JP5224866B2 - Automotive film - Google Patents
Automotive film Download PDFInfo
- Publication number
- JP5224866B2 JP5224866B2 JP2008083243A JP2008083243A JP5224866B2 JP 5224866 B2 JP5224866 B2 JP 5224866B2 JP 2008083243 A JP2008083243 A JP 2008083243A JP 2008083243 A JP2008083243 A JP 2008083243A JP 5224866 B2 JP5224866 B2 JP 5224866B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylic
- meth
- weight
- acrylic resin
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 claims description 123
- 239000004925 Acrylic resin Substances 0.000 claims description 109
- 229920000178 Acrylic resin Polymers 0.000 claims description 109
- 239000000178 monomer Substances 0.000 claims description 79
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 40
- -1 acrylic ester Chemical class 0.000 claims description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 26
- 238000010030 laminating Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 40
- 239000011347 resin Substances 0.000 description 40
- 239000000126 substance Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 238000005452 bending Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229940048053 acrylate Drugs 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000113 methacrylic resin Substances 0.000 description 11
- 230000002087 whitening effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000003379 elimination reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000516 sunscreening agent Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000475 sunscreen effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-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
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 241001093575 Alma Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- YLQPPAFWBWFABJ-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound C=CC1=CC=CC=C1C=C.CC(=C)C(=O)OCCOC(=O)C(C)=C YLQPPAFWBWFABJ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- XKNLMAXAQYNOQZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(CO)(CO)CO XKNLMAXAQYNOQZ-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-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
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Chemical group 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- MXURCXXGTSOMAQ-UHFFFAOYSA-N C(C=C)(=O)OCCOC(C=C)=O.C1=CC=CC=C1 Chemical compound C(C=C)(=O)OCCOC(C=C)=O.C1=CC=CC=C1 MXURCXXGTSOMAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OAKHANKSRIPFCE-UHFFFAOYSA-L calcium;2-methylprop-2-enoate Chemical compound [Ca+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O OAKHANKSRIPFCE-UHFFFAOYSA-L 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000021189 garnishes Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000000004 low energy electron diffraction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、自動車用フィルムに好適なアクリル樹脂フィルムに関する。 The present invention relates to an acrylic resin film suitable for an automobile film.
近年、自動車内外装部品の最外装に、基材の保護や加飾を目的として樹脂フィルムを導入する用途において、高意匠化の要求が高まっており、透明性に優れるアクリルフィルムが関心をもたれている。しかし、従来のアクリルフィルムでは、この用途において必要特性である耐薬品性、耐熱性、硬度および耐折り曲げ性、折り曲げ白化性が十分ではなかった。また、従来のアクリル樹脂は熱安定性が十分でなく、加工時の熱履歴による熱分解が原因でダイラインが生じ、フィルムの外観が悪化するという問題があった。 In recent years, there has been an increasing demand for high design in applications where resin films are introduced to the outermost exterior of automobile interior and exterior parts for the purpose of protecting and decorating the base material, and acrylic films with excellent transparency have attracted attention. Yes. However, conventional acrylic films have insufficient chemical resistance, heat resistance, hardness and bending resistance, and whitening resistance, which are necessary characteristics for this application. Further, the conventional acrylic resin has a problem that the thermal stability is not sufficient, and die lines are generated due to thermal decomposition due to thermal history during processing, and the appearance of the film is deteriorated.
そこで、これらの特性を付与した樹脂として、アクリル系樹脂をイミド化剤で処理し、高分子鎖中にイミド基を導入することにより得られるポリグルタルイミドが知られており、耐薬品性、耐熱性、熱安定性および硬度に優れる。特に耐熱性、耐薬品性に優れるものとして、メタクリル酸またはメタクリル酸第三ブチルエステル、もしくはその両方とをメタクリル酸メチルと共重合し、加熱処理することにより酸無水物単位を形成させた後、イミド化剤と反応させ、耐熱性、透明性、耐溶剤性を改良したイミド化アクリル樹脂が開示されている（特許文献１参照）。 Therefore, as a resin imparted with these characteristics, polyglutarimide obtained by treating an acrylic resin with an imidizing agent and introducing an imide group into a polymer chain is known, and has chemical resistance and heat resistance. Excellent in heat resistance, heat stability and hardness. In particular, as having excellent heat resistance and chemical resistance, methacrylic acid or methacrylic acid tert-butyl ester, or both are copolymerized with methyl methacrylate and heat-treated to form an acid anhydride unit, An imidized acrylic resin that has been reacted with an imidizing agent to improve heat resistance, transparency, and solvent resistance is disclosed (see Patent Document 1).
しかし、該樹脂は非常に脆いため、該樹脂をフィルム化し、基材にラミネートして用いるような場合に、加工特性として必要である耐折曲げ性に劣るという欠点を有していた。 However, since the resin is very brittle, when the resin is made into a film and laminated on a base material, it has a drawback that it is inferior in the bending resistance required as processing characteristics.
そこで、これらの欠点への対応として、特定組成のメタクリル酸エステル系重合およびアクリル酸エステル系架橋弾性体粒子からなり、かつ、該架橋弾性体粒子（Ｂ）の平均粒子径と多官能性単量体の使用量が特定の関係式を満たすメタクリル系樹脂組成物を、イミド化剤で処理して得られる耐薬品性、耐熱性、熱安定性、硬度に優れ、耐折り曲げ性および折り曲げ白化性を改良したイミド化アクリル樹脂が開示されている（特許文献２参照）。該イミド化アクリル樹脂は耐薬品性に優れるが、近年の自動車部材用途では日焼け止め薬剤［例えば、コパトーン（登録商標）］等にも対応できる耐薬品性を要求されるようになってきており、このような特殊な薬剤に対する耐薬品性において、更なる改良が望まれていた。 Therefore, as a countermeasure to these disadvantages, the polymer is composed of methacrylic ester-based polymerized and acrylate-based cross-linked elastic particles having a specific composition, and the cross-linked elastic particle (B) has an average particle size and a polyfunctional monomer. Excellent chemical resistance, heat resistance, thermal stability and hardness obtained by treating a methacrylic resin composition that satisfies the specific relational expression with the body with an imidizing agent. An improved imidized acrylic resin is disclosed (see Patent Document 2). The imidized acrylic resin is excellent in chemical resistance, but in recent automobile member applications, chemical resistance that can also be applied to sunscreen chemicals [for example, Copatone (registered trademark)] has been required. Further improvement in chemical resistance to such special drugs has been desired.
他方、予め不飽和カルボン酸を１５〜５０重量％共重合させた樹脂を加熱処理することによりグルタル酸無水物基を形成させ、耐熱性、耐溶剤性、光学等方性を改良したゴム含有アクリル樹脂が開示されている（特許文献３参照）。しかし、該樹脂のように酸無水物基を多く含む場合、有機溶剤などへの耐性に優れるものの、アルカリ水溶液などへの耐性が悪化するという欠点がある。 On the other hand, a rubber-containing acrylic having improved heat resistance, solvent resistance, and optical isotropy by forming a glutaric anhydride group by heat-treating a resin previously copolymerized with 15 to 50% by weight of an unsaturated carboxylic acid. Resin is disclosed (refer patent document 3). However, when the resin contains a large number of acid anhydride groups as in the case of the resin, it is excellent in resistance to an organic solvent, but has a disadvantage that resistance to an alkaline aqueous solution is deteriorated.
よって、各種耐薬品性のバランスや、折り曲げ性などの多岐にわたる物性を有し、ダイラインの少ない自動車用アクリルフィルムは存在せず、開発が望まれていた。
本発明は、各種薬品に対する耐薬品性、耐折り曲げ白化性に優れ、ダイラインの少ない自動車用アクリルフィルムを提供することを目的とする。 An object of the present invention is to provide an automotive acrylic film having excellent chemical resistance against various chemicals and resistance to bending whitening and having few die lines.
本発明者らは、鋭意検討の結果、所定量の（メタ）アクリル酸第三ブチルエステルを有するメタクリル酸エステル共重合体およびアクリル酸エステル架橋弾性体粒子からなり、加熱処理によりカルボン酸基が生成される（メタ）アクリル系樹脂組成物の酸価を制御することにより、耐日焼け止めクリーム性、耐アルカリ性および耐キシレン性に優れ、熱安定性、耐折り曲げ白化性を有する自動車用フィルムを製造することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention are composed of a methacrylic acid ester copolymer having a predetermined amount of (meth) acrylic acid tert-butyl ester and acrylic acid ester crosslinked elastic particles, and a carboxylic acid group is generated by heat treatment. By controlling the acid value of the (meth) acrylic resin composition to be produced, an automotive film having excellent sunscreen cream resistance, alkali resistance and xylene resistance, heat stability and antibending whitening resistance is produced. As a result, the present invention has been completed.
すなわち、本発明は、
アクリル酸アルキルエステル単量体５０〜１００重量％、メタクリル酸アルキルエステル単量体０〜５０重量％を含む単量体混合物１００重量部に対し、１分子あたり２個以上の非共役二重結合を有する多官能性単量体０．５〜５重量部を混合、重合して得られるアクリル酸エステル系架橋弾性体粒子（Ｂ）の存在下、（メタ）アクリル酸直鎖アルキルエステル７８〜９９重量％、（メタ）アクリル酸第三ブチルエステル１〜１５重量％を含む単量体混合物（Ａ）を重合して得られる（メタ）アクリル系樹脂（Ｃ）を加熱処理することによって得られる樹脂組成物を成形してなる自動車用アクリルフィルムであって、酸価が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である（メタ）アクリル樹脂組成物からなる自動車用アクリルフィルム（請求項１）に関する。
さらに、本発明は（メタ）アクリル樹脂（Ｃ）に、酸価が０．７ｍｍｏｌ／ｇ未満である熱可塑性樹脂（Ｄ）をブレンドしてなる、請求項１記載の自動車用アクリルフィルム（請求項２）に関する。
さらに、本発明は、請求項１または２に記載の自動車内装用アクリルフィルム（請求項３）に関する。
さらに、本発明は、請求項１または２に記載の自動車外装用アクリルフィルム（請求項４）に関する。
さらに、本発明は、請求項１または２に記載の自動車用アクリルフィルムを積層して得られる積層品（請求項５）に関する。
さらに、本発明は、請求項３に記載の自動車内装用アクリルフィルムを積層して得られる自動車内装用部品（請求項６）に関する。
さらに、本発明は、請求項４に記載の自動車外装用アクリルフィルムを積層して得られる自動車内装用部品（請求項７）に関する。
That is, the present invention
Two or more non-conjugated double bonds per molecule per 100 parts by weight of a monomer mixture containing 50 to 100% by weight of an acrylic acid alkyl ester monomer and 0 to 50% by weight of a methacrylic acid alkyl ester monomer (Meth) acrylic acid linear alkyl ester 78 to 99 weight in the presence of acrylic ester-based crosslinked elastic particles (B) obtained by mixing and polymerizing 0.5 to 5 parts by weight of polyfunctional monomer having %, A resin composition obtained by heat-treating a (meth) acrylic resin (C) obtained by polymerizing a monomer mixture (A) containing 1 to 15% by weight of (meth) acrylic acid tert-butyl ester An acrylic film for automobiles formed by molding an acrylic film for automobiles comprising a (meth) acrylic resin composition having an acid value of 0.3 mmol / g or more and less than 0.7 mmol / g Beam on (claim 1).
Furthermore, this invention blends the thermoplastic resin (D) whose acid value is less than 0.7 mmol / g to the (meth) acrylic resin (C), The acrylic film for motor vehicles of Claim 1 (Claim) Regarding 2).
Furthermore, this invention relates to the acrylic film for motor vehicle interiors of Claim 1 or 2 (Claim 3).
Furthermore, this invention relates to the acrylic film for motor vehicle exteriors of Claim 1 or 2 (Claim 4).
Furthermore, this invention relates to the laminated product (Claim 5) obtained by laminating | stacking the acrylic film for motor vehicles of Claim 1 or 2.
Furthermore, this invention relates to the components for motor vehicle interior obtained by laminating | stacking the acrylic film for motor vehicle interior of Claim 3.
Furthermore, this invention relates to the components for motor vehicle interior obtained by laminating | stacking the acrylic film for motor vehicle exterior of Claim 4.
本発明によれば、耐薬品性、耐折り曲げ白化性に優れ、ダイライン発生の抑制された自動車用アクリルフィルムを提供することが可能である。 ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the acrylic film for motor vehicles which was excellent in chemical resistance and bending whitening resistance, and the die line generation | occurrence | production was suppressed.
本発明は、（メタ）アクリル系樹脂組成物からなる自動車用フィルムに関するものである。本発明において「（メタ）アクリル系樹脂」とは、アクリル系樹脂および／またはメタクリル系樹脂を意味する。 The present invention relates to an automobile film comprising a (meth) acrylic resin composition. In the present invention, “(meth) acrylic resin” means an acrylic resin and / or a methacrylic resin.
本発明の（メタ）アクリル系樹脂組成物は、アクリル酸エステル系架橋弾性体粒子（Ｂ）の存在下、単量体混合物（Ａ）を重合して得られる（メタ）アクリル系樹脂（Ｃ）を加熱処理することによって得られる。 The (meth) acrylic resin composition of the present invention is a (meth) acrylic resin (C) obtained by polymerizing the monomer mixture (A) in the presence of the acrylic ester-based crosslinked elastic particles (B). Is obtained by heat treatment.
本発明のアクリル酸エステル系架橋弾性体粒子（Ｂ）は、アクリル酸アルキルエステル単量体５０〜１００重量％、メタクリル酸アルキルエステル単量体０〜５０重量％を含む単量体混合物（ｂ）１００重量部に対し、１分子あたり２個以上の非共役二重結合を有する多官能性単量体０．５〜５重量部を、１段以上で共重合させてなるものである（多段階に、単量体組成または反応条件を調整することも可能である。）。より好ましい単量体混合物（ｂ）の組成は、アクリル酸アルキルエステル単量体６０〜１００重量％、メタクリル酸アルキルエステル単量体０〜４０重量％を含むものである。メタクリル酸アルキルエステル単量体が５０重量％以下であれば、得られる（メタ）アクリル系樹脂組成物から形成しうるフィルムの耐折曲げ性の観点から、好ましい。 The acrylic ester-based crosslinked elastic particle (B) of the present invention is a monomer mixture (b) containing 50 to 100% by weight of an acrylic acid alkyl ester monomer and 0 to 50% by weight of a methacrylic acid alkyl ester monomer. It is obtained by copolymerizing 0.5 to 5 parts by weight of a polyfunctional monomer having 2 or more non-conjugated double bonds per molecule with respect to 100 parts by weight (multi-stage). It is also possible to adjust the monomer composition or reaction conditions. A more preferable composition of the monomer mixture (b) includes 60 to 100% by weight of an acrylic acid alkyl ester monomer and 0 to 40% by weight of a methacrylic acid alkyl ester monomer. A methacrylic acid alkyl ester monomer of 50% by weight or less is preferable from the viewpoint of the bending resistance of a film that can be formed from the resulting (meth) acrylic resin composition.
架橋弾性体粒子（Ｂ）に用いられる単量体混合物（ｂ）のアクリル酸アルキルエステル、メタクリル酸アルキルエステル等の反応性単量体としては、重合反応性やコストの点から、アルキル基の炭素数が１〜１２であるものが好ましい。その具体例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、アクリル酸メチル、アクリル酸ｎ−ブチル等があげられ、これらの単量体は単独で使用してもよく、２種以上を組合せて使用してもよい。 Examples of reactive monomers such as alkyl acrylates and alkyl methacrylates in the monomer mixture (b) used for the crosslinked elastic particles (B) include alkyl group carbons from the viewpoint of polymerization reactivity and cost. Those having a number of 1 to 12 are preferred. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate and the like, and these monomers may be used alone. Well, two or more types may be used in combination.
また、本発明の架橋弾性体粒子（Ｂ）の単量体混合物（ｂ）には、必要に応じて、アクリル酸アルキルエステル単量体、メタアクリル酸エステル単量体と共重合可能なエチレン系不飽和単量体等を共重合してもかまわない。共重合可能なエチレン系不飽和単量体としては、例えば、塩化ビニル、臭化ビニル等のハロゲン化ビニル、アクリロニトリル、メタクリロニトリル等のシアン化ビニル、ビニルトルエン、ビニルナフタレン、スチレン、α−メチルスチレン等の芳香族ビニル、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、塩化ビニリデン、弗化ビニリデン等のハロゲン化ビニリデン、アクリル酸、アクリル酸ナトリウム、アクリル酸カルシウム等のアクリル酸およびその塩、アクリル酸β−ヒドロキシエチル、アクリル酸ジメチルアミノエチル、アクリル酸グリシジル、アクリルアミド、Ｎ−メチロ−ルアクリルアミド等のアクリル酸アルキルエステル誘導体、メタクリル酸、メアクリル酸ナトリウム、メタアクリル酸カルシウム等のメタクリル酸およびその塩、メタクリルアミド、メタクリル酸β−ヒドロキシエチル、メタクリル酸ジメチルアミノエチル、メタクリル酸グリシジル等のメタクリル酸アルキルエステル誘導体等があげられる。これらの単量体は単独で使用してもよく、２種以上を組み合わせて使用してもよい。 In addition, the monomer mixture (b) of the crosslinked elastic particles (B) of the present invention includes an ethylene-based copolymerizable copolymer with an acrylic acid alkyl ester monomer and a methacrylic acid ester monomer, if necessary. An unsaturated monomer or the like may be copolymerized. Examples of copolymerizable ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl toluene, vinyl naphthalene, styrene, and α-methyl. Aromatic vinyl such as styrene, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid such as acrylic acid, sodium acrylate and calcium acrylate, and salts thereof , Β-hydroxyethyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, acrylamide, N-methylol acrylamide, and other alkyl acrylate derivatives, methacrylic acid, sodium methacrylate, calcium methacrylate, etc. Examples thereof include tacrylic acid and salts thereof, methacrylic acid alkyl ester derivatives such as methacrylamide, β-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate and glycidyl methacrylate. These monomers may be used alone or in combination of two or more.
本発明のアクリル酸エステル系架橋弾性体粒子（Ｂ）は、１分子あたり２個以上の非共役な反応性二重結合を有する多官能性単量体が共重合されているため、通常、得られる重合体が架橋弾性を示す。また、アクリル酸エステル系架橋弾性体粒子（Ｂ）の重合時に反応せずに残った多官能性単量体の一方の反応性官能基（二重結合）がグラフト交叉点となって、単量体混合物（Ａ）の一部が、アクリル酸エステル系架橋弾性体粒子（Ｂ）にグラフト化されるものと考えられる。 The acrylic ester-based crosslinked elastic particles (B) of the present invention are usually obtained because a polyfunctional monomer having two or more non-conjugated reactive double bonds per molecule is copolymerized. The resulting polymer exhibits crosslinking elasticity. In addition, one reactive functional group (double bond) of the polyfunctional monomer left unreacted during the polymerization of the acrylic ester-based crosslinked elastic particles (B) becomes a graft crossing point, A part of the body mixture (A) is considered to be grafted to the acrylate-based crosslinked elastic particles (B).
本発明において用いられる多官能性単量体としては、例えば、アリルメタクリレート、アリルアクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート、ジアリルフタレート、ジアリルマレート、ジビニルアジペート、ジビニルベンゼンエチレングリコールジメタクリレート、ジビニルベンゼンエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、ジプロピレングリコールジメタクリレートおよびジプロピレングリコールジアクリレート等があげられる。これらの多官能性単量体は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the polyfunctional monomer used in the present invention include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol dimethacrylate, divinyl. Benzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, Dipropylene glycol dimethacrylate And dipropylene glycol diacrylate and the like. These polyfunctional monomers may be used alone or in combination of two or more.
本発明のアクリル酸エステル系架橋弾性体粒子（Ｂ）における多官能性単量体の共重合量は、単量体混合物（ｂ）１００重量物に対して、０．５〜５重量部が好ましく、１．０〜４重量部がより好ましい。多官能性単量体の共重合量が０．５〜５重量部であれば、耐折り曲げ性、耐折り曲げ白化性および樹脂の流動性の観点から好ましい。 The copolymerization amount of the polyfunctional monomer in the acrylate-based crosslinked elastic particles (B) of the present invention is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the monomer mixture (b). 1.0 to 4 parts by weight is more preferable. If the copolymerization amount of the polyfunctional monomer is 0.5 to 5 parts by weight, it is preferable from the viewpoints of bending resistance, bending whitening resistance and resin fluidity.
本発明のアクリル酸エステル系架橋弾性体粒子（Ｂ）の平均粒子径は、５００〜２０００Åが好ましく、５００〜１６００Åがより好ましく、５００〜１２００Åがさらに好ましく、６００〜１２００Åが特に好ましい。平均粒子径が５００〜２０００Åであれば、耐折り曲げ性、耐折り曲げ白化性および透明性の視点から好ましい。 The average particle diameter of the acrylate ester-based crosslinked elastic particles (B) of the present invention is preferably 500 to 2000, more preferably 500 to 1600, even more preferably 500 to 1200, and particularly preferably 600 to 1200. An average particle size of 500 to 2000 mm is preferred from the viewpoint of bending resistance, bending whitening resistance and transparency.
本発明で用いられる（メタ）アクリル系樹脂（Ｃ）は、前記アクリル酸エステル系架橋弾性体粒子（Ｂ）の存在下に、メタクリル酸エステルを主成分とする単量体混合体（Ａ）を重合させて得られるものである。好ましくは、前記アクリル酸エステル系架橋弾性体粒子（Ｂ）５〜７５重量部の存在下に、後述する単量体混合物（Ａ）９５〜２５重量部を少なくとも１段階以上で重合させることより得られる。 The (meth) acrylic resin (C) used in the present invention comprises a monomer mixture (A) mainly composed of a methacrylic ester in the presence of the acrylic ester-based crosslinked elastic particles (B). It is obtained by polymerization. Preferably, it is obtained by polymerizing 95 to 25 parts by weight of the monomer mixture (A) described later in at least one stage in the presence of 5 to 75 parts by weight of the acrylic ester-based crosslinked elastic particles (B). It is done.
本発明の単量体混合物（Ａ）の組成は、（メタ）アクリル酸直鎖アルキルエステル８５〜９９重量％および（メタ）アクリル酸第三ブチルエステル１〜１５重量％を含むものが好ましく、（メタ）アクリル酸直鎖アルキルエステル８８〜９５重量％および（メタ）アクリル酸第三ブチルエステル５〜１２重量％がより好ましい。（メタ）アクリル酸第三ブチルエステルが１〜１５重量％であれば、得られるフィルムの無色透明性、耐折曲げ性、熱安定性および耐薬品性のバランスがとれるために、好ましい。特に、（メタ）アクリル酸第三ブチルエステルが１５重量％より多くなると、（メタ）アクリル系樹脂組成物の耐アルカリ性が低下する傾向があるため、上記範囲が好ましい。 The composition of the monomer mixture (A) of the present invention preferably contains 85 to 99% by weight of (meth) acrylic acid linear alkyl ester and 1 to 15% by weight of (meth) acrylic acid tert-butyl ester, More preferred are 88 to 95% by weight of a linear alkyl ester of methacrylic acid and 5 to 12% by weight of tert-butyl (meth) acrylate. If the (meth) acrylic acid tert-butyl ester is 1 to 15% by weight, it is preferable because the obtained film can have a balance of colorless transparency, bending resistance, thermal stability and chemical resistance. In particular, when the amount of (meth) acrylic acid tert-butyl ester is more than 15% by weight, the alkali resistance of the (meth) acrylic resin composition tends to decrease, so the above range is preferable.
単量体混合物（Ａ）の（メタ）アクリル酸直鎖アルキルエステルの反応性単量体としては、重合反応性やコストの点から、アルキル基の炭素数が１〜１２であるものが好ましい。その具体例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、アクリル酸メチル、アクリル酸ｎ−ブチル等があげられ、これらの単量体は単独で使用してもよく、２種以上を組合せて使用してもよい。 As the reactive monomer of the (meth) acrylic acid linear alkyl ester of the monomer mixture (A), those having an alkyl group with 1 to 12 carbon atoms are preferred from the viewpoint of polymerization reactivity and cost. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate and the like, and these monomers may be used alone. Well, two or more types may be used in combination.
本発明の単量体混合物（Ａ）には、必要に応じて、（メタ）アクリル酸直鎖アルキルエステル単量体、（メタ）アクリル酸第三ブチルエステル単量体と共重合可能なエチレン系不飽和単量体等を共重合してもかまわない。共重合可能なエチレン系不飽和単量体の具体例は、前記架橋弾性体粒子（Ｂ）で用いたものが使用可能である。 In the monomer mixture (A) of the present invention, an ethylene type copolymerizable with a (meth) acrylic acid linear alkyl ester monomer and a (meth) acrylic acid tert-butyl ester monomer, if necessary. An unsaturated monomer or the like may be copolymerized. As specific examples of the copolymerizable ethylenically unsaturated monomer, those used for the crosslinked elastic particles (B) can be used.
この際、単量体混合物（Ａ）においては、アクリル酸エステル系架橋弾性体粒子（Ｂ）にグラフト反応せずに、未グラフトの重合体となる成分（フリーポリマー）が生じる。 In this case, in the monomer mixture (A), a component (free polymer) that becomes an ungrafted polymer is generated without grafting to the acrylate-based crosslinked elastic particle (B).
（メタ）アクリル系樹脂（Ｃ）の一部［（Ｂ）およびグラフトされた（Ａ）］は、メチルエチルケトンに不溶となる。 A part of (meth) acrylic resin (C) [(B) and grafted (A)] becomes insoluble in methyl ethyl ketone.
本発明における（メタ）アクリル系樹脂（Ｃ）のグラフト率は、１００〜１６０％が好ましく、１２０〜１４０％がより好ましい。グラフト率が上記範囲であれば、得られる（メタ）アクリル系樹脂フィルムの無色透明性、折り曲げ白化性の面から好ましい。 The graft ratio of the (meth) acrylic resin (C) in the present invention is preferably 100 to 160%, more preferably 120 to 140%. If the graft ratio is in the above range, the obtained (meth) acrylic resin film is preferable from the viewpoint of colorless transparency and bending whitening.
なお、本発明の（メタ）アクリル系樹脂（Ｃ）のグラフト率とは、以下の方法で算出した値である。
すなわち、（メタ）アクリル系樹脂（Ｃ）１ｇをメチルエチルケトン４０ｍｌに溶解させ、遠心分離機（日立工機（株）製、ＣＰ６０Ｅ）を用い、回転数３０００ｒｐｍにて、１時間遠心分離し、デカンテーションにより、メチルエチルケトンに対する不溶分と可溶分とに分離する。得られたメチルエチルケトン不溶分を、アクリル酸エステル系架橋弾性体含有グラフト共重合体として、得られた次式により算出した。
グラフト率（％）＝｛（メチルエチルケトン不溶分の重量−アクリル酸エステル系架橋弾性体粒子（Ｂ）の重量）／アクリル酸エステル系架橋弾性体粒子（Ｂ）の重量｝×１００
In addition, the graft ratio of the (meth) acrylic resin (C) of the present invention is a value calculated by the following method.
That is, 1 g of (meth) acrylic resin (C) was dissolved in 40 ml of methyl ethyl ketone, and centrifuged for 1 hour at 3000 rpm using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), followed by decantation. To separate into insoluble and soluble in methyl ethyl ketone. The obtained methyl ethyl ketone insoluble matter was calculated as the acrylate ester-based crosslinked elastic body-containing graft copolymer by the following formula.
Graft ratio (%) = {(weight of insoluble matter of methyl ethyl ketone−weight of acrylic ester-based crosslinked elastic particle (B)) / weight of acrylic ester-based crosslinked elastic particle (B)} × 100
本発明の（メタ）アクリル系樹脂（Ｃ）の製造方法は特に限定されず、公知の乳化重合法、乳化−懸濁重合法、懸濁重合法などが適用可能であるが、乳化重合法が特に好ましい。 The production method of the (meth) acrylic resin (C) of the present invention is not particularly limited, and known emulsion polymerization methods, emulsion-suspension polymerization methods, suspension polymerization methods and the like can be applied. Particularly preferred.
アクリル酸エステル系架橋弾性体粒子（Ｂ）の重合、および単量体混合物（Ａ）の重合における開始剤としては、公知の有機系過酸化物、無機系過酸化物、アゾ化合物などの開始剤を使用することができる。具体的には、第三ブチルハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、スクシン酸パーオキサイド、パーオキシマレイン酸第三ブチルエステル、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド等の有機過酸化物や、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物、さらにアゾビスイソブチロニトリル等の油溶性開始剤も使用される。これらは単独で用いてもよく、２種以上併用してもよい。これらの開始剤は亜硫酸ナトリウム、チオ硫酸ナトリウム、ナトリウムホルムアルデヒドスルフォキシレート、アスコルビン酸、ヒドロキシアセトン酸、硫酸第一鉄、硫酸第一鉄とエチレンジアミン四酢酸２ナトリウムの錯体なとの還元剤と組み合わせた通常のレドックス型開始剤として使用してもよい。 Initiators such as known organic peroxides, inorganic peroxides, and azo compounds are used as initiators in the polymerization of the acrylic ester-based crosslinked elastic particles (B) and the polymerization of the monomer mixture (A). Can be used. Specifically, tertiary butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, succinic acid peroxide, peroxymaleic acid tertiary butyl ester, cumene hydroperoxide, benzoyl peroxide, etc. Organic peroxides, inorganic peroxides such as potassium persulfate and sodium persulfate, and oil-soluble initiators such as azobisisobutyronitrile are also used. These may be used alone or in combination of two or more. These initiators are combined with a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, hydroxyacetone acid, ferrous sulfate, ferrous sulfate and disodium ethylenediaminetetraacetate It may also be used as a normal redox type initiator.
前記有機系過酸化物は、重合系にそのまま添加する方法、単量体に混合して添加する方法、乳化剤水溶液に分散させて添加する方法など、公知の添加法で添加することができるが、透明性の点から、単量体に混合して添加する方法あるいは乳化剤水溶液に分散させて添加する方法が好ましい。 The organic peroxide can be added by a known addition method such as a method of adding to a polymerization system as it is, a method of adding a mixture to a monomer, a method of adding a dispersion in an aqueous emulsifier solution, and the like. From the viewpoint of transparency, a method of adding a mixture to a monomer or a method of adding it by dispersing in an aqueous emulsifier solution is preferable.
また、前記有機系過酸化物は、重合安定性、粒子径制御の点から、２価の鉄塩等の無機系還元剤および／またはホルムアルデヒドスルホキシル酸ソーダ、還元糖、アスコルビン酸等の有機系還元剤と組み合わせたレドックス系開始剤として使用するのが好ましい。 The organic peroxide is an organic reducing agent such as a divalent iron salt and / or organic solvents such as formaldehyde sulfoxylate, reducing sugar, ascorbic acid and the like from the viewpoint of polymerization stability and particle size control. It is preferably used as a redox initiator in combination with a reducing agent.
前記乳化重合に使用される界面活性剤にも特に限定はなく、通常の乳化重合用の界面活性剤であれば使用することができる。具体的には、例えば、アルキルスルホン酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム、ジオクチルスルフォコハク酸ナトリウム、ラウリル硫酸ナトリウム等の陰イオン性界面活性剤や、アルキルフェノール類、脂肪族アルコ−ル類とプロピレンオキサイド、エチレンオキサイドとの反応生成物等の非イオン性界面活性剤等が示される。これらの界面活性剤は単独で用いてもよく、２種以上併用してもよい。更に要すれば、アルキルアミン塩等の陽イオン性界面活性剤を使用してもよい。 The surfactant used for the emulsion polymerization is not particularly limited, and any surfactant for normal emulsion polymerization can be used. Specifically, for example, anionic surfactants such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium dioctylsulfosuccinate, sodium lauryl sulfate, alkylphenols, aliphatic alcohols and propylene oxide, Nonionic surfactants such as reaction products with ethylene oxide are shown. These surfactants may be used alone or in combination of two or more. Furthermore, if necessary, a cationic surfactant such as an alkylamine salt may be used.
アクリル酸エステル系架橋弾性体粒子（Ｂ）における単量体混合物（ｂ）および単量体混合物（Ａ）の重合における開始剤の添加量は、アクリル酸エステル系架橋弾性体粒子（Ｂ）または単量体混合物（Ａ）１００重量部に対し、０．０３〜３．５重量部の範囲が好ましく、０．１〜２．５重量部がより好ましく、０．２〜１．５重量部がさらに好ましい。開始剤の添加量が上記範囲であれば、得られる（メタ）アクリル組成物の機械強度、成形加工性の視点から好ましい。 The amount of the initiator in the polymerization of the monomer mixture (b) and the monomer mixture (A) in the acrylate-based crosslinked elastic particles (B) is the same as that of the acrylate-based crosslinked elastic particles (B) or single particles. The range of 0.03 to 3.5 parts by weight is preferable with respect to 100 parts by weight of the monomer mixture (A), more preferably 0.1 to 2.5 parts by weight, and further 0.2 to 1.5 parts by weight. preferable. If the addition amount of an initiator is the said range, it is preferable from a viewpoint of the mechanical strength of the (meth) acrylic composition obtained and a moldability.
本発明においては、単量体混合物（Ａ）を重合して得られるポリマーの分子量を制御するために、連鎖移動剤を使用することが可能である。連鎖移動剤としては、例えば、メチルメルカプタン、エチルメルカプタン、イソプロピルメルカプタン、ｎ−ブチルメルカプタン、第三ブチルメルカプタン、ｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｎ-ドデシルメルカプタン、エチルチオグリコレート、メルカプトエタノール、チオ−β−ナフトール、チオフェノール、ジメチルジスルフィド等が用いられる。連鎖移動剤の使用量としては、単量体混合物（Ａ）１００重量部に対し、０．０２〜２．２重量部％の範囲が好ましく、０．１〜１．５重量部がより好ましく、０．２〜１．０重量部がさらに好ましい。連鎖移動剤の使用量がこの範囲にあれば、得られる（メタ）アクリル組成物の機械強度、成形加工性の視点から好ましい。 In the present invention, a chain transfer agent can be used to control the molecular weight of the polymer obtained by polymerizing the monomer mixture (A). Examples of the chain transfer agent include methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, ethylthioglycolate, mercaptoethanol, Thio-β-naphthol, thiophenol, dimethyl disulfide and the like are used. The amount of chain transfer agent used is preferably in the range of 0.02 to 2.2 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture (A). 0.2-1.0 weight part is further more preferable. If the usage-amount of a chain transfer agent exists in this range, it is preferable from a viewpoint of the mechanical strength of a (meth) acrylic composition obtained, and a moldability.
本発明においては、（メタ）アクリル系樹脂（Ｃ）中のアクリル酸エステル系架橋弾性体粒子（Ｂ）の含有量は、（メタ）アクリル系樹脂（Ｃ）全体を１００重量％とした場合、５〜４０重量％が好ましく、１０〜３５％がより好ましい。アクリル酸エステル系架橋弾性体粒子（Ｂ）の含有量が上記範囲であれば、得られる（メタ）アクリル組成物の成形加工性、耐折曲性の視点から好ましい。 In the present invention, the content of the acrylic ester-based crosslinked elastic particles (B) in the (meth) acrylic resin (C) is 100% by weight of the entire (meth) acrylic resin (C). 5 to 40% by weight is preferable, and 10 to 35% is more preferable. When the content of the acrylic ester-based crosslinked elastic particles (B) is in the above range, it is preferable from the viewpoint of molding processability and bending resistance of the obtained (meth) acrylic composition.
（メタ）アクリル系樹脂（Ｃ）が、乳化重合等により、ラテックスとして得られた場合は、凝固、洗浄および乾燥の操作により、または、スプレー乾燥、凍結乾燥などによる処理により、（メタ）アクリル系樹脂（Ｃ）を分離、回収することができる。 When the (meth) acrylic resin (C) is obtained as a latex by emulsion polymerization or the like, the (meth) acrylic resin is obtained by coagulation, washing and drying operations, or by treatment such as spray drying or freeze drying. The resin (C) can be separated and recovered.
本発明の樹脂組成物においては、（メタ）アクリル系樹脂（Ｃ）に対して、必要に応じて、熱可塑性樹脂（Ｄ）を配合することが可能である。 In the resin composition of this invention, it is possible to mix | blend a thermoplastic resin (D) with respect to (meth) acrylic-type resin (C) as needed.
配合する熱可塑性樹脂（Ｄ）の酸価は、０．７ｍｍｏｌ／ｇ未満が好ましく、０．６ｍｍｏｌ／ｇ未満がより好ましい。熱可塑性樹脂（Ｄ）の酸価が０．７ｍｍｏｌ／ｇ未満であれば、得られる（メタ）アクリル系樹脂組成物の耐アルカリ性の視点から好ましい。
なお、本発明において、「酸価」とは、溶剤に溶解した樹脂に所定量の水酸化ナトリウム水溶液を加え、その溶液を塩酸水溶液で中和滴定することにより、測定した値である。
The acid value of the thermoplastic resin (D) to be blended is preferably less than 0.7 mmol / g, more preferably less than 0.6 mmol / g. If the acid value of the thermoplastic resin (D) is less than 0.7 mmol / g, it is preferable from the viewpoint of alkali resistance of the resulting (meth) acrylic resin composition.
In the present invention, the “acid value” is a value measured by adding a predetermined amount of an aqueous sodium hydroxide solution to a resin dissolved in a solvent and neutralizing the solution with an aqueous hydrochloric acid solution.
本発明における熱可塑性樹脂（Ｄ）としては、例えば、無水グルタル酸樹脂、ラクトン環化メタクリル系樹脂、（メタ）アクリル系樹脂、スチレン系樹脂、メタクリル酸メチル−スチレン共重合体、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂等があげられる。これらの中では、メタクリル系樹脂が（メタ）アクリル樹脂（Ｃ）との相溶性、透明性の点から、好ましい。 Examples of the thermoplastic resin (D) in the present invention include glutaric anhydride resin, lactone-cyclized methacrylic resin, (meth) acrylic resin, styrene resin, methyl methacrylate-styrene copolymer, polyethylene terephthalate resin, And polybutylene terephthalate resin. Among these, methacrylic resins are preferable from the viewpoint of compatibility with (meth) acrylic resin (C) and transparency.
本発明における熱可塑性樹脂（Ｄ）として（メタ）アクリル系樹脂を用いる場合、メタクリル酸アルキルエステル５０〜１００重量％、アクリル酸アルキルエステル０〜５０重量％および（メタ）アクリル酸０〜６重量％を含有する単量体混合物を、少なくとも１段以上で共重合させてなるものが好ましく、より好ましくは、メタクリル酸アルキルエステル６０〜１００重量％、アクリル酸アルキルエステル０〜４０重量％および（メタ）アクリル酸０〜４重量％を含有するものがより好ましい。特に、得られるフィルムの硬度、剛性を重視する場合には、メタクリル系重合体（Ｄ）の単量体混合物組成としては、メタクリル酸メチルを８０重量％以上含有するものが好ましく、８５重量％以上含有するものがより好ましく、９０重量％以上含有するものがさらに好ましく、９２重量％以上含有するものが特に好ましい。 When a (meth) acrylic resin is used as the thermoplastic resin (D) in the present invention, methacrylic acid alkyl ester 50 to 100% by weight, acrylic acid alkyl ester 0 to 50% by weight, and (meth) acrylic acid 0 to 6% by weight Is preferably obtained by copolymerizing a monomer mixture containing at least one or more stages, more preferably 60 to 100% by weight of methacrylic acid alkyl ester, 0 to 40% by weight of acrylic acid alkyl ester, and (meth). What contains 0 to 4 weight% of acrylic acid is more preferable. In particular, when emphasizing the hardness and rigidity of the resulting film, the monomer mixture composition of the methacrylic polymer (D) preferably contains 80% by weight or more of methyl methacrylate, and 85% by weight or more. What contains is more preferable, What contains 90 weight% or more is further more preferable, What contains 92 weight% or more is especially preferable.
熱可塑性樹脂（Ｄ）の配合比は、耐衝撃性、折り曲げ白化性の観点から、（メタ）アクリル系樹脂（Ｃ）５０〜１００重量部および熱可塑性樹脂（Ｄ）０〜５０重量部の範囲が好ましく、（メタ）アクリル系樹脂（Ｃ）５０〜９０重量部および熱可塑性樹脂（Ｄ）１０〜５０重量部の範囲がより好ましく、（メタ）アクリル系樹脂（Ｃ）６０〜８０重量部および熱可塑性樹脂（Ｄ）２０〜４０重量部の範囲がさらに好ましい。ブレンドの方法は特に限定されず、公知の方法を用いることが可能である。 The blending ratio of the thermoplastic resin (D) is in the range of 50 to 100 parts by weight of the (meth) acrylic resin (C) and 0 to 50 parts by weight of the thermoplastic resin (D) from the viewpoints of impact resistance and bending whitening. The range of 50 to 90 parts by weight of (meth) acrylic resin (C) and 10 to 50 parts by weight of thermoplastic resin (D) is more preferable, and 60 to 80 parts by weight of (meth) acrylic resin (C) and The range of 20 to 40 parts by weight of the thermoplastic resin (D) is more preferable. The blending method is not particularly limited, and a known method can be used.
本発明において「加熱処理」とは、（メタ）アクリル系樹脂（Ｃ）を所定の温度にて加熱することにより、（メタ）アクリル酸第三ブチルエステル基から第三ブチル基をイソブチレンとして熱脱離させ、カルボン酸基へと変換する工程をさす。 In the present invention, the term “heat treatment” means that the (meth) acrylic resin (C) is heated at a predetermined temperature to thermally desorb tert-butyl groups from (meth) acrylic acid tert-butyl ester groups to isobutylene. It refers to the step of separating and converting to a carboxylic acid group.
加熱処理は、（メタ）アクリル系樹脂（Ｃ）を加熱できるものであれば特に限定されないが、（メタ）アクリル系樹脂（Ｃ）を均一に加熱できる方法として、押出機による溶融混練が好ましい。 The heat treatment is not particularly limited as long as the (meth) acrylic resin (C) can be heated, but melt kneading with an extruder is preferable as a method for uniformly heating the (meth) acrylic resin (C).
カルボン酸基を形成させるための加熱処理の温度は、２００〜３２０℃が好ましく、２２０〜３００℃がより好ましい。加熱処理樹脂温度が２００〜３２０℃の温度であれば、第三ブチル基の脱離が起こりやすく、カルボン酸基が形成されやすいために好ましく、また、（メタ）アクリル系樹脂組成物の透明性の点から好ましい。 200-320 degreeC is preferable and, as for the temperature of the heat processing for forming a carboxylic acid group, 220-300 degreeC is more preferable. A heat treatment resin temperature of 200 to 320 ° C. is preferable because tert-butyl groups are easily removed and carboxylic acid groups are easily formed, and transparency of the (meth) acrylic resin composition. From the point of view, it is preferable.
本発明において、加熱処理に押出機を用いる場合は、例えば、単軸押出機、二軸押出機あるいは多軸押出機等があげられるが、単軸押出機が好ましく、二軸押出機がより好ましい。二軸押出機には非噛合い型同方向回転式、噛合い型同方向回転式、非噛合い型異方向回転式、噛合い型異方向回転式が含まれる。これらの押出機は、単独で用いても、直列につないでも構わない。 In the present invention, when an extruder is used for the heat treatment, for example, a single-screw extruder, a twin-screw extruder, a multi-screw extruder or the like can be mentioned, but a single-screw extruder is preferable, and a twin-screw extruder is more preferable. . The twin screw extruder includes a non-meshing type same direction rotating type, a meshing type same direction rotating type, a non-meshing type different direction rotating type, and a meshing type different direction rotating type. These extruders may be used alone or connected in series.
押出機を使用する場合は、副生するイソブチレンを除去するために、大気圧以下に減圧可能なベント口を装着することが好ましく、多段のベント口を装着することがより好ましい。また、本発明で使用する押出機は、多段のベント口を有していることが好ましいが、ベント口の圧力をゲージ圧力で−０．０９ＭＰａ以下に制御することが好ましい。ベント口の圧力が−０．０９ＭＰａより高いと、残存する単量体や副生成物の除去効率が落ちる傾向がある。 When using an extruder, in order to remove by-produced isobutylene, it is preferable to install a vent port that can be reduced to atmospheric pressure or less, and more preferably to install a multistage vent port. Moreover, although it is preferable that the extruder used by this invention has a multistage vent port, it is preferable to control the pressure of a vent port to -0.09 Mpa or less with a gauge pressure. If the pressure at the vent port is higher than -0.09 MPa, the removal efficiency of the remaining monomers and by-products tends to decrease.
（メタ）アクリル系樹脂（Ｃ）を加熱処理する際には、一般に用いられる酸化防止剤、熱安定剤、光安定剤、ラジカル捕捉剤などの耐候性安定剤や、触媒、可塑剤、滑剤、帯電防止剤、着色剤、収縮防止剤、抗菌・脱臭剤等を、単独または２種以上組み合わせて、本発明の目的が損なわれない範囲で添加してもよい。また、これらの添加剤は、（メタ）アクリル系樹脂組成物を成形加工する際に添加することも可能である。 When heat-treating the (meth) acrylic resin (C), commonly used weather resistance stabilizers such as antioxidants, heat stabilizers, light stabilizers, radical scavengers, catalysts, plasticizers, lubricants, Antistatic agents, coloring agents, antishrinking agents, antibacterial / deodorizing agents, and the like may be added singly or in combination of two or more, so long as the object of the present invention is not impaired. These additives can also be added when the (meth) acrylic resin composition is molded.
本発明における（メタ）アクリル樹脂組成物の酸価は、０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満が好ましく、０．４ｍｍｏｌ／ｇ以上、０．６ｍｍｏｌ／ｇ未満がより好ましい。（メタ）アクリル樹脂組成物の酸価が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満であると、得られる（メタ）アクリル系樹脂フィルムの耐日焼け止め剤性と耐アルカリ性とのバランスがとれるため、好ましい。また、熱安定性を改善でき、ダイラインの発生を抑制することができるため、好ましい。 The acid value of the (meth) acrylic resin composition in the present invention is preferably 0.3 mmol / g or more and less than 0.7 mmol / g, more preferably 0.4 mmol / g or more and less than 0.6 mmol / g. When the acid value of the (meth) acrylic resin composition is 0.3 mmol / g or more and less than 0.7 mmol / g, the balance between sunscreen resistance and alkali resistance of the obtained (meth) acrylic resin film is Since it can be taken, it is preferable. Moreover, since thermal stability can be improved and generation | occurrence | production of die line can be suppressed, it is preferable.
本発明の（メタ）アクリル系樹脂組成物のガラス転移温度は、１１０〜１４０℃であることが好ましく、１１５〜１３５℃であることがより好ましい。ガラス転移温度がこの範囲内であれば、成型加工性、耐熱性の点から好ましい。 The glass transition temperature of the (meth) acrylic resin composition of the present invention is preferably 110 to 140 ° C, and more preferably 115 to 135 ° C. A glass transition temperature within this range is preferable from the viewpoints of moldability and heat resistance.
本発明の自動車用アクリルフィルムは、上記（メタ）アクリル系樹脂組成物を成形してなるフィルムである。 The automotive acrylic film of the present invention is a film formed by molding the above (meth) acrylic resin composition.
本発明の自動車用アクリルフィルムの製造方法（成形方法）としては、例えば、通常の溶融押出法であるインフレーション法やＴダイ押出法、あるいはカレンダー法、更には溶剤キャスト法等があげられる。また、必要に応じて、メタクリル系樹脂組成物からフィルムを成形する際、フィルム両面をロールまたは金属ベルトに同時に接触させることにより、特に、ガラス転移温度以上の温度に加熱したロールまたは金属ベルトに同時に接触させることにより、表面性のより優れたフィルムを得ることも可能である。また、目的に応じて、フィルムの積層成形や二軸延伸によるフィルムの改質も可能である。 Examples of the production method (molding method) of the acrylic film for automobiles of the present invention include an ordinary melt extrusion method such as an inflation method, a T-die extrusion method, a calendar method, and a solvent casting method. In addition, when forming a film from a methacrylic resin composition, if necessary, by simultaneously bringing both surfaces of the film into contact with a roll or a metal belt, in particular, simultaneously with the roll or metal belt heated to a temperature equal to or higher than the glass transition temperature. By bringing them into contact, it is possible to obtain a film having a superior surface property. Further, depending on the purpose, film reforming by film lamination molding or biaxial stretching is also possible.
本発明の（メタ）アクリル樹脂組成物より得られる自動車用アクリルフィルムは、金属、プラスチックなどに積層して用いることができる。積層の方法としては、鋼板などの金属板に接着剤を塗布した後、金属板にフィルムを載せて乾燥させ貼り合わせるウエットラミネートや、ドライラミネート、エキストルージョンラミネート、ホットメルトラミネートなどが挙げられる。 The automotive acrylic film obtained from the (meth) acrylic resin composition of the present invention can be used by laminating on metal, plastic and the like. Examples of the laminating method include wet laminating, dry laminating, extrusion laminating, hot melt laminating, and the like, after applying an adhesive to a metal plate such as a steel plate, and then depositing the film on the metal plate and drying it.
プラスチック部品にフィルムを積層する方法としては、フィルムを金型内に配置しておき、射出成形にて樹脂を充填するフィルムインサート成形、ラミネートインジェクションプレス成形や、フィルムを予備成形した後金型内に配置し、射出成形にて樹脂を充填するフィルムインモールド成形などがあげられる。 As a method of laminating a film on a plastic part, the film is placed in a mold, and film insert molding in which resin is filled by injection molding, laminate injection press molding, or after preforming the film in the mold. Examples include film-in-mold molding that is arranged and filled with resin by injection molding.
本発明の（メタ）アクリル樹脂組成物を成形してなる自動車用アクリルフィルムのラミネート積層品としては、自動車内外装材などに使用することができる。自動車内装材としては、透明性、高度な耐薬品性、折り曲げ性が要求されるインストルメントパネルの加飾部位などに用いることができる。他方、自動車外装材としては、透明性、耐薬品性、耐候性、折り曲げ性が要求される、バンパー、サイドガーニッシュなどに用いることができる。また、本発明の自動車用アクリルフィルムは、自動車内装材および自動車外装材に要求されるダイラインと呼ばれる表面傷が少ないものであり、好適に用いられる。 The laminate laminate of an acrylic film for automobiles formed by molding the (meth) acrylic resin composition of the present invention can be used for automobile interior and exterior materials. As an automobile interior material, it can be used for a decorative part of an instrument panel which requires transparency, high chemical resistance, and bendability. On the other hand, as an automobile exterior material, it can be used for bumpers, side garnishes, etc. that require transparency, chemical resistance, weather resistance, and bendability. Moreover, the acrylic film for automobiles of the present invention has few surface scratches called die lines required for automobile interior materials and automobile exterior materials, and is preferably used.
本発明は、上述した各実施形態に限定されるものではなく、請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the scope of claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. Embodiments are also included in the technical scope of the present invention.
以下、実施例および比較例により、本発明をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these.
以下の製造例、実施例および比較例中の「部」は重量部、「％」は重量％を表す。略号は、それぞれ下記の物質を表す。
ＢＡ：アクリル酸ブチル
ＭＭＡ：メタクリル酸メチル
ＥＨＡ：２−エチルへキシルアクリレート
ｔＢｕＡ：ターシャリーブチルアクリレート
ＡｌＭＡ：アリルメタクリレート
ＣＨＰ：クメンハイドロパーオキサイド
ｔＤＭ：ターシャリードデシルメルカプタン。
In the following production examples, examples and comparative examples, “parts” represents parts by weight, and “%” represents% by weight. Each abbreviation represents the following substance.
BA: butyl acrylate MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate tBuA: tertiary butyl acrylate AlMA: allyl methacrylate CHP: cumene hydroperoxide tDM: tertiary lead decyl mercaptan
なお、以下の実施例および比較例で測定した物性の各測定方法は、次のとおりである。 In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.
（１）重合転化率の評価
得られたメタクリル系樹脂組成物（Ｃ）ラテックスを、熱風乾燥機内にて１２０℃で１時間乾燥して固形成分量を求め、重合転化率（％）＝１００×固形成分量／仕込み単量体の式により、重合転化率を算出した。
(1) Evaluation of polymerization conversion rate The obtained methacrylic resin composition (C) latex was dried in a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and the polymerization conversion rate (%) = 100 × The polymerization conversion rate was calculated from the formula of solid component amount / charged monomer.
（２）ラテックスの平均粒子径の評価
得られたアクリル酸エステル系架橋弾性体粒子（Ｂ）ラテックスを、ＬＥＥＤ＆ＮＯＲＴＨＲＵＰ ＩＮＳＴＲＵＭＥＮＴＳ社のＭＩＣＲＯＴＲＡＣ ＵＰＡ１５０を用い、光散乱法により体積平均粒子径（μｍ）を測定した。
(2) Evaluation of average particle size of latex The volume average particle size (μm) of the obtained acrylate-based crosslinked elastic particles (B) latex was measured by a light scattering method using MICROTRAC UPA150 manufactured by LEED & NORTHRU INSTRUMENTS. .
（３）酸価の測定
以下の手順に沿って酸価測定を行った。
１）樹脂の滴定：得られた樹脂ペレット０．３ｇを塩化メチレン３７．５ｍｌに溶解後、メタノール３７．５ｍｌを添加した。この溶液に、フェノールフタレイン／エタノール溶液（１ｗｔ％）を２滴添加した。０．１Ｎ水酸化ナトリウム水溶液５ｍｌを添加し、１時間攪拌した。この溶液に０．１Ｎ塩酸を滴下して溶液の赤紫色が消失するまでの０．１Ｎ−塩酸の滴下量Ａ（ｍｌ）を測定した。
２）ブランクの滴定:塩化メチレン３７．５ｍｌおよびメタノール３７．５ｍｌにフェノールフタレイン／エタノール溶液（１重量％）を２滴添加した。これに０．１Ｎ水酸化ナトリウム水溶液５ｍｌを添加した。この溶液に、０．１Ｎ塩酸を滴下して溶液の赤紫色が消失するまでの０．１Ｎ塩酸の滴下量Ｂ（ｍｌ）を測定した。
３）樹脂中の酸価（酸および酸無水物量の総量）をＣ（ｍｍｏｌ／ｇ）とし、次式で求めた。
Ｃ＝０．１×（５−Ａ−Ｂ）／０．３
(3) Measurement of acid value The acid value was measured according to the following procedure.
1) Titration of resin: 37.5 ml of methanol was added after dissolving 0.3 g of the obtained resin pellets in 37.5 ml of methylene chloride. Two drops of phenolphthalein / ethanol solution (1 wt%) were added to this solution. 5 ml of 0.1N sodium hydroxide aqueous solution was added and stirred for 1 hour. 0.1N hydrochloric acid was added dropwise to this solution, and the amount A (ml) of 0.1N hydrochloric acid was measured until the reddish purple color of the solution disappeared.
2) Blank titration: 2 drops of a phenolphthalein / ethanol solution (1 wt%) were added to 37.5 ml of methylene chloride and 37.5 ml of methanol. To this, 5 ml of 0.1N sodium hydroxide aqueous solution was added. To this solution, 0.1N hydrochloric acid was added dropwise, and a drop amount B (ml) of 0.1N hydrochloric acid until the reddish purple color of the solution disappeared was measured.
3) The acid value (total amount of acid and acid anhydride) in the resin was C (mmol / g), and the following formula was used.
C = 0.1 × (5-AB) /0.3
（４）ガラス転移温度（Ｔｇ）
得られた樹脂ペレット１０ｍｇを用いて、示差走査熱量計（ＤＳＣ、（株）島津製作所製、ＤＳＣ−５０型）を用いて、窒素雰囲気下、昇温速度２０℃／ｍｉｎで測定し、中点法により決定した。
(4) Glass transition temperature (Tg)
Using 10 mg of the obtained resin pellets, a differential scanning calorimeter (DSC, manufactured by Shimadzu Corporation, DSC-50 type) was used and measured at a heating rate of 20 ° C./min in a nitrogen atmosphere. Determined by law.
（５）耐折り曲げ性、折り曲げ白化性
得られたフィルムを１８０度折り曲げて、折り曲げ部の変化を目視で評価した。
○：折り曲げ部に白化が認められない。
×：折り曲げ部に白化が認められる。
−：折り曲げ部に割れが生じる。
(5) Bending resistance and bending whitening property The obtained film was bent 180 degrees, and the change of the bent portion was visually evaluated.
○: Whitening is not observed at the bent portion.
X: Whitening is recognized in a bending part.
-: A crack occurs in the bent portion.
（６）黄色度
得られたフィルムから、５０ｍｍ×５０ｍｍの試験片を切り出し、ＪＩＳ Ｋ７１０５−１９８１の６．３記載の方法により、日本電色工業（株）製分光式色差計ＳＥ−２０００を用いて測定した。
(6) Yellowness
A 50 mm × 50 mm test piece was cut out from the obtained film and measured using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method described in 6.3 of JIS K7105-1981.
（７）耐薬品性
＜耐アルカリ性＞
得られたフィルムを、０．１Ｍの水酸化ナトリウム水溶液に浸漬し、５５℃で４時間放置し、目視で試験片の変化を観測した。
○：変化が認められない。
△：微小な劣化が認められる。
×：樹脂の劣化、変色が認められる。
＜耐キシレン性＞
得られたフィルム上にキシレンを１滴（０．０２ｇ）滴下し、室温で乾くまで放置して、目視で滴下部の変化を観測した。
○：変化が認められない。
△：微小な塗布跡が認められる。
×：樹脂の劣化、変色が認められる。
＜耐日焼け止めクリーム［コパトーン（登録商標）］性＞
得られたフィルムに日焼け止め剤（コパトーン ウォーター・ベイビーズ・ローションＳＰＦ５０）を一滴（０．００５ｇ）滴下し、２×３ｃｍの範囲に刷毛を用いて延ばし、９０℃で２４時間放置して付着した日焼け止め剤をガーゼでふき取り、目視で塗布部の変化を観測した。
○：変化が認められない。
△：微小な塗布跡が認められる。
×：樹脂の劣化、変色が認められる。
(7) Chemical resistance <Alkali resistance>
The obtained film was immersed in a 0.1 M aqueous sodium hydroxide solution and allowed to stand at 55 ° C. for 4 hours, and changes in the test piece were observed visually.
○: No change is observed.
(Triangle | delta): Minute degradation is recognized.
X: Deterioration and discoloration of the resin are observed.
<Xylene resistance>
One drop (0.02 g) of xylene was dropped on the obtained film, left to dry at room temperature, and the change of the dropping part was visually observed.
○: No change is observed.
(Triangle | delta): A fine coating trace is recognized.
X: Deterioration and discoloration of the resin are observed.
<Sun resistance cream [Copatone (registered trademark)] properties>
One drop (0.005 g) of sunscreen agent (Copatone Water Baby Lotion SPF50) was added dropwise to the resulting film, and it was extended with a brush in the range of 2 x 3 cm. The stopper was wiped off with gauze, and changes in the coated part were observed visually.
○: No change is observed.
(Triangle | delta): A fine coating trace is recognized.
X: Deterioration and discoloration of the resin are observed.
（８）熱安定性評価 ＜滞留時の粘度減少測定＞
キャピログラフ（（株）東洋精機製作所製）を用いて、得られた樹脂ペレットを、２６０℃に加熱したシリンダー内に充填し、５分間予熱を加えた後、１φ×１０ｍｍのキャピラリーから２ｍｍ／分の速度にて押し出し、９０分経過した時点における初期溶融粘度からの減少率を測定した。
(8) Thermal stability evaluation <Measurement of viscosity reduction during residence>
Using a capillograph (manufactured by Toyo Seiki Seisakusho), the obtained resin pellets were filled into a cylinder heated to 260 ° C., preheated for 5 minutes, and then 2 mm / min from a 1φ × 10 mm capillary. The rate of decrease from the initial melt viscosity was measured when 90 minutes had passed after extrusion at a speed.
（９）ダイライン評価
得られたフィルムの長さ５ｍ分の表面を観察し、次の基準により評価をした。
○：ダイラインが殆ど認められない。
△：ダイラインが、認められる。
×：ダイラインが、著しい。
(9) Die line evaluation The surface of the obtained film for 5 m in length was observed and evaluated according to the following criteria.
○: Die line is hardly recognized.
Δ: Die line is recognized.
X: Die line is remarkable.
（製造例１）（メタ）アクリル系樹脂（Ｃ）の製造
攪拌機付き８Ｌ重合装置に、以下の物質を仕込んだ。
脱イオン水 ２００部
ジオクチルスルフォコハク酸ナトリウム ０．２５部
ソジウムホルムアルデヒドスルフォキシレート ０．１５部
エチレンジアミン四酢酸−２−ナトリウム ０．００５部
硫酸第一鉄 ０．００１５部
重合機内を窒素ガスで充分に置換し実質的に酸素のない状態とした後、内温を６０℃にし、表１中（１）に示したアクリル酸エステル系架橋弾性体粒子（Ｂ）の原料となる単量体混合物［すなわち、ＢＡ９０％およびＭＭＡ１０％からなる単量体混合物１００部に対し、ＡｌＭＡ２．１部およびＣＨＰ０．２部からなる単量体混合物］２０部を１０部／時間の割合で連続的に添加し、添加終了後、さらに０．５時間重合を継続し、アクリル酸エステル系架橋弾性体粒子（Ｂ）を得た。重合転化率は９９．５％であり、平均粒子径は８００Åであった。
その後、ジオクチルスルフォコハク酸ナトリウム０．３部を仕込んだ後、内温を６０℃にし、表１中（１）に示した単量体混合物（Ａ）［すなわち、ｔＢｕＡ１０％、ＭＭＡ９０％からなる単量体混合物１００部に対し、ｔＤＭ０．３４部およびＣＨＰ０．３４部からなる単量体混合物］８０部を１０部／時間の割合で連続的に添加し、さらに１時間重合を継続し、（メタ）アクリル系樹脂組成物（Ｃ）を得た。重合転化率は９９．０％であった。得られたラテックスを硫酸マグネシウムで塩析、凝固し、水洗、乾燥して（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（１）を得た。
(Production Example 1) Production of (meth) acrylic resin (C) The following substances were charged into an 8L polymerization apparatus equipped with a stirrer.
Deionized water 200 parts Sodium dioctylsulfosuccinate 0.25 parts Sodium formaldehyde sulfoxylate 0.15 parts Ethylenediaminetetraacetic acid-2-sodium 0.005 parts Ferrous sulfate 0.0015 parts Nitrogen gas in the polymerization machine The monomer used as a raw material for the acrylate ester-based crosslinked elastic particles (B) shown in Table 1 (1) after sufficiently substituting and making it substantially oxygen-free 20 parts of a mixture [ie, a monomer mixture comprising 2.1 parts of AlMA and 0.2 part of CHP to 100 parts of a monomer mixture comprising 90% BA and 10% MMA] is continuously added at a rate of 10 parts / hour. Then, after completion of the addition, the polymerization was further continued for 0.5 hours to obtain acrylic ester-based crosslinked elastic particles (B). The polymerization conversion was 99.5% and the average particle size was 800 mm.
Thereafter, 0.3 part of sodium dioctylsulfosuccinate was charged, the internal temperature was set to 60 ° C., and the monomer mixture (A) shown in (1) in Table 1 [that is, tBuA 10%, MMA 90%] 80 parts of a monomer mixture consisting of 0.34 parts of tDM and 0.34 parts of CHP per 100 parts of the monomer mixture] was continuously added at a rate of 10 parts / hour, and polymerization was continued for another hour ( A (meth) acrylic resin composition (C) was obtained. The polymerization conversion rate was 99.0%. The obtained latex was salted out with magnesium sulfate, coagulated, washed with water and dried to obtain a resin powder (1) of (meth) acrylic resin (C).
（製造例２〜４）
表１中（２）〜（４）に示したアクリル酸エステル系架橋弾性体粒子（Ｂ）および単量体混合物（Ａ）の組成により製造例１と同様に重合を行い、凝固、水洗、乾燥して得られた（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（２）〜（４）を得た。
(Production Examples 2 to 4)
Polymerization is carried out in the same manner as in Production Example 1 by the composition of the acrylic ester-based crosslinked elastic particles (B) and monomer mixture (A) shown in Tables (2) to (4), coagulation, water washing, and drying. Resin powders (2) to (4) of the (meth) acrylic resin (C) thus obtained were obtained.
（比較製造例１〜３）
表１中（５）〜（７）に示したアクリル酸エステル系架橋弾性体粒子（Ｂ）および単量体混合物（Ａ）の組成により製造例１と同様に重合を行い、凝固、水洗、乾燥して（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（５）〜（７）を得た。
(Comparative Production Examples 1 to 3)
Polymerization is carried out in the same manner as in Production Example 1 with the composition of the acrylic ester-based crosslinked elastic particles (B) and monomer mixture (A) shown in Table 1 (5) to (7), coagulation, washing with water, and drying. Thus, resin powders (5) to (7) of (meth) acrylic resin (C) were obtained.
（実施例１〜２）
（メタ）アクリル系樹脂組成物（Ｃ）の樹脂粉末（１）または（２）を、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、これらの（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表２に示した。
さらに、得られた（メタ）アクリル系樹脂組成物を、Ｔダイ付き４０ｍｍφ押出機を用いて、ダイス温度２６０℃にて成形し、幅２１ｃｍ、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表２に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１〜１５重量％の範囲内で含み、酸価の値が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である実施例１および２の（メタ）アクリル樹脂組成物を成形してなるフィルムでは、すべての耐薬品性が改良される。
(Examples 1-2)
The resin powder (1) or (2) of the (meth) acrylic resin composition (C) is pelletized by melt kneading by setting the cylinder temperature to 260 ° C. using a 40 mmφ single screw extruder with a vent. A (meth) acrylic resin composition was obtained. Moreover, in the NMR measurement of these (meth) acrylic resin compositions, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed.
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 2 together with the acid value of the (meth) acrylic resin composition.
Furthermore, the obtained (meth) acrylic resin composition was molded at a die temperature of 260 ° C. using a 40 mmφ extruder with a T die to obtain a film having a width of 21 cm and a thickness of 125 μm.
The properties of the obtained film were evaluated, and the results are shown in Table 2.
The monomer composition (A) contains (meth) acrylic acid tert-butyl ester in the range of 1 to 15% by weight, and the acid value is 0.3 mmol / g or more and less than 0.7 mmol / g. In the film formed by molding the (meth) acrylic resin composition of Examples 1 and 2, all chemical resistance is improved.
（比較例１）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（７）を、ベント付き４０ｍｍφ単軸押出機を用いて、シリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表２に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表２に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを含まず、酸価が０．３ｍｍｏｌ／ｇ未満である比較例１の（メタ）アクリル系樹脂組成物を成形してなるフィルムは、耐キシレン性、耐日焼け止め剤性が劣る。また、熱安定性が劣るため、ダイライン性が悪化する傾向がある。
(Comparative Example 1)
The resin powder (7) of the (meth) acrylic resin (C) was melt-kneaded with a vented 40 mmφ single-screw extruder at a cylinder temperature of 260 ° C., and pelletized (meth) acrylic A system resin composition was obtained.
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 2 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 2.
The monomer composition (A) does not contain (meth) acrylic acid tert-butyl ester and is formed by molding the (meth) acrylic resin composition of Comparative Example 1 having an acid value of less than 0.3 mmol / g. The film is inferior in xylene resistance and sunscreen resistance. Moreover, since heat stability is inferior, there exists a tendency for die line property to deteriorate.
（比較例２）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（５）を、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、得られた（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表２に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表２に示した。
（メタ）アクリル酸第三ブチルエステルを１５重量％より多く含み、酸価が０．７ｍｍｏｌ／ｇ以上である比較例２の（メタ）アクリル系樹脂組成物は耐アルカリ性が劣る。
(Comparative Example 2)
The (meth) acrylic resin (C) resin powder (5) was melt-kneaded with a vented 40 mmφ single screw extruder at a cylinder temperature of 260 ° C. and pelletized (meth) acrylic. A resin composition was obtained. Moreover, in the NMR measurement of the obtained (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed. .
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 2 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 2.
The (meth) acrylic resin composition of Comparative Example 2 containing more than 15% by weight of (meth) acrylic acid tert-butyl ester and having an acid value of 0.7 mmol / g or more has poor alkali resistance.
（実施例３）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（３）１００重量部に対して、メタクリル系樹脂ＨＴ１２１(ＡＬＴＵＧＬＡＳＳ製、酸価０．４５ｍｍｏｌ／ｇ)を３０部ブレンドし、４０ミリφベント付き単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、得られた（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１〜１５重量％の範囲内で含み、酸価の値が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である実施例２〜４の（メタ）アクリル系樹脂組成物ではすべての耐薬品性が改良されている。
(Example 3)
30 parts of methacrylic resin HT121 (manufactured by ALTUGLASS, acid value 0.45 mmol / g) is blended with 100 parts by weight of resin powder (3) of (meth) acrylic resin (C), Melting and kneading were carried out by setting the cylinder temperature to 260 ° C. using a shaft extruder, to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of the obtained (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed. .
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The monomer composition (A) contains (meth) acrylic acid tert-butyl ester in the range of 1 to 15% by weight, and the acid value is 0.3 mmol / g or more and less than 0.7 mmol / g. In the (meth) acrylic resin compositions of Examples 2 to 4, all chemical resistances are improved.
（実施例４）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（４）１００重量部に対してメタクリル系樹脂スミペックスＬＧ(住友化学（株）製、酸価０ｍｍｏｌ／ｇ)を３０部ブレンドし、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、この（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１〜１５重量％の範囲内で含み、酸価の値が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である実施例２〜４の（メタ）アクリル系樹脂組成物では、すべての耐薬品性が改良されている。
Example 4
30 parts of methacrylic resin Sumipex LG (manufactured by Sumitomo Chemical Co., Ltd., acid value 0 mmol / g) is blended with 100 parts by weight of resin powder (4) of (meth) acrylic resin (C), and 40 mmφ single unit with a vent is provided. Melting and kneading were carried out by setting the cylinder temperature to 260 ° C. using a shaft extruder, to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of this (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed.
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The monomer composition (A) contains (meth) acrylic acid tert-butyl ester in the range of 1 to 15% by weight, and the acid value is 0.3 mmol / g or more and less than 0.7 mmol / g. In the (meth) acrylic resin compositions of Examples 2 to 4, all chemical resistances are improved.
（実施例５）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（４）１００重量部に対してメタクリル系樹脂ＨＴ１２１（酸価０．４５ｍｍｏｌ／ｇ)を３０部ブレンドし、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、得られた（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１〜１５重量％の範囲内で含み、酸価の値が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である実施例２〜４の（メタ）アクリル系樹脂組成物ではすべての耐薬品性が改良されている。
(Example 5)
30 parts of methacrylic resin HT121 (acid value 0.45 mmol / g) is blended with 100 parts by weight of resin powder (4) of (meth) acrylic resin (C), and a 40 mmφ single screw extruder with a vent is used. Melt kneading was performed with the cylinder temperature set at 260 ° C. to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of the obtained (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed. .
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The monomer composition (A) contains (meth) acrylic acid tert-butyl ester in the range of 1 to 15% by weight, and the acid value is 0.3 mmol / g or more and less than 0.7 mmol / g. In the (meth) acrylic resin compositions of Examples 2 to 4, all chemical resistances are improved.
（比較例３）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（３）１００重量部に対してメタクリル系樹脂スミペックスＬＧ（酸価０ｍｍｏｌ／ｇ)を３０部ブレンドし、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、得られた（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体組成物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１〜１５重量％の範囲内で含んでいるが、酸価が０．３ｍｍｏｌ／ｇ未満である比較例４の（メタ）アクリル系樹脂組成物は耐キシレン性、耐日焼け止め剤性が劣る。また、熱安定性が劣るため、ダイライン性が悪化する傾向がある。
(Comparative Example 3)
30 parts of methacrylic resin Sumipex LG (acid value 0 mmol / g) is blended with 100 parts by weight of resin powder (3) of (meth) acrylic resin (C), and cylinder using a 40 mmφ single screw extruder with a vent. Melt kneading was performed at a temperature of 260 ° C. to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of the obtained (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed. .
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The monomer composition (A) contains (meth) acrylic acid tert-butyl ester in the range of 1 to 15% by weight, but the acid value is less than 0.3 mmol / g of (meth) ) Acrylic resin compositions are inferior in xylene resistance and sunscreen resistance. Moreover, since heat stability is inferior, there exists a tendency for die line property to deteriorate.
（比較例４）
（メタ）アクリル系樹脂（Ｃ）（６）の樹脂粉末１００重量部に対してメタクリル系樹脂ＨＴ１２１（酸価０．４５ｍｍｏｌ／ｇ)を３０部ブレンドし、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。またこの（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体混合物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１５重量％より多く含んでおり、酸価が０．７ｍｍｏｌ／ｇ以上である比較例５の（メタ）アクリル系樹脂組成物は耐アルカリ性が劣る。
(Comparative Example 4)
30 parts of methacrylic resin HT121 (acid value 0.45 mmol / g) is blended with 100 parts by weight of resin powder of (meth) acrylic resin (C) (6), and a 40 mmφ single screw extruder with a vent is used. Melt kneading was performed with the cylinder temperature set at 260 ° C. to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of this (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed.
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The (meth) acrylic resin composition of Comparative Example 5 containing more than 15% by weight of (meth) acrylic acid tert-butyl ester in the monomer mixture (A) and having an acid value of 0.7 mmol / g or more Is inferior in alkali resistance.
（比較例５）
（メタ）アクリル系樹脂（Ｃ）の樹脂粉末（６）１００重量部にメタクリル系樹脂スミペックスＬＧ（酸価０ｍｍｏｌ／ｇ)を３０部ブレンドし、ベント付き４０ｍｍφ単軸押出機を用いてシリンダ温度を２６０℃に設定して溶融混練を行い、ペレット化された（メタ）アクリル系樹脂組成物を得た。また、得られた（メタ）アクリル系樹脂組成物のＮＭＲ測定では、１．３〜１．５ｐｐｍ付近の第三ブチル基に由来するピークは消失しており、脱離反応の進行が確認される。
得られた（メタ）アクリル系樹脂組成物の特性を評価し、その結果を（メタ）アクリル系樹脂組成物の酸価と合わせて、表３に示した。
さらに、実施例１と同様の操作により、厚み１２５μｍのフィルムを得た。
得られたフィルムの特性を評価し、その結果を表３に示した。
単量体混合物（Ａ）に（メタ）アクリル酸第三ブチルエステルを１５重量％より多く含んでいる比較例６の（メタ）アクリル系樹脂組成物は、酸価が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満の範囲内にあっても、耐アルカリ性が劣る。
(Comparative Example 5)
30 parts of methacrylic resin Sumipex LG (acid value 0 mmol / g) is blended with 100 parts by weight of (meth) acrylic resin (C) resin powder (6), and the cylinder temperature is adjusted using a 40 mmφ single screw extruder with a vent. Melting and kneading was performed at 260 ° C. to obtain a pelletized (meth) acrylic resin composition. Moreover, in the NMR measurement of the obtained (meth) acrylic resin composition, the peak derived from the tertiary butyl group in the vicinity of 1.3 to 1.5 ppm disappears, and the progress of the elimination reaction is confirmed. .
The properties of the obtained (meth) acrylic resin composition were evaluated, and the results are shown in Table 3 together with the acid value of the (meth) acrylic resin composition.
Furthermore, a film having a thickness of 125 μm was obtained by the same operation as in Example 1.
The properties of the obtained film were evaluated, and the results are shown in Table 3.
The (meth) acrylic resin composition of Comparative Example 6 containing more than 15% by weight of (meth) acrylic acid tert-butyl ester in the monomer mixture (A) has an acid value of 0.3 mmol / g or more, Even in the range of less than 0.7 mmol / g, the alkali resistance is poor.
Claims (7)
（メタ）アクリル酸直鎖アルキルエステル８５〜９９重量％、（メタ）アクリル酸第三ブチルエステル１〜１５重量％を含む単量体混合物（Ａ）を重合して（ここで、アクリル酸エステル系架橋弾性体粒子（Ｂ）５〜７５重量部に対し単量体混合物（Ａ）９５〜２５重量部である）、単量体混合物（Ａ）の一部が、アクリル酸エステル系架橋弾性体粒子（Ｂ）にグラフト化されて得られる
（メタ）アクリル系樹脂（Ｃ）を加熱処理することによって得られる（メタ）アクリル樹脂組成物を成形してなる自動車用フィルムであって、
（メタ）アクリル樹脂組成物の酸価が０．３ｍｍｏｌ／ｇ以上、０．７ｍｍｏｌ／ｇ未満である、自動車用アクリルフィルム。 Two or more non-conjugated two per molecule per 100 parts by weight of monomer mixture (b) containing 50 to 100% by weight of acrylic acid alkyl ester monomer and 0 to 50% by weight of methacrylic acid alkyl ester monomer In the presence of acrylic ester-based crosslinked elastic particles (B) obtained by mixing and polymerizing 0.5 to 5 parts by weight of a polyfunctional monomer having a heavy bond,
A monomer mixture (A) containing 85 to 99% by weight of (meth) acrylic acid linear alkyl ester and 1 to 15% by weight of (meth) acrylic acid tert-butyl ester is polymerized (here, acrylic ester type The monomer mixture (A) is 95 to 25 parts by weight with respect to 5 to 75 parts by weight of the crosslinked elastic particles (B)), and a part of the monomer mixture (A) is an acrylate-based crosslinked elastic particle. A film for automobiles formed by molding a (meth) acrylic resin composition obtained by heat-treating a (meth) acrylic resin (C) obtained by grafting to (B) ,
The acrylic film for motor vehicles whose acid value of a (meth) acrylic resin composition is 0.3 mmol / g or more and less than 0.7 mmol / g.
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