JP6582396B2 - 積層体及びこれを用いる成形体 - Google Patents
積層体及びこれを用いる成形体 Download PDFInfo
- Publication number
- JP6582396B2 JP6582396B2 JP2014233567A JP2014233567A JP6582396B2 JP 6582396 B2 JP6582396 B2 JP 6582396B2 JP 2014233567 A JP2014233567 A JP 2014233567A JP 2014233567 A JP2014233567 A JP 2014233567A JP 6582396 B2 JP6582396 B2 JP 6582396B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylic
- styrene
- coating agent
- fatty acid
- acid ester
- 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.)
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 96
- -1 fatty acid ester Chemical class 0.000 claims description 78
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 40
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 36
- 239000000194 fatty acid Substances 0.000 claims description 36
- 229930195729 fatty acid Natural products 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- 229920000178 Acrylic resin Polymers 0.000 claims description 26
- 239000004925 Acrylic resin Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229920001890 Novodur Polymers 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 claims description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000012153 distilled water Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GCSPRLPXTPMSTL-IBDNADADSA-N [(2s,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[C@@]1([C@]2(CO)[C@H]([C@H](O)[C@@H](CO)O2)O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O GCSPRLPXTPMSTL-IBDNADADSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- 229920001353 Dextrin Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000019425 dextrin Nutrition 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- JYSWMLAADBQAQX-UHFFFAOYSA-N 2-prop-2-enoyloxyacetic acid Chemical compound OC(=O)COC(=O)C=C JYSWMLAADBQAQX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- UTDREDDDGVJRGG-UHFFFAOYSA-N 3-[4-(3-hydroxypropyl)phenyl]propan-1-ol Chemical compound OCCCC1=CC=C(CCCO)C=C1 UTDREDDDGVJRGG-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- HEMYIEDNNZJZSV-UHFFFAOYSA-N 4-prop-2-enoyloxybutanoic acid Chemical compound OC(=O)CCCOC(=O)C=C HEMYIEDNNZJZSV-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 1
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- BWHOZHOGCMHOBV-UHFFFAOYSA-N benzylideneacetone Chemical compound CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Wrappers (AREA)
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Description
<スチレン系樹脂シート(A)>
本発明で用いるスチレン系樹脂シート(A)は、スチレン系モノマー、及びこれと共重合可能な単量体とを重合させてなるスチレン系樹脂をシート状に成形したものであり、その厚みや成形方法等には特に限定されるものではない。
前述の、本発明で使用することができる複数の分岐を有し、且つ複数の重合性二重結合を有する多分岐状マクロモノマーとしては、ゲル物発生を抑制し、流動性を確保する観点から、多分岐状マクロモノマーの重量平均分子量(Mw)が、好ましくは1,000〜15,000、より好ましくは3,000〜8,000の範囲のものを用いる。
前記多分岐状マクロモノマーとスチレン系モノマー、必要に応じて併用されるその他の単量体類を共重合させると、多分岐状の樹脂と、重合条件により同時に生成する線状の樹脂及び低分岐樹脂との混合物である樹脂混合物が得られる。この時、前述の多分岐状マクロモノマーをこれ以外の単量体の総量に対して好ましくは50ppm〜1%、より好ましくは100ppm〜3000ppm(質量基準)の比率で用いることにより、多分岐状の樹脂の生成が容易であり、本発明に使用されるスチレン系樹脂の作製を安易にする。
スチレン系モノマー単独、又はこれと共重合可能な単量体との共重合体を得るための重合反応、更に前述の多分岐状マクロモノマーを併用してスチレン系樹脂シート(A)の原料とする樹脂(組成物)を製造する方法としては、種々の汎用されているスチレン系モノマーの重合方法を応用することができる。重合方式には特に限定はないが、塊状重合、懸濁重合、あるいは溶液重合が好ましい。中でも生産効率の点で特に連続塊状重合が好ましく、例えば一個以上の攪拌式反応器と可動部分の無い複数のミキシングエレメントが内部に固定されている管状反応器を組み込んだ連続塊状重合を行うことにより、優れた樹脂を得ることができる。重合開始剤を使用せずに熱重合させることもできるが、種々のラジカル重合開始剤を使用することが好ましい。また、重合に必要な懸濁剤や乳化剤などのような重合助剤は、通常のポリスチレンの製造に使用されるものを使用できる。
重合工程では、スチレン系モノマー、その他併用されるモノマーあるいは多分岐状マクロモノマーを単量体として用い、これらを共重合させることによって、スチレン系樹脂シート(A)の材料となるスチレン系樹脂(組成物)を得ることができる。重合装置の反応容器については特に限定されるものではない。重合工程の後に、未反応モノマーや溶剤分を揮発するための、好ましくは減圧下状態に調整した脱揮槽を通過させる。その後ペレット化され、本発明で用いるスチレン系樹脂シート(A)の材料となるスチレン系樹脂を得ることができる。
無延伸シートは、上記で得られたスチレン系樹脂(組成物)のペレットを押出機で溶融押出後、T−ダイによりシート状に溶融押出した後、冷却ロール等により冷却し作製できる。冷却温度としては、70〜90℃が好ましい。
二軸延伸シートは、押出機での溶融押出後、延伸機で縦横ニ軸に延伸することで得られる。例えば、まず、押出機にスチレン系樹脂(組成物)を供給し、T−ダイよりシート状に溶融押出する。その際、延伸前のシートが所定厚みになるようにキャスティングする。その後、二軸延伸可能な温度、例えば110〜145℃にシートを冷却して、縦方向(流れ方向)及び横方向(流れ方向に対するクロス方向)に延伸することで得られる。
本発明で用いるコート剤は、アクリル系樹脂を樹脂成分とするものであり、親水性であることを必須とする。なお、本発明において親水性とは、水溶性、水分散性のいずれであってもよいことを示す。
測定装置 ;東ソー株式会社製 HLC−8220GPC
カラム ;東ソー株式会社製 TSK−GUARDCOLUMN SuperHZ−L
+東ソー株式会社製 TSK−GEL SuperHZM−M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC−8020modelII
測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
本発明では、前述のアクリル系親水性コート剤(B)に、少なくとも1種類以上の糖由来の脂肪酸エステル(b)を含有させることを特徴とする。
本発明の積層体は、前述のスチレン系樹脂シート(A)に前記コート剤(B)を塗布し、乾燥させることで得ることができる。乾燥方法としては特に限定されるものではなく、例えば、樹脂シート(A)の温度がTgを超えない様に制御された乾燥装置を用い0.1〜30分程度の加熱乾燥にてコート剤(B)からなる被覆層を樹脂シート(A)上に形成させることができる。
前記で得られた積層体は、これを直接加熱方式または間接加熱方式によって加熱され、成形されて、本発明の成形体とすることができる。加熱成形の方法は、特に限定されるものではなく、真空成形機、熱板圧空成形機、真空圧空成形機等を用いて行うことができるが、温度制御が良好で、短時間加熱が可能なことから、熱板圧空成形機を用いての加熱成形が好適である。
前記で得られた本発明の成形体は、特に食品包装容器として好適に用いることができ、その防曇性、耐油性、及びスチレン系樹脂シートが本来有する透明性の観点から、蓋材として使用することが最も好ましい。この時、本発明の積層体における被覆層が内容物側になるように成形されていることが好ましい使用方法である。
還流冷却器、撹拌機および窒素導入管を具備した反応容器に、n−ブタノール136.8部を仕込んで撹拌を開始し、100℃まで昇温した。ここに窒素気流下で、メタクリル酸メチル29.3部、アクリル酸エチル29.3部、スチレン29.3部、メタクリル酸58.5部からなる単量体混合物と、t−ブチルパーオキシ−2−エチルヘキサノエート0.2部、n−ブタノール24.6部からなる反応開始剤混合物とを2時間かけて連続滴下した。同温度で2時間撹拌後、t−ブチルパーオキシ−2−エチルヘキサノエート0.6部、n−ブタノール16.6部からなる反応開始剤混合物を2時間かけて連続滴下した。同温度で1時間撹拌後、95℃に降温し、ジメチルエタノールアミン57.6部により中和を行い、イオン交換水738.7部を用いて水溶化を行い、水溶性アクリル樹脂を得た。水溶性アクリル樹脂は、不揮発分18%であった。更に蒸留水により希釈を行い不揮発分10%に調整した。更に、ショ糖ラウリン酸エステル(理研ビタミン株式会社社製リケマールA、HLB=15、固形分40%)をそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しアクリル系親水性コート剤B1を得た。
合成例1において、アクリル樹脂水溶液に対し、脂肪酸エステル(b)として、ショ糖ラウリン酸エステル、デキストリン(塩水港精糖株式会社製k−100粉体)をそれぞれの固形分が1.5%、1.4%、0.1%になる様に混合し蒸留水で希釈することでアクリル系親水性コート剤B2を得た。
合成例1において、アクリル樹脂水溶液に対し、ショ糖ラウリン酸エステル、ポリビニルアルコール(日本合成化学株式会社製ゴーセノールKP−08R)をそれぞれの固形分が1.5%、1.4%、0.1%になる様に混合し蒸留水で希釈することでアクリル系親水性コート剤B3を得た。
還流冷却器、撹拌機および窒素導入管を具備した反応容器に、イソプロピルアルコール220.8部を仕込んで撹拌を開始し、80℃まで昇温した。ここに窒素気流下で、メタクリル酸メチル157.9部、アクリル酸エチル201.9部、アクリル酸の80%水溶液54.6部からなる単量体混合物と、t−ブチルパーオキシ−2−エチルヘキサノエート4.1部、イソプロピルアルコール80.9部からなる反応開始剤混合物とを4時間かけて連続滴下した。同温度で3時間撹拌後、40℃に降温し、25%アンモニア水39.6部により中和を行い、イオン交換水257.3部を用いて水溶化を行い、水溶性アクリル樹脂を得た。水溶性アクリル樹脂は、不揮発分40%であった。更に蒸留水により希釈を行い不揮発分10%に調整した。更に、ショ糖ラウリン酸エステル、デキストリン(塩水港精糖株式会社製k−100粉体)をそれぞれの固形分が1.5%、1.4%、0.1%になる様に蒸留水で希釈しアクリル系親水性コート剤B4を得た。
還流冷却器、撹拌機および窒素導入管を具備した反応容器に、n−ブタノール186.5部を仕込んで撹拌を開始し、100℃まで昇温した。ここに窒素気流下で、メタクリル酸メチル115.8部、アクリル酸エチル94.2部、メタクリル酸140.0部からなる単量体混合物と、t−ブチルパーオキシ−2−エチルヘキサノエート3.5部、n−ブタノール163.5部からなる反応開始剤混合物とを4時間かけて連続滴下した。同温度で3時間撹拌後、40℃に降温し、ジメチルエタノールアミン137.6部により中和を行い、イオン交換水1025.0部を用いて水溶化を行い、不揮発分19%のアクリル樹脂水溶液を得た。更に、ショ糖ラウリン酸エステル、デキストリン(塩水港精糖株式会社製k−100粉体)をそれぞれの固形分が1.5%、1.4%、0.1%になる様に蒸留水で希釈しアクリル系親水性コート剤B5を得た。
B’1:ポリビニルアルコール:電気化学工業株式会社製ポバールB−17とショ糖ラウリン酸エステル(理研ビタミン株式会社社製リケマールA)、デキストリン(塩水港精糖株式会社製k−100粉体)を1.5%、1.4%、0.1%になる様に蒸留水で希釈し調整した。
表1〜3に示すモノマー組成比(MAA:メタクリル酸)を用い、連続塊状重合により共重合体を合成し、押出機にて1000μmの無延伸シートとした後、単発延伸機により縦方向(MD)2倍、横方向(CD)2倍に延伸を施した二軸延伸スチレン系樹脂シートを得た。
耐油性評価:成形体内側に中鎖脂肪酸油(不二精機株式会社製ホワイトF−2)を塗布し、90℃の恒温槽中に5分及び15分放置した後の外観を目視により確認し評価を行った。評価は白化の発生しなかったものを○、若干程度の白化が見られたものを△、明らかな白化が発生したものを×とした。
DIC株式会社製多分岐ポリスチレンHP−780ANを押出機にて1000μmの無延伸シートとした後、単発延伸機により縦方向(MD)2倍、横方向(CD)2倍に延伸を施した二軸延伸スチレン系樹脂シートを得た。その他は実施例1と同様に積層体を作製後、同様の評価を実施した。
Claims (9)
- スチレン系樹脂シート(A)の少なくとも片面に糖由来の脂肪酸エステル(b)を含むアクリル系親水性コート剤(B)を用いて形成された被覆層を有する積層体であり、
前記アクリル系親水性コート剤(B)が、アクリル酸又はメタクリル酸とメタクリル酸エステルとを必須の単量体成分としてなる共重合体であり、かつアミノアルコール又はアンモニアを中和剤として得られたアクリル系樹脂の水溶液であることを特徴とする積層体。 - 前記糖由来の脂肪酸エステル(b)が、ショ糖脂肪酸エステルである請求項1記載の積層体。
- 前記糖由来の脂肪酸エステル(b)と、前記アクリル系親水性コート剤(B)中に含まれるアクリル系樹脂(固形分)との合計質量に対し、前記脂肪酸エステル(b)が20〜50質量%の範囲で含まれるものである請求項1〜2の何れか1項記載の積層体。
- 前記アクリル系親水性コート剤(B)が、メタアクリル酸とメタクリル酸メチルとを単量体成分としてなる共重合体であり、かつアミノアルコール又はアンモニアを中和剤として得られたアクリル系樹脂の水溶液である請求項1〜3の何れか1項記載の積層体。
- 前記アクリル系親水性コート剤(B)のスチレン系樹脂シート(A)への塗布量が200〜8000mg/m2の範囲である請求項1〜4の何れか1項記載の積層体。
- 前記スチレン系樹脂シート(A)が二軸延伸スチレン系樹脂シートである請求項1〜5の何れか1項記載の積層体。
- 前記スチレン系樹脂シート(A)が、ポリスチレン、スチレン−(メタ)アクリルエステル共重合体、スチレン−メタクリル酸共重合体、または多分岐状ポリスチレンである請求項1〜6の何れか1項記載の積層体。
- 請求項1〜7の何れか1項記載の積層体を成形してなることを特徴とする成形体。
- 前記アクリル系親水性コート剤(B)からなる被覆層が内容物側になるように成形され、且つ内容物が食品である請求項8記載の成形体。
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