JP2016098254A - Laminate and molded body using the same - Google Patents
Laminate and molded body using the same Download PDFInfo
- Publication number
- JP2016098254A JP2016098254A JP2014233568A JP2014233568A JP2016098254A JP 2016098254 A JP2016098254 A JP 2016098254A JP 2014233568 A JP2014233568 A JP 2014233568A JP 2014233568 A JP2014233568 A JP 2014233568A JP 2016098254 A JP2016098254 A JP 2016098254A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- coating agent
- methacrylic acid
- acrylate
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 42
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 235000013305 food Nutrition 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 36
- 239000004925 Acrylic resin Substances 0.000 claims description 19
- 229920000178 Acrylic resin Polymers 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 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 13
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 13
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 10
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- 229920001890 Novodur Polymers 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- -1 alkyl styrene Chemical compound 0.000 description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- 238000000034 method Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- 235000014113 dietary fatty acids Nutrition 0.000 description 18
- 239000000194 fatty acid Substances 0.000 description 18
- 229930195729 fatty acid Natural products 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229930006000 Sucrose Natural products 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000006185 dispersion Substances 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
- 238000003756 stirring Methods 0.000 description 7
- 239000005720 sucrose Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 230000002087 whitening effect Effects 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 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
- 239000002202 Polyethylene glycol Substances 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 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
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 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
- 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
- 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
- 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 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 class 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 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
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 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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- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
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- 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
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
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- 239000007870 radical polymerization initiator Substances 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
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- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- KNZIIQMSCLCSGZ-UHFFFAOYSA-N non-1-enylbenzene Chemical compound CCCCCCCC=CC1=CC=CC=C1 KNZIIQMSCLCSGZ-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical compound CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
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- 230000002940 repellent Effects 0.000 description 1
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
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- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
- Wrappers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
本発明は、スチレン系樹脂シートを用いた積層体に関するものであり、詳しくは、スチレン系樹脂の有する成形性を損なわず、耐熱耐油性を付与したスチレン系樹脂シート及びこれから得られる成形体に関するものである。 The present invention relates to a laminate using a styrene resin sheet, and more particularly to a styrene resin sheet imparted with heat and oil resistance without impairing the moldability of the styrene resin and a molded article obtained therefrom. It is.
ポリスチレンから得られるシートは、透明性や剛性が優れ、また成形性に優れているため、主に食品包装用容器として使用されている。しかし、このポリスチレンから得られるシート製の容器は一般的な食品包装容器としては適しているものの、コンビニエンスストア等における、高出力の電子レンジで加熱する用途においては、その耐熱耐油性に不足することがあり、改良が求められていた。 Sheets obtained from polystyrene are excellent in transparency and rigidity, and are excellent in moldability, and are therefore mainly used as food packaging containers. However, although the sheet-made container obtained from polystyrene is suitable as a general food packaging container, its heat and oil resistance is insufficient in applications where it is heated in a high-power microwave oven at convenience stores. There was a need for improvement.
耐熱性を改善する手段として、例えば、スチレン系樹脂シートに用いる樹脂として、スチレン系モノマーと不飽和カルボン酸系モノマーとを併用してなる共重合体を使用し、特定の厚みと配向緩和応力に調整した二軸延伸シートが提供されている（例えば、特許文献１参照）。この方法によれば、耐熱性については一定の効果を上げているが、食品包装容器において求められる高度な成形性に不足することがあり、さらなる改良が求められている。 As a means for improving heat resistance, for example, as a resin used in a styrene resin sheet, a copolymer formed by using a styrene monomer and an unsaturated carboxylic acid monomer in combination is used. An adjusted biaxially stretched sheet is provided (see, for example, Patent Document 1). According to this method, the heat resistance has a certain effect, but the high formability required for food packaging containers may be insufficient, and further improvements are required.
また、前記特許文献１で提供された二軸延伸シートは、その厚みと配向緩和応力を高度に制御しなければならず、汎用性にも劣るものであった。 In addition, the biaxially stretched sheet provided in Patent Document 1 must have a highly controlled thickness and orientation relaxation stress, and is inferior in versatility.
これらの事情に鑑み、本発明が解決しようとする課題は、スチレン系樹脂シートが本来有する高度な成形性を損なわずに耐熱耐油性を向上させ、食品包装容器として好適に用いることができるスチレン系樹脂シートを含有する積層体及びこれを用いて得られる成形体を提供することにある。 In view of these circumstances, the problem to be solved by the present invention is to improve the heat and oil resistance without impairing the high moldability inherent in the styrene resin sheet, and can be suitably used as a food packaging container. It is providing the laminated body containing a resin sheet, and a molded object obtained using this.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、スチレン系モノマーとメタクリル酸とを特定比率で共重合してなる共重合体を用いたスチレン系樹脂シートに、親水性のコーティング剤を塗布することで、得られる積層体に成形性と耐熱耐油性とをバランスよく兼備させ、食品包装材として好適に用いることができる積層体が得られることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that a hydrophilic styrenic resin sheet using a copolymer obtained by copolymerizing a styrene monomer and methacrylic acid at a specific ratio is hydrophilic. By applying the coating agent, it was found that a laminate that can be suitably used as a food packaging material can be obtained by combining the resulting laminate with a good balance between moldability and heat and oil resistance, and completed the present invention. .
即ち、本発明は、メタクリル酸含有率が１質量％以上４質量％未満の、スチレン系モノマーとメタクリル酸との単量体混合物を重合してなるスチレン−メタクリル酸共重合体（Ａ）を用いた樹脂シートの少なくとも片面に、親水性コート剤（Ｂ）を用いて形成された被覆層を有することを特徴とする積層体及びそれを二次成形してなる成形体を提供するものである。 That is, the present invention uses a styrene-methacrylic acid copolymer (A) obtained by polymerizing a monomer mixture of a styrene monomer and methacrylic acid having a methacrylic acid content of 1% by mass or more and less than 4% by mass. The present invention provides a laminate having a coating layer formed using a hydrophilic coating agent (B) on at least one side of a resin sheet, and a molded body obtained by secondary molding thereof.
本発明の積層体は、二次成形する際の成形性（型再現性）を高度に有すると共に、加熱時の耐油性を有する。このため、スチレン系樹脂シートが本来有する成形性を損なわずに、成形体の耐熱耐油性が向上し、食品用途等の包装材として好適に用いることができる。 The laminate of the present invention has high moldability (mold reproducibility) during secondary molding and oil resistance during heating. For this reason, the heat and oil resistance of the molded body is improved without impairing the moldability inherent in the styrene resin sheet, and it can be suitably used as a packaging material for food applications.
以下に本発明の積層体について詳細に説明する。
＜樹脂シート＞
本発明で用いる樹脂シートは、メタクリル酸含有率が１質量％以上４質量％未満の、スチレン系モノマーとメタクリル酸との単量体混合物を重合してなるスチレン−メタクリル酸共重合体（Ａ）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。
The laminated body of this invention is demonstrated in detail below.
<Resin sheet>
The resin sheet used in the present invention is a styrene-methacrylic acid copolymer (A) obtained by polymerizing a monomer mixture of a styrene monomer and methacrylic acid having a methacrylic acid content of 1% by mass or more and less than 4% by mass. Is formed into a sheet shape, and the thickness, forming method, and the like are not particularly limited.
前記スチレン系モノマーとしては、例えば以下の物が挙げられる。スチレン及びその誘導体；例えばスチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、ヘキシルスチレン、ヘプチルスチレン、オクチルスチレンの如きアルキルスチレン、フルオロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレンの如きハロゲン化スチレン、更にニトロスチレン、アセチルスチレン、メトキシスチレン等があり、これを単独あるいは２種以上を組み合わせて用いることができる。 Examples of the styrenic monomer include the following. Styrene and its derivatives; for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, alkyl styrene such as octyl styrene, fluorostyrene, chlorostyrene , Halogenated styrene such as bromostyrene, dibromostyrene and iodostyrene, nitrostyrene, acetylstyrene, methoxystyrene and the like, which can be used alone or in combination of two or more.
前記スチレン−メタクリル酸共重合体（Ａ）を得るための単量体混合物には、スチレン系モノマーとメタクリル酸とを必須とし、メタクリル酸含有率がその混合物全量に対して1質量％以上４質量％未満であることを必須とする。メタクリル酸含有率が１質量％未満では、得られる積層体の耐熱性向上の効果が発現されず、４質量％以上では得られる積層体の二次成形性が不足することがある。なお、スチレン系モノマーとメタクリル酸以外の単量体、例えばアクリロニトリル、メタクリロニトリル、メタクリル酸メチル、アクリル酸ブチルなどのエステル誘導体などのビニルモノマー、無水マレイン酸、マレイミド、核置換マレイミドなどを、本発明の効果を阻害しない範囲で併用することもできるが、この場合は、単量体混合物中におけるメタクリル酸含有率を本発明の範囲で用いることが必須である。 In the monomer mixture for obtaining the styrene-methacrylic acid copolymer (A), a styrene monomer and methacrylic acid are essential, and the methacrylic acid content is 1% by mass or more and 4% by mass with respect to the total amount of the mixture. It must be less than%. When the methacrylic acid content is less than 1% by mass, the effect of improving the heat resistance of the obtained laminate is not exhibited, and when it is 4% by mass or more, the secondary formability of the obtained laminate may be insufficient. In addition, styrene monomers and monomers other than methacrylic acid, such as vinyl monomers such as acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate and other ester derivatives, maleic anhydride, maleimide, nucleus-substituted maleimide, etc. Although it can be used in combination as long as the effects of the invention are not inhibited, in this case, it is essential to use the methacrylic acid content in the monomer mixture within the scope of the present invention.
＜スチレン−メタクリル酸共重合体の製造方法＞
樹脂シートの原料となるスチレン−メタクリル酸共重合体（Ａ）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。
<Method for producing styrene-methacrylic acid copolymer>
As a method for producing the styrene-methacrylic acid copolymer (A) as a raw material for the resin sheet, various commonly used polymerization methods for styrene monomers can be applied. The polymerization method is not particularly limited, but bulk polymerization, suspension polymerization, or solution polymerization is preferable. Among them, continuous bulk polymerization is particularly preferable from the viewpoint of production efficiency.For example, by performing continuous bulk polymerization incorporating one or more stirred reactors and a tubular reactor in which a plurality of mixing elements having no moving parts are fixed. An excellent resin can be obtained. Although thermal polymerization can be performed without using a polymerization initiator, it is preferable to use various radical polymerization initiators. Moreover, what is used for manufacture of a normal polystyrene can be used for polymerization adjuvants, such as a suspending agent and an emulsifier required for superposition | polymerization.
重合反応での反応物の粘性を低下させるために、反応系に有機溶剤を添加してもよく、その有機溶剤としては、例えば、トルエン、エチルベンゼン、キシレン、アセトニトリル、ベンゼン、クロロベンゼン、ジクロロベンゼン、アニソール、シアノベンゼン、ジメチルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、メチルエチルケトン等が挙げられる。特にゲル化を抑制する観点からは有機溶剤を使用することが好ましい。 In order to reduce the viscosity of the reaction product in the polymerization reaction, an organic solvent may be added to the reaction system. Examples of the organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, and anisole. , Cyanobenzene, dimethylformamide, N, N-dimethylacetamide, methyl ethyl ketone and the like. In particular, it is preferable to use an organic solvent from the viewpoint of suppressing gelation.
前記ラジカル重合開始剤としては、特に制限はなく、例えば、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、２，２−ビス（４，４−ジ−ブチルパーオキシシクロヘキシル）プロパン等のパーオキシケタール類、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ヘキシルパーオキサイド等のジアルキルパーオキサイド類、ベンゾイルパーオキサイド、ジシナモイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシイシプロピルモノカーボネート等のパーオキシエステル類、Ｎ，Ｎ’−アゾビスイソブチルニトリル、Ｎ，Ｎ’−アゾビス（シクロヘキサン−１−カルボニトリル）、Ｎ，Ｎ’−アゾビス（２−メチルブチロニトリル）、Ｎ，Ｎ’−アゾビス（２，４−ジメチルバレロニトリル）、Ｎ，Ｎ’−アゾビス［２−（ヒドロキシメチル）プロピオニトリル］等が挙げられ、これらの１種あるいは２種以上を組み合わせて使用することができる。 The radical polymerization initiator is not particularly limited. For example, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4 , 4-di-butylperoxycyclohexyl) propane and other peroxyketals, cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di Dialkyl peroxides such as -t-hexyl peroxide, diacyl peroxides such as benzoyl peroxide and disinamoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxide Pao such as oxyisylpropyl monocarbonate Siesters, N, N′-azobisisobutylnitrile, N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis ( 2,4-dimethylvaleronitrile), N, N′-azobis [2- (hydroxymethyl) propionitrile] and the like, and these can be used alone or in combination.
更に、得られる共重合体の分子量が過度に大きくなりすぎないように連鎖移動剤を添加してもよい。連鎖移動剤としては、連鎖移動基を１つ有する単官能連鎖移動剤でも連鎖移動基を複数有する多官能連鎖移動剤でも使用できる。単官能連鎖移動剤としては、アルキルメルカプタン類、チオグリコール酸エステル類等が挙げられる。多官能連鎖移動剤としては、エチレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ソルビトール等の多価アルコール中のヒドロキシ基をチオグリコール酸または３−メルカプトプロピオン酸でエステル化したもの等が挙げられる。 Furthermore, you may add a chain transfer agent so that the molecular weight of the copolymer obtained may not become too large too much. As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having a plurality of chain transfer groups can be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolic acid esters. Polyfunctional chain transfer agents include ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and the like, the hydroxy group in thioglycolic acid or 3-mercaptopropionic acid And the like esterified with.
また、得られる共重合体のゲル発生抑制のために、長鎖アルコールやポリオキシエチレンアルキルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシオレイルエーテル、ポリオキシエチレンアルケニルエーテル等も使用することが可能である。 In addition, long chain alcohols, polyoxyethylene alkyl ethers, polyoxyethylene lauryl ethers, polyoxyoleyl ethers, polyoxyethylene alkenyl ethers, and the like can be used to suppress gel generation of the resulting copolymer. .
また、得られる共重合体及びシートの物性を損なわない範囲で、滑剤、帯電防止剤、酸化防止剤、熱安定剤、紫外線吸収剤、染料、可塑剤等も使用することが可能である。 In addition, a lubricant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, a dye, a plasticizer, and the like can be used as long as the physical properties of the obtained copolymer and sheet are not impaired.
＜重合工程・脱揮工程＞
重合工程では、単量体混合物を共重合させることによって、樹脂シートの材料となる共重合体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、本発明で用いる樹脂シートの材料となるスチレン−メタクリル酸共重合体（Ａ）を得ることができる。
<Polymerization process / devolatilization process>
In the polymerization step, a copolymer serving as a material for the resin sheet can be obtained by copolymerizing the monomer mixture. The reaction vessel of the polymerization apparatus is not particularly limited. After the polymerization step, it is passed through a devolatilization tank for volatilizing unreacted monomers and solvent, preferably adjusted to a reduced pressure state. Thereafter, it is pelletized to obtain a styrene-methacrylic acid copolymer (A) which is a material for the resin sheet used in the present invention.
本発明で用いる樹脂シートの材料となるスチレン−メタクリル酸共重合体（Ａ）は、前述のように製造してなるものを用いることができるが、市販されているものを用いてもよい。例えば、メタクリル酸の使用割合が高いスチレン−メタクリル酸共重合体を使用する場合は、この共重合体とポリスチレンとを混合し、メタクリル酸含有率が本発明で規定する範囲に調整したものであってもよい。 As the styrene-methacrylic acid copolymer (A) used as the material for the resin sheet used in the present invention, those produced as described above can be used, but commercially available ones may be used. For example, when using a styrene-methacrylic acid copolymer having a high methacrylic acid use ratio, this copolymer and polystyrene are mixed and the methacrylic acid content is adjusted to the range specified in the present invention. May be.
＜無延伸シート＞
無延伸シートは、上記で得られたスチレン−メタクリル酸共重合体（Ａ）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。
<Unstretched sheet>
The non-stretched sheet can be produced by melt-extruding the styrene-methacrylic acid copolymer (A) pellet obtained above with an extruder and then melt-extruding it into a sheet with a T-die and then cooling it with a cooling roll or the like. . As a cooling temperature, 70-90 degreeC is preferable.
＜二軸延伸シート＞
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−メタクリル酸共重合体（Ａ）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。
<Biaxially stretched sheet>
The biaxially stretched sheet is obtained by stretching in a longitudinal and lateral biaxial direction with a stretching machine after melt extrusion with an extruder. For example, first, a styrene-methacrylic acid copolymer (A) is supplied to an extruder and melt-extruded into a sheet form from a T-die. At that time, casting is performed so that the sheet before stretching has a predetermined thickness. Thereafter, the sheet is cooled to a temperature capable of biaxial stretching, for example, 110 to 145 ° C., and stretched in the longitudinal direction (flow direction) and the transverse direction (cross direction with respect to the flow direction).
延伸方法は、上記スチレン−メタクリル酸共重合体（Ａ）を溶融押出してシート状にした後、同時ニ軸延伸あるいは逐次ニ軸延伸を行うことができる。逐次ニ軸延伸の場合は、はじめに縦延伸処理を行い、次に横延伸を行うことが一般的である。特にニ軸延伸スチレン系シートでは、ロールを用いた縦延伸後、テンターを用いた横延伸を行なわれる。テンター法は広幅な製品がとれ、生産性が高いことがメリットである。 In the stretching method, the styrene-methacrylic acid copolymer (A) is melt-extruded into a sheet shape, and then simultaneous biaxial stretching or sequential biaxial stretching can be performed. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. In particular, in a biaxially stretched styrene-based sheet, a longitudinal stretching using a roll is followed by a lateral stretching using a tenter. The tenter method is advantageous in that a wide range of products can be obtained and productivity is high.
ロールを用いた縦延伸方法としては、低速ロールと高速ロールを同方向に回転させて樹脂をフラットに通紙し、延伸する方法と、低速ロールと高速ロールを逆回転させて樹脂をクロスに通紙し、延伸する方法とがあり、１段あるいは多段、フラットあるいはクロスの任意の組み合わせとすることができる。 As a longitudinal stretching method using a roll, a low-speed roll and a high-speed roll are rotated in the same direction to pass the resin flat, and a stretching method, and a low-speed roll and a high-speed roll are rotated in reverse to pass the resin through the cloth. There is a method of paper and drawing, and any combination of single-stage or multi-stage, flat or cross can be used.
具体的な延伸条件として、延伸倍率は目的に応じ異なるが、通常面倍率で１．５〜１５倍、より好ましくは４〜１０倍である。逐次延伸の場合の流れ方向の延伸倍率は１．２〜５倍で、好ましくは１．５〜３．０倍であり、流れ方向に対しそのクロス方向の延伸倍率は１．２〜５倍で、好ましくは１．５〜３．０倍である。同時ニ軸延伸の各方向の延伸倍率は１．５〜５倍である。また、この際の温度条件は、ＡＳＴＭＤ−１５０４に準拠し測定される配向緩和応力が０．２〜２．０ＭＰａ、より好ましくは０．４〜１．０ＭＰａとなるように行うのが良い。配向緩和応力が０．２ＭＰａ未満では、シートの耐衝撃性が不十分なものとなりやすく、２．０ＭＰａを超える場合、シートが延伸切れを起こし易く、また二次成形性の悪いものとなる可能性があるためである。一方、０．４〜１．０ＭＰａの範囲であると、得られたシートの折り割れ性が良好であるばかりでなく、シートの成形性自体も極めて良好となるのでより好ましい。 As specific stretching conditions, the stretching ratio varies depending on the purpose, but is usually 1.5 to 15 times, more preferably 4 to 10 times in terms of surface magnification. In the case of sequential stretching, the draw ratio in the flow direction is 1.2 to 5 times, preferably 1.5 to 3.0 times, and the draw ratio in the cross direction with respect to the flow direction is 1.2 to 5 times. The ratio is preferably 1.5 to 3.0 times. The draw ratio in each direction of simultaneous biaxial stretching is 1.5 to 5 times. Further, the temperature condition at this time is preferably such that the orientation relaxation stress measured according to ASTM D-1504 is 0.2 to 2.0 MPa, more preferably 0.4 to 1.0 MPa. If the orientation relaxation stress is less than 0.2 MPa, the impact resistance of the sheet is likely to be insufficient, and if it exceeds 2.0 MPa, the sheet is likely to be stretched and the secondary formability may be poor. Because there is. On the other hand, the range of 0.4 to 1.0 MPa is more preferable because not only the crackability of the obtained sheet is good, but also the formability of the sheet itself is extremely good.
また、この際、例えば、延伸前の原反シートを延伸温度１１０〜１４５℃で縦方向に上記の倍率で延伸し、次いで、延伸温度１１０〜１４５℃で上記縦方向に対してクロスする横方向に上記倍率で延伸が行われる。 At this time, for example, the raw sheet before stretching is stretched in the longitudinal direction at a stretching temperature of 110 to 145 ° C. at the above magnification, and then crossed with respect to the longitudinal direction at a stretching temperature of 110 to 145 ° C. Stretching is performed at the above magnification.
スチレン−メタクリル酸共重合体（Ａ）からなるニ軸延伸シートの厚さは、０．１〜０．５ｍｍであることが好ましい。このような二軸延伸シートはその強度の観点より、本発明で用いる樹脂シートとして好適に用いることができる。 The thickness of the biaxially stretched sheet made of the styrene-methacrylic acid copolymer (A) is preferably 0.1 to 0.5 mm. Such a biaxially stretched sheet can be suitably used as the resin sheet used in the present invention from the viewpoint of its strength.
＜親水性コート剤（Ｂ）＞
本発明では、前記の樹脂シートの少なくとも片面に、親水性コート剤（Ｂ）を塗布し、当該コート剤（Ｂ）からなる被覆層を形成させる。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。
<Hydrophilic coating agent (B)>
In this invention, a hydrophilic coating agent (B) is apply | coated to at least one side of the said resin sheet, and the coating layer which consists of the said coating agent (B) is formed. In addition, in this invention, hydrophilicity shows that any of water solubility and water dispersibility may be sufficient.
前記親水性コート剤（Ｂ）としては、例えば、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル等の糖由来の脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンポリグリセリン脂肪酸エステル、脂肪酸アルカノールアミド等のノニオン界面活性剤、レシチン等の両性界面活性剤や、樹脂中に親水性基を有するポリエステル、ポリビニルアルコール、ポリビニルピロリドン、ＳＭレジン、ＥＶＡ樹脂、ウレタン樹脂、メラミン樹脂、ＳＢＲ、セルロース系樹脂、フェノール樹脂、ロジンエステル、ビニル樹脂、フッ素系樹脂、ポリグリコール、ポリアミド樹脂、ポリイミド樹脂、その他天然物由来の樹脂、親水性基を有するアクリル系樹脂、アクリル変性エポキシ樹脂、エポキシ樹脂等の水溶性又は水分散体が挙げられる。また樹脂自体は親水性を有さないものであっても、これを界面活性剤等を用いて水中に分散させてなるものであってもよい。 Examples of the hydrophilic coating agent (B) include sugar-derived fatty acid esters such as sucrose fatty acid ester and sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, poly Nonionic surfactants such as oxyethylene polyoxypropylene block copolymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene polyglycerin fatty acid ester, fatty acid alkanolamide, and amphoteric interfaces such as lecithin Activators, polyesters with hydrophilic groups in the resin, polyvinyl alcohol, polyvinyl pyrrolidone, SM resin, EVA resin, urea Resin, melamine resin, SBR, cellulose resin, phenol resin, rosin ester, vinyl resin, fluorine resin, polyglycol, polyamide resin, polyimide resin, other resin derived from natural products, acrylic resin having a hydrophilic group, Water-soluble or aqueous dispersions such as acrylic-modified epoxy resins and epoxy resins can be mentioned. Moreover, even if the resin itself does not have hydrophilicity, the resin itself may be dispersed in water using a surfactant or the like.
これらの中でも、樹脂シート（Ａ）への塗布性に優れ、また得られる積層体における耐熱耐油性を容易に向上させることができる点、並びに食品包装材としての使用が可能である点より、ショ糖脂肪酸エステルコート剤、アクリル系樹脂の水溶液あるいは水分散液であるアクリル系親水性コート剤を用いることが好ましく、中鎖脂肪酸油等の強い浸食性を示す油に対しての高い耐油性を示すことからアクリル系樹脂の水溶液あるいは水分散液であるアクリル系親水性コート剤が特に好ましい。 Among these, it is excellent in applicability to the resin sheet (A), can easily improve heat and oil resistance in the resulting laminate, and can be used as a food packaging material. It is preferable to use a sugar fatty acid ester coating agent, an acrylic hydrophilic coating agent that is an aqueous solution or dispersion of an acrylic resin, and exhibits high oil resistance against oils that exhibit strong erosion properties such as medium chain fatty acid oils. Accordingly, an acrylic hydrophilic coating agent that is an aqueous solution or an aqueous dispersion of an acrylic resin is particularly preferable.
＜ショ糖脂肪酸系コート剤＞
前記ショ糖脂肪酸エステルは、ショ糖と、脂肪酸メチルエステル等のような脂肪酸の低級アルコールエステルとをエステル交換して得られるものが挙げられ、具体的には、ショ糖ステアリン酸エステル、ショ糖パルミチン酸エステル、ショ糖ラウリン酸エステル、ショ糖オレイン酸エステル、および、これらの混合物等が挙げられる。また、ショ糖脂肪酸エステルには、モノエステル、ジエステルおよびトリエステルが存在するが、防曇性を併せ持つことが出来るため、ショ糖脂肪酸モノエステルの含有率が５０モル％以上で、ＨＬＢ値が１３〜１８であるものがより好ましい。
<Sucrose fatty acid-based coating agent>
Examples of the sucrose fatty acid ester include those obtained by transesterification of sucrose and a lower alcohol ester of a fatty acid such as fatty acid methyl ester, specifically, sucrose stearate ester, sucrose palmitate Examples thereof include acid esters, sucrose laurate esters, sucrose oleate esters, and mixtures thereof. Further, sucrose fatty acid esters include monoesters, diesters and triesters, but since they can have antifogging properties, the sucrose fatty acid monoester content is 50 mol% or more, and the HLB value is 13 What is -18 is more preferable.
また、ソルビタン脂肪酸エステルとしては、例えば、ソルビタンモノステアレート、ソルビタントリステアレート、ソルビタンモノラウレート、ソルビタンモノオレエート、ソルビタンモノパルミテート等が挙げられ、単独でも２種以上を併用してもよい。 Examples of the sorbitan fatty acid ester include sorbitan monostearate, sorbitan tristearate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate and the like, and may be used alone or in combination of two or more. .
＜アクリル系親水性コート剤＞
前記アクリル系樹脂は、アクリロイル基を有する単量体の重合体であって、親水性を示すものであれば良く、例えば、カルボキシ基、ヒドロキシ基等を有するアクリル系単量体を用いて得られる重合体が挙げられる。また、これらのアクリル系単量体と共重合可能なその他のビニル系単量体を、本発明の効果を損なわない範囲で用いてなる共重合体であってもよい。
<Acrylic hydrophilic coating agent>
The acrylic resin is a polymer of a monomer having an acryloyl group, and may be any polymer that exhibits hydrophilicity. For example, the acrylic resin can be obtained using an acrylic monomer having a carboxy group, a hydroxy group, or the like. A polymer is mentioned. Moreover, the copolymer which uses the other vinyl-type monomer copolymerizable with these acrylic monomers in the range which does not impair the effect of this invention may be sufficient.
前記親水性を有するアクリル系単量体としては、ヒドロキシ基を有する単量体としては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレート、２，３−ジヒドロキシプロピルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルメタクリレート、２，３−ジヒドロキシプロピルメタクリレート等が挙げられ、単独でも、２種以上を併用してもよい。これらの中でも、水酸基価が高い重合体が得られ、アクリル系樹脂に親水性を付与しやすい点で、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレートを用いることが好ましい。 Examples of the hydrophilic acrylic monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2,3-dihydroxypropyl acrylate. , 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate and the like, and may be used alone or in combination of two or more. Among these, it is preferable to use 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate because a polymer having a high hydroxyl value is obtained and hydrophilicity is easily imparted to the acrylic resin.
また、カルボキシ基を有するアクリル系単量体としては、例えば、メタアクリル酸、（アクリロイルオキシ）酢酸、アクリル酸２−カルボキシエチル、アクリル酸３−カルボキシプロピル、コハク酸１−［２−（アクリロイルオキシ）エチル］、フタル酸１−（２−アクリロイルオキシエチル）、ヘキサヒドロフタル酸水素２−（アクリロイルオキシ）エチル及びこれらのラクトン変性物等の不飽和モノカルボン酸；マレイン酸等の不飽和ジカルボン酸；無水コハク酸や無水マレイン酸等の酸無水酸と、ペンタエリスリトールトリアクリレート等の水酸基含有多官能（メタ）アクリレートモノマーとを反応させて得られるカルボキシル基含有多官能（メタ）アクリレート等が挙げられる。これらは単独で用いても良いし、２種類以上を併用しても良い。これらの中でも、得られるアクリル系樹脂に親水性を容易に付与できる観点より、メタアクリル酸、（アクリロイルオキシ）酢酸、アクリル酸２−カルボキシエチル、アクリル酸３−カルボキシプロピルが好ましく、メタアクリル酸が特に好ましい。 Examples of the acrylic monomer having a carboxy group include methacrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, and 1- [2- (acryloyloxy) succinate. ) Ethyl], 1- (2-acryloyloxyethyl) phthalate, 2- (acryloyloxy) ethyl hexahydrophthalate, and lactone-modified products thereof; unsaturated dicarboxylic acids such as maleic acid; A carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting an acid anhydride such as succinic anhydride or maleic anhydride with a hydroxyl-containing polyfunctional (meth) acrylate monomer such as pentaerythritol triacrylate. . These may be used alone or in combination of two or more. Among these, methacrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, and 3-carboxypropyl acrylate are preferable, and methacrylic acid is preferable from the viewpoint of easily imparting hydrophilicity to the resulting acrylic resin. Particularly preferred.
前記その他のビニル系単量体としては、例えば、（メタ）アクリル酸エステル系単量体が挙げられる。具体的には、（メタ）アクリルメチルメタアクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、アミノエチル（メタ）アクリレート、Ｎ−モノアルキルアミノアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート、２−アジリジニルエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、アリル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート等が挙げられる。これらは、１種または２種以上の混合物として用いることができる。 Examples of the other vinyl monomers include (meth) acrylic acid ester monomers. Specifically, (meth) acrylic methyl methacrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3 3, -tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate, 2-azi Lydinylethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, allyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl ( And (meth) acrylate. These can be used as one kind or a mixture of two or more kinds.
更に一般にラジカル重合反応に用いることができるものであってもよく、例えば、酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；（メタ）アクリロニトリル等のニトリル基含有エチレン性不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルベンゼン、ジアリルフタレート等の芳香族環を有するビニル化合物等が挙げられる。これらは、１種または２種以上の混合物として用いることができる。特にスチレン等の芳香族環を有するビニル化合物は、耐黄変性、耐水性等を向上できる事から好ましく用いる事が出来る。 Further, those that can be generally used for radical polymerization reaction may be used. For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether , Vinyl ethers such as amyl vinyl ether and hexyl vinyl ether; nitrile group-containing ethylenically unsaturated monomers such as (meth) acrylonitrile; styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylbenzene And vinyl compounds having an aromatic ring such as diallyl phthalate. These can be used as one kind or a mixture of two or more kinds. In particular, a vinyl compound having an aromatic ring such as styrene can be preferably used since yellowing resistance and water resistance can be improved.
更に、官能基を有するエチレン性不飽和単量体も用いることが可能で、例としては、Ｎ−メチロールメタアクリルアミド、Ｎ−イソプロポキシメチルメタアクリルアミド、Ｎ−ブトキシメチルメタアクリルアミド、Ｎ−イソブトキシメチルメタアクリルアミド等のメチロールアミド基またはそのアルコキシ化物含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩等のシリル基含有重合性単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール或いはメチルエチルケトオキシム付加物等のイソシアナート基及び／またはブロック化イソシアナート基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン等のオキサゾリン基含有重合性単量体；メタアクリルアミド、Ｎ−モノアルキルメタアクリルアミド、Ｎ，Ｎ−ジアルキルメタアクリルアミド等のアミド基含有重合性単量体；アクロレイン、ジアセトンメタアクリルアミド等のカルボニル基含有重合性単量体等が挙げられる。 Furthermore, an ethylenically unsaturated monomer having a functional group can also be used. Examples thereof include N-methylol methacrylamide, N-isopropoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N-isobutoxymethyl. A methylolamide group such as methacrylamide or a polymerizable monomer containing an alkoxylate thereof; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltri Methoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltrii Silyl group-containing polymerizable monomers such as propoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and hydrochloride thereof; (meth) acryloyl isocyanate, (meth) acryloyl isocyanate Isocyanate groups and / or blocked isocyanate group-containing polymerizable monomers such as phenol or methyl ethyl ketoxime adduct of natoethyl; oxazoline groups such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Polymerizable monomer; Amide group-containing polymerizable monomer such as methacrylamide, N-monoalkylmethacrylamide, N, N-dialkylmethacrylamide; Carbonyl group-containing polymerizable monomer such as acrolein, diacetone methacrylamide Etc.
その他のビニル単量体としては、イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等を使用することができる。 As other vinyl monomers, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like can be used.
これらのその他のビニル系単量体を併用する場合、耐熱耐油性の付与が容易である観点よりメタクリル酸エステル系単量体を用いることが好ましく、特に、メタクリル酸メチルを用いることが好ましい。 When these other vinyl monomers are used in combination, a methacrylic acid ester monomer is preferably used from the viewpoint of easily imparting heat and oil resistance, and methyl methacrylate is particularly preferably used.
前記アクリル系樹脂は、前述の単量体、又はその混合物を従来知られている乳化重合法、溶液重合法等のラジカル重合によって合成することができる。 The acrylic resin can be synthesized by radical polymerization such as a conventionally known emulsion polymerization method or solution polymerization method using the above-mentioned monomer or a mixture thereof.
具体的には、溶液重合法の場合、溶剤の存在下、例えば、カルボキシ基を有する（メタ）アクリル系単量体、又は単量体混合物と重合開始剤とを、好ましくは４０℃〜１６０℃の温度下で混合、攪拌し、ラジカル重合を進行させる方法が挙げられる。その後、塩基性化合物によりカルボキシル基を中和し、水を添加することによって水溶化することができる。その際、中和率は４０〜１００％、特には、５０〜１００％であることが好ましい。また場合に応じて水溶化後に脱溶剤をすることで、含有溶剤量を低減できる。 Specifically, in the case of a solution polymerization method, in the presence of a solvent, for example, a (meth) acrylic monomer having a carboxy group or a monomer mixture and a polymerization initiator are preferably 40 ° C to 160 ° C. The method of mixing and stirring at the temperature of this and advancing radical polymerization is mentioned. Thereafter, the carboxyl group can be neutralized with a basic compound and water-solubilized by adding water. At that time, the neutralization rate is preferably 40 to 100%, and particularly preferably 50 to 100%. Moreover, depending on the case, the solvent content can be reduced by removing the solvent after water solubilization.
乳化重合法の場合は、乳化剤を含有する水性媒体中に、単量体あるいは単量体混合物を添加、攪拌しながら乳化分散させ、重合反応させる方法である。具体的には、水又は必要に応じてアルコールのような有機溶剤を含む水性媒体中に乳化剤を添加し、４０℃〜１００℃の加熱攪拌の下、前記単量体あるいは単量体混合物及びラジカル重合開始剤を一括仕込み、連続滴下又は分割添加し、重合する方法である。このとき、乳化剤と水とで単量体混合物を予め乳化させて得られる水分散液又は水溶液を、同様に滴下しても良い。 In the case of the emulsion polymerization method, a monomer or a monomer mixture is added to an aqueous medium containing an emulsifier, and the mixture is emulsified and dispersed while stirring to cause a polymerization reaction. Specifically, an emulsifier is added to water or an aqueous medium containing an organic solvent such as alcohol as necessary, and the monomer or monomer mixture and radical are heated and stirred at 40 ° C to 100 ° C. In this method, a polymerization initiator is charged all at once, continuously dropped or dividedly added, and polymerization is performed. At this time, an aqueous dispersion or aqueous solution obtained by pre-emulsifying the monomer mixture with an emulsifier and water may be similarly dropped.
前記乳化重合法で使用できる乳化剤としては、一般的な乳化重合法に使用できるものであれば、アニオン性、カチオン性及びノニオン性いずれの乳化剤でも特に制限なく使用することができる。 As an emulsifier that can be used in the emulsion polymerization method, any anionic, cationic or nonionic emulsifier can be used without particular limitation as long as it can be used in a general emulsion polymerization method.
アニオン性乳化剤としては、例えば、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル、ポリオキシアルキレン多環フェニルエーテル硫酸エステル、ジアルキルサクシネートスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩等が挙げられる。 Examples of the anionic emulsifier include sulfates of higher alcohols, alkylbenzene sulfonates, polyoxyalkylene alkylphenyl ether sulfates, polyoxyalkylene polycyclic phenyl ether sulfates, dialkyl succinate sulfonates, and alkyl diphenyl ether disulfonates. Etc.
カチオン性乳化剤としては、例えば、アルキルトリメチルアンモニウムクロライド、ジアルキルジメチルアンモニウムクロライド、アルキルベンジルジメチルアンモニウムクロライド等が挙げられる。 Examples of the cationic emulsifier include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and alkylbenzyldimethylammonium chloride.
ノニオン性乳化剤としては、例えばポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレン多環フェニルエーテル等を挙げることができ、これらの１種または２種以上を混合して使用することができる。 Examples of nonionic emulsifiers include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene polycyclic phenyl ethers, and the like, and one or more of these may be used in combination. it can.
前記重合開始剤としては、例えば、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ラウロイルパーオキサイド、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエート、ラウロイルパーオキサイド、商品名「ナイパーＢＭＴ−Ｋ４０」（日油株式会社製；ｍ−トルオイルパーオキサイドとベンゾイルパーオキサイドの混合物）等の有機過酸化物や、アゾビスイソブチロニトリル、商品名「ＡＢＮ−Ｅ」［株式会社日本ファインケム製；２，２’−アゾビス（２−メチルブチロニトリル）］等のアゾ系化合物等を使用することができる。 Examples of the polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyoctoate, and t-butyl peroxide. Organic peroxides such as oxybenzoate, lauroyl peroxide, trade name “Niper BMT-K40” (manufactured by NOF Corporation; mixture of m-toluoyl peroxide and benzoyl peroxide), azobisisobutyronitrile, An azo compound such as a trade name “ABN-E” [manufactured by Nippon Finechem Co., Ltd .; 2,2′-azobis (2-methylbutyronitrile)] and the like can be used.
また、前記アクリル系樹脂を製造する際に使用可能な溶剤としては、例えばメタノール、エタノール、プロパノール、ブタノール、エチレングリコールメチルエーテル、ジエチレングリコールメチルエーテルなどのアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどのエーテル類、ヘキサン、ヘプタン、オクタンなどの炭化水素類、ベンゼン、トルエン、キシレン、クメンなどの芳香族類、酢酸エチル、酢酸ブチル等を使用することができる。 Examples of the solvent that can be used in producing the acrylic resin include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, and diethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones, tetrahydrofuran, dioxane, ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane, octane, aromatics such as benzene, toluene, xylene, cumene, ethyl acetate, butyl acetate, etc. Can be used.
中和剤としては、各種塩基化合物を使用する事が出来る。例えば、水酸化ナトリウムまたは水酸化カリウムなどのような各種の無機塩基；モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノプロピルアミン、イソブチルアミン、またはジプロピルアミンのような各種のアルキルアミンなどをはじめ、さらには、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、２−ジメチルアミノ−２−メチル−１−プロパノール、２−アミノ−２−メチル−１−プロパノール、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミンのような各種のアミノアルコール類、またはモルホリンなどのような各種の有機アミン類；あるいはアンモニアなどが挙げられ、これらを単独又は２種以上併用して使用できる。 Various basic compounds can be used as the neutralizing agent. For example, various inorganic bases such as sodium hydroxide or potassium hydroxide; various alkyls such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, isobutylamine, or dipropylamine In addition to amines, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino Various types such as 2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine Mino alcohols or various organic amines such as morpholine; or the like can be mentioned ammonia, can be used in combination singly or two or more.
前記アクリル系樹脂としては、その重量平均分子量（Ｍｗ）が、１，０００〜２００，０００の範囲であることが好ましく、積層体としての耐熱耐油性及び樹脂生産性の観点から１０，０００〜１２０，０００の範囲がより好ましい。 The acrylic resin preferably has a weight average molecular weight (Mw) in the range of 1,000 to 200,000, and is 10,000 to 120 from the viewpoint of heat and oil resistance and resin productivity as a laminate. The range of 1,000 is more preferred.
前記アクリル系樹脂のガラス転移温度（Ｔｇ）としては、３０〜１３０℃の範囲が好ましく、積層体としての耐熱性及び成形性の観点から６０〜１００℃の範囲がより好ましい。 As a glass transition temperature (Tg) of the said acrylic resin, the range of 30-130 degreeC is preferable, and the range of 60-100 degreeC is more preferable from a heat resistant and moldable viewpoint as a laminated body.
前記アクリル系樹脂の酸価としては、２０〜２８０ｍｇＫＯＨの範囲が好ましく、水溶性及び耐水性の観点から６０〜２７０ｍｇＫＯＨの範囲がより好ましい。 The acid value of the acrylic resin is preferably in the range of 20 to 280 mgKOH, and more preferably in the range of 60 to 270 mgKOH from the viewpoint of water solubility and water resistance.
なお、本発明で用いるアクリル系樹脂の分子量は、中和前の重合体を用い、以下の方法により、測定した。
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）
In addition, the molecular weight of acrylic resin used by this invention was measured with the following method using the polymer before neutralization.
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
また、親水性コート剤（Ｂ）の不揮発分としては、塗布量の調整が容易である観点より、１〜４０質量％の範囲に調整することが好ましい。 Moreover, as a non volatile matter of a hydrophilic coating agent (B), it is preferable to adjust to the range of 1-40 mass% from a viewpoint that adjustment of an application quantity is easy.
更にまた、本発明で用いる親水性コート剤（Ｂ）には、本発明の効果を損なわない範囲で、その他の添加剤等を併用してもよい。 Furthermore, you may use together other additives etc. in the hydrophilic coating agent (B) used by this invention in the range which does not impair the effect of this invention.
＜積層体の製造方法＞
本発明の積層体は、前述の樹脂シートに前記親水性コート剤（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親水性コート剤（Ｂ）からなる被覆層を樹脂シート上に形成させることができる。
<Method for producing laminate>
The laminated body of this invention can be obtained by apply | coating the said hydrophilic coating agent (B) to the above-mentioned resin sheet, and making it dry. The drying method is not particularly limited. For example, a hydrophilic coating agent (B) is obtained by heating and drying for about 0.1 to 30 minutes using a drying apparatus controlled so that the temperature of the resin sheet does not exceed Tg. ) Can be formed on the resin sheet.
親水性コート剤（Ｂ）の塗布方法としても、特に限定されるものではなく、例えば、スプレーコーター、ロールコーター、グラビアロールコーター、ナイフコーター、エアーナイフコーター、ローターダンプニング、アプリケーター方式等が挙げられる。 The method for applying the hydrophilic coating agent (B) is not particularly limited, and examples thereof include a spray coater, a roll coater, a gravure roll coater, a knife coater, an air knife coater, a rotor dampening, and an applicator method. .
親水性コート剤（Ｂ）の塗布量としては、本発明の効果が十分に発揮され、且つコスト面での折り合いがつく限りにおいて、種々選択されるものであるが、耐熱耐油性と成形性とのバランスに優れる観点から、１０〜８０００ｍｇ／ｍ２の範囲であるであることが好ましく、２００〜１５００ｍｇ／ｍ２の範囲であることが特に好ましく、更に好ましくは２００〜１０００ｍｇ／ｍ２である。 The coating amount of the hydrophilic coating agent (B) is variously selected as long as the effect of the present invention is sufficiently exhibited and the cost can be compromised. from the viewpoint of excellent balance, it is preferable that at in the range of 10~8000mg / m 2, particularly preferably in the range of 200~1500mg / m 2, more preferably from 200 to 1000 mg / m 2.
また、親水性コート剤（Ｂ）の塗布前に、樹脂シートの塗布面を予め親水化処理しておくことが好ましい。 Moreover, it is preferable to hydrophilize the application surface of the resin sheet in advance before applying the hydrophilic coating agent (B).
前記親水化処理としては、例えば、酸処理、火炎処理、コロナ処理等が挙げられる。これらの親水化処理を施した樹脂シート表面のぬれ係数は、３８ｍＮ／ｍ以上であることが好ましく、該親水性コート剤（Ｂ）を均一に塗布し、十分な効果を得るためには４５〜６０ｍＮ／ｍの範囲内であることが特に好ましい。ここで、ぬれ係数は、ＪＩＳ Ｋ−６７８６に記載された方法により測定される値である。 Examples of the hydrophilization treatment include acid treatment, flame treatment, and corona treatment. The wetting coefficient of the surface of the resin sheet subjected to these hydrophilic treatments is preferably 38 mN / m or more. In order to uniformly apply the hydrophilic coating agent (B) and obtain a sufficient effect, it is 45 to 45 mN / m. A range of 60 mN / m is particularly preferable. Here, the wetting coefficient is a value measured by the method described in JIS K-6786.
＜成形体の製造方法＞
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、なかでも温度制御が良好で、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。
<Method for producing molded body>
The laminate obtained above is heated and molded by a direct heating method or an indirect heating method to obtain the molded product of the present invention. The method of heat forming is not particularly limited, and can be performed using a vacuum forming machine, a hot plate pressure forming machine, a vacuum pressure forming machine, etc., among which temperature control is good and heating can be performed for a short time. Since it is possible, heat molding using a hot plate pressure forming machine is preferable.
＜成形体の使用＞
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、その耐油性、及びスチレン系樹脂シートが本来有する透明性、及び成形性の観点から、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。
<Use of molded body>
The molded article of the present invention obtained above can be suitably used particularly as a food packaging container, and is used as a lid from the viewpoint of its oil resistance, transparency inherent in the styrene-based resin sheet, and moldability. Most preferably. At this time, it is a preferable usage method that the coating layer in the laminate of the present invention is shaped so as to be on the contents side.
以下に実施例を用いて本発明を更に具体的に説明する。本発明はもとより、これらの実施例の範囲に限定されるべきものではない。以下、「部」「％」は特に断りのない限り、質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention should not be limited to the scope of these examples. Hereinafter, “part” and “%” are based on mass unless otherwise specified.
合成例１：アクリル系親水性コート剤（Ｂ１）の合成
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。その際の重量平均分子量は12万であった。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％のアクリル系親水性コート剤（Ｂ１）を調整した。
Synthesis Example 1: Synthesis of acrylic hydrophilic coating agent (B1) 136.8 parts of n-butanol was charged into a reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube, and stirring was started up to 100 ° C. The temperature rose. Under a nitrogen stream, a monomer mixture comprising 29.3 parts of methyl methacrylate, 29.3 parts of ethyl acrylate, 29.3 parts of styrene, and 58.5 parts of methacrylic acid, and t-butylperoxy-2 -A reaction initiator mixture consisting of 0.2 parts of ethylhexanoate and 24.6 parts of n-butanol was continuously added dropwise over 2 hours. After stirring at the same temperature for 2 hours, a reaction initiator mixture consisting of 0.6 parts of t-butylperoxy-2-ethylhexanoate and 16.6 parts of n-butanol was continuously added dropwise over 2 hours. After stirring at the same temperature for 1 hour, the temperature was lowered to 95 ° C., neutralized with 57.6 parts of dimethylethanolamine, and water-solubilized with 738.7 parts of ion-exchanged water to obtain a water-soluble acrylic resin. The weight average molecular weight at that time was 120,000. The water-soluble acrylic resin had a nonvolatile content of 18%. Furthermore, it diluted with distilled water and prepared the acrylic hydrophilic coating agent (B1) of 10% of non volatile matters.
合成例２：アクリル系親水性コート剤（Ｂ２）の合成
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、アクリル樹脂水溶液としてアクリル系親水性コート剤（Ｂ２）を得た。不揮発分は１９％であった。
Synthesis Example 2: Synthesis of acrylic hydrophilic coating agent (B2) Into a reaction vessel equipped with a reflux condenser, a stirrer and a nitrogen introduction tube, 186.5 parts of n-butanol was charged and stirring was started up to 100 ° C. The temperature rose. Under a nitrogen stream, a monomer mixture consisting of 115.8 parts of methyl methacrylate, 94.2 parts of ethyl acrylate, 140.0 parts of methacrylic acid, and t-butylperoxy-2-ethylhexanoate 3 The reaction initiator mixture consisting of 0.5 part and 163.5 parts of n-butanol was continuously added dropwise over 4 hours. After stirring at the same temperature for 3 hours, the temperature was lowered to 40 ° C., neutralized with 137.6 parts of dimethylethanolamine, water-solubilized with 1025.0 parts of ion-exchanged water, and acrylic hydrophilic as an acrylic resin aqueous solution. A coating agent (B2) was obtained. The nonvolatile content was 19%.
実施例１〜１３、及び比較例１〜５
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。
Examples 1 to 13 and Comparative Examples 1 to 5
A monomer composition ratio (MAA: methacrylic acid) shown in Tables 1 to 3 was used to synthesize a copolymer by continuous bulk polymerization to form an unstretched sheet of 1000 μm with an extruder, and then machine direction (MD) with a single stretcher. ) A biaxially stretched styrene-based resin sheet stretched twice and transversely (CD) twice was obtained.
得られたシートに、表１〜３で示したコート剤をバーコーターを用いて塗工後、８０℃に調節された恒温槽にて３０分乾燥させ積層体を得た。 The coating agent shown in Tables 1 to 3 was applied to the obtained sheet using a bar coater, and then dried in a thermostatic bath adjusted to 80 ° C. for 30 minutes to obtain a laminate.
得られた積層体を用いて真空圧空成形機を使用して容器状の成形体を製造した。容器形状は、深さ２０ｍｍ、開口部８４ｍｍ×８４ｍｍ、絞り比０．２４である。成形条件はスチレン１００％延伸シート（ＢＯＰＳ）が偏肉不良を起こさず、良好な型再現性となる、間接加熱ヒーター温度３５０℃、シート加熱時間９秒とした。 Using the obtained laminate, a container-like molded body was produced using a vacuum / pressure forming machine. The container has a depth of 20 mm, an opening of 84 mm × 84 mm, and a drawing ratio of 0.24. The molding conditions were an indirect heating heater temperature of 350 ° C. and a sheet heating time of 9 seconds, in which a styrene 100% stretched sheet (BOPS) did not cause uneven thickness defects and had good mold reproducibility.
得られた成形体を用い、耐油性、耐熱性及び成形性の評価を行った。
耐油性評価：成形体の内側にサラダ油（日清オイリオグループ株式会社製食品調合油）を刷毛で塗布後、９０℃で５分及び３０分暴露を行い、外観を目視にて評価した。
３０分で白化が発生しなかったもの：５、
３０分で僅かに白化が発生したが５分までは白化の発生しなかったもの：４、
３０分で明らかに白化が発生したが５分までは白化の発生しなかったもの：３、
５分で僅かに白化が発生したもの：２、
５分で明らかに白化が発生したもの：１
Using the obtained molded body, oil resistance, heat resistance and moldability were evaluated.
Evaluation of oil resistance: Salad oil (food formula oil manufactured by Nisshin Oillio Group Co., Ltd.) was applied to the inside of the molded body with a brush, then exposed at 90 ° C. for 5 minutes and 30 minutes, and the appearance was visually evaluated.
No whitening occurred in 30 minutes: 5,
Slight whitening occurred in 30 minutes, but no whitening occurred until 5 minutes: 4,
Clear whitening occurred in 30 minutes, but no whitening occurred until 5 minutes: 3,
Slight whitening occurred in 5 minutes: 2,
Clear whitening occurred in 5 minutes: 1
耐熱性評価：耐油性試験後の成形体の４隅の高さ変化率を測定することで評価した。
高さ保持率が９８％以上のもの：○、
高さ保持率が９０％以上９８％未満のもの：△、
高さ保持率が９０％未満のもの：×
Evaluation of heat resistance: Evaluated by measuring the height change rate of the four corners of the molded product after the oil resistance test.
Those with a height retention of 98% or more: ○,
Those having a height retention of 90% or more and less than 98%: Δ,
Those with a height retention of less than 90%: ×
成形性評価：成形体の底コーナー部のＲ（ｍｍ）をＲゲージを用いて測定することで評価した。
３ｍｍ未満のもの：○、
３ｍｍ以上のもの：×
Moldability evaluation: R (mm) at the bottom corner of the molded body was measured by measuring with an R gauge.
Less than 3 mm: ○,
3 mm or more: ×
使用したコート剤の詳細は以下の通りである。
Ｂ３：ポリエステル樹脂水分散体：ユニチカ株式会社製エリーテルＫＴ−９２０４（固形分２３％）
Ｂ４：変性エポキシ樹脂水分散体：ＤＩＣ株式会社製９１５２（固形分２３％）
Ｂ５：フッ素系撥水撥油樹脂水分散体：旭硝子株式会社製ＡＧ−６０Ｅ（固形分２３％）
Ｂ６：ヒドロキシセルロース水溶液：フジケミカル株式会社製ＨＥＣ ＡＧ−１５Ｆ（３％水溶液）
Ｂ７：ポリビニルアルコール水溶液：電気化学工業株式会社製ポバールＢ−１７（３％水溶液）
Ｂ８：ショ糖ラウリン酸エステル水溶液：理研ビタミン株式会社製リケマールＡ（ＨＬＢ＝１５、固形分４１％）
Ｂ９：ポリグリセリン脂肪酸エステル水溶液：理研ビタミン株式会社製ポエム−００２１（ＨＬＢ＝１５．５、固形分４０％）
Ｂ’：ジメチルシリコン：東レダウコーニング株式会社製
Details of the coating agent used are as follows.
B3: Polyester resin aqueous dispersion: Elitel KT-9204 (solid content 23%) manufactured by Unitika Ltd.
B4: Modified epoxy resin aqueous dispersion: 9152 manufactured by DIC Corporation (solid content 23%)
B5: Fluorine-based water / oil repellent resin water dispersion: AG-60E manufactured by Asahi Glass Co., Ltd. (solid content: 23%)
B6: Hydroxycellulose aqueous solution: HEC AG-15F (3% aqueous solution) manufactured by Fuji Chemical Co., Ltd.
B7: Polyvinyl alcohol aqueous solution: Poval B-17 (3% aqueous solution) manufactured by Denki Kagaku Kogyo Co., Ltd.
B8: Sucrose laurate aqueous solution: Rikenmar A manufactured by Riken Vitamin Co., Ltd. (HLB = 15, solid content 41%)
B9: Polyglycerol fatty acid ester aqueous solution: Poem-0021 manufactured by Riken Vitamin Co., Ltd. (HLB = 15.5, solid content 40%)
B ': Dimethyl silicon: Toray Dow Corning Co., Ltd.
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| JP2016098253A (en) * | 2014-11-18 | 2016-05-30 | Dic株式会社 | Laminate and molded body using the same |
| JP2016098255A (en) * | 2014-11-18 | 2016-05-30 | Dic株式会社 | Laminate and molded body using the same |
| JP2017206612A (en) * | 2016-05-18 | 2017-11-24 | Dic株式会社 | Laminated sheet and molded body using the same |
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| JPH05318580A (en) * | 1992-05-26 | 1993-12-03 | Dainippon Ink & Chem Inc | Biaxially stretched synthetic resin sheet |
| JPH0912752A (en) * | 1995-06-26 | 1997-01-14 | Daicel Chem Ind Ltd | Oil-resistant sheet |
| JP2000309645A (en) * | 1999-04-26 | 2000-11-07 | Dainippon Ink & Chem Inc | Biaxially oriented styrene-based resin sheet |
| JP2004202838A (en) * | 2002-12-25 | 2004-07-22 | Dainippon Ink & Chem Inc | Biaxially stretched aromatic vinyl resin sheet and molded article |
| JP2005330299A (en) * | 2004-05-18 | 2005-12-02 | San Dic Kk | Styrenic resin biaxially stretched sheet and thermoformed product |
| JP2007077364A (en) * | 2005-09-16 | 2007-03-29 | Asahi Kasei Life & Living Corp | Oil resistant film and molded container using the same |
| JP2007277428A (en) * | 2006-04-07 | 2007-10-25 | Asahi Kasei Chemicals Corp | Oil resistant film, and molded container using the same |
| JP2015229330A (en) * | 2014-06-06 | 2015-12-21 | デンカ株式会社 | Oil-resistant polystyrene-based resin sheet and molded container therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016098253A (en) * | 2014-11-18 | 2016-05-30 | Dic株式会社 | Laminate and molded body using the same |
| JP2016098255A (en) * | 2014-11-18 | 2016-05-30 | Dic株式会社 | Laminate and molded body using the same |
| JP2017206612A (en) * | 2016-05-18 | 2017-11-24 | Dic株式会社 | Laminated sheet and molded body using the same |
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