CN117916165A - Polypropylene packaging material - Google Patents
Polypropylene packaging material Download PDFInfo
- Publication number
- CN117916165A CN117916165A CN202280060977.5A CN202280060977A CN117916165A CN 117916165 A CN117916165 A CN 117916165A CN 202280060977 A CN202280060977 A CN 202280060977A CN 117916165 A CN117916165 A CN 117916165A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- layer
- ethylene
- packaging material
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 147
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 142
- -1 Polypropylene Polymers 0.000 title claims abstract description 137
- 239000005022 packaging material Substances 0.000 title claims abstract description 52
- 229920001971 elastomer Polymers 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000000806 elastomer Substances 0.000 claims abstract description 50
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 165
- 230000004888 barrier function Effects 0.000 claims description 26
- 230000003746 surface roughness Effects 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 18
- 239000002344 surface layer Substances 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 10
- 229920005673 polypropylene based resin Polymers 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 abstract description 20
- 239000000796 flavoring agent Substances 0.000 abstract description 17
- 235000019634 flavors Nutrition 0.000 abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 29
- 229910052760 oxygen Inorganic materials 0.000 description 29
- 239000001301 oxygen Substances 0.000 description 29
- 239000012790 adhesive layer Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 238000004898 kneading Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000003463 adsorbent Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 150000004291 polyenes Chemical class 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Chemical class 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-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
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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Landscapes
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Abstract
The present invention relates to a polypropylene packaging material comprising an ethylene-propylene block copolymer having a matrix of a resin containing polypropylene as a main component and a spindle-shaped polypropylene elastomer as a domain-structured phase-dispersed structure, which provides a packaging material having all of drop impact resistance, blocking resistance, sliding properties and flavor properties at low temperatures.
Description
Technical Field
The present invention relates to a polypropylene packaging material, and more particularly, to a polypropylene packaging material having drop impact resistance, blocking resistance, sliding properties, and flavor properties, which can be preferably used for food packaging, and a laminate having a surface layer comprising the packaging material.
Background
Packaging materials made of propylene polymers are widely used as packaging materials for accommodating various foods because they exhibit heat sealability and are excellent in heat resistance, hygienic properties and flavor. In recent years, from the viewpoints of weight reduction and economy, the packaging container has been made thinner, and in order to cope with use in cold regions and the like, drop impact resistance (impact resistance) at low temperatures has been demanded. Propylene block copolymers, which are polypropylene having such high drop impact resistance, are also referred to as impact polypropylene, are used for packaging materials.
In addition, as other properties required for the packaging material, blocking resistance is available. That is, although it is required that blocking does not easily occur when the films are bonded to each other, the film composed of the propylene block copolymer is required to be further modified because it is blended with a soft rubber component and thus lacks blocking resistance.
In order to improve such properties such as drop impact resistance and blocking resistance, for example, patent document 1 below proposes a propylene resin composition comprising a propylene block copolymer and an ethylene/α -olefin copolymer.
Patent document 2 below proposes a multilayer film which uses a polypropylene block copolymer and has a surface layer in which substantially spherical elastomer particles are dispersed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-161033
Patent document 2: japanese patent laid-open No. 2006-198977
Disclosure of Invention
Problems to be solved by the invention
In containers such as trays and cups, container molding, filling and sealing of contents, packaging, and the like are continuously performed while being conveyed by a conveyor line, and therefore, there is also a demand for a container having a conveying property, that is, a sliding property, which does not cause clogging of the container on a production line, and there is also a demand for a polypropylene packaging material having an excellent sliding property. In addition, it is also important in food applications, especially without compromising the flavor of the contents.
However, in the packaging materials using the propylene block copolymer described in patent documents 1 and 2, it is difficult to sufficiently satisfy all of the drop impact resistance, blocking resistance and slidability under low temperature conditions. In addition, it is difficult to provide a packaging material having both of these properties as well as appearance characteristics and flavor.
Accordingly, an object of the present invention is to provide a polypropylene-based packaging material having all of drop impact resistance, blocking resistance, sliding property, and flavor properties under low temperature conditions, and a laminate comprising the packaging material as a surface layer.
Technical proposal
According to the present invention, there is provided a polypropylene packaging material characterized by comprising an ethylene-propylene block copolymer having a phase-dispersed structure in which a polypropylene elastomer in the form of a spindle is a domain, wherein the ethylene-propylene block copolymer comprises a resin mainly composed of polypropylene as a matrix.
In the packaging material of the present invention, the following is preferable.
[1] The aspect ratio of the domains is in the range of 1.2 to 9.0.
[2] The domains have a short diameter in the range of 0.2 to 4.0 μm and a long diameter in the range of 0.5 to 5.0 μm.
[3] The polypropylene elastomer is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of the polypropylene-based resin.
[4] The polypropylene elastomer has a weight average molecular weight (Mw) of 50 to 100 tens of thousands and a number average molecular weight (Mn) of 1 to 30 tens of thousands.
[5] The polypropylene-based resin has a weight average molecular weight (Mw) of 30 to 80 tens of thousands and a number average molecular weight (Mn) of 1 to 30 tens of thousands.
[6] The polypropylene resin composition contains 1 to 30 parts by mass of the homopolypropylene per 100 parts by mass of the ethylene-propylene block copolymer.
[7] The surface roughness (Sa) is 0.15-1.0 mu m.
[8] Has any shape of sheet, film, tray, cup.
Further, according to the present invention, there is provided a laminate comprising a polypropylene layer as a surface layer, wherein the polypropylene layer is composed of an ethylene-propylene block copolymer as the polypropylene packaging material, and the polypropylene layer has a surface roughness Sa of 0.15 to 1.0 μm.
In the laminate of the present invention, the following is preferable.
[1] At least provided with: the polypropylene layer is provided as an inner layer and an outer layer, and has an oxygen-absorbing layer and a gas barrier layer as an intermediate layer.
[2] In the shape of a tray or cup.
Further, according to the present invention, there is provided a method for producing a laminate comprising a polypropylene layer as a surface layer, the polypropylene layer comprising an ethylene-propylene block copolymer, wherein a homopolypropylene as a viscosity adjuster is blended with the ethylene-propylene block copolymer, melt kneading is performed, the viscosity of MFR (230 ℃,2.16kg load) is adjusted to a range of 0.1 to 10g/10 minutes, and the melt resin after the viscosity adjustment is extruded, thereby forming a surface layer having a surface roughness of 0.15 to 1.0 μm.
In the method for producing a laminate of the present invention, the following is preferable.
[1] The homopolypropylene is blended in an amount of 1 to 30 parts by mass per 100 parts by mass of the ethylene-propylene block copolymer.
[2] The polypropylene elastomer is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of the ethylene-propylene block copolymer.
[3] The polypropylene elastomer has a weight average molecular weight (Mw) of 50 to 100 tens of thousands and a number average molecular weight (Mn) of 1 to 30 tens of thousands.
[4] The polypropylene-based resin has a weight average molecular weight (Mw) of 30 to 80 tens of thousands and a number average molecular weight (Mn) of 1 to 30 tens of thousands.
Effects of the invention
The packaging material of the present invention has a resin containing polypropylene as a main component as a matrix, and a spindle-shaped polypropylene-based elastomer is a domain-dispersed structure, and by controlling the shape and size of the spindle-shaped domain, excellent drop impact resistance and both sliding property and blocking resistance can be achieved.
In addition, the use of a specific polypropylene-based elastomer can exhibit excellent flavor.
Further, in the laminate of the present invention, by providing the polypropylene-based packaging material as a surface layer, the surface roughness (Sa) of the surface layer is 0.15 to 1.0 μm, and excellent drop impact resistance and both sliding property and blocking resistance can be achieved. In addition, in the laminate of the present invention, the propylene-based polymer having the molecular weight in the above range is also excellent in flavor.
In the method for producing a laminate of the present invention, the viscosity of the ethylene-propylene block copolymer can be adjusted to a viscosity suitable for molding by blending the homopolypropylene, and thus the moldability (workability) can be improved without impairing the drop impact resistance of the laminate.
Drawings
Fig. 1 is a diagram for explaining the shape of a domain in a packaging material of the present invention.
Detailed Description
(Polypropylene packaging Material)
As described above, the packaging material of the present invention is characterized by having a phase-dispersed structure in which a polypropylene-based elastomer in a spindle shape is a domain, and a resin mainly composed of polypropylene is used as a matrix.
In the present invention, the impact resistance against falling is further improved by dispersing the spindle-shaped domains composed of the polypropylene-based elastomer in the matrix composed of the resin containing polypropylene as a main component, and by controlling the dispersion particle diameter of the domains composed of the rubber component, not only the impact resistance against falling but also both the sliding property and the blocking resistance can be achieved.
That is, in the packaging material using the propylene block copolymer, in order to exhibit excellent drop impact resistance even at low temperatures, it is preferable that the content of the rubber component (polypropylene-based elastomer) is large and that the domains (dispersed particles) composed of the rubber component are finely dispersed not only from the viewpoint of drop impact resistance but also from the viewpoint of appearance characteristics. On the other hand, in order to improve the blocking resistance and the sliding property, it is preferable that the content of the rubber component is small and that the size of the dispersed particles composed of the rubber component is such that irregularities are formed on the surface.
In the present invention, from such a viewpoint, it has been found that a dispersion structure having a spindle-shaped domain composed of a polypropylene-based elastomer formed in a matrix composed of a resin mainly composed of polypropylene can achieve both excellent drop impact resistance and blocking resistance and sliding properties.
In the present invention, in order to exhibit excellent drop impact resistance due to the domains composed of the polypropylene-based elastomer, it is preferable that the spindle-shaped domains have an aspect ratio in the range of 1.2 to 9.0, 1.2 to 8.0, 1.9 to 8.0, and particularly 1.9 to 5.0. When the aspect ratio is large, the drop impact resistance is good, but the slidability tends to be poor. The domains preferably have a short diameter of 0.2 to 4.0. Mu.m, particularly preferably 0.2 to 2.0. Mu.m, and a long diameter of 0.5 to 5.0. Mu.m, particularly preferably 0.5 to 3.0. Mu.m. The method for measuring the short and long diameters of the domain will be described later.
The domain size of the equivalent circle is preferably in the range of 0.5 μm to 5.0. Mu.m, particularly preferably in the range of 0.5 μm to 1.0. Mu.m. When the domain size is too small, the surface irregularities are not formed, and when the domain size is too large, the irregularities are formed, and the slidability is good, but the drop impact resistance tends to be poor.
The shape and size of the domains are controlled by the molecular weight and composition of the polypropylene-based elastomer and the resin mainly comprising polypropylene as a matrix; the method for producing the resin such as kneading is determined.
In the packaging material of the present invention, the polypropylene-based elastomer is preferably contained in an amount of 1 to 30 parts by mass, particularly preferably 5.0 to 25 parts by mass, based on 100 parts by mass of the resin mainly composed of polypropylene. When the amount of the polypropylene-based elastomer is less than the above range, the drop impact resistance may not be sufficiently improved as compared with the case where the amount is within the above range, whereas when the amount is more than the above range, not only the blocking resistance and the sliding property are reduced but also the flavor is reduced, and the surface irregularities are also increased, and the appearance characteristics are deteriorated as compared with the case where the amount is within the above range.
[ Polypropylene-based resin ]
In the packaging material of the present invention, the polypropylene-based resin is a homo-polypropylene or a random polypropylene obtained by polymerizing a propylene-based monomer as a main component of the polypropylene.
The weight average molecular weight (Mw) of the polypropylene-based resin is preferably in the range of 30 to 80 tens of thousands, particularly preferably 30 to 60 tens of thousands, and the number average molecular weight (Mn) is preferably in the range of 1 to 30 tens of thousands, particularly preferably 5 to 20 tens of thousands. When the molecular weight of the resin containing polypropylene as a main component is smaller than the above-mentioned range, the drop impact resistance and the hygienic property may be reduced as compared with the case where the molecular weight of the resin containing polypropylene as a main component is within the above-mentioned range, and when the molecular weight of the resin containing polypropylene as a main component is larger than the above-mentioned range, the moldability may be reduced due to the abnormal resin pressure as compared with the case where the molecular weight is within the above-mentioned range.
Further, from the viewpoints of heat resistance and moldability, the meso pentad fraction (mesopentad fraction) ([ mmmm ]) of the resin containing polypropylene as a main component, which is an index of stereoregularity, is preferably in the range of 95 to 99.
[ Polypropylene elastomer ]
In the packaging material of the present invention, examples of the polypropylene-based elastomer constituting the spindle-shaped domain include propylene-ethylene-based elastomers. As the propylene-ethylene elastomer, a random copolymer of propylene and ethylene and a mass ratio of ethylene units to propylene units in the range of 15:85 to 50:50 are preferable. In addition, if necessary, an elastomer copolymerized with an α -olefin or the like may be used in order to improve compatibility and drop impact resistance.
The polypropylene elastomer preferably has a weight average molecular weight (Mw) of 50 to 100,000, preferably 65 to 100,000, more preferably 70 to 100,000, particularly preferably 70 to 90,000, and a number average molecular weight (Mn) of 1 to 30,000, preferably 2 to 20,000, particularly preferably 10 to 20,000. When the molecular weight is smaller than the above range, the domain shape becomes prismatic, the particle diameter is small, the surface roughness of the container becomes smooth, and the blocking resistance and sliding property may not be satisfied, as compared with the case where the molecular weight is within the above range, whereas when the molecular weight is larger than the above range, the domain shape becomes substantially spherical, the particle diameter is large, and the dispersion becomes sparse, and thus the drop impact resistance may be poor. Further, the flavor tends to be lowered.
Therefore, the mass ratio and the molecular weight of the ethylene unit and the propylene unit of the polypropylene elastomer are controlled; the molecular weight of the resin containing polypropylene as a main component can extend the domain of the polypropylene elastomer to a spindle shape having the above aspect ratio, and can improve the compatibility of both, and can achieve both the drop impact resistance and the blocking resistance and the sliding property by micro-dispersion of the above size.
The polypropylene-based elastomer of the present invention is assumed to have a spindle shape as follows. In a container formed by secondary processing of a film, sheet, cup, tray, or the like, the resin is stretched in the direction of extrusion (molding). Therefore, the domain shape in the resin also follows, and the front end in the extrusion direction becomes thinner, and becomes a spindle shape as shown in fig. 1. But can be considered as: the domain shape varies depending on the molecular weight of the matrix and domain, the molecular weight of the domain itself, and the compatibility of the matrix with the domain. For example, when the molecular weight of the domain is low and the compatibility of the domain with the matrix is high, the domain becomes prismatic, and the surface roughness is low and smooth, so that the slidability is presumed to be poor. On the other hand, when the molecular weight of the domain is high and the compatibility between the domain and the matrix is low, the domain becomes substantially spherical, and it is presumed that the drop impact resistance is poor. The compatibility is affected by the composition of the polypropylene-based elastomer, the addition of the ethylene- α -olefin copolymer, and the like.
[ Ethylene-propylene Block copolymer ]
The ethylene-propylene block copolymer having a phase dispersion structure in which a polypropylene-based resin is the main component and a spindle-shaped polypropylene-based elastomer is the domain has an MFR (230 ℃ C., 2.16kg load) of 0.1 to 10g/10 min, particularly 0.2 to 5g/10 min, and is preferable in terms of molding.
The resin containing polypropylene as a main component, the raw material of the polypropylene-based elastomer, or a part of the raw material may be derived not only from petroleum but also from a material obtained by chemical recycling from waste plastics by a monomer technique such as vaporization or oiling, or an ethylene-propylene block copolymer produced from a biomass material derived from plants or the like. Biomass can be measured by measuring radioactive carbon concentration or the like. In addition, when producing a resin or polypropylene elastomer containing polypropylene as a main component, it is desirable to produce the resin or polypropylene elastomer in a catalyst system in which SVHC substances such as phthalate compounds, which are highly interesting substances (Substance of Very High Concern) in the regulations of chemical registration, evaluation, approval and restriction (Registration, evaluation, authorization and Restriction of Chemicals (REACH)) in europe, are not used in view of reducing environmental load in the polymerization stage from the starting materials.
[ Other Components ]
In addition to the above-mentioned ethylene-propylene block copolymer, it is preferable to blend homo-polypropylene as a viscosity modifier in the packaging material of the present invention.
That is, in a resin composition comprising polypropylene as a main component and a polypropylene-based elastomer, there is a tendency that the polypropylene-based elastomer has a high molecular weight and tends to have a high viscosity and poor moldability in order to achieve both the drop impact resistance and the sliding property, and therefore, the extrusion properties of the molten resin can be improved by blending the homopolypropylene, and the moldability (workability) can be improved without impairing the drop impact resistance of the packaging material.
From the viewpoint of viscosity adjustment, the MFR (230 ℃ C., 2.16kg load) of the homopolypropylene is preferably in the range of 0.5 to 20g/10 min.
The homopolypropylene is preferably added in an amount of 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the ethylene-propylene block copolymer.
In order to further improve the drop impact resistance, the packaging material of the present invention may contain a rubber component such as an ethylene- α -olefin copolymer, an elastomer, or a plastomer, such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, or linear low-density polyethylene. In order to improve slidability, a lubricant such as calcium stearate and an anti-blocking agent such as silica particles may be added; the rubber component is used in combination with the above-mentioned rubber component. If necessary, a known additive such as an antioxidant may be blended in a small amount.
In recent years, due to the increase in environmental problems, it is also important to blend, as a part of the plastic removal, a material obtained by subjecting waste plastics to chemical recycling by a monomer technique such as gasification or oiling, or a biomass material derived from plants.
(Preparation of Polypropylene-based packaging Material)
The packaging material of the present invention can be produced by a known method such as a method of melt extrusion or a method of melt kneading the pellets by a kneader.
In the present invention, in order to bring the domains of the polypropylene-based elastomer into a spindle-shaped dispersion state of the above-described size and aspect ratio, it is necessary to perform melt kneading, and it is necessary to appropriately adjust kneading conditions according to the viscosity of the resin to be used, and the like.
The temperature conditions in the melt kneading are not particularly limited, and are preferably in the range of 170 to 270 ℃. At temperatures lower than the above range, kneading may not be performed efficiently, and at temperatures higher than the above range, deterioration of the resin may occur.
The packaging material of the present invention may be produced by molding a resin obtained by melt kneading into a desired shape such as a film, sheet, or tube by a known production method such as extrusion molding or injection molding, or may be produced by thermoforming the obtained sheet into a shape such as a cup or tray.
The surface roughness (Sa) of the packaging material of the present invention is preferably in the range of 0.15 to 1.0. Mu.m. Thus, excellent blocking resistance and slidability can be exhibited without impairing the appearance characteristics. The surface roughness (Sa) is the arithmetic average height of the lines: the Ra is an extension of the parameters of the surface, and is an average of absolute values of differences between the heights of the points with respect to the average surface of the surface, which is specified by ISO 25178.
(Laminate)
In the present invention, the molded article may be a single layer of the resin composition comprising the ethylene-propylene block copolymer, or may be a laminate having a multilayer structure including other layers.
In the case of producing such a multilayer structure, the polypropylene layer composed of the above-mentioned ethylene-propylene block copolymer resin composition is preferably a surface layer (outermost layer or innermost layer), and particularly preferably an outermost layer. That is, the surface layer of the laminate has a dispersion structure in which spindle-shaped domains composed of a polypropylene-based elastomer are dispersed in a matrix composed of a resin containing polypropylene as a main component, whereby the drop impact resistance is further improved, excellent drop impact resistance can be exhibited even at low temperatures, and excellent slidability and blocking resistance can be exhibited by the surface roughness falling within the above-described range.
[ Multilayer Structure ]
In the laminate of the present invention, it is important that the polypropylene layer is a surface layer (outermost layer or innermost layer), and at least the outermost layer, preferably both the outermost layer and the innermost layer are used. The top layer may have various multilayer structures as long as it is composed of a polypropylene layer, and it is preferable to have a gas barrier layer, an oxygen absorbing layer, an adhesive layer, a recovery layer (REGRIND LAYER), an adsorbent-containing layer, and other conventionally known layers as intermediate layers.
The laminate of the present invention is not limited to this, and the following layer structure is exemplified.
Examples are shown: polypropylene layer (outermost layer)/adhesive layer/gas barrier layer/adhesive layer/polypropylene skin layer (innermost layer), polypropylene layer (outermost layer)/adhesive layer/gas barrier layer/adhesive layer/oxygen absorbing layer/polypropylene layer (innermost layer), polypropylene layer (outermost layer)/adhesive layer/gas barrier layer/adhesive layer/polypropylene layer (innermost layer), polypropylene layer (outermost layer)/recovery layer/adhesive layer/gas barrier layer/adhesive layer/oxygen absorbing layer/polypropylene layer (innermost layer), polypropylene layer (outermost layer)/recovery layer/adhesive layer/gas barrier layer/adhesive layer/polypropylene skin layer (outermost layer), polypropylene layer (outermost layer)/recovery layer/adhesive layer/gas barrier layer/oxygen absorbing layer/gas barrier layer/adhesive layer/adsorbent-containing layer/polypropylene layer (innermost layer) with a gas barrier resin as a matrix resin, and the like.
The innermost layer may be modified to be the polypropylene layer, or may be a layer made of an easily releasable resin other than the polypropylene layer.
In the laminate of the present invention, the layer thicknesses of the respective layers vary depending on the form of the laminate, the production method, etc., and it cannot be specified in a general manner that, when the laminate is a film or sheet, the thickness of the polypropylene skin layer (outermost layer) is preferably in the range of 5 to 800 μm, particularly preferably 5 to 500 μm, and the thickness of the polypropylene skin layer (innermost layer) is preferably in the range of 5 to 800 μm, particularly preferably 5 to 500 μm. In the case where the thickness of the other layers is within the above-described thickness range of the outermost layer and the innermost layer, the gas barrier layer (total thickness in the case of forming a plurality of layers) is preferably within a range of 5 to 500 μm, particularly preferably within a range of 5 to 200 μm, and the oxygen-absorbing layer is preferably within a range of 5 to 500 μm, particularly preferably within a range of 5 to 200 μm. In the case of providing the recovery layer, it is preferably formed within a range of 50 to 1000. Mu.m, particularly preferably 50 to 800. Mu.m. In the case of providing the adsorbent-containing layer, the adsorbent-containing layer is preferably formed within a range of 5 to 500. Mu.m, particularly preferably within a range of 5 to 300. Mu.m.
In the case where the laminate of the present invention is a multilayer container (such as a cup or a tray) formed by thermoforming by pressure molding, the thickness of the polypropylene skin layer (outermost layer) in the main body portion which is the thinnest wall portion of the multilayer container is preferably 1 to 160 μm, particularly preferably 1 to 100 μm, and the thickness of the polypropylene skin layer (innermost layer) is preferably 1 to 160 μm, particularly preferably 1 to 100 μm. In the case where the thickness of the other layers is within the above-described thickness range of the outermost layer and the innermost layer, the gas barrier layer (total thickness in the case of forming a plurality of layers) is preferably 1 to 100 μm, particularly preferably 1 to 40 μm, and the oxygen absorbing layer is preferably 1 to 100 μm, particularly preferably 1 to 40 μm. In the case of providing the recovery layer, it is preferably formed within a range of 10 to 200. Mu.m, particularly preferably 10 to 160. Mu.m. In the case of providing the adsorbent-containing layer, the adsorbent-containing layer is preferably formed within a range of 1 to 100. Mu.m, particularly preferably 1 to 60. Mu.m.
This can fully exhibit the effects of each layer such as gas barrier properties, oxygen absorbability, and flavor without impairing the drop impact resistance and moldability.
[ Gas barrier layer ]
In the laminate of the present invention, the gas barrier layer may be formed of a conventionally known barrier resin, and particularly preferably an ethylene-vinyl alcohol copolymer. In terms of the gas barrier properties, the ethylene-vinyl alcohol copolymer is preferably a saponified copolymer of: in the present invention, it is particularly preferable to blend an ethylene-vinyl alcohol copolymer having an ethylene content of 20 to 35mol% with an ethylene-vinyl alcohol copolymer having an ethylene content of 36 to 50mol% in a blend ratio (mass ratio) of 90:10 to 50:50, particularly 80:20 to 60:40, to obtain a copolymer saponified product obtained by saponifying an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60mol%, particularly 25 to 50mol% to a saponification degree of 96% or more, particularly 99mol% or more. Thus, the gas barrier layer maintains excellent gas barrier properties and improves moldability, and thus can be molded into a laminate having no appearance unevenness.
The ethylene-vinyl alcohol copolymer should have a molecular weight sufficient to form a film, desirably, an intrinsic viscosity of 0.01dl/g or more, particularly 0.05dl/g or more, as measured at 30℃in a mixed solvent having a [ phenol/water ] mass ratio of 85/15.
Examples of the gas barrier resin other than the ethylene-vinyl alcohol copolymer include: polyamide such as nylon 6, nylon 6-6, nylon 6/6-6 copolymer, poly (m-xylylenediamine adipamide) (MXD 6), nylon 6-10, nylon 11, nylon 12, nylon 13, and the like. In these polyamides, the number of amide groups per 100 carbon atoms is preferably in the range of 5 to 50, particularly preferably 6 to 20. These polyamides should also have a molecular weight sufficient to form a film, for example, it is desirable that the relative viscosity measured in concentrated sulfuric acid (concentration 1.0 g/dl) is 1.1 or more, particularly 1.5 or more, at 30 ℃.
The polyamide may be blended with an ethylene-vinyl alcohol copolymer, and the blending ratio (mass ratio) of the ethylene-vinyl alcohol copolymer to the polyamide is preferably 50:50 to 99:1.
In addition, as described later when using polyamide as the oxygen absorbing resin composition matrix resin, the terminal amino concentration of 40eq/10 6 g or more of polyamide resin is not absorbed oxygen oxidative degradation, so is ideal.
[ Oxygen-absorbing layer ]
In the laminate of the present invention, the oxygen-absorbing layer may be composed of a resin composition containing, as a matrix resin, the above-mentioned propylene-based polymer constituting the polypropylene layer, a known propylene-based polymer (hereinafter, these may be collectively referred to simply as "propylene-based polymer"), a gas barrier resin, a recycled resin, or the like, and the above-mentioned matrix resin contains an inorganic oxygen absorber or an organic oxygen absorber composed of (i) an oxidizing organic component and (ii) a transition metal catalyst (oxidation catalyst).
(Inorganic oxygen absorbent)
Examples of the inorganic oxygen absorber include: iron powder, titanium oxide, cerium oxide, ferrous salts, dithionite, sulfite, halogenated metals, zeolite, and the like. Iron powder and halogenated metals are particularly desirable. As the iron powder, known iron powder such as reduced iron powder, atomized iron powder, electrolytic iron powder, carbonyl iron powder and the like can be used. Among them, reduced iron powder having a large specific surface area and porous is preferably used, and rotary kiln reduced iron powder (rotary reduced iron powder) is particularly preferably used. The reduced iron powder of the rotary kiln has high purity and large specific surface area, and thus has excellent oxygen absorption performance. One kind of these iron powders may be used, or two or more kinds may be used in combination. The content of the iron powder in the oxygen absorber is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the oxygen absorber.
Examples of the metal halide include: halides of alkali metals, alkaline earth metals, copper, zinc, iron, and the like. Specifically, there may be mentioned: sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, magnesium chloride, barium chloride, and the like. Among them, sodium chloride is preferred. One kind of these halogenated metals may be used, or two or more kinds may be used in combination.
The metal halide is preferably blended in an amount of 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the iron powder as a main agent of the oxygen absorber. By blending 0.1 part by mass or more of the halogenated metal with respect to 100 parts by mass of the iron powder, a sufficient oxygen absorbing performance can be obtained. Further, by blending 10 parts by mass or less of the halogenated metal with respect to 100 parts by mass of the iron powder, it is possible to suppress a decrease in oxygen absorption performance due to a decrease in the iron powder content, and also it is possible to suppress an appearance defect due to exudation of the halogenated metal and adhesion of the halogenated metal to the content.
The oxygen absorber of the present invention may contain an alkaline substance in addition to the iron powder and the halogenated metal. By including the alkaline substance, the amount of hydrogen generated by the reaction of iron and water can be reduced. Examples of the alkaline substance include: magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and the like. Among them, calcium hydroxide and calcium oxide as a dehydrate of calcium hydroxide are preferable. One kind of these basic substances may be used, or two or more kinds may be used in combination.
(Organic oxygen absorbent)
(I) Oxidative organic component
Examples of the oxidizing organic component include polymers containing ethylenically unsaturated groups. The polymer has a carbon-carbon double bond, and the double bond portion, particularly, the α methylene group adjacent to the double bond portion is easily oxidized by oxygen, thereby capturing oxygen.
The polymer having an ethylenically unsaturated group may be a homopolymer of a polyene derived from a polyene as a monomer, or may be an oxidative polymer such as a random copolymer or a block copolymer obtained by combining two or more of the above-mentioned polyenes with other monomers.
Among the polymers derived from polyenes, polybutadiene (BR), polyisoprene (IR), natural rubber, nitrile rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber, ethylene-propylene-diene rubber (EPDM) and the like are preferable, but of course not limited thereto.
In addition to the above-mentioned polymer containing an ethylenically unsaturated group, a polymer which itself is easily oxidized, for example, polypropylene, an ethylene/propylene copolymer, or poly (m-xylylene adipamide) having a terminal amino group concentration of less than 40eq/106g, etc., may be used as the oxidizing organic component.
From the viewpoint of moldability and the like, the viscosity of the above-mentioned oxidative polymer or its copolymer at 40℃is preferably in the range of 1 to 200 Pa.s.
These polyene polymers are preferably acid-modified polyene polymers having carboxylic acid groups, carboxylic acid anhydride groups and hydroxyl groups introduced.
The oxidizing organic component composed of these oxidizing polymers or copolymers thereof is preferably contained in the oxygen-absorbing resin at a ratio of 0.01 to 10 mass%.
(Ii) Transition metal catalyst
The transition metal catalyst is preferably a group VIII metal of the periodic table such as iron, cobalt, and nickel, and may be a group I metal such as copper and silver; group IV metals such as tin, titanium, zirconium, etc.; a group V metal such as vanadium; group VI metals such as chromium; group VII metals such as manganese, and the like.
The transition metal catalyst is usually used in the form of an inorganic salt, an organic salt or a complex salt of the above transition metal having a low valence. The inorganic salts include: halides such as chlorides, oxygen-containing salts of sulfur such as sulfates, oxygen-containing salts of nitrogen such as nitrates, oxygen-containing salts of phosphorus such as phosphates, silicates, and the like. The organic salts include: carboxylates, sulfonates, phosphonates, and the like. Further, as the complex of the transition metal, a complex with β -diketone or β -ketoester is exemplified.
The transition metal catalyst is preferably contained in the oxygen-absorbing resin in a concentration of 100 to 3000ppm in terms of the concentration of transition metal atoms (mass concentration basis).
[ Adhesive layer ]
In the laminate of the present invention, an adhesive layer may be formed between the layers as needed, and in particular, in the case where the gas barrier layer is made of an ethylene-vinyl alcohol copolymer, the gas barrier layer and the polypropylene layer forming the inner and outer layers have poor adhesion, so that the adhesive layer is preferably interposed.
As the adhesive resin used for the adhesive layer, the following thermoplastic resins can be mentioned: thermoplastic resins containing carbonyl (-CO-) groups based on carboxylic acids, carboxylic anhydrides, carboxylic acid salts, carboxylic acid amides, carboxylic esters, etc., in the main chain or side chains in a concentration of 1 to 700 milliequivalents (meq)/100 g of resin, in particular 10 to 500 (meq)/100 g of resin.
Preferable examples of the adhesive resin include: ethylene-acrylic acid copolymer, ionomer olefin copolymer, maleic anhydride grafted polyethylene, maleic anhydride modified polypropylene, maleic anhydride grafted polypropylene, acrylic acid grafted polyolefin, ethylene-vinyl acetate copolymer, a blend of ethylene-vinyl alcohol copolymer and maleic anhydride modified olefin resin, and the like, and maleic anhydride modified polypropylene or maleic anhydride grafted polypropylene can be particularly preferably used. The adhesive resin may be used alone or in combination of two or more, or may be blended with a polyolefin resin.
[ Adsorbent-containing layer ]
In the laminate of the present invention, the adsorbent-containing layer formed as needed is preferably located on the inner layer side of the oxygen absorbing layer, whereby transfer of byproducts generated by the oxygen absorbing reaction into the container can be suppressed, and the flavor of the content can be improved.
The adsorbent is preferably blended with the propylene polymer and the reclaimed resin.
As the adsorbent, a porous inorganic material containing silicate as a main component, for example, zeolite or activated clay powder obtained by acid treatment of smectite clay mineral such as montmorillonite, is preferable, and particularly, as a high silica zeolite (silica/alumina ratio of 100 or more) of Na-type ZSM5 zeolite, it is preferable that the adsorbent has excellent function of capturing odor peculiar to plastics and capturing the oxidative decomposition product.
Such an adsorbent is generally preferably incorporated in the adsorbent-containing layer in an amount of 0.5 to 10 mass%.
[ Easily peelable layer ]
In the laminate of the present invention, for example, when the laminate of the present invention is a flanged tray or cup obtained by thermoforming a multi-layered sheet, the innermost layer of the laminate is preferably an easily peelable layer (easily openable layer). That is, in such a tray or cup, the lid is significantly improved in unsealability by forming the upper surface of the flange portion to which the lid member is joined as an easily peelable layer.
As such an easily releasable layer, for example, it is preferable that the easily releasable layer is formed of a blend of a propylene polymer and a vinyl polymer, in which at least the joint surface with the flange portion is a cap made of a propylene polymer or a vinyl polymer.
The propylene-based polymer includes, in addition to homopolypropylene: random copolymers of propylene with ethylene or other alpha-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like. The vinyl polymer may be: homopolymers of ethylene such as Low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), and medium/high density polyethylene (MDPE, HDPE); or a copolymer or ionomer of ethylene with other α -olefin such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc., vinyl monomer such as (meth) acrylic acid, ethyl (meth) acrylate, methyl (meth) acrylate, vinyl acetate, styrene, etc.
(Method for producing laminate)
In the method for producing a laminate of the present invention, a homo-polypropylene as a viscosity modifier is blended with the ethylene-propylene block copolymer, and the melt is kneaded and a molten resin having a viscosity of MFR (230 ℃ C., 2.16kg load) adjusted to a range of 0.2 to 5g/10 minutes is extruded, whereby a laminate having a surface layer with a surface roughness (Sa) of 0.15 to 1.0. Mu.m, particularly preferably 0.15 to 0.80. Mu.m, is formed.
As described above, by blending the homopolypropylene in an amount of 1 to 40 parts by mass, particularly 1 to 30 parts by mass, per 100 parts by mass of the ethylene-propylene block copolymer, the viscosity of the resin composition can be adjusted to the above range without impairing the excellent properties of the laminate of the present invention such as drop impact resistance, blocking resistance and slidability, and the surface roughness (Sa) of the polypropylene layer can be adjusted to the above range. That is, when the MFR of the resin composition is lower than the above range, a desired laminate cannot be obtained due to an abnormal resin pressure, or fluctuation due to unstable flow may occur, and the surface roughness (Sa) may not be adjusted to the above range. When the MFR is higher than the above range, the smoothness of the surface layer tends to be high, and it is difficult to adjust the surface roughness (Sa) to the above range.
The melt-kneading of the ethylene-propylene block copolymer and the homo-polypropylene can be carried out by a known method such as a method of dry-mixing the pellets thereof by a mixer or the like and then melt-extruding the pellets, or a method of melt-kneading the pellets thereof by a kneader.
In the present invention, in order to set the structural domain of the polypropylene-based elastomer in a spindle-shaped dispersion state of the above-described size, it is necessary to perform melt kneading, and it is necessary to appropriately adjust kneading conditions according to the viscosity of the resin to be used, and the like.
The temperature conditions in the melt kneading are not particularly limited, and are preferably in the range of 170 to 270 ℃. At temperatures lower than the above range, kneading may not be performed efficiently, and at temperatures higher than the above range, deterioration of the resin may occur.
The laminate of the present invention can be produced by a conventionally known method in addition to using the melt resin (blend) having the MFR adjusted as described above, but is not limited thereto, and can be formed into a multilayer film, a multilayer sheet, a multilayer tube or the like by laminating with other layers by a coextrusion method, a coinjection method, an extrusion lamination method, or by preparing a single-layer film or sheet from the blend by extrusion molding in advance and laminating with other layers by a dry lamination method. Further, the multilayer sheet can be molded into a shape such as a cup or a tray by thermoforming.
In the method for producing a laminate of the present invention, it is preferable that the intermediate layer constituting the laminate is formed of a resin having a heat shrinkage similar to that of the resin composition (blend) constituting the polypropylene layer. For example, by using a resin composition (blend) constituting the polypropylene layer as a matrix for the oxygen-absorbing resin layer, curling offset due to the difference in shrinkage of the molded laminate can be suppressed, and occurrence of molding failure can be suppressed.
Further, according to the production method of the present invention, since a laminate having a polypropylene surface layer with a surface roughness (Sa) in the range of 0.15 to 1.0 μm can be molded, the slidability is improved, and even when the molding step, the filling/sealing step, the packaging step, and the like are continuously performed on a conveyor line, the container is not clogged, and excellent productivity can be exhibited.
The other layers are not limited to this, and examples thereof are as follows: conventionally known layers used in polypropylene-based multilayer packaging materials, such as a gas barrier layer, an oxygen absorbing layer, a recovery layer, an easily releasable layer, and an adhesive layer.
In the case of a multilayer structure, it is desirable that the resin or resin composition constituting the other layer has a heat shrinkage rate similar to that of the ethylene-propylene block copolymer, whereby curling offset due to the difference in shrinkage rate of the laminated sheet can be suppressed, and occurrence of molding failure can be suppressed.
Examples
The present invention is further illustrated by experimental examples, but the present invention is not limited to these examples.
Experimental examples 1 to 5
Using a 6-7-layer multilayer sheet molding machine, each resin was melt kneaded by a single screw extruder, extruded from a T die into a sheet form at a T die temperature of 230 ℃, brought into contact with a cooling roll, and cured and wound, thereby molding a 500 μm thick multilayer sheet. The layer structure is from the outside the outermost PP layer/recovery layer/adhesive layer/barrier layer/adhesive layer/oxygen scavenger layer/inner PP layer/easy-to-peel adhesive layer.
The outermost PP layer and the inner PP layer were used with particles of an ethylene-propylene block copolymer composed of a polypropylene-based resin and a polypropylene-based elastomer having the compositions and molecular weights shown in table 1, and a white coloring resin. The following materials were used in the recovery layer: to 100 parts by mass of the waste material obtained by crushing a part of the multilayer sheet, the decorative part, and the sheet skeleton generated in the test, 44 parts by mass of the ethylene-propylene block copolymer shown in table 1 was blended, and a compatibilizer and a white coloring resin were added. The adhesive layer used was a maleic anhydride-modified polypropylene, and the oxygen scavenger layer used was a resin composition obtained by kneading 29 parts by mass of an iron-based oxygen absorber (a mixture of 100 parts by mass of reduced iron powder, 2 parts by mass of sodium chloride, and 1 part by mass of calcium hydroxide) with 71 parts by mass of atactic polypropylene having an mfr of 0.6g/10 min. The easily releasable adhesive layer is a resin obtained by dry-blending polypropylene and polyethylene.
Further, the resulting multilayered sheet was heated to 145 ℃, and plunger-assisted vacuum-pressure molding was performed, whereby a flanged multilayered tray was molded.
The container is sized to have a flange outside diameter: long axis: 155mm short axis: 120mm; caliber: long axis: 135mm short axis: 100mm; bottom outside diameter: long axis: 115mm x minor axis: 90mm; the height is 35mm.
Experimental example 6
A multilayer tray was molded in the same manner as in Experimental example 1, except that 17.7 parts by mass of homopolypropylene having MFR of 2.0g/10 min (230 ℃ C., 2.16kg load) was dry-blended with 100 parts by mass of the resins of the outermost PP layer and the inner PP layer.
The various measurement methods are described below.
< Structural analysis of ethylene-propylene Block copolymer >
In the ethylene-propylene block copolymers used in examples 1 to 5, the blending ratio and molecular weight of the polypropylene-based resin (PP component) and the polypropylene-based elastomer (rubber component) were determined by 13 C-NMR measurement (japan electronics system) and GPC measurement (Agilent system). As a pretreatment of the measurement sample, the resin was dissolved by refluxing with xylene, cooled, and then subjected to solid-liquid separation. The xylene-soluble fraction was reprecipitated with toluene, and the precipitate was filtered and dried, and then the mass was measured as the amount of the rubber component. The xylene insoluble fraction was redissolved and reprecipitated with methanol, and the resin after filtration and drying was used as the PP component. In experimental example 6, the homopolypropylene was dry blended, and thus, the calculated value was obtained.
(1) Dispersion state (domain shape and size)
By transmission electron microscopy: TEM (manufactured by Hitachi Co., ltd.) was used to observe a section cut parallel to the drawing direction at the time of sheet production at the bottom of the obtained multilayer tray. As a pretreatment, samples cut from the multilayer tray were adhered to a low Wen Zhi table, cut into a flat surface by a low-temperature system (manufactured by Leica) using an ultra-thin microtome (manufactured by Leica) to which a diamond knife was attached, and vapor-stained with a metal oxide to prepare an ultra-thin slice.
The whole domain of the polypropylene elastomer of the outermost PP layer of the multilayer tray was measured from the obtained TEM photograph (20 μm. Times.20 μm square) by image analysis type particle size distribution software (Mac-View, mountech Co.), the respective short and long diameters were measured, and the domain sizes of the aspect ratio and equivalent circle were calculated.
(2) Surface roughness Sa (unit μm)
From the bottom of the resulting multi-layered tray, 10mm x 10mm pieces of samples were cut. The shape of the outer surface of the container was measured using a noncontact surface shape measuring machine (zygo). In the measurement and image analysis, metroPro (Ver.9.1.4.64-bit) was used as an application program. A range of 282 μm by 212 μm was measured, and the raw data obtained was cut off to a wavelength of 1.326 μm or less for denoising. The average value was calculated from n=5.
(3) Slidability (Unit N)
The sliding properties of the obtained multilayer tray were measured using a friction measuring machine (eastern ocean precision mechanism), and the drag resistance value was obtained using the load applied to the load cell at the time of measurement as a kinetic friction force. The measurement was performed at a speed of 100mm/min in a state where a multi-layered tray was placed on an SUS plate and a weight of 600g was loaded in an environment of 50% RH at 23 ℃. The average value was calculated from n=5. The evaluation criteria are as follows.
And (2) the following steps: less than 2.5N.
Delta: 2.5N or more and less than 3.0N.
X: 3.0N or more.
(4) Drop impact resistance
200G of distilled water was added to the multilayer tray obtained, heat-sealed with a lidstock, boiled and sterilized at 95℃for 30 minutes, and then stored at 5℃for 24 hours. After storage, the tray was allowed to fall from a height of 150cm at 5℃to determine the falling strength of the multi-layered tray. The number of N is 20. The evaluation criteria are as follows.
And (2) the following steps: the number of cracks was 3 or less.
Delta: the number of cracks is less than 10.
X: more than 10 cracks.
(5) Flavor of flavor
200G of distilled water was added to the multilayer tray obtained, heat-sealed with a lid, sterilized by boiling at 95℃for 30 minutes, and stored at room temperature for 24 hours. After storage, sensory evaluation by the four-point method was performed by 10 panelists to determine average score. The evaluation criteria are as follows. 0 is odorless and 4 is a level at which a very good taste is perceived.
And (2) the following steps: less than 2.5.
Delta: 2.5 or more and less than 3.5.
X: 3.5 or more.
Based on the obtained results, the polypropylene-based elastomers of examples 1 and 6 were spindle-shaped, and were excellent in both slidability and drop impact resistance, and particularly, the resin of example 6 was low in viscosity and excellent in film forming property. The drop impact resistance of experimental example 2 was slightly lower, and it was considered that the impact was less affected by the polypropylene-based elastomer. The drop impact resistance of examples 3 and 5 was slightly lower, and it was considered that the impact was affected by the shape and particle size of the polypropylene elastomer. Further, as a result of poor flavor, it is presumed that the effect of the molecular weight of the polypropylene elastomer is exerted. Experimental example 4 shows that the drop impact resistance is good but the sliding property is poor. This is presumably because the polypropylene elastomer has a prismatic shape and a high aspect ratio, and thus the surface roughness is smooth and the contact area is large.
TABLE 1
Industrial applicability
The packaging material and the laminate having the layer comprising the packaging material as a surface layer of the present invention are excellent in drop impact resistance, blocking resistance and flavor, and have excellent sliding properties, so that they are excellent in transportation on a production line. Therefore, the packaging material and the laminate can be preferably used for packaging materials for accommodating foods produced in large quantities, and particularly preferably used for containers such as cooked rice and the like for which flavor is important. Further, the packaging material and the laminate are composed of a propylene-based polymer having excellent heat resistance, and therefore, can be preferably used as a packaging material such as a pouch (pouch) with retort sterilization or the like.
Claims (17)
1.A polypropylene packaging material characterized by comprising an ethylene-propylene block copolymer,
The ethylene-propylene block copolymer has a phase dispersion structure in which a polypropylene-based elastomer in a spindle shape is a domain, and a resin mainly composed of polypropylene is used as a matrix.
2. The polypropylene-based packaging material according to claim 1, wherein,
The aspect ratio of the domains is in the range of 1.2 to 9.0.
3. The polypropylene-based packaging material according to claim 1 or 2, wherein,
The domains have a short diameter in the range of 0.2 to 4.0 μm and a long diameter in the range of 0.5 to 5.0 μm.
4. The polypropylene-based packaging material according to any one of claim 1 to 3, wherein,
The polypropylene elastomer is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of the polypropylene-based resin.
5. The polypropylene-based packaging material according to any one of claims 1 to 4, wherein,
The weight average molecular weight Mw of the polypropylene elastomer is 50-100 ten thousand, and the number average molecular weight Mn is 1-30 ten thousand.
6. The polypropylene-based packaging material according to any one of claims 1 to 5, wherein,
The weight average molecular weight Mw of the resin with polypropylene as the main component is 30-80 ten thousand, and the number average molecular weight Mn is 1-30 ten thousand.
7. The polypropylene-based packaging material according to any one of claims 1 to 6, wherein,
The polypropylene resin composition contains 1 to 30 parts by mass of the homopolypropylene per 100 parts by mass of the ethylene-propylene block copolymer.
8. The polypropylene-based packaging material according to any one of claims 1 to 7, wherein,
The surface roughness Sa is 0.15-1.0 mu m.
9. The polypropylene-based packaging material according to any one of claims 1 to 7, wherein,
Has any form of sheet, film, tray and cup.
10. A laminate comprising a surface layer of a polypropylene layer composed of the ethylene-propylene block copolymer as the polypropylene packaging material according to any one of claims 1 to 7,
The surface roughness Sa of the polypropylene layer is 0.15-1.0 mu m.
11. The laminate according to claim 10, wherein,
At least provided with: the polypropylene layer is provided as an inner layer and an outer layer, and has an oxygen-absorbing layer and a gas barrier layer as an intermediate layer.
12. The laminate according to claim 10 or 11, wherein,
In the shape of a tray or cup.
13. A method for producing a laminate, characterized by comprising a polypropylene layer as a surface layer, wherein the polypropylene layer is composed of an ethylene-propylene block copolymer,
The melt-kneaded ethylene-propylene block copolymer is blended with a homopolypropylene as a viscosity adjuster, and the melt-kneaded ethylene-propylene block copolymer is melt-kneaded to adjust the MFR viscosity at 230℃under a load of 2.16kg to a range of 0.1 to 10g/10 minutes, and the melt-kneaded resin after the viscosity adjustment is extruded to form a surface layer having a surface roughness of 0.15 μm to 1.0. Mu.m.
14. The method for producing a laminate according to claim 13, wherein,
The homopolypropylene is blended in an amount of 1 to 30 parts by mass per 100 parts by mass of the ethylene-propylene block copolymer.
15. The method for producing a laminate according to claim 13 or 14, wherein,
The polypropylene elastomer is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of the ethylene-propylene block copolymer.
16. The method for producing a laminate according to any one of claims 13 to 15, wherein,
The weight average molecular weight Mw of the polypropylene elastomer is 50-100 ten thousand, and the number average molecular weight Mn is 1-30 ten thousand.
17. The method for producing a laminate according to any one of claims 13 to 16, wherein,
The weight average molecular weight Mw of the resin with polypropylene as the main component is 30-80 ten thousand, and the number average molecular weight Mn is 1-30 ten thousand.
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| JP2021-148931 | 2021-09-13 | ||
| JP2021148931A JP2023041517A (en) | 2021-09-13 | 2021-09-13 | Laminate having polypropylene layer |
| JP2021-148930 | 2021-09-13 | ||
| PCT/JP2022/034180 WO2023038148A1 (en) | 2021-09-13 | 2022-09-13 | Polypropylene-based packaging material |
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