JP2021154681A - Multilayer sheet and method for producing the same, and container body - Google Patents
Multilayer sheet and method for producing the same, and container body Download PDFInfo
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- JP2021154681A JP2021154681A JP2020059753A JP2020059753A JP2021154681A JP 2021154681 A JP2021154681 A JP 2021154681A JP 2020059753 A JP2020059753 A JP 2020059753A JP 2020059753 A JP2020059753 A JP 2020059753A JP 2021154681 A JP2021154681 A JP 2021154681A
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- JP
- Japan
- Prior art keywords
- resin
- resin composition
- multilayer sheet
- composition layer
- styrene
- Prior art date
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- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000011342 resin composition Substances 0.000 claims abstract description 86
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 59
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 59
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 48
- 239000004626 polylactic acid Substances 0.000 claims abstract description 48
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 99
- 239000011347 resin Substances 0.000 claims description 82
- 229920005989 resin Polymers 0.000 claims description 82
- 239000004793 Polystyrene Substances 0.000 claims description 25
- 229920002223 polystyrene Polymers 0.000 claims description 25
- 238000005227 gel permeation chromatography Methods 0.000 claims description 17
- 235000013305 food Nutrition 0.000 claims description 13
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 229920001890 Novodur Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 93
- 239000003921 oil Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 102100026918 Phospholipase A2 Human genes 0.000 description 1
- 101710096328 Phospholipase A2 Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
Description
本発明は、多層シート及びその製造方法、並びに容器本体に関する。 The present invention relates to a multilayer sheet, a method for producing the same, and a container body.
スーパーマーケット、コンビニエンスストア、デパ−ト、弁当店等の店舗において、食料品や加工食品等を販売する際に使用される容器として、ポリスチレン系樹脂を用いた容器が幅広く使用されている。特にポリスチレン系樹脂の押出シートから成形した容器は軽量であること、断熱性が高いこと、安価であること等の理由から多く用いられている。 In stores such as supermarkets, convenience stores, department stores, and lunch boxes, containers using polystyrene-based resin are widely used as containers used when selling foods, processed foods, and the like. In particular, containers formed from polystyrene resin extruded sheets are often used because of their light weight, high heat insulating properties, and low cost.
しかしながら、ポリスチレン系樹脂は耐油性に乏しく、食品中の油分により可塑化が進行し、穴開きに至る問題があった。 However, polystyrene-based resins have poor oil resistance, and there is a problem that plasticization progresses due to the oil content in foods, leading to perforation.
そこで、ポリスチレン系樹脂の耐油性を改善するために種々の検討がなされてきた。例えば、ポリスチレン系樹脂に、ポリエチレンやポリプロピレン等のオレフィン系樹脂を配合する方法（例えば、特許文献１〜３参照）が挙げられる。
また、ポリスチレンにスチレン系ブロック共重合体ゴム及びスチレン−アクリロニトリル共重合体を配合した成形体が提案されている（特許文献４）。
Therefore, various studies have been made to improve the oil resistance of polystyrene-based resins. For example, a method of blending an olefin resin such as polyethylene or polypropylene with a polystyrene resin (see, for example, Patent Documents 1 to 3) can be mentioned.
Further, a molded product in which polystyrene is blended with a styrene-based block copolymer rubber and a styrene-acrylonitrile copolymer has been proposed (Patent Document 4).
しかし、特許文献１〜３のようなポリスチレン系樹脂とオレフィン系樹脂とからなる樹脂組成物では、両樹脂の相溶性が悪く、単純ブレンド品では、機械的強度が低下し、層状剥離も発生して、実用に耐えるものではない。そこで、相溶性を向上させるため、スチレン−ブタジエンブロック共重合体ゴムやその水素添加重合体、スチレン−イソプレンブロック共重合体やその水素添加重合体、又はエチレン−オクテン共重合体等を更に添加しているが、十分に満足できるものではない。 However, in the resin composition composed of the polystyrene-based resin and the olefin-based resin as in Patent Documents 1 to 3, the compatibility between the two resins is poor, and in the simple blended product, the mechanical strength is lowered and layered peeling occurs. Therefore, it is not practically usable. Therefore, in order to improve compatibility, styrene-butadiene block copolymer rubber and its hydrogenated polymer, styrene-isoprene block copolymer and its hydrogenated polymer, ethylene-octene copolymer and the like are further added. However, it is not fully satisfactory.
また、ポリスチレン系樹脂とオレフィン系樹脂からなる樹脂組成物においては、耐油性を向上させるために、相当量のオレフィン系樹脂を混練する必要がある。そのため、ポリスチレン系樹脂の特徴である剛性、耐熱性がかえって損なわれてしまうという問題もある。 Further, in the resin composition composed of the polystyrene-based resin and the olefin-based resin, it is necessary to knead a considerable amount of the olefin-based resin in order to improve the oil resistance. Therefore, there is also a problem that the rigidity and heat resistance, which are the characteristics of polystyrene-based resins, are rather impaired.
特許文献４の成形体は耐熱性が不足しており、特にコンビニエンスストアで近年標準となっている高出力の電子レンジを用いて加熱する用途においては、容器の変形をきたす問題があった。 The molded product of Patent Document 4 lacks heat resistance, and there is a problem that the container is deformed particularly in an application of heating using a high-power microwave oven, which has become a standard in convenience stores in recent years.
また、近年の温暖化抑制の観点から二酸化炭素の低減が求められており、見かけ上二酸化炭素を排出しない「カーボンニュートラル」なポリエステル系樹脂の１つとしてポリ乳酸が注目されている。しかし、ポリ乳酸は耐久性の面で実用性に劣る。そこで、スチレン系樹脂とのアロイ化により、ポリ乳酸の有効利用化を図れれば、環境負荷低減の観点から非常に有意である。 In addition, reduction of carbon dioxide is required from the viewpoint of suppressing global warming in recent years, and polylactic acid is attracting attention as one of "carbon-neutral" polyester-based resins that apparently does not emit carbon dioxide. However, polylactic acid is inferior in practicality in terms of durability. Therefore, if polylactic acid can be effectively used by alloying with a styrene resin, it is very significant from the viewpoint of reducing the environmental load.
以上から本発明は、耐油性が高く、環境負荷の小さい多層シートを提供することを目的とする。 From the above, it is an object of the present invention to provide a multilayer sheet having high oil resistance and a small environmental load.
上記課題を解決すべく鋭意検討した結果、最表面側にある第１の樹脂組成物層に、スチレン系樹脂を主成分とし、所定割合のポリ乳酸及び特定のアクリル系樹脂を含有させることで、ポリ乳酸により環境負荷低減効果が発現し、アクリル系樹脂により、耐油性の低いスチレン系樹脂に対し高い耐油性が付与されることを見出し、本発明を完成した。すなわち、本発明は下記のとおりである。 As a result of diligent studies to solve the above problems, the first resin composition layer on the outermost surface side contains a styrene resin as a main component, and contains a predetermined ratio of polylactic acid and a specific acrylic resin. We have found that polylactic acid exerts an effect of reducing environmental load, and that an acrylic resin imparts high oil resistance to a styrene resin having low oil resistance, and completed the present invention. That is, the present invention is as follows.
［１］ スチレン系樹脂を主成分として含む樹脂組成物層を２層以上積層した多層シートであって、前記樹脂組成物層のうち、一方の最表面側にある第１の樹脂組成物層が、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む多層シート。
［２］ 前記アクリル系樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で得られるピークトップ分子量（Ｍｐ）が１００万〜６００万である［１］に記載の多層シート。
［３］ 前記第１の樹脂組成物層における前記スチレン系樹脂が、ゴム変性ポリスチレンである［１］又は［２］に記載の多層シート。
［４］ 前記第１の樹脂組成物層以外の樹脂組成物層における前記スチレン系樹脂が、ゴム変性ポリスチレンである［１］〜［３］のいずれかに記載の多層シート。
［５］ 前記第１の樹脂組成物層以外の樹脂組成物層が、ポリ乳酸及びアクリル系樹脂を含む［１］〜［４］のいずれかに記載の多層シート。
［６］ 前記第１の樹脂組成物層上に、第２の樹脂組成物層と第３の樹脂組成物層をこの順に含む［１］〜［５］のいずれかに記載の多層シート。
［７］ スチレン系樹脂を主成分として含む２以上の樹脂組成物層を一体化させて共押出成形する工程を含む多層シートの製造方法であって、前記２以上の樹脂組成物層のうち、一方の最表面側に形成される第１の樹脂組成物層が、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む多層シートの製造方法。
［８］ 前記アクリル系樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で得られるピークトップ分子量（Ｍｐ）が１００万〜６００万である［７］に記載の多層シートの製造方法。
［９］ ［１］〜［６］のいずれかに記載の多層シートの成形体からなる容器本体。
［１０］ 前記第１の樹脂組成物層が内表面に配置されてなる［９］に記載の容器本体。
［１１］ 食品収納用である［９］又は［１０］に記載の容器本体。
[1] A multilayer sheet in which two or more resin composition layers containing a styrene-based resin as a main component are laminated, and the first resin composition layer on the outermost surface side of one of the resin composition layers is , A multilayer sheet containing 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin.
[2] The multilayer sheet according to [1], wherein the peak top molecular weight (Mp) obtained by gel permeation chromatography (GPC) of the acrylic resin is 1 million to 6 million.
[3] The multilayer sheet according to [1] or [2], wherein the styrene-based resin in the first resin composition layer is rubber-modified polystyrene.
[4] The multilayer sheet according to any one of [1] to [3], wherein the styrene-based resin in the resin composition layer other than the first resin composition layer is rubber-modified polystyrene.
[5] The multilayer sheet according to any one of [1] to [4], wherein the resin composition layer other than the first resin composition layer contains polylactic acid and an acrylic resin.
[6] The multilayer sheet according to any one of [1] to [5], wherein the second resin composition layer and the third resin composition layer are contained in this order on the first resin composition layer.
[7] A method for producing a multilayer sheet, which comprises a step of integrating two or more resin composition layers containing a styrene resin as a main component and coextruding them, among the two or more resin composition layers. A method for producing a multilayer sheet in which the first resin composition layer formed on the outermost surface side contains 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin.
[8] The method for producing a multilayer sheet according to [7], wherein the peak top molecular weight (Mp) obtained by gel permeation chromatography (GPC) of the acrylic resin is 1 million to 6 million.
[9] A container body made of a molded product of the multilayer sheet according to any one of [1] to [6].
[10] The container body according to [9], wherein the first resin composition layer is arranged on an inner surface.
[11] The container body according to [9] or [10] for storing food.
本発明によれば、耐油性が高く、環境負荷の小さい多層シートを提供することができる。また、本発明によれば、上記に加え、耐衝撃性を向上させた多層シートを提供することができる。さらに、本発明の多層シートは、例えばパール調となり、容器本体とした際に高級感を付与することができる。 According to the present invention, it is possible to provide a multilayer sheet having high oil resistance and a small environmental load. Further, according to the present invention, in addition to the above, it is possible to provide a multilayer sheet having improved impact resistance. Further, the multilayer sheet of the present invention has, for example, a pearl tone, and can give a high-class feeling when it is used as a container body.
以下、本発明の実施形態について詳細に説明する。
［多層シート］
本実施形態に係る多層シートは、スチレン系樹脂を主成分として含む樹脂組成物層を２層以上積層した多層シートであって、樹脂組成物層のうち、一方の最表面側にある第１の樹脂組成物層が、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む。上記アクリル系樹脂のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で得られるピークトップ分子量（Ｍｐ）は好ましくは１００万〜６００万となっている。また、第１の樹脂組成物層以外の層として、第２の樹脂組成物層、第３の樹脂組成物、・・・等が積層されて、本実施形態に係る多層シートが構成されている。
Hereinafter, embodiments of the present invention will be described in detail.
[Multi-layer sheet]
The multilayer sheet according to the present embodiment is a multilayer sheet in which two or more layers of a resin composition containing a styrene resin as a main component are laminated, and is a first layer on the outermost surface side of one of the resin composition layers. The resin composition layer contains 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin. The peak top molecular weight (Mp) obtained by gel permeation chromatography (GPC) of the above-mentioned acrylic resin is preferably 1 million to 6 million. Further, as a layer other than the first resin composition layer, a second resin composition layer, a third resin composition, ..., Etc. are laminated to form a multilayer sheet according to the present embodiment. ..
本明細書において、「主成分」とは各構成成分中で質量割合が最も多い成分をいう。例えば、スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む樹脂組成物層中に「スチレン系樹脂を主成分として含む」という場合、上記３成分のなかでスチレン系樹脂の質量割合が最も多いことを意味する。
以下、各層などについて説明する。
In the present specification, the "main component" means the component having the largest mass ratio among the constituent components. For example, when the resin composition layer containing a styrene resin, polylactic acid, and an acrylic resin "contains a styrene resin as a main component", the mass ratio of the styrene resin is the largest among the above three components. Means.
Hereinafter, each layer and the like will be described.
（１）第１の樹脂組成物層
（スチレン系樹脂）
スチレン系樹脂は、芳香族ビニル化合物の単量体を重合して得られるものである。芳香族ビニル化合物の単量体は、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、２，４−ジメチルスチレン等の公知のものが使用できるが、好ましくはスチレンである。これらの単量体は単独で用いてもよいし、併用してもよい。また、これらの単量体と共重合可能なアクリロニトリル、（メタ）アクリル酸、（メタ）アクリル酸エステル等の単量体や無水マレイン酸等の単量体も、スチレン系樹脂の性能を損なわない程度のものであれば添加して重合したものであってもよい。
(1) First resin composition layer (styrene resin)
The styrene resin is obtained by polymerizing a monomer of an aromatic vinyl compound. As the monomer of the aromatic vinyl compound, known ones such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and 2,4-dimethylstyrene can be used, but styrene is preferable. These monomers may be used alone or in combination. Further, monomers such as acrylonitrile, (meth) acrylic acid, and (meth) acrylic acid ester that can be copolymerized with these monomers and monomers such as maleic anhydride do not impair the performance of the styrene resin. As long as it is of a certain degree, it may be added and polymerized.
スチレン系樹脂は必要に応じて共役ジエン系ゴム状重合体を加えてゴム変性を行ってもよい。ゴム変性に用いる共役ジエン系ゴム状重合体としては、ポリブタジエン、スチレン−ブタジエンのランダムまたはブロック共重合体、ポリイソプレン、ポリクロロプレン、スチレン−イソプレンのランダム、ブロック又はグラフト共重合体、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴムなどが挙げられるが、特にポリブタジエン、スチレン−ブタジエンのランダム、ブロックが好ましい。また、これらは一部水素添加されていてもよい。 If necessary, the styrene-based resin may be rubber-modified by adding a conjugated diene-based rubber-like polymer. As the conjugated diene rubber-like polymer used for rubber modification, polybutadiene, styrene-butadiene random or block copolymer, polyisoprene, polychloroprene, styrene-isoprene random, block or graft copolymer, ethylene-propylene rubber , Ethylene-propylene-diene rubber and the like, but polybutadiene and styrene-butadiene random and block are particularly preferable. In addition, these may be partially hydrogenated.
このようなスチレン系樹脂としては例えば、ポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン（ＨＩＰＳ）、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体）、ＡＳ樹脂（アクリロニトリル−スチレン共重合体）、ＭＳ樹脂（メチルメタクリレート−スチレン共重合体）、ＡＡＳ樹脂（アクリロニトリル−アクリルゴム−スチレン共重合体）、ＡＥＳ樹脂（アクリロニトリル−エチレンプロピレン−スチレン共重合体）等が挙げられる。この中では、ゴム変性ポリスチレンが、樹脂組成物の耐衝撃性を高くすることができるため好ましい。 Examples of such styrene-based resins include polystyrene (GPPS), rubber-modified polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), and MS resin (methyl). Memethacrylate-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene-styrene copolymer) and the like. Among these, rubber-modified polystyrene is preferable because it can increase the impact resistance of the resin composition.
スチレン系樹脂の分子量は、ピークトップ分子量（Ｍｐ）で１万〜５０万が好ましく、３万〜４０万であることがより好ましい。ピークトップ分子量（Ｍｐ）が１万〜５０万であることで、流動性と耐熱性のバランスに優れた樹脂組成物が得られる。
なお、本明細書において、ピークトップ分子量（Ｍｐ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定にて、以下の方法にて単分散ポリスチレンの溶出曲線より各溶出時間における分子量を算出し、ポリスチレン換算の分子量として算出するものである。
機種：昭和電工株式会社製Ｓｈｏｄｅｘ ＧＰＣ−１０１
カラム：ポリマーラボラトリーズ社製 ＰＬｇｅｌ １０μｍ ＭＩＸＥＤ−Ｂ
移動相：テトラヒドロフラン
流量：１．０ｍｌ／分
試料濃度：０．２質量％
注入量：１００μｌ
温度：オーブン４０℃、注入口３５℃、検出器３５℃
検出器：示差屈折計
The molecular weight of the styrene resin is preferably 10,000 to 500,000, more preferably 30,000 to 400,000, in terms of peak top molecular weight (Mp). When the peak top molecular weight (Mp) is 10,000 to 500,000, a resin composition having an excellent balance between fluidity and heat resistance can be obtained.
In the present specification, the peak top molecular weight (Mp) is converted into polystyrene by calculating the molecular weight at each elution time from the elution curve of monodisperse polystyrene by the following method by gel permeation chromatography (GPC) measurement. It is calculated as the molecular weight of.
Model: Showa Denko Corporation Shodex GPC-101
Column: Polymer Laboratories PLgel 10 μm MIXED-B
Mobile phase: tetrahydrofuran Flow rate: 1.0 ml / min Sample concentration: 0.2% by mass
Injection volume: 100 μl
Temperature: Oven 40 ° C, inlet 35 ° C, detector 35 ° C
Detector: Differential refractometer
ここで、ピークトップ分子量（Ｍｐ）は、上記のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で得られる分子量分布のピークの頂点の位置から求められるものであるが、このＧＰＣにおいて複数のピークを有する場合には、最も大きい面積比を有するピークに相当するピークについての分子量である。 Here, the peak top molecular weight (Mp) is obtained from the position of the apex of the peak of the molecular weight distribution obtained by the above gel permeation chromatography (GPC), but when there are a plurality of peaks in this GPC. Is the molecular weight for the peak corresponding to the peak with the largest area ratio.
第１の樹脂組成物層中のスチレン系樹脂の含有量は５５〜８９質量％であることが好ましく、６５〜８０質量％であることがより好ましい。含有量が５５〜８９質量％であることで、耐油性と耐衝撃性を両立することができる。 The content of the styrene-based resin in the first resin composition layer is preferably 55 to 89% by mass, more preferably 65 to 80% by mass. When the content is 55 to 89% by mass, both oil resistance and impact resistance can be achieved at the same time.
（ポリ乳酸）
ポリ乳酸としては、ポリ（Ｌ−乳酸）を用いることが好ましい。また、二酸化炭素排出量削減という観点から植物由来原料を用いることが好ましい。
(Polylactic acid)
As the polylactic acid, it is preferable to use poly (L-lactic acid). Further, it is preferable to use a plant-derived raw material from the viewpoint of reducing carbon dioxide emissions.
ポリ乳酸がポリ（Ｌ−乳酸）の場合、Ｄ−乳酸成分の比率によってその結晶化速度が異なる。食品容器のような成形体とする際の成形性を考慮すると、Ｄ−乳酸成分の比率は０．０１〜５．０モル％とであることが好ましく、０．０１〜１．５モル％であることがより好ましい。 When polylactic acid is poly (L-lactic acid), the crystallization rate differs depending on the ratio of the D-lactic acid component. Considering the moldability when forming a molded product such as a food container, the ratio of the D-lactic acid component is preferably 0.01 to 5.0 mol%, preferably 0.01 to 1.5 mol%. More preferably.
ポリ乳酸の分子量は、ピークトップ分子量（Ｍｐ）で５万〜４０万であることが好ましく、１０〜３０万であることがより好ましい。ピークトップ分子量（Ｍｐ）が５万以上であると、成形体とした際の機械的特性や耐熱性が良好になり、４０万以下であると成形体とする際の成形性を良好に維持することができる。 The molecular weight of polylactic acid is preferably 50,000 to 400,000, more preferably 100,000 to 300,000 in terms of peak top molecular weight (Mp). When the peak top molecular weight (Mp) is 50,000 or more, the mechanical properties and heat resistance of the molded product are good, and when it is 400,000 or less, the moldability of the molded product is maintained well. be able to.
第１の樹脂組成物層中のポリ乳酸の含有量は１０〜４２質量％であり、１５〜３５であることが好ましく、２０〜３０質量％であることがより好ましい。ポリ乳酸の含有量が１０質量％未満であると、耐油性が低下してしまう。また、４０質量％を超えると耐衝撃性が低下してしまう。 The content of polylactic acid in the first resin composition layer is 10 to 42% by mass, preferably 15 to 35%, and more preferably 20 to 30% by mass. If the content of polylactic acid is less than 10% by mass, the oil resistance is lowered. Further, if it exceeds 40% by mass, the impact resistance is lowered.
（アクリル系樹脂）
アクリル系樹脂は、アクリル系単量体などの重合により得られるものである。ここで、アクリル系樹脂のピークトップ分子量（Ｍｐ）は、既述のとおり、１００万〜６００万であることが好ましく、１５０万〜４５０万であることがより好ましく、３００万〜４５０万であることがさらに好ましい。ピークトップ分子量（Ｍｐ）が１００万未満であると、高級感が損なわれてしてしまう場合がある。また、６００万を超えると成形性が悪化し製膜困難にしてしまう場合がある。
(Acrylic resin)
The acrylic resin is obtained by polymerizing an acrylic monomer or the like. Here, as described above, the peak top molecular weight (Mp) of the acrylic resin is preferably 1 million to 6 million, more preferably 1.5 million to 4.5 million, and 3 million to 4.5 million. Is even more preferable. If the peak top molecular weight (Mp) is less than 1 million, the sense of quality may be impaired. On the other hand, if it exceeds 6 million, the moldability may deteriorate and film formation may become difficult.
アクリル系単量体の種類は、本発明の効果を損なわない限り特に制限されず、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ブチルアクリレート、２−エチルへキシルアクリレート、ベンジルアクリレート、シクロヘキシルアクリレート、フェニルアクリレート、クロロエチルアクリレート等のアクリレート単量体や、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、２−エチルヘキシルメタクリレート、ベンジルメタクリレート、シクロヘキシルメタクリレート、フェニルメタクリレート、クロロエチルメタクリレート等のメタクリレート単量体の単独重合体、あるいはこれらの単量体２種以上を共重合させた共重合体等を用いることができる。 The type of acrylic monomer is not particularly limited as long as the effects of the present invention are not impaired, and for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl. Acrylate monomers such as acrylate and chloroethyl acrylate, and methacrylate monomers such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate and chloroethyl methacrylate alone. A polymer or a copolymer obtained by copolymerizing two or more of these monomers can be used.
アクリル系樹脂の構成単位はメタクリル酸メチル単位が主成分であり、その含有量が６０質量％以上であることが好ましく、７０質量％以上であることがより好ましい。 The main component of the acrylic resin is a methyl methacrylate unit, and the content thereof is preferably 60% by mass or more, more preferably 70% by mass or more.
アクリル系樹脂の重合方法としては、例えば、乳化重合、ソープフリー乳化重合、微細懸濁重合、懸濁重合、塊状重合、溶液重合等の公知の重合方法が挙げられる。これらの重合方法の中でも、高分子量体の生成が容易であることから、乳化重合が好ましい。アクリル系樹脂を乳化重合によって製造するときの乳化剤としては、公知の乳化剤を用いることができる。例えば、アニオン性乳化剤、ノニオン性乳化剤、高分子乳化剤、分子内にラジカル重合可能な不飽和二重結合を有する反応性乳化剤が挙げられる。 Examples of the polymerization method of the acrylic resin include known polymerization methods such as emulsion polymerization, soap-free emulsion polymerization, fine suspension polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Among these polymerization methods, emulsion polymerization is preferable because it is easy to generate a high molecular weight compound. A known emulsifier can be used as the emulsifier when the acrylic resin is produced by emulsion polymerization. Examples thereof include anionic emulsifiers, nonionic emulsifiers, polymer emulsifiers, and reactive emulsifiers having an unsaturated double bond capable of radical polymerization in the molecule.
アクリル系樹脂は上記のアクリル系単量体の他に本発明の効果を損なわない限りこれらと共重合可能なビニル単量体を添加して重合したものでもよく、例えば、α−オレフィン、ビニル芳香族類、不飽和ニトリル類、不飽和カルボン酸またはこれらのエステル、エチレングリコールジ（メタ）アクリレート等の多価不飽和化合物等の単量体を添加していてもよい。 The acrylic resin may be polymerized by adding a vinyl monomer copolymerizable with the above acrylic monomers as long as the effects of the present invention are not impaired. For example, α-olefin and vinyl fragrance. Monomers such as groups, unsaturated nitriles, unsaturated carboxylic acids or esters thereof, and polyunsaturated compounds such as ethylene glycol di (meth) acrylate may be added.
第１の樹脂組成物層中のアクリル系樹脂の含有量は１〜７質量％であり、２〜４質量％であることが好ましく、２．５〜３．５質量％であることがより好ましい。アクリル系樹脂の含有量が１質量％未満であると、高級感が低下してしまう。また、７質量％を超えると成形性が悪化し製膜困難にしてしまう。 The content of the acrylic resin in the first resin composition layer is 1 to 7% by mass, preferably 2 to 4% by mass, and more preferably 2.5 to 3.5% by mass. .. If the content of the acrylic resin is less than 1% by mass, the sense of quality is lowered. Further, if it exceeds 7% by mass, the moldability deteriorates and it becomes difficult to form a film.
（２）第１の樹脂組成物層以外の樹脂組成物層
第１の樹脂組成物層以外の樹脂組成物層もスチレン系樹脂を主成分とすることが好ましく、当該スチレン系樹脂は、ゴム変性スチレン系樹脂であることが好ましい。これにより多層シートの耐衝撃性を向上させることができる。
また、第１の樹脂組成物層以外の樹脂組成物層は少なくとも１層が、スチレン系樹脂を主成分とし、ポリ乳酸及びアクリル系樹脂を含むことが好ましい。
なお、スチレン系樹脂、ポリ乳酸及びアクリル系樹脂の好ましい具体例や配合等については、第１の樹脂組成物層におけるものと同様であるが、第１の樹脂組成物層と同一の組成とする必要はない。
(2) Resin composition layer other than the first resin composition layer It is preferable that the resin composition layer other than the first resin composition layer also contains a styrene-based resin as a main component, and the styrene-based resin is rubber-modified. It is preferably a styrene resin. This makes it possible to improve the impact resistance of the multilayer sheet.
Further, it is preferable that at least one layer of the resin composition layer other than the first resin composition layer contains a styrene resin as a main component and contains polylactic acid and an acrylic resin.
The preferred specific examples and formulations of the styrene resin, polylactic acid, and acrylic resin are the same as those in the first resin composition layer, but have the same composition as the first resin composition layer. There is no need.
本実施形態に係る多層シートは、例えば、第１の樹脂組成物層上に、第２の樹脂組成物層を有する２層構成多層シート、第１の樹脂組成物層上に、第２の樹脂組成物層と第３の樹脂組成物層とをこの順に含む３層構成多層シートが実用上好ましく挙げられる。 The multilayer sheet according to the present embodiment is, for example, a two-layer structure multilayer sheet having a second resin composition layer on the first resin composition layer, and a second resin on the first resin composition layer. Practically preferable is a three-layer structure multilayer sheet containing the composition layer and the third resin composition layer in this order.
２層構成多層シートの場合の第２の樹脂組成物層は、（ａ）スチレン系樹脂を含み、ポリ乳酸及びアクリル系樹脂を含まない構成、（ｂ）スチレン系樹脂及びポリ乳酸を含み、アクリル系樹脂を含まない構成、（ｃ）スチレン系樹脂及びアクリル系樹脂を含み、ポリ乳酸を含まない構成、（ｃ）スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む構成が挙げられるが、シートの耐衝撃性向上の観点から、（ａ）スチレン系樹脂を含み、ポリ乳酸及びアクリル系樹脂を含まない構成であることが好ましい。 The second resin composition layer in the case of the two-layer structure multilayer sheet has a structure of (a) containing a styrene resin and not containing a polylactic acid and an acrylic resin, and (b) containing a styrene resin and a polylactic acid and acrylic. Examples thereof include a configuration containing no based resin, a configuration containing (c) a styrene resin and an acrylic resin and not containing polylactic acid, and a configuration containing (c) a styrene resin, polylactic acid, and an acrylic resin. From the viewpoint of improving the impact resistance of the above, it is preferable that the structure contains (a) a styrene resin and does not contain a polylactic acid and an acrylic resin.
２層構成多層シートの場合の第１の樹脂組成物層の厚みＴ１と第２の樹脂組成物層の厚みＴ２との厚み比（Ｔ２／Ｔ１）は、９０／１０〜５０／５０であることが好ましく、８５／１５〜７５／２５であることがより好ましい。厚み比（Ｔ２／Ｔ１）が９０／１０〜５０／５０であることで、シートの外観を損なわず、耐衝撃性を有するシートを製膜することができる。 The thickness ratio (T2 / T1) of the thickness T1 of the first resin composition layer and the thickness T2 of the second resin composition layer in the case of the two-layer structure multilayer sheet shall be 90/10 to 50/50. Is preferable, and 85/15 to 75/25 is more preferable. When the thickness ratio (T2 / T1) is 90/10 to 50/50, it is possible to form a film having impact resistance without impairing the appearance of the sheet.
３層構成多層シートの場合の第２の樹脂組成物層は、（ａ）スチレン系樹脂を含み、ポリ乳酸及びアクリル系樹脂を含まない構成、（ｂ）スチレン系樹脂及びポリ乳酸を含み、アクリル系樹脂を含まない構成、（ｃ）スチレン系樹脂及びアクリル系樹脂を含み、ポリ乳酸を含まない構成、（ｄ）スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む構成が挙げられる。
また、第３の樹脂組成物層は、（ａ）スチレン系樹脂を含み、ポリ乳酸及びアクリル系樹脂を含まない構成、（ｂ）スチレン系樹脂及びポリ乳酸を含み、アクリル系樹脂を含まない構成、（ｃ）スチレン系樹脂及びアクリル系樹脂を含み、ポリ乳酸を含まない構成、（ｄ）スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む構成が挙げられる。
The second resin composition layer in the case of the three-layer structure multilayer sheet has a structure of (a) containing a styrene resin and not containing polylactic acid and an acrylic resin, and (b) containing a styrene resin and a polylactic acid, and acrylic. Examples thereof include a configuration containing no based resin, a configuration containing (c) a styrene resin and an acrylic resin and not containing polylactic acid, and a configuration containing (d) a styrene resin, polylactic acid, and an acrylic resin.
The third resin composition layer has a structure of (a) containing a styrene resin and not containing polylactic acid and an acrylic resin, and (b) a structure containing styrene resin and polylactic acid and not containing an acrylic resin. , (C) A configuration containing a styrene resin and an acrylic resin and not containing polylactic acid, and (d) a configuration containing styrene resin, polylactic acid, and an acrylic resin.
シートの耐衝撃性保持、およびバイオマス度向上の観点から、第２の樹脂組成物層は、（ａ）スチレン系樹脂を含み、ポリ乳酸及びアクリル系樹脂を含まない構成、又は（ｄ）スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む構成であり、第３の樹脂組成物層は、（ｄ）スチレン系樹脂、ポリ乳酸、及びアクリル系樹脂を含む構成であることが好ましい。 From the viewpoint of maintaining the impact resistance of the sheet and improving the degree of biomass, the second resin composition layer has a structure (a) containing a styrene resin and not containing polylactic acid and an acrylic resin, or (d) a styrene resin. The composition contains a resin, polylactic acid, and an acrylic resin, and the third resin composition layer preferably contains (d) a styrene resin, polylactic acid, and an acrylic resin.
３層構成多層シートの場合の第１の樹脂組成物層の厚みＴ１と第２の樹脂組成物層の厚みＴ２との厚み比（Ｔ２／Ｔ１）は、８０／１０〜５０／２５であることが好ましく、７０／１５〜５０／２５であることがより好ましい。厚み比（Ｔ２／Ｔ１）が８０／１０〜５０／２５であることで、シートの外観を損なわず、耐衝撃性を有するシートを製膜することができる。
また、第１の樹脂組成物層の厚みＴ１と第３の樹脂組成物層の厚みＴ３との厚み比（Ｔ３／Ｔ１）は、１０／２５〜２５／２５であることが好ましく、１５／２５〜２５／２５であることがより好ましい。厚み比（Ｔ３／Ｔ１）が１０／２５〜２５／２５であることで、シート外観を損なわず、耐衝撃性を有するシートを製膜することができる。
The thickness ratio (T2 / T1) of the thickness T1 of the first resin composition layer and the thickness T2 of the second resin composition layer in the case of the three-layer structure multilayer sheet shall be 80/10 to 50/25. Is preferable, and 70/15 to 50/25 is more preferable. When the thickness ratio (T2 / T1) is 80/10 to 50/25, it is possible to form a film having impact resistance without impairing the appearance of the sheet.
The thickness ratio (T3 / T1) of the thickness T1 of the first resin composition layer and the thickness T3 of the third resin composition layer is preferably 10/25 to 25/25, and is preferably 15/25. More preferably, it is ~ 25/25. When the thickness ratio (T3 / T1) is 10/25 to 25/25, it is possible to form a film having impact resistance without impairing the appearance of the sheet.
以上のような多層シートは、その全厚が０．１〜３．０ｍｍであることが好ましく、０．２〜１．５ｍｍであることがより好ましい。全厚が０．１〜３．０ｍｍであることで絶対的な強度が不足することなく、柔軟なシートを製膜することができる。 The total thickness of the multilayer sheet as described above is preferably 0.1 to 3.0 mm, more preferably 0.2 to 1.5 mm. Since the total thickness is 0.1 to 3.0 mm, a flexible sheet can be formed without insufficient absolute strength.
また、多層シートの各層は、本発明の目的を損なわない範囲で添加剤、例えば可塑剤、展着剤、溶剤、紫外線吸収剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、着色剤、染顔料、充填剤、着色防止剤、補強剤、相溶化剤、結晶化促進剤、難燃剤、難燃助剤等を含有することができる。 In addition, each layer of the multilayer sheet contains additives such as a plasticizer, a spreading agent, a solvent, an ultraviolet absorber, an antioxidant, an antioxidant, a light stabilizer, and an antistatic agent, as long as the object of the present invention is not impaired. It can contain a colorant, a dye pigment, a filler, an antistatic agent, a reinforcing agent, a compatibilizer, a crystallization accelerator, a flame retardant, a flame retardant aid and the like.
［多層シートの製造方法］
本実施形態に係る多層シートは、スチレン系樹脂を主成分として含む２以上の樹脂組成物層を一体化させて共押出成形する工程を経て製造することができる。このとき、２以上の樹脂組成物層のうち、一方の最表面側に形成される第１の樹脂組成物層は、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む。このときアクリル系樹脂のピークトップ分子量（Ｍｐ）は１００万〜６００万とすることが好ましい。
なお、スチレン系樹脂、ポリ乳酸、アクリル系樹脂などの詳細については既述のとおりである。
[Manufacturing method of multilayer sheet]
The multilayer sheet according to the present embodiment can be produced through a step of coextruding by integrating two or more resin composition layers containing a styrene resin as a main component. At this time, of the two or more resin composition layers, the first resin composition layer formed on the outermost surface side contains 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin. .. At this time, the peak top molecular weight (Mp) of the acrylic resin is preferably 1 million to 6 million.
The details of the styrene resin, polylactic acid, acrylic resin and the like are as described above.
ここで、各樹脂組成物層を形成するための樹脂組成物は、例えば、ミキサー型混合機、Ｖ型ブレンダー、及びタンブラー型混合機等の混合装置を用いて、スチレン系樹脂をはじめとした各種原料を予め混合しておき、その混合物を溶融混練することによって、製造することができる。溶融混練装置としては、特に限定されないが、例えば、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等が挙げられる。さらに、押出機等の溶融混練装置の途中から他の原料や添加剤などを別途添加してもよい。 Here, various resin compositions for forming each resin composition layer include styrene-based resins and the like by using a mixing device such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer. It can be produced by mixing the raw materials in advance and melt-kneading the mixture. The melt-kneading device is not particularly limited, and examples thereof include a Banbury type mixer, a kneader, a roll, a single-screw extruder, a special single-screw extruder, and a twin-screw extruder. Further, other raw materials, additives and the like may be added separately from the middle of the melt-kneading device such as an extruder.
また、共押出成形の方法としては、一般的な共押出多層法であるフィードブロック方式やマルチマニホールド方式により、多層シートのすべての層を一体化させて、吐出口のリップから一枚のシート状に押出し、冷却ロールの間を通して固化させ、シートを巻き取る方法が好ましい。ダイスは、Ｔダイス（Ｔダイともいう）が好ましく用いられる。なお、共押出多層法で多層シートを製造する際は、各層となる樹脂組成物の流動性を合わせることが好ましい。 In addition, as a co-extrusion molding method, all layers of the multi-layer sheet are integrated by a feed block method or a multi-manifold method, which are general co-extrusion multi-layer methods, and a single sheet is formed from the lip of the discharge port. A method of extruding the sheet, solidifying it through the cooling rolls, and winding the sheet is preferable. As the die, a T die (also referred to as a T die) is preferably used. When producing a multilayer sheet by the coextrusion multilayer method, it is preferable to match the fluidity of the resin compositions to be the layers.
［容器本体］
本実施形態に係る容器本体は、既述の本発明の多層シートの成形体からなる。特に、第１の樹脂組成物層が容器本体の内表面に配置されてなることが好ましい。第１の樹脂組成物層は耐油性が高いため、容器本体が食品収納用である場合に内表面が第１の樹脂組成物層であると好適となる。
[Container body]
The container body according to the present embodiment is made of the above-mentioned molded body of the multilayer sheet of the present invention. In particular, it is preferable that the first resin composition layer is arranged on the inner surface of the container body. Since the first resin composition layer has high oil resistance, it is preferable that the inner surface is the first resin composition layer when the container body is for storing food.
本実施形態に係る容器本体は、耐油性が求められる用途に特に好適であるが、なかでも食品収納用（すなわち食品を内容物とする包装容器や食品容器の蓋材等で構成）であることが好ましい。特に当該食品が油脂を含む食品である場合に好適である。また、食品容器、食品容器の蓋材は、電子レンジ加熱用、冷蔵用とすることができる。 The container body according to the present embodiment is particularly suitable for applications requiring oil resistance, but is particularly suitable for storing food (that is, composed of a packaging container containing food as a content, a lid material for the food container, etc.). Is preferable. It is particularly suitable when the food is a food containing fats and oils. Further, the food container and the lid material of the food container can be used for heating or refrigerating in a microwave oven.
容器本体を得るための成形加工方法としては、シートの真空成型、圧空成形、真空圧空成形等の公知の方法が挙げられる。 Examples of the molding processing method for obtaining the container main body include known methods such as vacuum forming, vacuum forming, and vacuum forming of a sheet.
以下、実施例に基づいて本発明をさらに具体的に説明するが本発明は当該実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the Examples.
実施例及び比較例で使用した材料の表記は以下の通りである。
（ＰＬＡ１）ポリ乳酸 海正生物材料社製ＲＥＶＯＤＥ１９０（Ｄ型比率：０．５モル％）
（ＰＬＡ２）ポリ乳酸 海正生物材料社製ＲＥＶＯＤＥ１１０（Ｄ型比率：２．５モル％）
（ＰＳ１）ゴム変性ポリスチレン：ＨＩＰＳ 東洋スチレン（株）製 Ｅ６４０Ｎ
（ＰＳ２）ゴム変性ポリスチレン：ＨＩＰＳ 東洋スチレン（株）製 Ｈ８５０Ｎ
The notation of the materials used in the examples and comparative examples is as follows.
(PLA1) Polylactic acid REVODE190 manufactured by Kaisei Biomaterials Co., Ltd. (D type ratio: 0.5 mol%)
(PLA2) Polylactic acid REVODE110 manufactured by Kaisei Biomaterials Co., Ltd. (D type ratio: 2.5 mol%)
(PS1) Rubber-modified polystyrene: E640N manufactured by HIPS Toyo Styrene Co., Ltd.
(PS2) Rubber-modified polystyrene: HIPS H850N manufactured by Toyo Styrene Co., Ltd.
（ＡＲ１）下記の製造方法にて作製したアクリル樹脂
−製造方法−
温度計、窒素導入管、冷却管および攪拌装置を備えたセパラブルフラスコ（容量５リットル）に、分散媒としてイオン交換水３００質量部、乳化剤としてドデシルベンゼンスルホンナトリウム１．１質量部、連鎖移動剤としてｎ−オクチルメルカプタン０．００７質量部、単量体としてメタクリル酸メチル８５質量部、アクリル酸ブチル１５質量部を投入した。このセパラブルフラスコに窒素気流を通じることにより、フラスコ内雰囲気の窒素置換を行なった。次いで、内温を６０℃まで昇温させ、過硫酸カリウム０．１５質量部、イオン交換水５質量部を加えた。その後、加熱攪拌を２時間継続して重合を終了し、アクリル樹脂ラテックスを得た。
得られたアクリル樹脂ラテックスを２５℃まで冷却後、酢酸カルシウム５質量部を含む７０℃の温水５００質量部中に滴下した後、９０℃まで昇温させて凝析させた。得られた凝析物を分離洗浄後、６０℃で１２時間乾燥させて、アクリル樹脂（ＡＲ１）を得た。アクリル樹脂（ＡＲ１）のピークトップ分子量（Ｍｐ）は、１５０万であった。
(AR1) Acrylic resin produced by the following production method-Manufacturing method-
In a separable flask (capacity: 5 liters) equipped with a thermometer, nitrogen introduction tube, cooling tube and stirrer, 300 parts by mass of ion-exchanged water as a dispersion medium, 1.1 parts by mass of sodium dodecylbenzenesulfone as an emulsifier, and a chain transfer agent. As a result, 0.007 parts by mass of n-octyl mercaptan, 85 parts by mass of methyl methacrylate and 15 parts by mass of butyl acrylate were added as monomers. Nitrogen was replaced in the atmosphere inside the flask by passing a nitrogen stream through the separable flask. Next, the internal temperature was raised to 60 ° C., and 0.15 parts by mass of potassium persulfate and 5 parts by mass of ion-exchanged water were added. Then, heating and stirring were continued for 2 hours to complete the polymerization, and an acrylic resin latex was obtained.
The obtained acrylic resin latex was cooled to 25 ° C., dropped into 500 parts by mass of warm water at 70 ° C. containing 5 parts by mass of calcium acetate, and then heated to 90 ° C. for coagulation. The obtained coagulated product was separated and washed, and then dried at 60 ° C. for 12 hours to obtain an acrylic resin (AR1). The peak top molecular weight (Mp) of the acrylic resin (AR1) was 1.5 million.
（ＡＲ２、ＡＲ３、ａｒ１、）
上記のＡＲ１の製造方法において、各種原料仕込み量を調整してピークトップ分子量（Ｍｐ）を変更した以外は上記と同様の製造条件で作製したアクリル樹脂ＡＲ２、ＡＲ３、ａｒ１を得た。
なお、アクリル樹脂ＡＲ２、ＡＲ３、ａｒ１のゲルパーミエーションクロマトグラフィー（ＧＰＣ）で得られるピークトップ分子量（Ｍｐ）はそれぞれ、４５０万、３００万、９０万であった。
(AR2, AR3, ar1,)
In the above-mentioned production method of AR1, acrylic resins AR2, AR3, and ar1 produced under the same production conditions as above except that the amount of various raw materials charged was adjusted to change the peak top molecular weight (Mp) were obtained.
The peak top molecular weights (Mp) obtained by gel permeation chromatography (GPC) of the acrylic resins AR2, AR3, and ar1 were 4.5 million, 3 million, and 900,000, respectively.
［実施例１］
第１の樹脂層となる樹脂組成物を、以下の方法で準備した。すなわち、ポリ乳酸（ＰＬＡ１）の３０質量部と、ゴム変性ポリスチレン（ＰＳ１）の６７質量部と、アクリル樹脂（ＡＲ１）の３質量部を、ヘンシェルミキサーで予備混合し、次いで二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）を用いて溶融混練し、さらにストランドをペレタイザーに通して、第１の樹脂層用組成物のペレットを得た。なお、二軸押出機はＴＥＭ２６ＳＳ（東芝機械社製）を用い、シリンダー設定温度は２００℃、樹脂組成物の吐出量は３０ｋｇ／時間の条件で運転した。
[Example 1]
The resin composition to be the first resin layer was prepared by the following method. That is, 30 parts by mass of polylactic acid (PLA1), 67 parts by mass of rubber-modified polystyrene (PS1), and 3 parts by mass of acrylic resin (AR1) were premixed with a Henschel mixer, and then a twin-screw extruder (Toshiba). It was melt-kneaded using TEM26SS manufactured by Kikai Co., Ltd., and the strands were further passed through a pelletizer to obtain pellets of the composition for the first resin layer. The twin-screw extruder used was TEM26SS (manufactured by Toshiba Machine Co., Ltd.), and was operated under the conditions that the cylinder set temperature was 200 ° C. and the discharge amount of the resin composition was 30 kg / hour.
次いで、上記第１の樹脂層として、４０ｍｍ押出機を用い、第１の樹脂組成物のペレットを押し出し、また第２の樹脂層として、６５ｍｍ押出機を使用してゴム変性ポリスチレン（ＰＳ１）を押し出し、それぞれの溶融樹脂をフィードブロックを経由させて、幅７００ｍｍのＴダイ中に送り、一体化させた２種２層とし、冷却後のシート全体の厚さが０．４ｍｍ、及びシート全体の厚さに対する第１の樹脂層／第２の樹脂層の厚さの割合が、２０／８０とした層構成を有する多層シートを押し出した。なお、実施例１の多層シートの配合や層構成は表１にも示した。Ｔダイのリップから押し出された実施例１の多層シートは、その後３本のロールを用いて冷却し、巻取機にて巻取りを行った。なお、シート押出のシリンダー、ダイス設定温度は２００℃、多層シートの吐出量は３５ｋｇ／時間の条件で運転した。 Next, as the first resin layer, a 40 mm extruder was used to extrude the pellets of the first resin composition, and as the second resin layer, a 65 mm extruder was used to extrude the rubber-modified polystyrene (PS1). , Each molten resin is sent into a T-die with a width of 700 mm via a feed block to form two types and two layers integrated, and the thickness of the entire sheet after cooling is 0.4 mm, and the thickness of the entire sheet. A multilayer sheet having a layer structure in which the ratio of the thickness of the first resin layer to the thickness of the second resin layer was 20/80 was extruded. The composition and layer composition of the multilayer sheet of Example 1 are also shown in Table 1. The multilayer sheet of Example 1 extruded from the lip of the T-die was then cooled using three rolls and wound by a winder. The sheet extrusion cylinder and die set temperature were 200 ° C., and the discharge rate of the multilayer sheet was 35 kg / hour.
［実施例２〜１０、比較例１〜４］
実施例２〜１０、比較例１〜４の各多層シートは、最表面側にある第１の樹脂組成物の各樹脂の組成、配合比率を表１に示したように設定し、製膜装置の各ヒーター温度、吐出量、リップ幅は適宜調整したが、基本的には実施例１と同じ手順で、同じ装置を用いて作製した。
[Examples 2 to 10, Comparative Examples 1 to 4]
In each of the multilayer sheets of Examples 2 to 10 and Comparative Examples 1 to 4, the composition and the compounding ratio of each resin of the first resin composition on the outermost surface side are set as shown in Table 1, and the film forming apparatus is set. The heater temperature, discharge amount, and lip width of each of the above were adjusted as appropriate, but basically, they were produced by the same procedure as in Example 1 and using the same apparatus.
［実施例１１］
多層シートの第１及び第３の樹脂層として、４０ｍｍ押出機を２台使用して実施例１の第１の樹脂層用組成物のペレットを押し出し、多層シートの第２の樹脂層として、６５ｍｍ押出機を用いて実施例１と同じゴム変性ポリスチレン（ＰＳ１）を押し出し、それぞれの溶融樹脂をフィードブロックを経由させて、幅７００ｍｍのＴダイ中に送り、中芯層と最表面層を全て一体化させた２種３層とし、冷却後のシート全体の厚さが０．４ｍｍ、及びシート全体の厚さに対する第１の樹脂層／第２の樹脂層／第３の樹脂層の厚さの割合が、２０／６０／２０とした層構成を有する多層シートを押し出した。なお、実施例１１の多層シートの層構成は表２にも示した。Ｔダイのリップから押し出された実施例１１の多層シートは、その後３本のロールを用いて冷却し、巻取機にて巻取りを行った。
[Example 11]
The pellets of the composition for the first resin layer of Example 1 were extruded using two 40 mm extruders as the first and third resin layers of the multilayer sheet, and 65 mm as the second resin layer of the multilayer sheet. The same rubber-modified polystyrene (PS1) as in Example 1 is extruded using an extruder, and each molten resin is sent into a T-die having a width of 700 mm via a feed block, and the core layer and the outermost surface layer are all integrated. The thickness of the entire sheet after cooling is 0.4 mm, and the thickness of the first resin layer / second resin layer / third resin layer relative to the thickness of the entire sheet. A multilayer sheet having a layer structure in which the ratio was 20/60/20 was extruded. The layer structure of the multilayer sheet of Example 11 is also shown in Table 2. The multilayer sheet of Example 11 extruded from the lip of the T-die was then cooled using three rolls and wound by a winder.
［実施例１２〜２１、比較例５〜８］
実施例１２〜２１、比較例５〜８の各多層シートは、最表面側にある第１及び第３の樹脂組成物の各樹脂の組成、配合比率を表２に示したように設定し、製膜装置の各ヒーター温度、吐出量、リップ幅は適宜調整したが、基本的には実施例１０と同じ手順で、同じ装置を用いて作製した。
なお、実施例２０は、第２の樹脂層に５０％のリサイクルを想定し、基本的には実施例１０と同じ手順で、同じ装置を用い、多層シートを製膜したものである。
[Examples 12 to 21, Comparative Examples 5 to 8]
In each of the multilayer sheets of Examples 12 to 21 and Comparative Examples 5 to 8, the composition and blending ratio of each resin of the first and third resin compositions on the outermost surface side were set as shown in Table 2. The temperature, discharge rate, and lip width of each heater of the film-forming device were appropriately adjusted, but basically the same procedure as in Example 10 was used to produce the film.
In Example 20, it is assumed that 50% of the second resin layer is recycled, and basically the same procedure as in Example 10 is used to form a multi-layer sheet using the same apparatus.
＜バイオマス度の算出＞
実施例１〜２１、比較例１〜８の多層シートについて、ＰＬＡ（ポリ乳酸）の含有率をバイオマス度とした。バイオマス度は、ＰＬＡの配合量から求めることができる。また、以下の測定方法を用いても算出することができる。多層シート１ｇ（Ａ（ｇ）とする）を精秤し、メチルエチルケトンを添加し２時間振とうした。フィルタろ過後、ろ過物にクロロホルムを添加し２時間振とうした。遠心分離（１４００ｒｐｍ、３０分）後の上澄みにメタノールを添加し、樹脂分を再沈させた。フィルタろ過後、真空乾燥機（１２５℃、２時間）にて乾燥させた後の試料の質量（Ｂ（ｇ）とする）を測定した。測定されたＡ、Ｂから下式によりバイオマス度を算出した。
バイオマス度（％）＝Ｂ／Ａ×１００
結果を表１，２に示す。
<Calculation of biomass degree>
The PLA (polylactic acid) content of the multilayer sheets of Examples 1 to 21 and Comparative Examples 1 to 8 was defined as the degree of biomass. The degree of biomass can be determined from the blending amount of PLA. It can also be calculated using the following measurement method. 1 g (referred to as A (g)) of the multilayer sheet was precisely weighed, methyl ethyl ketone was added, and the mixture was shaken for 2 hours. After filtration through the filter, chloroform was added to the filtrate and shaken for 2 hours. Methanol was added to the supernatant after centrifugation (1400 rpm, 30 minutes) to reprecipitate the resin component. After filtering with a filter, the mass (referred to as B (g)) of the sample after drying in a vacuum dryer (125 ° C., 2 hours) was measured. The degree of biomass was calculated from the measured A and B by the following formula.
Biomass degree (%) = B / A x 100
The results are shown in Tables 1 and 2.
＜耐油性の測定方法＞
実施例１〜２１、比較例１〜８の多層シートについて、幅１５ｍｍ、シートの押出方向に３００ｍｍの試験片を切出し定歪み耐油試験評価用試験片とした。定歪み耐油性試験装置を用いて、ガーゼを当てた試験片の屈曲部にスポイトで薬品を０．０５ｍｌ塗布し、２４時間後の試験片が、割れが生じている場合「×」、クレーズが生じている場合は「△」、変化がない場合は「○」と３段階で比較評価した。
耐油性に関しては、本試験では「○」、「△」であれば、本発明の効果を発現しているとした。結果を表１，２に示す。
ひずみ量：０．５％
使用薬品：サラダ油
<Measurement method of oil resistance>
For the multilayer sheets of Examples 1 to 21 and Comparative Examples 1 to 8, a test piece having a width of 15 mm and a width of 300 mm in the extrusion direction of the sheet was cut out and used as a test piece for constant strain oil resistance test evaluation. Using a constant strain oil resistance test device, apply 0.05 ml of chemicals with a dropper to the bent part of the test piece to which gauze is applied, and if the test piece after 24 hours is cracked, "x", craze If it occurred, it was evaluated as "Δ", and if there was no change, it was evaluated as "○" on a three-point scale.
Regarding the oil resistance, in this test, if it was "○" or "Δ", it was considered that the effect of the present invention was exhibited. The results are shown in Tables 1 and 2.
Strain amount: 0.5%
Chemicals used: Salad oil
＜耐衝撃性の測定方法＞
本発明における耐衝撃性はＡＳＴＭ−Ｄ３４２０に従ってフィルムインパクト強度により評価した。実施例１〜２１、比較例１〜８の総厚み０．４ｍｍの多層シートについて、７０ｍｍ×７０ｍｍに切出し測定した。耐衝撃性は３．０ｋＪ／ｍｍ以上であれば、本発明の効果を発現しているとした。結果を表１，２に示す。
<Measurement method of impact resistance>
The impact resistance in the present invention was evaluated by the film impact strength according to ASTM-D3420. The multilayer sheets having a total thickness of 0.4 mm in Examples 1 to 21 and Comparative Examples 1 to 8 were cut out and measured in a size of 70 mm × 70 mm. It is said that the effect of the present invention is exhibited when the impact resistance is 3.0 kJ / mm or more. The results are shown in Tables 1 and 2.
＜高級感（光沢度）＞
容器の高級感は光沢度にて評価した。ＪＩＳ Ｚ ８７４１に従って、試料面に６０°の入射角で規定の開き角の光束を入射し，鏡面反射方向に反射する規定の開き角の光束を受光器で測定した。光沢度が低いほど容器成形時の容器に高級感が得られるとした。光沢度が１５以下を「○」、１６〜１８を「△」、１８超を「×」と３段階で比較評価した。本試験では、「○」、「△」であれば、本発明の効果を発現しているとした。結果を表１，２に示す。
<Luxury (glossiness)>
The luxury of the container was evaluated by the glossiness. According to JIS Z 8741, a luminous flux having a specified opening angle was incident on the sample surface at an incident angle of 60 °, and a luminous flux having a specified opening angle reflected in the specular reflection direction was measured with a receiver. It is said that the lower the glossiness, the higher the quality of the container when molding the container. A glossiness of 15 or less was evaluated as "◯", 16 to 18 was evaluated as "Δ", and a glossiness of more than 18 was evaluated as "x" on a three-point scale. In this test, if it is "○" or "Δ", it is considered that the effect of the present invention is exhibited. The results are shown in Tables 1 and 2.
＜製膜性＞
Ｔダイ押出にて、製膜性を評価した。製膜が可能であった場合を「○」、張力が高すぎるため製膜不可の場合を「×」とした。結果を表１，２に示す。
<Film formation>
The film-forming property was evaluated by T-die extrusion. The case where film formation was possible was marked with "○", and the case where film formation was not possible due to too high tension was marked with "x". The results are shown in Tables 1 and 2.
実施例１〜２１、比較例１〜８の評価結果から、本実施例により、耐油性が高く、環境負荷の少なく、また実施例１〜９及び実施例１１〜２０ではピークトップ分子量（Ｍｐ）が所定の範囲にあるアクリル樹脂を用いることで光沢が良くなり、容器本体とした際に高級感を出すことができる多層シートを提供できることが確認された。
なお、比較例４、９ではアクリル系樹脂を多く添加すると製膜することができず、評価に値するものが得られなかったため製膜性が「×」であった。
From the evaluation results of Examples 1 to 21 and Comparative Examples 1 to 8, according to this example, the oil resistance is high and the environmental load is small, and in Examples 1 to 9 and Examples 11 to 20, the peak top molecular weight (Mp) is high. However, it was confirmed that by using an acrylic resin in a predetermined range, the gloss is improved, and it is possible to provide a multi-layer sheet that can give a high-class feeling when used as a container body.
In Comparative Examples 4 and 9, when a large amount of acrylic resin was added, film formation could not be performed, and no film worthy of evaluation was obtained, so that the film formation property was "x".
Claims (11)
前記樹脂組成物層のうち、一方の最表面側にある第１の樹脂組成物層が、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む多層シート。 A multi-layer sheet in which two or more resin composition layers containing a styrene-based resin as a main component are laminated.
A multilayer sheet in which the first resin composition layer on the outermost surface side of the resin composition layer contains 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin.
前記２以上の樹脂組成物層のうち、一方の最表面側に形成される第１の樹脂組成物層が、ポリ乳酸を１０〜４２質量％、アクリル系樹脂を１〜７質量％含む多層シートの製造方法。 A method for producing a multilayer sheet, which comprises a step of integrating two or more resin composition layers containing a styrene resin as a main component and coextruding them.
Of the two or more resin composition layers, the first resin composition layer formed on the outermost surface side is a multilayer sheet containing 10 to 42% by mass of polylactic acid and 1 to 7% by mass of an acrylic resin. Manufacturing method.
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