積層体に使用される他の熱可可塑性重合体は、特に制限されない。他の熱可可塑性重合体として、ポリカーボネート系重合体、塩化ビニル系重合体、フッ化ビニリデン系重合体、酢酸ビニル系重合体、マレイン酸系共重合体、メタクリル樹脂、ABS樹脂、AES樹脂、またはAS樹脂は、本発明の樹脂フィルムとの接着性が良好なので好ましい。熱可塑性重合体成形品は、フィルム、シート、板などのような面状成形品であってもよいし、管、棒などの線状成形品であってもよいし、レンズ、プリズム、容器などのような各種形状の成形品であってもよい。
多層構造アクリル系重合体のラテックスを採取して、堀場製作所社製レーザー回折/散乱式粒子径分布測定装置LA-910を用い、光散乱法によりその平均粒子径を求めた。
ASTM-D1238に準じて、230℃、3.8kg荷重でのメルトフローレート(以下「MFR」と表記する。)を測定した。
JIS K7121に準拠して、示差走査熱量測定装置(島津製作所製、DSC-50)を用いて、250℃まで一度昇温し、次いで室温まで冷却し、次いで室温から230℃までを20℃/分で昇温させる条件にてDSC曲線を測定した。このDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度(以下、「Tg」と表記する。)とした。
被測定物を105℃に設定された熱風乾燥機内で3時間加熱し、加熱前後での重量変化より水分率を求めた。
試験試料2gをアセトン50mLに入れ常温にて24時間撹拌した。得られた液全量を、遠心分離機(日立工機(株)製、CR20GIII)を用いて、回転数20000rpm、温度0℃、180分間の条件にて、遠心分離した。上澄み液と沈殿物を分け採り、
それぞれを50℃にて8時間真空下で乾燥させて、アセトン可溶分およびアセトン不溶分を得た。
アセトン可溶分またはアセトン不溶分を1g精秤し、クロロホルム50mLで溶解させた。5分間の窒素置換を行った。その後、ブロモチモールブルーを数滴添加した。N/100 KOHエタノール溶液を用いて中和滴定を行った。
対照試料ブランクとして、5分間の窒素置換を行ったクロロホルム50mLについて上記同様に中和滴定を行った。次式により酸価C(mmol/g)を算出した。
C=(A-B)×0.01×F
A=;試験試料における滴定数量(mL)、B=;対照試料におけるブランクの滴定数量(mL)、F=;N/100 KOHエタノール溶液のファクター
樹脂フィルムから50mm×50mmの試験片を切り出した。室温下でヘイズ(H0)をJISK7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
次いで、試験片を80℃の水に1時間浸漬した。その後、フィルム表面に付着した水滴を取り除き、フィルムが室温になった状態で、ヘイズを測定した。
室温におけるヘイズから温水浸漬後におけるヘイズへの増加量(ΔH80)を算出した。
樹脂フィルムから50mm×50mmの試験片を切り出した。室温下でヘイズ(H0)をJISK7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
次いで、試験片を100℃の水に4時間浸漬した。その後、フィルム表面に付着した水滴を取り除き、100℃に設定された熱風乾燥機内で8時間乾燥させた。フィルムが室温になった状態で、ヘイズを測定した。
室温におけるヘイズから沸水浸漬後におけるヘイズへの増加量(ΔH100)を算出した。
攪拌機および採取管付オートクレーブに、精製されたMMA92部、およびMA8部を入れて単量体混合物を調製した。単量体混合物に重合開始剤(2,2’-アゾビス(2-メチルプロピオニトリル)、水素引抜能:1%、1時間半減期温度:83℃)0.006部およびnOM0.15部を加え、溶解させて原料液を得た。窒素ガスにより製造装置内の酸素ガスを追出した。
前記原料液を、オートクレーブから、温度140℃に制御された連続流通式槽型反応器に、平均滞留時間120分間となるように、一定流量で供給して、重合転化率57%で塊状重合させて、アクリル系樹脂[B1]を得た。
前記の槽型反応器から排出される液を240℃に加温し、250℃に制御されたオープンベントと真空ベントとを具える二軸押出機に一定流量で供給して、押出機供給口で断熱フラッシュ蒸発させた。断熱フラッシュ蒸発で揮発した成分(単量体、二量体、三量体など)をオープンベントから排出した。二軸スクリューによる溶融混練で揮発した成分(単量体など)を押出機供給口よりも下流側に設けられた6Torrに減圧された真空ベントから排出した。揮発成分がほぼ除去された樹脂成分を二軸スクリュで押し出してストランドを得、該ストランドをペレタイザーでカットして、アクリル系樹脂[B1]をペレット化した。アクリル系樹脂[B1]は、Tgが110℃、MFRが2g/10minであった。
攪拌機および採取管付オートクレーブに、精製されたMMA94部、およびMA6部を入れて単量体混合物を調製した。単量体混合物に重合開始剤(2,2’-アゾビス(2-メチルプロピオニトリル)、水素引抜能:1%、1時間半減期温度:83℃)0.006部およびnOM0.35部を加え、溶解させて原料液を得た。窒素ガスにより製造装置内の酸素ガスを追出した。
前記原料液を、オートクレーブから、温度140℃に制御された連続流通式槽型反応器に、平均滞留時間120分間となるように、一定流量で供給して、重合転化率57%で塊状重合させて、アクリル系樹脂[B2]を得た。
前記の槽型反応器から排出される液を240℃に加温し、250℃に制御されたオープンベントと真空ベントとを具える二軸押出機に一定流量で供給して、押出機供給口で断熱フラッシュ蒸発させた。断熱フラッシュ蒸発で揮発した成分(単量体、二量体、三量体など)をオープンベントから排出した。二軸スクリューによる溶融混練で揮発した成分(単量体など)を押出機供給口よりも下流側に設けられた6Torrに減圧された真空ベントから排出した。揮発成分がほぼ除去された樹脂成分を二軸スクリュで押し出してストランドを得、該ストランドをペレタイザーでカットして、アクリル系樹脂[B2]をペレット化した。アクリル系樹脂[B2]は、Tgが112℃、MFRが10g/10minであった。
(工程1)
撹拌機、温度計、窒素ガス導入部、単量体導入管および還流冷却器を具える反応容器内に、イオン交換水150部、ドデシルベンゼンスルホン酸ナトリウム1.3部および炭酸ナトリウム0.05部を仕込み、容器内を窒素ガスで充分に置換して実質的に酸素の影響がない状態とした。その後、反応容器内の温度を80℃にした。反応容器内に過硫酸カリウム0.015部を投入し、5分間撹拌した。次いで、MMA4部、nBA4部およびALMA0.02部からなる単量体混合物を20分間かけて連続的に滴加し、乳化重合を行った。滴加終了後、さらに30分間撹拌し、乳化重合を転化率98%以上となるように行って、重合体(a)を含有するラテックスを得た。
重合体(a)を含有するラテックスの入った反応器内に、過硫酸カリウム0.030部を投入し、5分間撹拌した。次いで、MMA4部、nBA26部およびALMA0.9部からなる単量体混合物を40分間かけて連続的に滴加し、シード乳化重合を行った。滴加終了後、さらに30分間撹拌し、シード乳化重合を転化率98%以上となるように行って、重合体(a)と重合体(b)と含有するラテックスを得た。
重合体(a)と重合体(b)と含有するラテックスの入った反応器内に、過硫酸カリウム0.055部を投入し、5分間撹拌した。その後、MMA56部、nBA6部およびnOM0.2部からなる単量体混合物を100分間かけて連続的に滴加してシード重合を行った。滴加終了後、さらに60分間撹拌し、シード乳化重合を転化率98%以上となるように行って、重合体(a)、重合体(b)および重合体(c)を含有するラテックス(以下、ラテックス[1]と表記する。)を得た。光散乱法により決定されたラテックス[1]の平均粒子径は0.09μmであった。ラテックス[1]の単量体単位組成比および平均粒子径を表1に示す。
ラテックス[1]を-20℃の雰囲気に4時間置いて凍結させた。得られた凍結物を3倍量の80℃の水に投入して融解させて、スラリーを得た。スクリューデカンタ式遠心分離機を用いて2100Gの遠心力によりスラリーの洗浄および脱水を行った。続いてスラリー濃度10%になるようにイオン交換水を加え、再度スクリューデカンタ式遠心分離機で洗浄および脱水を行った。
その後、80℃に設定された連続式流動層乾燥機にて脱水されたスラリーを乾燥させて、コアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A1]と表記する。)を得た。アクリル系重合体[A1]をベント付単軸スクリュー式押出機に供給して、ベント真空圧力5Torr、溶融押出温度245℃の条件下にてペレット化した。押出機での滞留時間は2.5分間であった。
ペレット化されたアクリル系重合体[A1]を80℃で乾燥させた。乾燥させたアクリル系重合体[A1]は、水分率が0.06質量%、MFRが2.0g/10分、Tgが93℃、アセトン不溶分の酸価が0.004mmol/g、アセトン可溶分の酸価が0.009mmol/gであった。アクリル系重合体[A1]の特性値等を表2に示す。
乾燥させたアクリル系重合体[A1]70部、アクリル系樹脂[B1]30部、および紫外線吸収剤(2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]、製品名LA-31、ADEKA社製)2部を混ぜ合わせた。得られた混合物を、ベント付単軸押出機に供給して、滞留時間3.5分、265℃で溶融させ、Tダイから押し出した。押し出されたフィルム状溶融樹脂を鏡面ロールに巻き取って、厚さ50μmの樹脂フィルムを得た。得られた樹脂フィルムは、Tgが100℃、アセトン不溶分の酸価が0.012mmol/g、アセトン可溶分の酸価が0.008mmol/gであった。
該樹脂フィルムは、室温においてヘイズが0.4%、ΔH80が2.4%、ΔH100が2.3%であった。耐温水白化性および耐沸水白化性に優れていることがわかる。結果を表3に示す。
工程3におけるアクリル系重合体[A1]およびアクリル系樹脂[B1]の量をそれぞれ90部および10部に変更し、工程3におけるベント付単軸押出機における滞留時間を3.0分間に変更し、且つフィルム厚さを55μmに変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
工程3におけるアクリル系重合体[A1]およびアクリル系樹脂[B1]の量をそれぞれ80部および20部に変更し、且つ工程3におけるベント付単軸押出機における溶融温度を270℃に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
工程3におけるアクリル系樹脂[B1]をアクリル系樹脂[B2]に変え、工程3におけるベント付単軸押出機における溶融温度を260℃に、滞留時間を3.0分間に変更し、且つフィルム厚さを60μmに変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
アクリル系重合体[A1]およびアクリル系樹脂[B1]の量をそれぞれ100部および0部に変更し、且つ工程3におけるベント付単軸押出機における溶融温度を270℃に、滞留時間を4.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
工程1における単量体混合物を表1に示すものに変更した以外は実施例1の工程1と同じ方法でラテックス[2]を得た。光散乱法により決定されたラテックス[2]の平均粒子径は0.09μmであった。
ラテックス[1]の代わりにラテックス[2]を用いた以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A4]と表記する。)を得た。アクリル系重合体[A4]の特性等を表2に示す。
アクリル系重合体[A1]70部およびアクリル系樹脂[B1]30部をアクリル系重合体[A4]90部およびアクリル系樹脂[B1]10部に変え、工程3におけるベント付単軸押出機における溶融温度を270℃に、滞留時間を5.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
洗浄および脱水の回数を3回に変更した以外は実施例6の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A5]と表記する。)を得た。アクリル系重合体[A5]の特性等を表2に示す。
アクリル系重合体[A4]90部およびアクリル系樹脂[B1]10部をアクリル系重合体[A5]100部に変え、工程3におけるベント付単軸押出機における滞留時間を4.0分間に変更した以外は実施例6と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
実施例1の工程1における単量体混合物を表1に示すものに変更した以外は実施例1の工程1と同じ方法でラテックス[3]を得た。光散乱法により決定されたラテックス[3]の平均粒子径は0.09μmであった。
ラテックス[1]の代わりにラテックス[3]を用い、溶融押出温度を250℃に変えた以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A8]と表記する。)を得た。アクリル系重合体[A8]の特性等を表2に示す。
アクリル系重合体[A1]70部、アクリル系樹脂[B1]30部および紫外線吸収剤2部をアクリル系重合体[A8]100部に変え、工程3におけるベント付単軸押出機における溶融温度を270℃に、滞留時間を3.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表3に示す。
アクリル系重合体[A8]100部をアクリル系重合体[A8]70部およびアクリル系樹脂[B2]30部に変え、工程3におけるベント付単軸押出機における溶融温度を265℃に、滞留時間を2.5分間に変更した以外は実施例8と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
工程2における80℃の乾燥を行わなかった以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A2]と表記する。)を得た。アクリル系重合体[A2]の特性等を表2に示す。
アクリル系重合体[A1]70部およびアクリル系樹脂[B1]30部をアクリル系重合体[A2]100部に変え、工程3におけるベント付単軸押出機における溶融温度を260℃に、滞留時間を2.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
実施例1の工程1における単量体混合物を表1に示すものに変更した以外は実施例1の工程1と同じ方法でラテックス[4]を得た。光散乱法により決定されたラテックス[4]の平均粒子径は0.09μmであった。
ラテックス[1]の代わりにラテックス[4]を用いた以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A9]と表記する。)を得た。アクリル系重合体[A9]の特性等を表2に示す。
アクリル系重合体[A2]100部をアクリル系重合体[A9]100部に変え、工程3におけるベント付単軸押出機における溶融温度を270℃に、滞留時間を3.0分間に変更した以外は実施例10と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
実施例1の工程1における単量体混合物を表1に示すものに変更した以外は実施例1の工程1と同じ方法でラテックス[5]を得た。光散乱法により決定されたラテックス[5]の平均粒子径は0.09μmであった。
ラテックス[1]の代わりにラテックス[5]を用い、溶融押出温度を250℃に変えた以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A10]と表記する。)を得た。アクリル系重合体[A10]の特性等を表2に示す。
アクリル系重合体[A8]100部をアクリル系重合体[A10]100部に変え、工程3におけるベント付単軸押出機における溶融温度を265℃に、滞留時間を3.5分間に変更した以外は実施例8と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
アクリル系重合体[A1]90部、アクリル系樹脂[B1]10部および紫外線吸収剤2部を、アクリル系重合体[A10]85部、アクリル系樹脂[B2]15部および紫外線吸収剤3部に変更した以外は実施例2と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
実施例1の工程1における単量体混合物を表1に示すものに変更した以外は実施例1の工程1と同じ方法でラテックス[6]を得た。光散乱法により決定されたラテックス[6]の平均粒子径は0.09μmであった。
ラテックス[1]の代わりにラテックス[6]を用い、溶融押出温度を250℃に変えた以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A11]と表記する。)を得た。アクリル系重合体[A11]の特性等を表2に示す。
アクリル系重合体[A1]70部およびアクリル系樹脂[B1]30部をアクリル系重合体[A11]88部およびアクリル系樹脂[B2]12部に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
ラテックス[1]の代わりにラテックス[6]を用い、溶融押出温度を250℃に変え、80℃の乾燥を行わなかった以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A12]と表記する。)を得た。アクリル系重合体[A12]の特性等を表2に示す。
アクリル系重合体[A2]100部をアクリル系重合体[A12]100部に変更し、滞留時間を2.5分間に変えた以外は実施例10と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表4に示す。
実施例1の工程3における押出機での滞留時間を18分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。樹脂フィルムの特性等を表5に示す。
工程2における洗浄および脱水の回数を1回に変更した以外は実施例1の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A3]と表記する。)を得た。アクリル系重合体[A3]の特性等を表2に示す。
アクリル系重合体[A1]70部、アクリル系樹脂[B1]30部および紫外線吸収剤2部をアクリル系重合体[A3]100部に変え、工程3におけるベント付単軸押出機における滞留時間を6.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表5に示す。
アクリル系重合体[A1]70部、アクリル系樹脂[B1]30部および紫外線吸収剤2部をアクリル系重合体[A1]100部に変え、工程3におけるベント付単軸押出機における溶融温度を290℃に、滞留時間を4.0分間に変更した以外は実施例1と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表5に示す。
工程2における80℃の乾燥を行わなかった以外は実施例6の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A6]と表記する。)を得た。アクリル系重合体[A6]の特性等を表2に示す。
アクリル系重合体[A4]90部をアクリル系重合体[A6]90部に変え、工程3におけるベント付単軸押出機における滞留時間を10.0分間に変更した以外は実施例6と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表5に示す。
工程2における80℃の乾燥を自然乾燥に変えた以外は実施例6の工程2と同じ方法でコアシェル多層構造アクリル系重合体(以下、アクリル系重合体[A7]と表記する。)を得た。アクリル系重合体[A7]の特性等を表2に示す。
アクリル系重合体[A4]90部をアクリル系重合体[A7]90部に変え、工程3におけるベント付単軸押出機における滞留時間を18.0分間に変更した以外は実施例6と同じ方法で樹脂フィルムを得た。得られた樹脂フィルムの特性等を表5に示す。
比較例4の工程3におけるアクリル系重合体[A6]およびアクリル系樹脂[B1]の量をそれぞれ80部および20部に変更し、且つ押出機での滞留時間を5分間に変更した以外は比較例4と同じ方法で樹脂フィルムを得た。樹脂フィルムの特性等を表5に示す。
Claims (12)
- 多層構造アクリル系重合体を含有して成り、且つ
アセトン不溶分の酸価が0.018mmol/g以下で、アセトン可溶分の酸価が0.012mmol/g以下で、ガラス転移温度が80℃以上で、且つ厚さが5~300μmである樹脂フィルム。 - 多層構造アクリル系重合体は、重合体(a)、重合体(b)、および重合体(c)を含有してなるものであり、
重合体(a)は、メチルメタクリレートに由来する構造単位40~98.99質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~60質量%、グラフト化剤に由来する構造単位0.01~1質量%、および架橋剤に由来する構造単位0~0.5質量%からなる重合体であり;
重合体(b)は、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位70~99.5質量%、メチルメタクリレートに由来する構造単位0~30質量%、グラフト化剤に由来する構造単位0.5~5質量%、および架橋剤に由来する構造単位0~5質量%からなる重合体であり;且つ
重合体(c)は、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%からなるガラス転移温度80℃以上の重合体である、請求項1に記載の樹脂フィルム。 - 乳化重合を行って多層構造アクリル系重合体を含有するラテックスを得、
該ラテックスを凝固させてスラリーを得、
該スラリーを洗浄および脱水し、
脱水されたスラリーを乾燥させて多層構造アクリル系重合体を得、
アクリル系樹脂0~35質量%と前記で得られた多層構造アクリル系重合体65~100質量%との混合物を溶融させ押出成形することを含む、請求項1または2に記載の樹脂フィルムの製造方法。 - 前記脱水されたスラリーを乾燥させて多層構造アクリル系重合体を得た後、
該多層構造アクリル系重合体を押出機に供給してペレット化し、
該ペレット化した多層構造アクリル系重合体を乾燥して、前記混合物の製造に用いることを含む、請求項3に記載の樹脂フィルムの製造方法。 - 乳化剤の存在下に、メチルメタクリレート40~98.99質量%、アルキル基の炭素数が1~8であるアルキルアクリレート1~60質量%、グラフト化剤0.01~1質量%、および架橋剤0~0.5質量%を重合して重合体(a)を含有するラテックス(I)を得;
ラテックス(I)の存在下に、アルキル基の炭素数が1~8であるアルキルアクリレート70~99.5質量%、メチルメタクリレート0~30質量%、グラフト化剤0.5~5質量%、および架橋剤0~5質量%を重合して重合体(a)と重合体(b)とを含有するラテックス(II)を得;
ラテックス(II)の存在下に、メチルメタクリレート80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレート1~20質量%を重合して重合体(a)と重合体(b)と重合体(c)とを含有してなるラテックス(III)を得、
該ラテックス(III)を凝固させてスラリーを得、
該スラリーを洗浄および脱水し、
脱水されたスラリーを乾燥させて重合体(a)と重合体(b)と重合体(c)とを含有してなる多層構造アクリル系重合体を得、
アクリル系樹脂0~35質量%と前記で得られた多層構造アクリル系重合体65~100質量%との混合物を溶融させ押出成形することを含む、請求項2に記載の樹脂フィルムの製造方法。 - 前記脱水されたスラリーを乾燥させて重合体(a)と重合体(b)と重合体(c)とを含有してなる多層構造アクリル系重合体を得た後、
該多層構造アクリル系重合体を押出機に供給してペレット化し、
該ペレット化した多層構造アクリル系重合体を乾燥して、前記混合物の製造に用いることを含む、請求項5に記載の樹脂フィルムの製造方法。 - スラリーの洗浄および脱水は、スクリューデカンタ式遠心分離機を用いて少なくとも2回行う、請求項3~6のいずれかひとつに記載の樹脂フィルムの製造方法。
- スラリーの乾燥またはペレット化した多層構造アクリル系重合体の乾燥は、水分率が0.1質量%未満になるように行う、請求項3~7のいずれかひとつに記載の樹脂フィルムの製造方法。
- スラリーの洗浄および脱水は、アセトン不溶分の酸価が0.008mmol/g以下で且つアセトン可溶分の酸価が0.012mmol/g以下である多層構造アクリル系重合体が得られるように、繰り返し行う、請求項3~8のいずれかひとつに記載の樹脂フィルムの製造方法。
- 押出成形は、押出機を用い、且つ押出機での滞留時間を5分間以下および樹脂温度を280℃以下にして行う、請求項3~9のいずれかひとつに記載の樹脂フィルムの製造方法。
- 請求項1または2に記載の樹脂フィルムからなる少なくともひとつの層と、他の熱可塑性重合体の成形品からなる少なくともひとつの層とを有する積層体。
- 他の熱可塑性重合体が、ポリカーボネート系重合体、塩化ビニル系重合体、フッ化ビニリデン系重合体、酢酸ビニル系重合体、マレイン酸系共重合体、メタクリル樹脂、ABS樹脂、AES樹脂およびAS樹脂から選ばれる少なくともひとつである、請求項11に記載の積層体。
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Cited By (13)
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JP2020029545A (ja) * | 2018-08-24 | 2020-02-27 | テクノUmg株式会社 | アクリルゴム系グラフト共重合体および熱可塑性樹脂組成物 |
JP7200542B2 (ja) | 2018-08-24 | 2023-01-10 | テクノUmg株式会社 | アクリルゴム系グラフト共重合体および熱可塑性樹脂組成物 |
JP2020075405A (ja) * | 2018-11-07 | 2020-05-21 | 株式会社クラレ | アクリル系樹脂フィルムの製造方法 |
JP7149480B2 (ja) | 2018-11-07 | 2022-10-07 | 株式会社クラレ | アクリル系樹脂フィルムの製造方法 |
CN113227221A (zh) * | 2018-12-20 | 2021-08-06 | Lg Mma股份有限公司 | 丙烯酸层压薄膜、其制备方法及利用其制备的装饰片材 |
CN113227221B (zh) * | 2018-12-20 | 2023-09-12 | Lg Mma股份有限公司 | 丙烯酸层压薄膜、其制备方法及利用其制备的装饰片材 |
JPWO2020175516A1 (ja) * | 2019-02-28 | 2020-09-03 | ||
JP7332678B2 (ja) | 2019-02-28 | 2023-08-23 | 株式会社クラレ | (メタ)アクリル系重合体凝固物の製造方法及び成形品 |
WO2020175516A1 (ja) * | 2019-02-28 | 2020-09-03 | 株式会社クラレ | (メタ)アクリル系重合体凝固物の製造方法及び成形品 |
JPWO2020241690A1 (ja) * | 2019-05-28 | 2020-12-03 | ||
WO2020241690A1 (ja) * | 2019-05-28 | 2020-12-03 | 株式会社クラレ | アクリル系ゴム粒子およびメタクリル樹脂組成物 |
JP7364126B1 (ja) | 2021-06-02 | 2023-10-18 | Dic株式会社 | アクリル樹脂水分散体、その製造方法及び水性塗料 |
JP2023545181A (ja) * | 2021-06-02 | 2023-10-26 | Dic株式会社 | アクリル樹脂水分散体、その製造方法及び水性塗料 |
Also Published As
Publication number | Publication date |
---|---|
EP3521350A1 (en) | 2019-08-07 |
TW201817803A (zh) | 2018-05-16 |
KR102430116B1 (ko) | 2022-08-05 |
US20200024410A1 (en) | 2020-01-23 |
CN109715712B (zh) | 2021-11-09 |
US20220379539A1 (en) | 2022-12-01 |
KR20190055808A (ko) | 2019-05-23 |
EP3521350A4 (en) | 2020-05-27 |
JP6934881B2 (ja) | 2021-09-15 |
CN109715712A (zh) | 2019-05-03 |
TWI745438B (zh) | 2021-11-11 |
JPWO2018062378A1 (ja) | 2019-07-11 |
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