CN112300477A - 淀粉掺混聚乙烯树脂组合物和使用其的包装材料 - Google Patents
淀粉掺混聚乙烯树脂组合物和使用其的包装材料 Download PDFInfo
- Publication number
- CN112300477A CN112300477A CN202010760529.9A CN202010760529A CN112300477A CN 112300477 A CN112300477 A CN 112300477A CN 202010760529 A CN202010760529 A CN 202010760529A CN 112300477 A CN112300477 A CN 112300477A
- Authority
- CN
- China
- Prior art keywords
- starch
- mass
- parts
- polyethylene resin
- resin composition
- 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.)
- Pending
Links
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 88
- 239000011342 resin composition Substances 0.000 title claims abstract description 70
- 239000005022 packaging material Substances 0.000 title abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 88
- 235000019698 starch Nutrition 0.000 claims abstract description 87
- 239000008107 starch Substances 0.000 claims abstract description 82
- 238000004898 kneading Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- -1 polyethylene Polymers 0.000 claims description 33
- 239000004698 Polyethylene Substances 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 229920003043 Cellulose fiber Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920006167 biodegradable resin Polymers 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000006864 oxidative decomposition reaction Methods 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 239000004645 polyester resin Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 229920003232 aliphatic polyester Polymers 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001254 oxidized starch Substances 0.000 description 4
- 235000013808 oxidized starch Nutrition 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- KMHZPJNVPCAUMN-UHFFFAOYSA-N Erbon Chemical compound CC(Cl)(Cl)C(=O)OCCOC1=CC(Cl)=C(Cl)C=C1Cl KMHZPJNVPCAUMN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920003354 Modic® Polymers 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 206010002199 Anaphylactic shock Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 240000006766 Cornus mas Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 235000010804 Maranta arundinacea Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 244000145580 Thalia geniculata Species 0.000 description 1
- 235000012419 Thalia geniculata Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 240000004922 Vigna radiata Species 0.000 description 1
- 235000010721 Vigna radiata var radiata Nutrition 0.000 description 1
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/06—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Biodiversity & Conservation Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
本发明提供使用淀粉可代替市售的通用塑料的生物降解性树脂组合物和使用其的膜等包装材料。上述课题通过一种淀粉掺混聚乙烯树脂组合物解决,所述组合物是将如下混合物熔融混炼,并在最终阶段将水分减压脱水而得到,所述混合物中,相对于100质量份的总聚乙烯树脂,包括120质量份以下且10质量份以上的淀粉、30~90质量份的在总聚乙烯树脂内导入有羧基的改性聚乙烯树脂、0.1~5质量份的具有多官能环氧基的化合物、相对于100质量份的淀粉为10~60质量份的多元醇系增塑剂、相对于100质量份的淀粉为0~30质量份的水。
Description
技术领域
本发明涉及在作为天然来源的物质的淀粉中组合作为通用包装材料的聚乙烯树脂而得的树脂组合物和使用该树脂组合物的包装材料。
背景技术
近年来,被称为“微塑料”的废弃塑料通过化学分解等而细碎的残渣堆积在海水中和土壤中,对生态系统和食物链造成不良影响,这已成为社会问题。此外,来源于石油资源的塑料在从原料到废弃处理的整个生命周期排出大量的二氧化碳,这成为地球变暖的一个原因。
为了降低这些环境负荷,设计了各种由土壤中或海水中的细菌生物降解的脂族聚酯树脂并已投入实际使用。代表性的生物降解性的脂族聚酯树脂可列举出:将作为二羧酸单体的琥珀酸或己二酸、对苯二甲酸和作为二醇单体的乙二醇或1,4-丁二醇脱水缩聚而得的物质,将同时具有羧基和羟基的乙醇酸脱水缩聚而得的物质,将乳酸的加热脱水聚合物在减压下加热分解而得到的丙交酯在金属催化剂下聚合而得的聚乳酸等。这些或其它的脂族聚酯树脂作为低环境负荷材料而市售,膜或片材也已投入实际使用。
但是,现状是生物降解性的脂族聚酯树脂不仅价格比通用的芳族聚酯树脂或聚烯烃树脂高,而且没有达到可代替现有的通用树脂所具有的强度物性、性状等的水平。因此,为了压缩膜或片材等的制备成本,完成了各种设计,并已投入实际使用。
专利文献1的发明是涉及生物降解性的脂族聚酯树脂与淀粉的组合物的发明,其特征在于,淀粉中的一部分在葡萄糖单元的C-2和C-3间断开分子,是其末端由羧基修饰的氧化淀粉的糊化物(低于50%)。
本发明人也痛心于这样的地球环境的恶化,致力于使用淀粉的材料的开发。于是,通过在淀粉中组合生物降解性的脂族聚酯树脂,并在其中掺混水溶性高分子,从而利用其羟基或丙烯酰基来提高聚酯树脂的羟基末端或羧基末端与淀粉的羟基之间的亲和性,使淀粉本身也可与聚酯树脂充分地混合,从而可制备膜等,并对此提出了专利申请(专利文献2)。然后,由于其在制备膜等时淀粉容易褐变,所以通过进一步加入抗氧化剂也解决了该褐变问题,对此也提出了专利申请(专利文献3)。
现有技术文献
专利文献
专利文献1:日本特开07-277353号公报
专利文献2:日本特开2018-53165号公报
专利文献3:日本特开2018-188574号公报。
发明内容
发明所要解决的课题
但是,关于专利文献1,由于需要使用并非通用品的特殊的氧化淀粉,或经过使用次氯酸钠水溶液的繁杂的工序来使淀粉氧化,所以与通用淀粉相比价格高,担心树脂组合物的加工成本上升。此外,在万一有次氯酸钠残留的情况下,有时也会因它们与人体粘膜接触而发生被称为“过敏性休克”的症状等。
其原因在于,因为淀粉对聚酯树脂的亲和性低,所以通过使其成为氧化淀粉来大幅增加羧基而解决亲和性问题。
专利文献2、3解决了这样的问题,使用可容易且廉价地获得的通用的淀粉,并且可稳定且均匀地混合,但脂族聚酯树脂价格高,即使加入淀粉来降低成本,也不容易代替市售的通用塑料。
本发明的目的在于,提供使用淀粉可代替市售的通用塑料的生物降解性树脂组合物和使用其的膜等包装材料。
解决课题的手段
本发明人为了解决上述课题而进行了深入研究,着眼于作为廉价且具有实用性的强度物性的包装材料的聚乙烯树脂。于是,首先,在淀粉中加入水制成糊化糊状,并加入聚乙烯树脂粒料制成复合物。但是,若利用水的糊化因蒸发或气化而减少,则淀粉分子彼此再次形成氢键,会成为硬而脆的干面条状,从而再次发生凝聚和相分离。因此,掺混不容易蒸发的甘油或单甘油酯等多元醇系增塑剂和不损害原料物性的范围的水。另一方面,不具有极性基的聚乙烯树脂与淀粉无亲和性。因此,添加在聚乙烯中接枝有羧酸酐的改性聚乙烯树脂。由此,改性聚乙烯树脂的酸酐基与淀粉的羟基形成酯键,可提高两相的亲和性。通过在其中进一步掺混多官能地具有与上述极性基(特别是酸酐基)有反应性的环氧基的化合物,发生由局部的分子键合引起的高分子化,可提高制成膜等的情况下的强度,从而完成本发明。
即,本发明提供淀粉掺混聚乙烯树脂组合物,其是将如下混合物熔融混炼,并在最终阶段将水分减压脱水而得到,所述混合物中,相对于100质量份的总聚乙烯树脂,包括120质量份以下且10质量份以上的淀粉、30~90质量份的在总聚乙烯树脂内导入有羧基的改性聚乙烯树脂、0.1~5质量份的具有多官能环氧基的化合物、相对于100质量份的淀粉为10~60质量份的多元醇系增塑剂、相对于100质量份的淀粉为0~30质量份的水。
即使使用上述树脂组合物,在从熔融混炼至成型期间也容易发生由淀粉的氧化引起的热褐变。因此,通过在该树脂组合物中掺混抗氧化剂,可防止淀粉的褐变。因此,本发明提供还掺混有0.1~0.8质量份的抗氧化剂的上述淀粉掺混聚乙烯树脂组合物。
若本发明的树脂组合物被废弃,则淀粉和多元醇系增塑剂被生物降解,可有助于降低环境负荷。此外,通过在该树脂组合物中掺混在所期望的实用期限后使聚乙烯的分子量降低的氧化分解剂,树脂组合物中的聚乙烯的分解也被促进而低分子化,从而被微生物等分解。因此,本发明也可作为还掺混有0.1~3质量份的使聚乙烯树脂的分子量降低的氧化分解剂的上述淀粉掺混聚乙烯树脂组合物来提供。
另外,若在本发明的树脂组合物中掺混天然来源的纤维素纤维,则可在维持组合物的生物降解性的同时提高其强度。因此,本发明提供还掺混有相对于100质量份的淀粉为1~10质量份的纤维素纤维的上述淀粉掺混聚乙烯树脂组合物。
若本发明的树脂组合物中使用的聚乙烯使用由天然来源的原料制备的物质,则成为表示碳循环量在环境上中立的“碳中和”,有助于防止地球变暖。因此,本发明提供聚乙烯树脂是由天然来源的原料得到的物质的根据上述任一所述的淀粉掺混聚乙烯树脂组合物。
然后,若使用这样的树脂组合物,制备膜、片材、在纸或膜、金属箔等基材上的熔融挤出层合物、吹塑瓶、注射成型物等,则它们即使被废弃,也会生物降解。因此,本发明提供由上述树脂组合物形成的膜、片材、吹塑瓶、注射成型物、将上述树脂组合物在纸基材上进行熔融挤出层合而得的层叠体。
关于本发明的树脂组合物,若将全部成分一次性混合,则无法得到均匀分散的组合物,需要对淀粉预先添加多元醇系增塑剂和水来均匀地混合增塑。因此,本发明提供上述淀粉掺混聚乙烯树脂组合物的制备方法,所述组合物是在淀粉中加入多元醇系增塑剂和水并均匀地搅拌混合,将在该混合物中加入聚乙烯树脂、改性聚乙烯树脂和具有多官能环氧基的化合物并均匀地搅拌混合而成的混合物熔融混炼,在最终阶段将水分减压脱水而得到。
发明的效果
本发明的树脂组合物以通用材料为主要材料,价格便宜且强度优异,而且由于淀粉是主要材料之一,所以生物降解性也高。另外,若进一步掺混使聚乙烯的分子量降低的氧化分解剂,则将聚乙烯分子断开,从而促进生物降解,因此作为整体被生物降解,可解决环境污染的问题。
具体实施方式
首先,对本发明的树脂组合物中使用的聚乙烯树脂进行说明。该聚乙烯树脂可以是任何聚乙烯树脂,可使用高密度聚乙烯、低密度聚乙烯、直链状低密度聚乙烯等。从本发明的主旨出发,聚乙烯树脂优选由天然来源的原料得到的物质,例如以使被称为生物质的甘蔗等发酵而得到的乙醇为原料制备的聚乙烯树脂。为了使聚乙烯树脂与淀粉均匀地相容,特别优选MFR (190℃下)为0.1~20g/10分钟左右的物质。适宜的MFR可根据成型方法、组成任意地选择。
接下来,对本发明的树脂组合物中使用的淀粉进行说明。
对于淀粉无特殊限制,可使用市售品。例如,可列举出玉米淀粉、小麦淀粉、米淀粉、高粱淀粉等谷类淀粉,甘薯淀粉、马铃薯淀粉、木薯淀粉等薯类淀粉,绿豆淀粉等豆类淀粉,葛淀粉、山慈菇淀粉(dogtooth violet starch)、蕨淀粉等野草类淀粉。这些淀粉可使用未经任何化学修饰的生淀粉,也可使用化学修饰淀粉。作为化学修饰淀粉的实例,可列举出氧化淀粉、乙酰化淀粉、醚化淀粉、交联淀粉等。
关于本发明的树脂组合物中的淀粉的掺混比例,相对于100质量份的总聚乙烯树脂,淀粉为120质量份以下且10质量份以上,优选为100质量份以下且30质量份以上,更优选为100质量份以下且50质量份以上。若超过120质量份,则由于淀粉的再凝聚,不仅树脂组合物的混炼容易变得不均匀,而且使用该组合物得到的膜、片材的强度显著降低,因此在实用上不优选。另一方面,若低于10质量份,则无法期待生物降解性带来的环境负荷显著降低的效果。
需说明的是,本说明书中的“100质量份的总聚乙烯树脂”是指聚乙烯树脂和改性聚乙烯树脂的总量,总聚乙烯树脂也包括作为聚乙烯树脂组合物的氧化分解剂母料在内。
对本发明中使用的多元醇系增塑剂进行说明。多元醇系增塑剂被用作为淀粉的增塑剂,因此难以蒸发且成型为膜后也残留的物质为宜。具体而言,优选具有在熔融混炼温度下不气化的沸点和高燃点的物质,若举例,则为甘油、甘油酯、二醇、聚乙烯醇、乙烯-聚乙烯醇共聚物、山梨糖醇等。甘油酯的实例为单甘油酯或二甘油酯等,二醇的实例为乙二醇、三乙二醇、聚乙二醇、丙二醇等。其中特别优选的是甘油。
相对于100质量份的淀粉,多元醇系增塑剂的掺混比例为10~60质量份左右,优选为20~50质量份左右。若低于10质量份,则淀粉的增塑不充分,在熔融混炼和此后的成膜或成型时淀粉彼此容易再凝聚,该部分的物理强度局部降低而不优选。另一方面,若超过60质量份,则未参与增塑的剩余的多元醇系增塑剂在进行熔融混炼或成膜/成型的挤出机内作为润滑剂起副作用,容易使利用螺杆的混炼产生故障而不优选。在掺混多元醇系增塑剂时进一步优选加入0~30质量份的水。水在下一工序的熔融混炼时促进淀粉的α化。由于α化淀粉的粘性强且透明性优异,所以有助于提高本发明的树脂组合物的强度物性和透明性。但是,已知α化淀粉经过长时间后会再次转变为β化淀粉(老化),老化淀粉会使本发明的树脂组合物的诸物性降低。作为抑制老化的方法,已知快速脱水,为了得到本发明的良好的树脂组合物,优选在熔融混炼时通过通风进行减压脱水。
对导入有羧基的改性聚乙烯树脂进行说明。该改性聚乙烯树脂优选在低密度、线型低密度或高密度的聚乙烯上接枝聚合不饱和二羧酸酐或不饱和羧酸而得的接枝共聚物。作为不饱和二羧酸酐的实例,可列举出马来酸酐、邻苯二甲酸酐、衣康酸酐、柠康酸酐、中康酸酐、富马酸酐等,作为不饱和羧酸的实例,可列举出丙烯酸、甲基丙烯酸等,其中从处理的容易性、耐热性等观点出发,优选常用的马来酸酐和邻苯二甲酸酐。对于接枝共聚的比例,相对于100质量份的聚乙烯,不饱和二羧酸酐为0.01~5质量份,优选为0.05~3质量份左右是适当的。若低于0.01质量份,则淀粉相与聚乙烯相的相容性不足。改性聚乙烯树脂可通过上述掺混进行接枝改性,也可使用市售的物质。
由于上述理由,改性聚乙烯也优选MFR (190℃下)为0.1~20g/10分钟的物质。
改性聚乙烯树脂的掺混比例为100质量份的总聚乙烯树脂中的30~90质量份左右。若低于30质量份,则与淀粉相具有亲和性的极性基不足,得到的成膜、成型物中产生宏观的相分离,其外观和物理强度显著降低。另一方面,超过90质量份虽然不会对得到的成膜、成型物造成任何不良影响,但市售的该树脂价格高而挤压制备成本,因此不优选。
对本发明中使用的具有多官能环氧基的化合物和/或具有碳化二亚胺的化合物进行说明。其中多官能是指具有多个环氧基的意思。该化合物本身具有的环氧基与改性聚乙烯的羧基、淀粉葡萄糖具有的羟基反应或形成氢键,使亲和力增大。
作为该化合物的优选的实例,可列举出苯乙烯-(甲基)丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物、甲基丙烯酸缩水甘油酯均聚物、乙烯-甲基丙烯酸缩水甘油酯共聚物。作为该化合物的其它的优选实例,可列举出环氧化大豆油或环氧化亚麻籽油等环氧化高级脂肪酸酯。通过ASTM-D 1652的方法测定的环氧值优选为0.5~2.5meq/g。更优选的环氧值为1.0~4.0meq/g。若环氧值低于0.5meq/g,则树脂组合物的相容性不充分,不仅外观降低,而且无法期待物理强度的提高。另一方面,若超过4.0meq/g,则分子间的交联反应过度地进行,导致在成型时产生大量凝胶异物等故障,因此不优选。苯乙烯-(甲基)丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物的实例例如记载在日本特开2005-154690号公报中,另外,市售有BASF Japan Ltd.的JONCRYL、东亚合成株式会社的ARUFON等。苯乙烯-(甲基)丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物可单独使用或将2种以上组合使用。
相对于100质量份的总聚乙烯树脂,具有多官能环氧基的化合物和/或具有碳化二亚胺的化合物的掺混比例为0.1~5质量份左右。若低于0.1质量份,则两相的结合或亲和性不充分,在得到的成膜、成型物中产生宏观的相分离,其外观和物理强度显著降低。另一方面,若超过5质量份,则在两相间产生过度的结合,树脂组合物的粘度显著增加。因此,在最差的情况下无法得到成膜、成型物。
对本发明中使用的抗氧化剂进行说明。抗氧化剂优选为了减少树脂组合物中掺混的淀粉在熔融混炼时或成型时产生的被称为“褐变”的氧化反应而配制。相对于100质量份的总聚乙烯树脂,优选的掺混比例为0.1~0.8质量份。若低于0.1质量份,则无法得到充分的褐变抑制效果,另一方面,若超过0.8质量份,则不必要地使制备成本上升,因此不优选。作为优选的抗氧化剂,可列举出苯酚系抗氧化剂、磷系抗氧化剂、生育酚、抗坏血酸。从这些的组中选择1种以上的单一物质或并用是有效的。最优选以苯酚系和磷系的并用来配制。
对本发明中使用的使聚乙烯的分子量降低的氧化分解剂进行说明。其例如由热塑性聚合物、直接生物降解性成分、切断脂肪酸等热塑性成分的碳-碳键的氧化成分、过渡金属成分和受阻酚构成的物质(日本特许第2961138号),由Novon Japan Inc.以“DEGRA-NOVON”(注册商标)的商品名发售。另外,也有以“P-Life”的商品名由P-Life Japan Inc.发售的制品。通过在聚乙烯中掺混使该聚乙烯的分子量降低的氧化分解剂,可利用紫外线或温度、氧、微生物等,使聚乙烯氧化降解而低分子化,最终成为水、二氧化碳和生物质。
相对于100质量份的总聚乙烯树脂,使聚乙烯的分子量降低的氧化分解剂的掺混量为0.1~3质量份左右,优选为0.2~2质量份左右。若低于0.1质量份,则作为氧化引发反应的自由基的产生不充分,将聚乙烯自然放置在室外的情况下的经时降解几乎不变,缺乏作为添加效果的吸引力。另一方面,若超过3质量份,则氧化反应快,从生物降解的观点出发是有效的,但得到的树脂组合物有在作为制品应维持形状的期限(例如,若为食品包装,则为有效期)前开始损坏或分解之虞。需说明的是,上述市售品均作为使氧化分解剂分散在聚乙烯树脂而得的母料市售。该母料也成为总聚乙烯树脂的一部分。
接下来,对本发明中可作为物理强度的强化成分而掺混的纤维素纤维进行说明。纤维素纳米纤维在物性上也是适宜的,但价格高。具体而言,最优选的是将天然纤维素微细化而得的粉末,即多用于食品、化妆品、树脂填充材料等并且廉价的纤维素粉。优选的纤维素纤维的掺混量相对于100质量份的淀粉为1~10重量部。若超过10质量份,则虽然在进行熔融混炼或成膜、成型的挤出机的前端具备被称为筛网的除去异物或降解物的膜,但过量的纤维素纤维会堵塞该筛网,从而也有难以长时间连续运转的情况,因而是不合适的。通过添加纤维素纤维,可提高本发明的膜或片材的强度,特别是可提高与成型方向一致的纵向的拉伸强度。
若是物性上需要,则在本发明的树脂组合物中也可掺混添加剂。例如,可列举出常用作膜的润滑剂的硬脂酸钙、油酸酰胺、芥酸酰胺等,常用作膜的防粘连剂的微粒状的合成沸石等,作为着色颜料的氧化钛粒子或碳黑等。
接下来,对本发明的树脂组合物的制备方法进行说明。
本发明的树脂组合物若将全部成分一次性混合,则不能均匀地分散,例如,即使制作膜,外观也会变差,因此制备工序也是重要的。
因此,首先,对淀粉预先加入所需量的多元醇系增塑剂、根据需要的水,在常温下均匀地搅拌混合而制成湿润粉状。若将多元醇系增塑剂或水在淀粉的1个位置一次性混合,则容易形成“团块”,因此优选以遍及淀粉整体的方式散布。在加入纤维素纤维的情况下,可在该工序中加入。混合机可利用亨舍尔混合机或制面机的混合装置、其它的连续混合装置等。该混合装置必须是容易上下左右搅拌的混合机构。
然后,在其中进一步加入聚乙烯树脂等其它的成分并搅拌,进行熔融混炼。抗氧化剂、具有多官能环氧基的化合物和/或具有碳化二亚胺的化合物、根据需要掺混的聚乙烯的氧化分解剂也可在此加入。聚乙烯树脂和改性聚乙烯树脂可以是粒料的状态,也可以是被称为毛屑(フラフ)的粉末状。
改性聚乙烯树脂除了使用预先制备的物质以外,也可通过在聚乙烯中加入不饱和二羧酸酐和/或不饱和羧酸与有机过氧化物等自由基引发剂并进行熔融混炼,从而在该熔融混炼工序内制备。
熔融混炼挤出机可以是单轴挤出机,但从混炼性的观点出发,优选双轴挤出机,另外,优选带有在混炼中可进行抽吸排气的通风机构的挤出机。混炼温度优选设为100℃~170℃,但若温度高,则淀粉有褐变的倾向,因此在能够混炼的范围内在低温下进行为宜。
虽然从挤出机挤出成绳状的树脂组合物可直接成型为膜等,但通常进行冷却并用造粒机制成粒料。冷却可以是水冷、空冷中的任一种,但在水冷的情况下,由于在粒料中吸收水分,从而在将其成型为膜等时起泡,所以需要在成型前将得到的粒料干燥,因而优选空冷。
得到的树脂组合物可成型加工为膜、片材、在纸基材上挤出层合而形成的层叠材料、吹塑瓶、注射成型物等。
虽然该树脂组合物含有大量的淀粉,但具有即使淋上雨水等也能够耐受的充分的耐水性。将本发明中得到的膜在90℃的热水中煮沸30分钟后,虽然取出的膜的干燥重量减少约3%,但未发现膜外观的变化。即,因含水或浸渍而脱落的淀粉极少,具有实用上没有问题的耐水性。
在制成膜或片材的情况下,可采用使用T型模等的流延法或吹塑(吹胀)法,或压延法。成膜温度为100~165℃是适当的。膜或片材的厚度无限制,例如为20~400μm左右,通常为30~100μm左右。膜或片材也可多层挤出,在这种情况下,也可在相邻的单面或两面上设置聚乙烯层。由于用本发明的树脂组合物形成的膜或片材稍有淀粉气味,所以可通过在表面设置聚乙烯层来遮蔽淀粉气味。另外,由于强度也不及聚乙烯膜,所以也可对其进行补充。另外,在进行层合的情况下,由于优选层叠面是平滑的,所以也可利用多层对其进行补充。聚乙烯层的厚度可以是总厚度的20~50%左右。这些聚乙烯层由在相邻层的树脂组合物中掺混的聚乙烯的氧化分解剂产生的自由基的链转移反应而最终被分解。
在纸基材上进行挤出层合的情况下的层合层的厚度为10~60μm左右,通常为15~50μm左右。纸基材的种类亦无限制,例如为瓦楞芯纸、纸容器用纸板、杂纸板等。
实施例
列举实施例来对本发明进行更具体的说明。
使用的材料如下所示。
聚乙烯树脂
LLDPE
“HARMOREX NH745N”Japan polyethylene Corporation制品,
密度=0.913g/cm3,MFR=8.0g/10分钟;
“EVOLUE SP1071C”Prime Polymer Co., Ltd.制品,
密度=0.910g/cm3,MFR=10.0g/10分钟;
Bio-LDPE
“BRASKEM SBC818”丰田通商株式会社制,
密度=0.918g/cm3,MFR=8.3g/10分钟;
淀粉(生)
玉米淀粉 Oji Cornstarch Co.,Ltd.制 商品名:生淀粉;
纤维素纤维
纤维素粉KC FLOCK 日本制纸株式会社制
商品名:W-50;
多元醇系增塑剂
甘油 和光纯药株式会社制
单甘油酯“RIKEMAL” RIKEN VITAMIN CO., LTD.制;
有机过氧化物
“KAYAHEXA AD” Kayaku Akzo Corporation制;
改性聚乙烯树脂
马来酸酐接枝聚乙烯
“MODIC M545” Mitsubishi Chemical Corporation制,
密度=0.900g/cm3,MFR=6.0g/10分钟;
gPE
在参考例中制备的马来酸酐接枝聚乙烯;
具有多官能环氧基的化合物
JC:苯乙烯-(甲基)丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物,BASF Japan Ltd.制;
抗氧化剂
Irg1010:苯酚系抗氧化剂“IRGANOX1010”,Ciba Specialty Chemicals制
Irg168:磷系抗氧化剂“IRGAFOS168”,BASF Japan Ltd.制;
氧化分解剂
“DEGRA-NOVON”Novon Japan Inc.制(在聚乙烯树脂中分散有5质量%的氧化分解剂的母料)
“P-LIFE GREEN20”P-Life Japan Inc.制(在聚乙烯树脂中分散有20质量%的氧化分解剂的母料)。
使用的搅拌机
亨舍尔混合机 NIPPON COKE & ENGINEERING CO., LTD.制FM20C型
容量20L。
使用的挤出机
日本制钢株式会社制带有通风机构的双轴挤出机
44mmφ L/D30。
使用的T型模成膜机
TANABE PLASTICS MACHINERY CO.,LTD.制,供料头式双层模具,
唇长度=370mm,唇间隔=2mm。
使用的吹塑成膜机
3层空冷式吹塑成膜机,其包含:
直径=300mmφ的圆形模具,和
具备直径=55mmφ、L/D=25的螺杆的第1挤出机,
具备直径=65mmφ、L/D=28的螺杆的第2挤出机,
具备直径=55mmφ、L/D=25的螺杆的第3挤出机。
使用的挤出层合机
包含唇面长度=2000mm的T型模和具备直径=120mmφ、L/D=32的螺杆的挤出机的层合机。
树脂组合物的制作
将规定量的生淀粉放入亨舍尔混合机的槽内,边搅拌边滴加散布规定量的甘油或单甘油酯,进一步搅拌5分钟以上得到湿润粉末物。然后,再次边搅拌边加入规定量的聚乙烯树脂、改性聚乙烯树脂、苯乙烯-(甲基)丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物、抗氧化剂和氧化分解剂并搅拌10分钟,得到湿润粉与粒料混合的状态的表1的各树脂组合物。
需说明的是,在表1中100质量份的总聚乙烯树脂为聚乙烯树脂、改性聚乙烯树脂和氧化分解剂的母料的总量。另外,表1的多元醇系增塑剂的列中,其添加量表示为相对于100质量份的总聚乙烯树脂的值,并且( )内表示相对于100质量份的淀粉的值。
参考例:马来酸酐接枝聚乙烯的制备
将由100质量份的Bio-LDPE、1质量份的马来酸酐、0.03质量份的KAYAHEXA AD和0.47质量份的溶剂甲醇调制的稀溶液放入挤出机(上述日本制钢株式会社制带有通风机构的双轴挤出机),通过熔融混炼,制作改性聚乙烯树脂。关于熔融混炼,使通风运转,从筒上游部分起依次在110℃、120℃、130℃、140℃的设定温度下进行。从KAYAHEXA AD的减半分解温度和接枝效率出发,改性温度设定为140℃。使通风运转的原因在于,未反应的马来酸酐残留时会阻碍相容化,因此将其除去。
表1
※ 质量份的值是相对于100质量份的总聚乙烯树脂的值。但是,在质量份中( )内记载的值是相对于100质量份的淀粉的值
※“拉伸强度”和“伸长率”的纵向是与膜的成型方向一致的方向,横向是与成型方向垂直的方向。
实施例1~7
将表1所示的总聚乙烯树脂、淀粉、多元醇系增塑剂、具有多官能环氧基的化合物和抗氧化剂进行亨舍尔混合而得的树脂组合物放入挤出机,边使通风运转边在140℃下熔融混炼,以约5分钟的停留时间进行挤出,在室温~30℃下进行空冷而得到淀粉掺混聚乙烯树脂组合物的粒料。然后,将得到的各粒料用上述T型模成膜机成膜,制作流延膜。此时,T型模成膜机从筒上游部起依次设定为100℃、130℃、150℃、155℃、165℃,模具温度设为165℃。
实施例8
使用上述吹塑成膜机,在3层的挤出机中投入与表1的实施例3相同的淀粉掺混聚乙烯树脂组合物,在从模具的熔融挤出温度为155℃、吹塑比=2.7、成膜速度=23m/分钟下制作总厚度为70μm的单层吹塑膜。
实施例9
在上述挤出层合机中投入与表1的实施例3相同的淀粉掺混聚乙烯树脂组合物,在作为基材的单位面积重量为50g/m2的漂白牛皮纸上在熔融挤出温度160℃下以厚度为25μm进行层叠。
实施例10
在实施例3中不使用MODIC M545,在作为主聚乙烯树脂的EVOLUE SP1071C中掺混溶解于甲醇中的马来酸酐和KAYAHEXA AD,在熔融混炼时同时制作改性聚乙烯树脂,将得到的淀粉掺混聚乙烯树脂组合物的粒料用上述T型模成膜机成膜,制作流延膜。此时,T型模成膜机从筒上游部起依次设定为100℃、130℃、150℃、155℃、165℃,模具温度设为165℃。
实施例11
将表1的实施例3的组成中的甘油减量至75%,且剩余的25%设为水,将得到的淀粉掺混聚乙烯树脂组合物的粒料用上述T型模成膜机成膜,制作流延膜。此时,T型模成膜机从筒上游部起依次设定为100℃、130℃、150℃、155℃、165℃,模具温度设为165℃。
实施例1~8、10和11的评价方法
依据JIS K-6760,在试样宽度为15mm、拉伸强度为200mm/min、卡盘间距为100mm下测定得到的各膜的拉伸强度。
另外,纵向、横向的伸长率也依据JIS K-6760进行测定。
关于生物降解性评价,将预先测定了干燥重量的流延膜埋藏于25℃的活性污泥中静置。在180日后取出,进行清洗和干燥,测定其重量,以静置前后的重量减少率(%)作为指标。
评价结果
实施例1~8、10和11
实施例1~8、10和11中的粒料没有褐变而为淡黄色。各流延膜或吹塑膜也为淡黄色,淀粉的颗粒无法被目视确认,而是均匀混合,表面也光滑。将各流延膜或吹塑膜的厚度、拉伸强度、伸长率、生物降解性示出于表1中。
尝试制作比较例1~3的样品的粒料,但熔融状态下的张力不充分,难以造粒。查明了无论是缺少构成本发明的树脂组合物的改性聚乙烯、多元醇系增塑剂、多官能环氧化合物中的哪一种,都不能形成所期望的树脂组合物。
实施例9
在漂白牛皮纸上挤出层合而得的实施例的层叠体,作为常用的纸容器,在外观和强度物性上是可以实用的水平。
产业上的可利用性
使用本发明的树脂组合物的包装材料的制品由于生物降解性良好,且不会产生环境污染的问题,所以可代替目前使用的聚乙烯等各种包装材料。
Claims (12)
1.淀粉掺混聚乙烯树脂组合物,其是将如下混合物熔融混炼,并在最终阶段将水分减压脱水而得到,所述混合物中,相对于100质量份的总聚乙烯树脂,包括120质量份以下且10质量份以上的淀粉、30~90质量份的在总聚乙烯树脂内导入有羧基的改性聚乙烯树脂、0.1~5质量份的具有多官能环氧基的化合物和/或具有碳化二亚胺的化合物、相对于100质量份的淀粉为10~60质量份的多元醇系增塑剂、相对于100质量份的淀粉为0~30质量份的水。
2.根据权利要求1所述的淀粉掺混聚乙烯树脂组合物,其中还掺混有相对于100质量份的总聚乙烯树脂为0.1~0.8质量份的抗氧化剂。
3.根据权利要求1或2所述的淀粉掺混聚乙烯树脂组合物,其中还掺混有相对于100质量份的总聚乙烯树脂为0.1~3质量份的使聚乙烯树脂的分子量降低的氧化分解剂。
4.根据权利要求1~3中任一项所述的淀粉掺混聚乙烯树脂组合物,其中还掺混有相对于100质量份的淀粉为1~10质量份的纤维素纤维。
5.根据权利要求1~4中任一项所述的淀粉掺混聚乙烯树脂组合物,其中,聚乙烯树脂是由天然来源的原料得到的。
6.膜或片材,其由根据权利要求1~5中任一项所述的树脂组合物形成。
7.多层膜或多层片材,其是在权利要求6的膜或片材的单面或两面层叠聚乙烯树脂层而得。
8.层叠体,其是将权利要求1~5中任一项所述的树脂组合物在纸基材上熔融挤出层合而得。
9.吹塑瓶,其由权利要求1~5中任一项所述的树脂组合物形成。
10.注射成型物,其由根据权利要求1~5中任一项所述的树脂组合物形成。
11.根据权利要求1所述的淀粉掺混聚乙烯树脂组合物的制备方法,其中,在淀粉中加入多元醇系增塑剂或多元醇系增塑剂和水并均匀地搅拌混合,在该混合物中加入聚乙烯树脂、改性聚乙烯树脂和具有多官能环氧基的化合物并均匀地搅拌混合。
12.根据权利要求11所述的淀粉掺混聚乙烯树脂组合物的制备方法,其中,改性聚乙烯树脂是就地在聚乙烯中加入不饱和二羧酸酐和/或不饱和羧酸和自由基引发剂并熔融混炼而制备的。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019142870 | 2019-08-02 | ||
JP2019-142870 | 2019-08-02 | ||
JP2020-099062 | 2020-06-08 | ||
JP2020099062A JP6830302B1 (ja) | 2019-08-02 | 2020-06-08 | 澱粉配合ポリエチレン樹脂組成物およびそれを用いた包装材料 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112300477A true CN112300477A (zh) | 2021-02-02 |
Family
ID=74483645
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010760529.9A Pending CN112300477A (zh) | 2019-08-02 | 2020-07-31 | 淀粉掺混聚乙烯树脂组合物和使用其的包装材料 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112300477A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112793274A (zh) * | 2021-02-04 | 2021-05-14 | 台州市创嘉新材料有限公司 | 一种防静电可降解薄膜及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255744A (ja) * | 2004-03-10 | 2005-09-22 | Agri Future Joetsu Co Ltd | 生分解性樹脂組成物、その製造方法、その成形品及びこの成形品の成形方法 |
JP2008024764A (ja) * | 2006-07-19 | 2008-02-07 | Showa Highpolymer Co Ltd | 生分解性樹脂組成物および生分解性フィルム |
CN103906805A (zh) * | 2011-11-15 | 2014-07-02 | 昭和电工株式会社 | 生物降解性树脂组合物和生物降解性膜 |
JP2018053165A (ja) * | 2016-09-30 | 2018-04-05 | 三国紙工株式会社 | 脂肪族ポリエステル樹脂組成物およびそれを用いた包装材料 |
JP2018188574A (ja) * | 2017-05-10 | 2018-11-29 | 三国紙工株式会社 | 脂肪族ポリエステル樹脂組成物およびそれを用いた包装材料 |
-
2020
- 2020-07-31 CN CN202010760529.9A patent/CN112300477A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255744A (ja) * | 2004-03-10 | 2005-09-22 | Agri Future Joetsu Co Ltd | 生分解性樹脂組成物、その製造方法、その成形品及びこの成形品の成形方法 |
JP2008024764A (ja) * | 2006-07-19 | 2008-02-07 | Showa Highpolymer Co Ltd | 生分解性樹脂組成物および生分解性フィルム |
CN103906805A (zh) * | 2011-11-15 | 2014-07-02 | 昭和电工株式会社 | 生物降解性树脂组合物和生物降解性膜 |
JP2018053165A (ja) * | 2016-09-30 | 2018-04-05 | 三国紙工株式会社 | 脂肪族ポリエステル樹脂組成物およびそれを用いた包装材料 |
JP2018188574A (ja) * | 2017-05-10 | 2018-11-29 | 三国紙工株式会社 | 脂肪族ポリエステル樹脂組成物およびそれを用いた包装材料 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112793274A (zh) * | 2021-02-04 | 2021-05-14 | 台州市创嘉新材料有限公司 | 一种防静电可降解薄膜及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1490435B1 (en) | Lactic acid-based resin composition | |
JP5588867B2 (ja) | ポリエチレンとポリ(ヒドロキシカルボン酸)のブレンド | |
KR101525658B1 (ko) | 식품부산물인 소맥피 또는 대두피를 활용한 바이오 매스 필름용 조성물 및 이를 이용한 바이오매스 필름 | |
KR101436916B1 (ko) | 식물체 바이오매스를 이용한 친환경 사출 성형품 및 그 제조방법 | |
NL2017891B1 (en) | Biaxially stretched starch-based foil | |
US10457023B2 (en) | Bi-axially stretched article and silage film | |
KR101214983B1 (ko) | 바이오 플라스틱 및 이의 제조방법 | |
JP2003073539A (ja) | 高強度生分解性樹脂組成物及び成形品 | |
JP2017513974A (ja) | サイレージフイルム | |
KR101443020B1 (ko) | 바이오매스 필름용 조성물 및 이를 이용한 바이오매스 필름 | |
US8324320B2 (en) | Blends of polar low density ethylene copolymers and poly(hydroxy carboxylic acid)s | |
US20230014582A1 (en) | Biodegradable resin composition and method for producing same | |
JP2018188574A (ja) | 脂肪族ポリエステル樹脂組成物およびそれを用いた包装材料 | |
KR101287034B1 (ko) | 식물체 바이오매스를 이용한 친환경 바이오 베이스 펠릿 및 그 제조방법 | |
CN112300477A (zh) | 淀粉掺混聚乙烯树脂组合物和使用其的包装材料 | |
JP6830302B1 (ja) | 澱粉配合ポリエチレン樹脂組成物およびそれを用いた包装材料 | |
CN111923546B (zh) | 一种环保降解防水涂层包装纸及其制备方法 | |
JP5623479B2 (ja) | 樹脂組成物及びこれを用いたフィルム、積層体 | |
JP6102201B2 (ja) | 変性脂肪族ポリエステル共重合体およびその製造方法 | |
KR101327480B1 (ko) | 바이오 베이스 쓰레기 봉투 및 이의 제조방법 | |
EP2110406A1 (en) | Polyethylene and poly(hydroxy carboxylic acid) blends | |
KR101478999B1 (ko) | 바이오플라스틱 면상 발열체용 시트 및 이의 제조방법 | |
JP7246691B2 (ja) | 樹脂組成物 | |
KR101750624B1 (ko) | 가소화 바이오매스를 이용한 친환경 실리콘 원료 조성물, 및 이의 압출성형품 | |
KR102595757B1 (ko) | 물성이 향상된 수계 생분해성 조성물, 이를 포함하는 제품 및 수계 생분해성 제품의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210202 |
|
WD01 | Invention patent application deemed withdrawn after publication |