JPWO2020175699A1 - Foam sheet and adhesive tape - Google Patents
Foam sheet and adhesive tape Download PDFInfo
- Publication number
- JPWO2020175699A1 JPWO2020175699A1 JP2020516486A JP2020516486A JPWO2020175699A1 JP WO2020175699 A1 JPWO2020175699 A1 JP WO2020175699A1 JP 2020516486 A JP2020516486 A JP 2020516486A JP 2020516486 A JP2020516486 A JP 2020516486A JP WO2020175699 A1 JPWO2020175699 A1 JP WO2020175699A1
- Authority
- JP
- Japan
- Prior art keywords
- foam sheet
- resin
- mass
- bio
- polyolefin 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
- 239000006260 foam Substances 0.000 title claims abstract description 148
- 239000002390 adhesive tape Substances 0.000 title claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 49
- 238000005187 foaming Methods 0.000 claims abstract description 34
- 229920013716 polyethylene resin Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 229920005989 resin Polymers 0.000 description 42
- 239000011347 resin Substances 0.000 description 42
- 238000004132 cross linking Methods 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 17
- 239000004088 foaming agent Substances 0.000 description 16
- -1 polyethylene Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 230000005865 ionizing radiation Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000019399 azodicarbonamide Nutrition 0.000 description 4
- 229920006025 bioresin Polymers 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical group 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KIDLQRSWTHZIAF-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylhexane Chemical compound CC(C)CC(C)(C)CC(OOC(C)(C)C)OOC(C)(C)C KIDLQRSWTHZIAF-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001659 Renewable Polyethylene Polymers 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FEQIZAAVROKFGB-UHFFFAOYSA-L [Cl-].[Cl-].[Zr+3].[SiH3]C(C(C(C)(C)C)(C)[N-]C1C=CC=C1)C Chemical compound [Cl-].[Cl-].[Zr+3].[SiH3]C(C(C(C)(C)C)(C)[N-]C1C=CC=C1)C FEQIZAAVROKFGB-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 239000011359 shock absorbing material Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Adhesive Tapes (AREA)
Abstract
発泡体シートは、バイオ系ポリオレフィン樹脂（Ａ）を含む発泡体シートであり、発泡体シートにおけるバイオ率が４０質量％以上、厚みが０．０５〜１．５ｍｍ、発泡倍率が１．５〜２０倍である。The foam sheet is a foam sheet containing the bio-based polyolefin resin (A), and the bio ratio in the foam sheet is 40% by mass or more, the thickness is 0.05 to 1.5 mm, and the foaming ratio is 1.5 to 20. It is double.
Description
本発明は、バイオ系ポリオレフィン樹脂を含有する発泡体シート、及び発泡体シートを備える粘着テープに関する。 The present invention relates to a foam sheet containing a bio-based polyolefin resin and an adhesive tape provided with the foam sheet.
樹脂を発泡させることにより得られる発泡体シートは、例えば、建築、エレクトロニクス及び車輌等の各種分野において広く利用されている。発泡体シートに用いられる樹脂としては、石油由来の樹脂が一般的であるが、その製造過程や廃棄過程等において多くの二酸化炭素を排出するため、環境への負荷が問題になっている。そこで、このような問題を解決するために、天然由来の樹脂を用いる検討がなされている。 Foam sheets obtained by foaming a resin are widely used in various fields such as construction, electronics, and vehicles. As the resin used for the foam sheet, a resin derived from petroleum is generally used, but since a large amount of carbon dioxide is emitted in the manufacturing process and the disposal process thereof, the burden on the environment has become a problem. Therefore, in order to solve such a problem, studies have been made on the use of naturally derived resins.
例えば特許文献１には、天然由来エチレンに由来する成分を含むポリエチレン（バイオ系ポリエチレン）を用い、ＡＳＴＭ Ｄ６８６６（２００４年制定）によって測定されるバイオマス度が２５％以上である発泡体が記載されている。また、特許文献２には、天然由来エチレン成分を含む低密度ポリエチレン系樹脂を２０質量％以上１００質量％以下含み、バイオマス度が２５％以上であり、ゲル分率が５％以上６０％以下である発泡体が記載されている。 For example, Patent Document 1 describes a foam having a biomass degree of 25% or more as measured by ASTM D6866 (established in 2004) using polyethylene (biopolyethylene) containing a component derived from naturally-derived ethylene. There is. Further, Patent Document 2 contains a low-density polyethylene resin containing a naturally-derived ethylene component in an amount of 20% by mass or more and 100% by mass or less, a biomass degree of 25% or more, and a gel fraction of 5% or more and 60% or less. A foam is described.
近年、電子機器は、小型化及び各種部品の高機能化が進んでおり、それに伴い、電子機器用途に用いる発泡体シートは、薄くしつつ、耐衝撃性、柔軟性などの各種性能を高めることが求められている。一方で、環境負荷を低減させることも求められつつあり、電子機器用途に用いられる発泡体シートでも、バイオ樹脂を用いて環境負荷を低くしつつ、耐衝撃性等の各種性能を良好にすることが求められている。 In recent years, electronic devices have become smaller and more sophisticated in various parts, and along with this, the foam sheets used for electronic devices have been made thinner while improving various performances such as impact resistance and flexibility. Is required. On the other hand, it is also required to reduce the environmental load, and even in the foam sheet used for electronic equipment applications, various performances such as impact resistance should be improved while reducing the environmental load by using bioresin. Is required.
本発明は、バイオ樹脂を含有し、環境負荷を低くした発泡体シートにおいて、厚みを薄くしても、耐衝撃性等の各種性能が良好な発泡体シートを提供することを課題とする。 An object of the present invention is to provide a foam sheet containing a bioresin and having a low environmental load, which has good various performances such as impact resistance even if the thickness is reduced.
本発明者らは、鋭意研究を重ねた結果、発泡体シート中のバイオ率を４０質量％以上としたうえで、厚みを０．０５〜１．５ｍｍ、発泡倍率を１．５〜２０倍に調整することにより、上記課題を解決できることを見出し、以下の本発明を完成させた。 As a result of diligent research, the present inventors have set the biorate in the foam sheet to 40% by mass or more, the thickness to 0.05 to 1.5 mm, and the foaming ratio to 1.5 to 20 times. We have found that the above problems can be solved by making adjustments, and have completed the following invention.
すなわち、本発明は、下記［１］〜［１２］に関する。
［１］バイオ系ポリオレフィン樹脂（Ａ）を含む発泡体シートであり、発泡体シートにおけるバイオ率が４０質量％以上、厚みが０．０５〜１．５ｍｍ、発泡倍率が１．５〜２０倍である発泡体シート。
［２］前記バイオ系ポリオレフィン樹脂（Ａ）以外のポリオレフィン樹脂（Ｂ）をさらに含有する、上記［１］に記載の発泡体シート。
［３］前記ポリオレフィン樹脂（Ｂ）が、ポリエチレン樹脂、及びエチレン−酢酸ビニル共重合体から選ばれる１種である、上記［２］に記載の発泡体シート。
［４］前記ポリエチレン樹脂が、メタロセン化合物の重合触媒で重合されたポリエチレン樹脂を含む上記［２］又は［３］に記載の発泡体シート。
［５］前記ポリエチレン樹脂のメルトインデックス（ＭＩ）が、１．０〜１２ｇ／１０分以上である上記［３］又は［４］に記載の発泡体シート。
［６］バイオ系ポリオレフィン樹脂（Ａ）のメルトインデックスが１．５〜１２ｇ／１０分以上である上記［１］〜［５］のいずれか１項に記載の発泡体シート。
［７］ＭＤ方向及びＴＤ方向の平均気泡径はいずれもが、２０〜３５０μｍ以下である上記［１］〜［６］のいずれか1項に記載の発泡体シート。
［８］ＺＤ方向における平均気泡径に対する、ＭＤ及びＴＤ方向における平均気泡径の比が１．８〜９である上記［１］〜［７］のいずれか１項に記載の発泡体シート。
［９］前記発泡体シート中の最大気泡径が５００μｍ以下である、上記［１］〜［８］のいずれか１項に記載の発泡体シート。
［１０］２５％圧縮強度が２００ｋＰａ以下である、上記［１］〜［９］のいずれか１項に記載の発泡体シート。
［１１］電子機器用である上記［１］〜［１０］のいずれか１項に記載の発泡体シート。
［１２］上記［１］〜［１１］のいずれかに記載の発泡体シートと、前記発泡体シートの片面又は両面に設けられる粘着材とを備える、粘着テープ。That is, the present invention relates to the following [1] to [12].
[1] A foam sheet containing the bio-based polyolefin resin (A), which has a bio ratio of 40% by mass or more, a thickness of 0.05 to 1.5 mm, and a foaming ratio of 1.5 to 20 times. A foam sheet.
[2] The foam sheet according to the above [1], which further contains a polyolefin resin (B) other than the bio-based polyolefin resin (A).
[3] The foam sheet according to the above [2], wherein the polyolefin resin (B) is one selected from a polyethylene resin and an ethylene-vinyl acetate copolymer.
[4] The foam sheet according to the above [2] or [3], wherein the polyethylene resin contains a polyethylene resin polymerized with a polymerization catalyst of a metallocene compound.
[5] The foam sheet according to the above [3] or [4], wherein the melt index (MI) of the polyethylene resin is 1.0 to 12 g / 10 minutes or more.
[6] The foam sheet according to any one of the above [1] to [5], wherein the bio-based polyolefin resin (A) has a melt index of 1.5 to 12 g / 10 minutes or more.
[7] The foam sheet according to any one of the above [1] to [6], wherein the average bubble diameter in both the MD direction and the TD direction is 20 to 350 μm or less.
[8] The foam sheet according to any one of the above [1] to [7], wherein the ratio of the average cell diameter in the MD and TD directions to the average cell diameter in the ZD direction is 1.8 to 9.
[9] The foam sheet according to any one of [1] to [8] above, wherein the maximum bubble diameter in the foam sheet is 500 μm or less.
[10] The foam sheet according to any one of [1] to [9] above, wherein the 25% compressive strength is 200 kPa or less.
[11] The foam sheet according to any one of the above [1] to [10] for electronic devices.
[12] An adhesive tape comprising the foam sheet according to any one of the above [1] to [11] and an adhesive material provided on one side or both sides of the foam sheet.
本発明によれば、バイオ樹脂を含有し、環境負荷を低くした発泡体シートにおいて、厚みを薄くしたような場合であっても、耐衝撃性等の各種性能を良好にできる。 According to the present invention, in a foam sheet containing a bioresin and having a low environmental load, various performances such as impact resistance can be improved even when the thickness is reduced.
［発泡体シート］
本発明の発泡体シートは、少なくともバイオ系ポリオレフィン樹脂（Ａ）を含む発泡体であり、発泡体シートにおけるバイオ率が４０質量％以上、厚みが０．０５〜１．５ｍｍ、発泡倍率が１．５〜２０倍であるものである。
本発明においては、発泡体シートのバイオ率を４０質量％以上にすると共に発泡倍率を特定の範囲に調整することにより、環境負荷が低く、かつ厚みが薄い発泡体シートにおいても、気泡割合を一定以上としつつ最大気泡径を小さくすることが可能になる。本発明では、その結果、薄い発泡体シートであっても、耐衝撃性等の発泡体シートに必要な各種性能を付与することが可能になる。
以下、本発明を詳細に説明する。[Effervescent sheet]
The foam sheet of the present invention is a foam containing at least a bio-based polyolefin resin (A), and the bio ratio in the foam sheet is 40% by mass or more, the thickness is 0.05 to 1.5 mm, and the foaming ratio is 1. It is 5 to 20 times.
In the present invention, by setting the bio-ratio of the foam sheet to 40% by mass or more and adjusting the foaming ratio to a specific range, the bubble ratio is constant even in the foam sheet having a low environmental load and a thin thickness. While doing the above, it is possible to reduce the maximum bubble diameter. As a result, in the present invention, even a thin foam sheet can be imparted with various performances required for the foam sheet such as impact resistance.
Hereinafter, the present invention will be described in detail.
〔バイオ系ポリオレフィン樹脂（Ａ）〕
本発明の発泡体シートは、少なくともバイオ系ポリオレフィン樹脂（Ａ）を含む発泡体である。本発明に用いるバイオ系ポリオレフィン樹脂（Ａ）は、天然由来成分を含むポリオレフィン樹脂であり、具体的には、天然由来エチレンを構成単位として含むポリエチレン系樹脂が挙げられる。より具体的には、天然由来エチレンの単独重合体、天然由来エチレンと、石油由来オレフィンとの共重合体が挙げられ、これらの中でも、入手容易性等の観点から、天然由来エチレンと石油由来オレフィンとの共重合体が好ましい。石油由来オレフィンとしては、エチレン、プロピレン、１−ブテン、及び１−ヘキセンから選ばれる１種以上であることが好ましく、中でもエチレンが好ましい。また、バイオ系ポリオレフィン樹脂（Ａ）は、天然由来エチレンを構成単位として含むエチレン−酢酸ビニル共重合体でもよい。
バイオ系ポリオレフィン樹脂（Ａ）は、１種単独で使用してもよいし、２種以上を併用してもよい。[Bio-based polyolefin resin (A)]
The foam sheet of the present invention is a foam containing at least a bio-based polyolefin resin (A). The bio-based polyolefin resin (A) used in the present invention is a polyolefin resin containing a naturally-derived component, and specific examples thereof include a polyethylene-based resin containing naturally-derived ethylene as a constituent unit. More specifically, a homopolymer of naturally-derived ethylene and a copolymer of naturally-derived ethylene and a petroleum-derived olefin can be mentioned. Among these, from the viewpoint of availability and the like, naturally-derived ethylene and petroleum-derived olefin can be mentioned. A copolymer with is preferred. The petroleum-derived olefin is preferably one or more selected from ethylene, propylene, 1-butene, and 1-hexene, and ethylene is particularly preferable. Further, the bio-based polyolefin resin (A) may be an ethylene-vinyl acetate copolymer containing naturally-derived ethylene as a constituent unit.
The bio-based polyolefin resin (A) may be used alone or in combination of two or more.
バイオ系ポリオレフィン樹脂（Ａ）において、天然由来エチレンに由来する構成単位の含有量は、４０〜９８質量％であることが好ましく、７５〜９７質量％がより好ましく、８５〜９６質量％がさらに好ましい。すなわち、バイオ系ポリオレフィン樹脂（Ａ）のバイオ率は、４０〜９８質量％であることが好ましく、７５〜９７質量％がより好ましく、８５〜９６質量％がさらに好ましい。
天然由来エチレンに由来する構成単位の含有量を上記下限値以上とすると、環境負荷が低くなり、例えば二酸化炭素の削減効果なども高められる。一方、天然由来エチレンに由来する構成単位の含有量を上限値以下とすると、後述する発泡性樹脂シートを得る際に結晶化速度が小さくなるため、幅方向に均一な厚みの発泡性樹脂シートを得やすくなり、発泡体シートが薄くなっても各種物性が良好となりやすい。In the bio-based polyolefin resin (A), the content of the structural unit derived from naturally-derived ethylene is preferably 40 to 98% by mass, more preferably 75 to 97% by mass, still more preferably 85 to 96% by mass. .. That is, the bio-ratio of the bio-based polyolefin resin (A) is preferably 40 to 98% by mass, more preferably 75 to 97% by mass, and even more preferably 85 to 96% by mass.
When the content of the constituent unit derived from naturally-derived ethylene is set to the above lower limit value or more, the environmental load is reduced and, for example, the effect of reducing carbon dioxide is enhanced. On the other hand, when the content of the structural unit derived from naturally-derived ethylene is set to the upper limit or less, the crystallization rate becomes low when the foamable resin sheet described later is obtained, so that a foamable resin sheet having a uniform thickness in the width direction can be obtained. It is easy to obtain, and even if the foam sheet becomes thin, various physical properties tend to be good.
バイオ系ポリオレフィン樹脂（Ａ）のメルトインデックス（ＭＩ）は、好ましくは１．５〜１２ｇ／１０分以上である。メルトインデックスが前記範囲であると、樹脂が柔軟でありながらも発泡が適切に進行する。そのため、発泡体シートの柔軟性が向上すると共に、最大気泡径を小さくし、発泡体シートの耐衝撃性、柔軟性などを向上させることができる。これらの観点から、バイオ系ポリオレフィン樹脂（Ａ）のメルトインデックスは、２．０〜１０ｇ／１０分がより好ましく、２．２〜７．０ｇ／１０分が更に好ましく、２．４〜５．０ｇ／１０分がより更に好ましい。
なお、本明細書においてメルトインデックスは、ＡＳＴＭ Ｄ１２３８に従い、１９０℃、２．１６ｋｇ荷重の条件で測定するとよい。
バイオ系ポリオレフィン樹脂（Ａ）の密度は、例えば０．９００〜０．９４０ｇ／ｃｍ３であり、好ましくは０．９１０〜０．９３０ｇ／ｃｍ３である。バイオ系ポリオレフィン樹脂（Ａ）は、密度が上記範囲内であると、耐衝撃性、柔軟性などの発泡体として要求される各種性能を良好にしやすくなる。The melt index (MI) of the bio-based polyolefin resin (A) is preferably 1.5 to 12 g / 10 minutes or more. When the melt index is in the above range, foaming proceeds appropriately while the resin is flexible. Therefore, the flexibility of the foam sheet can be improved, the maximum bubble diameter can be reduced, and the impact resistance and flexibility of the foam sheet can be improved. From these viewpoints, the melt index of the bio-based polyolefin resin (A) is more preferably 2.0 to 10 g / 10 minutes, further preferably 2.2 to 7.0 g / 10 minutes, and 2.4 to 5.0 g. / 10 minutes is even more preferable.
In this specification, the melt index may be measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM D1238.
Density of bio-based polyolefin resin (A) is, for example, 0.900~0.940g / cm 3, preferably 0.910~0.930g / cm 3. When the density of the bio-based polyolefin resin (A) is within the above range, it becomes easy to improve various performances required as a foam such as impact resistance and flexibility.
バイオ系ポリオレフィン樹脂（Ａ）は、天然由来エチレン及び必要に応じて石油由来オレフィンなどを用いて公知の方法により製造することができる。バイオ系ポリオレフィン樹脂（Ａ）の原料である天然由来エチレンは、例えば、天然原料であるサトウキビから得られる糖質を、発酵剤である酵母サッカロマイセス・セレビシエを用いて発酵させ、エタノールを生成し、そのエタノールをγ−アルミナ等の触媒を用いて３００℃を超える温度の接触反応によってエチレンに転化することで得られる。 The bio-based polyolefin resin (A) can be produced by a known method using naturally-derived ethylene and, if necessary, petroleum-derived olefins. Naturally-derived ethylene, which is the raw material of the bio-polyolefin resin (A), is produced, for example, by fermenting sugar obtained from sugar cane, which is a natural raw material, with yeast Saccharomyces cerevisiae, which is a fermenting agent, to produce ethanol. It is obtained by converting ethanol to ethylene by a contact reaction at a temperature exceeding 300 ° C. using a catalyst such as γ-alumina.
〔バイオ系ポリオレフィン樹脂（Ａ）以外の樹脂〕
発泡体シートは、バイオ系ポリオレフィン樹脂（Ａ）以外の樹脂を含んでもよく、例えば、ポリオレフィン樹脂（Ｂ）を含むことが好ましい。ポリオレフィン樹脂（Ｂ）は、一般的に石油由来ポリオレフィンから製造された石油系ポリオレフィン樹脂である。ポリオレフィン樹脂（Ｂ）を使用することで、発泡体シートを薄くすることが可能になる。また、発泡体シートの圧縮強度、最大気泡径及び平均気泡径を後述の範囲内に調整しやすくなる。
ポリオレフィン樹脂（Ｂ）としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エチル共重合体等が挙げられ、これらの中ではポリエチレン樹脂、及びエチレン−酢酸ビニル共重合体から選択される少なくとも１種が好ましく、ポリエチレン樹脂がより好ましい。ポリオレフィン樹脂（Ｂ）は、１種単独で使用してもよいし、２種以上を併用してもよい。[Resin other than bio-based polyolefin resin (A)]
The foam sheet may contain a resin other than the bio-based polyolefin resin (A), and for example, it is preferable to contain the polyolefin resin (B). The polyolefin resin (B) is a petroleum-based polyolefin resin generally produced from petroleum-derived polyolefin. By using the polyolefin resin (B), it becomes possible to make the foam sheet thinner. Further, it becomes easy to adjust the compressive strength, the maximum cell diameter and the average cell diameter of the foam sheet within the range described later.
Examples of the polyolefin resin (B) include polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like, among which polyethylene resin and ethylene-vinyl acetate are used together. At least one selected from the polymer is preferable, and polyethylene resin is more preferable. The polyolefin resin (B) may be used alone or in combination of two or more.
≪ポリエチレン樹脂≫
ポリエチレン樹脂としては、チーグラー・ナッタ化合物、メタロセン化合物、酸化クロム化合物等の重合触媒で重合されたポリエチレン樹脂が挙げられ、好ましくはメタロセン化合物の重合触媒で重合されたポリエチレン樹脂が用いられる。メタロセン化合物の重合触媒で重合されたポリエチレン樹脂を使用することで、後述する架橋などを均一にでき、薄型化しても柔軟性などの発泡体としての各種性能を良好にしやすくなる。また、最大気泡径を小さくしやすくなる。≪Polyethylene resin≫
Examples of the polyethylene resin include polyethylene resins polymerized with a polymerization catalyst such as a Cheegler-Natta compound, a metallocene compound, and a chromium oxide compound, and a polyethylene resin polymerized with a polymerization catalyst of a metallocene compound is preferably used. By using a polyethylene resin polymerized with a polymerization catalyst of a metallocene compound, cross-linking and the like, which will be described later, can be made uniform, and even if the thickness is reduced, various performances as a foam such as flexibility can be easily improved. In addition, it becomes easy to reduce the maximum bubble diameter.
また、ポリエチレン樹脂としては、密度が０．９３０ｇ／ｃｍ３以下である低密度ポリエチレン（ＬＤＰＥ）が好ましく、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）がより好ましい。直鎖状低密度ポリエチレンを用いることにより、発泡体シートに柔軟性を付与するとともに、発泡体シートを薄くすることが可能になる。直鎖状低密度ポリエチレンは、エチレン（例えば、全モノマー量に対して７５質量％以上、好ましくは９０質量％以上）と必要に応じて少量のα−オレフィンとを共重合することにより得られる直鎖状低密度ポリエチレンがより好ましい。
α−オレフィンとしては、例えば、プロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−ヘプテン、及び１−オクテン等が挙げられる。なかでも、炭素数４〜１０のα−オレフィンが好ましい。Further, as the polyethylene resin, low density polyethylene (LDPE) having a density of 0.930 g / cm 3 or less is preferable, and linear low density polyethylene (LLDPE) is more preferable. By using the linear low-density polyethylene, it becomes possible to impart flexibility to the foam sheet and to make the foam sheet thinner. The linear low-density polyethylene is obtained by copolymerizing ethylene (for example, 75% by mass or more, preferably 90% by mass or more with respect to the total amount of monomers) and, if necessary, a small amount of α-olefin. Chain low density polyethylene is more preferred.
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Of these, α-olefins having 4 to 10 carbon atoms are preferable.
発泡体シートを薄くしながらも柔軟性をより一層良好にする観点からは、上記したメタロセン化合物の重合触媒により重合されたポリエチレン樹脂が、直鎖状低密度ポリエチレンであることが好ましい。
ポリエチレン樹脂の密度は、０．８７０〜０．９３０ｇ／ｃｍ３が好ましく、０．８９０〜０．９２５ｇ／ｃｍ３がより好ましく、０．９００〜０．９２３ｇ／ｃｍ３が更に好ましい。ポリエチレン樹脂としては、複数のポリエチレン樹脂を用いることもでき、また、上記した密度範囲以外のポリエチレン樹脂を加えてもよい。From the viewpoint of further improving the flexibility while making the foam sheet thinner, the polyethylene resin polymerized by the above-mentioned polymerization catalyst of the metallocene compound is preferably linear low-density polyethylene.
The density of the polyethylene resin is preferably 0.870~0.930g / cm 3, more preferably 0.890~0.925g / cm 3, more preferably 0.900~0.923g / cm 3. As the polyethylene resin, a plurality of polyethylene resins may be used, or polyethylene resins other than the above-mentioned density range may be added.
ポリエチレン樹脂のメルトインデックスは１．０〜１２ｇ／１０分であることが好ましく、１．５〜８ｇ／１０分であることがより好ましく、１．８〜４．５ｇ／１０分であることが更に好ましい。ポリエチレン樹脂のメルトインデックスが上記範囲内であると、発泡が適切に行われて発泡体シートの最大気泡径を小さくしやすくなると共に、発泡体シートの加工性、成形性が良好になる。 The melt index of the polyethylene resin is preferably 1.0 to 12 g / 10 minutes, more preferably 1.5 to 8 g / 10 minutes, and further preferably 1.8 to 4.5 g / 10 minutes. preferable. When the melt index of the polyethylene resin is within the above range, foaming is appropriately performed, the maximum bubble diameter of the foam sheet can be easily reduced, and the processability and moldability of the foam sheet are improved.
（メタロセン化合物）
メタロセン化合物としては、遷移金属をπ電子系の不飽和化合物で挟んだ構造を有するビス（シクロペンタジエニル）金属錯体等の化合物を挙げることができる。より具体的には、チタン、ジルコニウム、ニッケル、パラジウム、ハフニウム、及び白金等の四価の遷移金属に、１又は２以上のシクロペンタジエニル環又はその類縁体がリガンド（配位子）として存在する化合物を挙げることができる。
このようなメタロセン化合物は、活性点の性質が均一であり各活性点が同じ活性度を備えている。メタロセン化合物を用いて合成した重合体は、分子量、分子量分布、組成、組成分布等の均一性が高いため、メタロセン化合物を用いて合成した重合体を含むシートを架橋した場合には、架橋が均一に進行する。その結果、均一に延伸できるため、発泡体シートの厚みが均一になりやすく、発泡体シートを薄くしやすくなる。(Metallocene compound)
Examples of the metallocene compound include compounds such as a bis (cyclopentadienyl) metal complex having a structure in which a transition metal is sandwiched between π-electron unsaturated compounds. More specifically, one or more cyclopentadienyl rings or their analogs are present as ligands in tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum. Can be mentioned.
In such a metallocene compound, the properties of active sites are uniform, and each active site has the same activity. Since the polymer synthesized using the metallocene compound has high uniformity in molecular weight, molecular weight distribution, composition, composition distribution, etc., when a sheet containing the polymer synthesized using the metallocene compound is crosslinked, the cross-linking is uniform. Proceed to. As a result, since the foam sheet can be uniformly stretched, the thickness of the foam sheet tends to be uniform, and the foam sheet tends to be thin.
リガンドとしては、例えば、シクロペンタジエニル環、インデニル環等を挙げることができる。これらの環式化合物は、炭化水素基、置換炭化水素基又は炭化水素−置換メタロイド基により置換されていてもよい。炭化水素基としては、例えば、メチル基、エチル基、各種プロピル基、各種ブチル基、各種アミル基、各種ヘキシル基、２−エチルヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種セチル基、フェニル基等が挙げられる。なお、「各種」とは、ｎ−、ｓｅｃ−、ｔｅｒｔ−、ｉｓｏ−を含む各種異性体を意味する。
また、環式化合物をオリゴマーとして重合したものをリガンドとして用いてもよい。
更に、π電子系の不飽和化合物以外にも、塩素や臭素等の一価のアニオンリガンド又は二価のアニオンキレートリガンド、炭化水素、アルコキシド、アリールアミド、アリールオキシド、アミド、アリールアミド、ホスフィド、アリールホスフィド等を用いてもよい。Examples of the ligand include a cyclopentadienyl ring, an indenyl ring and the like. These cyclic compounds may be substituted with a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group. Examples of the hydrocarbon group include a methyl group, an ethyl group, various propyl groups, various butyl groups, various amyl groups, various hexyl groups, 2-ethylhexyl groups, various heptyl groups, various octyl groups, various nonyl groups and various decyl groups. , Various cetyl groups, phenyl groups and the like. In addition, "various" means various isomers including n-, sec-, tert-, and iso-.
Further, a cyclic compound polymerized as an oligomer may be used as a ligand.
Furthermore, in addition to π-electron unsaturated compounds, monovalent anion ligands such as chlorine and bromine, divalent anion chelate ligands, hydrocarbons, alkoxides, arylamides, aryloxides, amides, arylamides, phosphides, and aryls. You may use phosphide or the like.
四価の遷移金属やリガンドを含むメタロセン化合物としては、例えば、シクロペンタジエニルチタニウムトリス（ジメチルアミド）、メチルシクロペンタジエニルチタニウムトリス（ジメチルアミド）、ビス（シクロペンタジエニル）チタニウムジクロリド、ジメチルシリルテトラメチルシクロペンタジエニル−ｔ−ブチルアミドジルコニウムジクロリド等が挙げられる。
メタロセン化合物は、特定の共触媒（助触媒）と組み合わせることにより、各種オレフィンの重合の際に触媒としての作用を発揮する。具体的な共触媒としては、メチルアルミノキサン（ＭＡＯ）、ホウ素系化合物等が挙げられる。なお、メタロセン化合物に対する共触媒の使用割合は、１０〜１００万モル倍が好ましく、５０〜５，０００モル倍がより好ましい。Examples of metallocene compounds containing tetravalent transition metals and ligands include cyclopentadienyl titaniumtris (dimethylamide), methylcyclopentadienyl titaniumtris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, and dimethyl. Examples thereof include silyltetramethylcyclopentadienyl-t-butylamide zirconium dichloride.
The metallocene compound exerts an action as a catalyst in the polymerization of various olefins by combining with a specific co-catalyst (co-catalyst). Specific examples of the co-catalyst include methylaluminoxane (MAO), boron-based compounds and the like. The ratio of the cocatalyst used to the metallocene compound is preferably 10 to 1 million mol times, more preferably 50 to 5,000 mol times.
≪ポリプロピレン樹脂≫
ポリオレフィン樹脂（Ｂ）として使用されるポリプロピレン樹脂としては、例えば、ポリプロピレンや、プロピレンを５０質量％以上含有するプロピレン−エチレン共重合体、プロピレンを５０質量％以上含有するプロピレン−α−オレフィン共重合体等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。
プロピレン−α−オレフィン共重合体を構成するα−オレフィンとしては、具体的には、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン等が挙げることができ、これらの中では、炭素数６〜１２のα−オレフィンが好ましい。≪Polypropylene resin≫
Examples of the polypropylene resin used as the polyolefin resin (B) include polypropylene, a propylene-ethylene copolymer containing 50% by mass or more of propylene, and a propylene-α-olefin copolymer containing 50% by mass or more of propylene. And so on. These may be used alone or in combination of two or more.
Specific examples of the α-olefin constituting the propylene-α-olefin copolymer include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Among these, α-olefins having 6 to 12 carbon atoms are preferable.
ポリプロピレン樹脂の密度は、０．８７０〜０．９３０ｇ／ｃｍ３が好ましく、０．８９０〜０．９２５ｇ／ｃｍ３がより好ましく、０．９００〜０．９２３ｇ／ｃｍ３が更に好ましい。ポリプロピレン樹脂としては、複数のポリプロピレン樹脂を用いることもでき、また、上記した密度範囲以外のポリプロピレン樹脂を加えてもよい。The density of the polypropylene resin is preferably 0.870~0.930g / cm 3, more preferably 0.890~0.925g / cm 3, more preferably 0.900~0.923g / cm 3. As the polypropylene resin, a plurality of polypropylene resins may be used, or polypropylene resins other than the above-mentioned density range may be added.
≪エチレン−酢酸ビニル共重合体≫
ポリオレフィン樹脂（Ｂ）として使用するエチレン−酢酸ビニル共重合体は、例えば、酢酸ビニルの含有量（ＶＡ量）が、好ましくは５〜４０質量％、より好ましくは１２〜３５質量％、更に好ましくは１５〜３０質量％であるエチレン−酢酸ビニル共重合体が挙げられる。エチレン−酢酸ビニル共重合体中の酢酸ビニルの含有量が前記範囲内であると、最大気泡径を小さくすることができ、柔軟性に優れる発泡体シートを得ることができる。≪Ethylene-vinyl acetate copolymer≫
The ethylene-vinyl acetate copolymer used as the polyolefin resin (B) has, for example, a vinyl acetate content (VA amount) of preferably 5 to 40% by mass, more preferably 12 to 35% by mass, and even more preferably. Examples thereof include ethylene-vinyl acetate copolymers having an amount of 15 to 30% by mass. When the content of vinyl acetate in the ethylene-vinyl acetate copolymer is within the above range, the maximum bubble diameter can be reduced and a foam sheet having excellent flexibility can be obtained.
本発明においては、例えば、分子量、共重合体成分の酢酸ビニルの量、融点等が異なる２種類以上のものを組み合わせて使用することができる。
なお、本発明で用いるエチレン−酢酸ビニル共重合体は、エチレンと酢酸ビニルの他、酢酸ビニルの一部を加水分解して生成したビニルアルコールを含むものでもよい。
このようなエチレン−酢酸ビニル共重合体としては、例えば、東ソー株式会社製「ウルトラセン」、三井・デュポンポリケミカル株式会社製「エバフレックス」、宇部丸善ポリエチレン株式会社製「ＵＢＥポリエチレン」、旭化成ケミカルズ株式会社製「サンテック」等が挙げられる。In the present invention, for example, two or more kinds having different molecular weights, the amount of vinyl acetate as a copolymer component, the melting point and the like can be used in combination.
The ethylene-vinyl acetate copolymer used in the present invention may contain, in addition to ethylene and vinyl acetate, vinyl alcohol produced by hydrolyzing a part of vinyl acetate.
Examples of such ethylene-vinyl acetate copolymers include "Ultrasen" manufactured by Tosoh Corporation, "Evaflex" manufactured by Mitsui-Dupont Polychemical Co., Ltd., "UBE Polyethylene" manufactured by Ube-Maruzen Polyethylene Co., Ltd., and Asahi Kasei Chemicals. Examples include "Suntech" manufactured by Suntech Co., Ltd.
エチレン−酢酸ビニル共重合体の密度は、０．９００〜０．９８０ｇ／ｃｍ３が好ましく、０．９１０〜０．９７５ｇ／ｃｍ３がより好ましく、０．９２０〜０．９６０ｇ／ｃｍ３が更に好ましい。エチレン−酢酸ビニル共重合体としては、複数のエチレン−酢酸ビニル共重合体を用いることもでき、また、上記した密度範囲以外のエチレン−酢酸ビニル共重合体を加えてもよい。Ethylene - Density vinyl acetate copolymer is preferably 0.900~0.980g / cm 3, more preferably 0.910~0.975g / cm 3, further is 0.920~0.960g / cm 3 preferable. As the ethylene-vinyl acetate copolymer, a plurality of ethylene-vinyl acetate copolymers may be used, or an ethylene-vinyl acetate copolymer other than the above-mentioned density range may be added.
エチレン−酢酸ビニル共重合体のメルトインデックスは１．５〜１５ｇ／１０分であることが好ましく、２．０〜１０ｇ／１０分であることがより好ましく、２．５〜５ｇ／１０分であることが更に好ましい。エチレン−酢酸ビニル共重合体のメルトインデックスが前記範囲内であると、発泡体シートの最大気泡径を小さくしやすくなると共に、発泡体シートの加工性、成形性が良好になる。 The melt index of the ethylene-vinyl acetate copolymer is preferably 1.5 to 15 g / 10 minutes, more preferably 2.0 to 10 g / 10 minutes, and 2.5 to 5 g / 10 minutes. Is even more preferable. When the melt index of the ethylene-vinyl acetate copolymer is within the above range, the maximum bubble diameter of the foam sheet can be easily reduced, and the workability and moldability of the foam sheet can be improved.
〔各樹脂の含有量〕
発泡体シートにおけるバイオ系ポリオレフィン樹脂（Ａ）の含有量は、環境への負荷を低減して発泡体シートのバイオ率を高める観点から、樹脂成分全量基準で４２質量％以上が好ましく、５０質量％以上がより好ましく、６０質量％以上が更に好ましい。また、発泡体シートを薄型化し、かつ発泡体としての性能を良好にしやすくするためには、バイオ系ポリオレフィン樹脂（Ａ）以外の樹脂を含んでいたほうがよい。そのような観点から、バイオ系ポリオレフィン樹脂（Ａ）の含有量は、９５質量％以下が好ましく、８５質量％以下がより好ましく、７５質量％以下がさらに好ましい。[Content of each resin]
The content of the bio-based polyolefin resin (A) in the foam sheet is preferably 42% by mass or more, preferably 50% by mass, based on the total amount of the resin component, from the viewpoint of reducing the load on the environment and increasing the bio ratio of the foam sheet. The above is more preferable, and 60% by mass or more is further preferable. Further, in order to make the foam sheet thinner and to facilitate the performance as a foam, it is better to contain a resin other than the bio-based polyolefin resin (A). From such a viewpoint, the content of the bio-based polyolefin resin (A) is preferably 95% by mass or less, more preferably 85% by mass or less, and further preferably 75% by mass or less.
ポリオレフィン樹脂（Ｂ）の含有量は、樹脂成分全量基準で５質量％以上が好ましく、１５質量％以上がより好ましく、２５質量％以上が更に好ましく、そして、５８質量％以下が好ましく、５０質量％以下がより好ましく、４０質量％以下が更に好ましい。ポリオレフィン樹脂（Ｂ）の含有量をこれら下限値以上とすることで、シートを薄くしやすくなり、かつ耐衝撃性、柔軟性、機械強度などの発泡体シートで必要とされる各種物性が良好となりやすくなる。また、これら上限値以下とすることで、環境負荷を低くして、発泡体シートのバイオ率を高めやすくなる。 The content of the polyolefin resin (B) is preferably 5% by mass or more, more preferably 15% by mass or more, further preferably 25% by mass or more, and preferably 58% by mass or less, preferably 50% by mass, based on the total amount of the resin component. The following is more preferable, and 40% by mass or less is further preferable. By setting the content of the polyolefin resin (B) to these lower limit values or more, it becomes easy to make the sheet thinner, and various physical properties required for the foam sheet such as impact resistance, flexibility, and mechanical strength become good. It will be easier. Further, by setting the value to or less than these upper limit values, it becomes easy to reduce the environmental load and increase the biorate of the foam sheet.
ポリオレフィン樹脂（Ｂ）がメタロセン化合物の重合触媒で重合されたポリエチレン樹脂を含む場合、そのポリエチレン樹脂は、ポリオレフィン樹脂（Ｂ）として、単独で使用することが好ましいが、他のポリオレフィン樹脂（Ｂ）と併用してもよい。
メタロセン化合物の重合触媒で重合されたポリエチレン樹脂の含有量は、ポリオレフィン樹脂（Ｂ）全量基準で、４０〜１００質量％が好ましく、５０〜１００質量％がさらに好ましく、８５〜１００質量％がさらに好ましい。メタロセン化合物の重合触媒で重合されたポリエチレン樹脂の含有量を多くすることで、発泡体シートの柔軟性などを良好にしやすくなり、また、架橋などを均一にでき、シートを薄型化でき、かつ最大気泡径を小さくしやすくなる。When the polyolefin resin (B) contains a polyethylene resin polymerized with a polymerization catalyst of a metallocene compound, the polyethylene resin is preferably used alone as the polyolefin resin (B), but with other polyolefin resins (B). It may be used together.
The content of the polyethylene resin polymerized by the polymerization catalyst of the metallocene compound is preferably 40 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass based on the total amount of the polyolefin resin (B). .. By increasing the content of the polyethylene resin polymerized by the polymerization catalyst of the metallocene compound, it becomes easier to improve the flexibility of the foam sheet, the cross-linking can be made uniform, the sheet can be made thinner, and the maximum. It becomes easy to reduce the bubble diameter.
＜発泡体シートにおけるバイオ率＞
本発明の発泡体シートにおけるバイオ率は４０質量％以上である。バイオ率を４０質量％未満にすると、環境への負荷を低減することができない。この観点から、バイオ率は、５０質量％以上が好ましく、６０質量％以上がより好ましい。上限値に特に制限はないが、発泡体シートの強度、柔軟性、製造コストなどの観点から、９０質量％以下が好ましく、８２質量％以下がより好ましく、７５質量％以下がさらに好ましく、６８質量％以下がよりさらに好ましい。<Bio-rate in foam sheet>
The biorate in the foam sheet of the present invention is 40% by mass or more. If the biorate is less than 40% by mass, the burden on the environment cannot be reduced. From this viewpoint, the biorate is preferably 50% by mass or more, more preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of strength, flexibility, manufacturing cost, etc. of the foam sheet, 90% by mass or less is preferable, 82% by mass or less is more preferable, 75% by mass or less is further preferable, and 68% by mass is used. % Or less is even more preferable.
発泡体シートのバイオ率は、発泡体シート全量に対するバイオ系ポリオレフィン樹脂（Ａ）の含有割合に、バイオ系ポリオレフィン樹脂（Ａ）のバイオ率を乗じて得ることができる。発泡体シート全量とは、樹脂組成物全量から発泡剤及び製造時に揮発する成分の量を除いて算出できる。また、バイオ系ポリオレフィン樹脂（Ａ）のバイオ率は、ＡＳＴＭ Ｄ６８６６に規定されている測定方法により測定されたバイオマス度である。 The bio-ratio of the foam sheet can be obtained by multiplying the content ratio of the bio-based polyolefin resin (A) with respect to the total amount of the foam sheet by the bio-ratio of the bio-based polyolefin resin (A). The total amount of the foam sheet can be calculated by subtracting the amount of the foaming agent and the components volatilized during production from the total amount of the resin composition. The biorate of the bio-based polyolefin resin (A) is the degree of biomass measured by the measuring method specified in ASTM D6866.
＜発泡体シートの厚み＞
本発明の発泡体シートの厚みは０．０５〜１．５ｍｍである。厚みを０．０５ｍｍ未満とすると、発泡体シートの機械強度、耐衝撃性などの発泡体シートの性能を十分に良好にできない。また、厚みを１．５ｍｍより大きくすると薄型化が難しくなり、小型化した電子機器に好適に使用できない。薄型化しつつ、発泡体シートの性能を十分に発揮させる観点から、発泡体シートの厚みは、好ましくは１．２ｍｍ以下、より好ましくは０．９ｍｍ以下、更に好ましくは０．６ｍｍ以下であり、また、好ましくは０．０８ｍｍ以上であり、さらに好ましくは０．１０ｍｍ以上である。<Thickness of foam sheet>
The thickness of the foam sheet of the present invention is 0.05 to 1.5 mm. If the thickness is less than 0.05 mm, the performance of the foam sheet such as the mechanical strength and impact resistance of the foam sheet cannot be sufficiently improved. Further, if the thickness is larger than 1.5 mm, it becomes difficult to reduce the thickness, and it cannot be suitably used for miniaturized electronic devices. From the viewpoint of fully exerting the performance of the foam sheet while reducing the thickness, the thickness of the foam sheet is preferably 1.2 mm or less, more preferably 0.9 mm or less, still more preferably 0.6 mm or less, and further. It is preferably 0.08 mm or more, and more preferably 0.10 mm or more.
＜発泡倍率＞
本発明の発泡体シートの発泡倍率は１．５〜２０倍である。発泡体シートの発泡倍率を１．５倍未満とすると、気泡割合が低くなり、柔軟性などの発泡体としての性能が不十分となる。一方、発泡倍率が２０倍を超えると、最大気泡径が大きくなり、その結果、耐衝撃性等の発泡体シートの各種性能を向上させにくくなる。これらの観点から、発泡体シートの発泡倍率は１．８〜１５倍が好ましく、２．５〜１０倍が更に好ましい。なお、発泡倍率とは、発泡前と発泡後の比容積（単位：ｃｃ／ｇ）を測定し、発泡後の比容積／発泡前の比容積によって算出されたものをいう。<Effervescence magnification>
The foaming ratio of the foam sheet of the present invention is 1.5 to 20 times. When the foaming ratio of the foam sheet is less than 1.5 times, the bubble ratio becomes low, and the performance as a foam such as flexibility becomes insufficient. On the other hand, when the foaming ratio exceeds 20 times, the maximum bubble diameter becomes large, and as a result, it becomes difficult to improve various performances of the foam sheet such as impact resistance. From these viewpoints, the foaming ratio of the foam sheet is preferably 1.8 to 15 times, more preferably 2.5 to 10 times. The foaming ratio is calculated by measuring the specific volume before and after foaming (unit: cc / g) and calculating the specific volume after foaming / the specific volume before foaming.
＜最大気泡径及び平均気泡径＞
本発明の発泡体シートの最大気泡径は、５００μｍ以下が好ましい。最大気泡径が前記上限値以下であると、シートを薄くしても耐衝撃性等の発泡体シートの各種性能を向上させることができる。発泡体シートの耐衝撃性等を十分に確保する観点から、発泡体シートの最大気泡径は３８０μｍ以下がより好ましく、３００μｍ以下がさらに好ましい。また、発泡体シートの最大気泡径は、５０μｍ以上が好ましく、８０μｍ以上がより好ましく、１００μｍ以上が更に好ましい。<Maximum bubble diameter and average bubble diameter>
The maximum bubble diameter of the foam sheet of the present invention is preferably 500 μm or less. When the maximum bubble diameter is not more than the upper limit value, various performances of the foam sheet such as impact resistance can be improved even if the sheet is thinned. From the viewpoint of sufficiently ensuring the impact resistance of the foam sheet, the maximum bubble diameter of the foam sheet is more preferably 380 μm or less, further preferably 300 μm or less. The maximum bubble diameter of the foam sheet is preferably 50 μm or more, more preferably 80 μm or more, and further preferably 100 μm or more.
本発明の発泡体シートのＭＤ方向及びＴＤ方向の平均気泡径はいずれもが、２０〜３５０μｍ以下であることが好ましい。平均気泡径が上記範囲であると、最大気泡径も小さくなり、２５％圧縮強度を所望の範囲にしつつ、耐衝撃性、衝撃吸収性などの性能を向上させることができる。これら観点からＭＤ方向及びＴＤ方向の平均気泡径はいずれもが、３０〜２５０μｍが好ましく、５０〜２００μｍがより好ましく、６０〜１４０μｍが更に好ましい。
更に、発泡体シートのＺＤ方向の平均気泡径は、耐衝撃性、衝撃吸収性などを確保する観点から、５〜２５０μｍが好ましく、１０〜１４０μｍがより好ましく、１５〜１００μｍが更に好ましく、２０〜６０μｍがより更に好ましい。The average cell diameter in the MD direction and the TD direction of the foam sheet of the present invention is preferably 20 to 350 μm or less. When the average bubble diameter is in the above range, the maximum bubble diameter is also reduced, and the performance such as impact resistance and impact absorption can be improved while keeping the 25% compressive strength in a desired range. From these viewpoints, the average bubble diameter in the MD direction and the TD direction is preferably 30 to 250 μm, more preferably 50 to 200 μm, still more preferably 60 to 140 μm.
Further, the average cell diameter in the ZD direction of the foam sheet is preferably 5 to 250 μm, more preferably 10 to 140 μm, further preferably 15 to 100 μm, and 20 to 20 to 20 from the viewpoint of ensuring impact resistance, impact absorption and the like. 60 μm is even more preferable.
平均気泡径は下記の要領で測定したものをいう。
発泡体シートを５０ｍｍ四方にカットしたものを測定用の発泡体シートサンプルとして用意した。これを液体窒素に１分間浸した後にカミソリ刃でＭＤ方向、及びＴＤ方向に沿ってそれぞれ厚み方向に切断した。この断面をデジタルマイクロスコープ（株式会社キーエンス製「ＶＨＸ−９００」）を用いて２００倍の拡大写真を撮り、ＭＤ方向、及びＴＤ方向のそれぞれにおける長さ２ｍｍ分の切断面に存在する全ての気泡について気泡径を測定し、その操作を５回繰り返した。そして、全ての気泡の平均値をＭＤ方向、及びＴＤ方向の平均気泡径とした。また、測定したすべての気泡について、ＺＤ方向の気泡径も測定し、その平均値をＺＤ方向の平均気泡径とした。さらに、測定した全ての気泡径の中で最大の値を最大気泡径とした。
なお、本発明において「ＭＤ」は、Machine Directionを意味し、発泡体シートの押出方向等と一致する方向を意味する。また、「ＴＤ」は、Transverse Directionを意味し、ＭＤに直交し且つ発泡体シートに平行な方向を意味する。更に「ＺＤ」は、Thickness Directionを意味し、ＭＤ及びＴＤのいずれにも垂直な方向である。The average bubble diameter is measured as follows.
A foam sheet cut into 50 mm squares was prepared as a foam sheet sample for measurement. After immersing this in liquid nitrogen for 1 minute, it was cut in the thickness direction along the MD direction and the TD direction with a razor blade. A 200x magnified photograph of this cross section was taken using a digital microscope (“VHX-900” manufactured by KEYENCE CORPORATION), and all bubbles existing on the cut surface having a length of 2 mm in each of the MD direction and the TD direction. The bubble diameter was measured and the operation was repeated 5 times. Then, the average value of all the bubbles was taken as the average bubble diameter in the MD direction and the TD direction. In addition, the bubble diameter in the ZD direction was also measured for all the measured bubbles, and the average value was taken as the average bubble diameter in the ZD direction. Further, the maximum value among all the measured bubble diameters was defined as the maximum bubble diameter.
In the present invention, "MD" means a machine direction, and means a direction that coincides with the extrusion direction of the foam sheet or the like. Further, "TD" means a transverse direction, and means a direction orthogonal to the MD and parallel to the foam sheet. Further, "ZD" means a thickness direction, which is a direction perpendicular to both MD and TD.
＜気泡径の比＞
ＺＤ方向における平均気泡径に対する、ＭＤ及びＴＤ方向における平均気泡径の比（以下、“（ＭＤ＋ＴＤ）／２ＺＤ”ともいう）は１．３〜１０が好ましく、１．８〜９がより好ましく、２〜８が更に好ましく、２．５〜６がよりさらに好ましい。なお、ＭＤ及びＴＤ方向における平均気泡径の比は、ＭＤ方向における平均気泡径と、ＴＤ方向における平均気泡径の平均値である。
（ＭＤ＋ＴＤ）／２ＺＤが上記範囲内であると、ＭＤ方向及びＴＤ方向に延びた形状の気泡になるため、シートを薄くしても耐衝撃性、柔軟性、衝撃吸収性などに優れた発泡体シートを得やすくなる。なお、（ＭＤ＋ＴＤ）／２ＺＤは発泡倍率を上記した範囲に調整しつつ、発泡体シートの製造時に延伸することにより調整できる。<Ratio of bubble diameter>
The ratio of the average cell diameter in the MD and TD directions (hereinafter, also referred to as “(MD + TD) / 2ZD”) to the average cell diameter in the ZD direction is preferably 1.3 to 10 and more preferably 1.8 to 9. ~ 8 is more preferable, and 2.5 to 6 is even more preferable. The ratio of the average bubble diameters in the MD and TD directions is the average value of the average bubble diameter in the MD direction and the average bubble diameter in the TD direction.
When (MD + TD) / 2ZD is within the above range, bubbles having a shape extending in the MD direction and the TD direction are formed, so that a foam having excellent impact resistance, flexibility, impact absorption, etc. even if the sheet is thinned. It becomes easier to obtain a sheet. In addition, (MD + TD) / 2ZD can be adjusted by stretching the foam sheet at the time of manufacturing while adjusting the foaming ratio within the above range.
＜２５％圧縮強度＞
発泡体シートの２５％圧縮強度は、例えば３５０ｋＰａ以下であるが、柔軟性の観点からは、２００ｋＰａ以下が好ましく、１６０ｋＰａ以下がより好ましく、１００ｋＰａ以下がさらに好ましい。また、柔軟性を良好にしつつ、耐衝撃性及び機械強度なども良好にする観点からは、発泡体シートの２５％圧縮強度は、２０ｋＰａ以上が好ましく、３５ｋＰａ以上がより好ましく、４０ｋＰａ以上がより更に好ましい。
２５％圧縮強度は、樹脂の種類、気泡径、発泡倍率等によって調整可能であり、例えば、発泡倍率を高くすると２５％圧縮強度の値を低くできる。
なお、２５％圧縮強度は、発泡体シートをＪＩＳ Ｋ６７６７に準拠して測定したものをいう。<25% compressive strength>
The 25% compressive strength of the foam sheet is, for example, 350 kPa or less, but from the viewpoint of flexibility, it is preferably 200 kPa or less, more preferably 160 kPa or less, still more preferably 100 kPa or less. Further, from the viewpoint of improving the impact resistance and the mechanical strength while improving the flexibility, the 25% compressive strength of the foam sheet is preferably 20 kPa or more, more preferably 35 kPa or more, and further more preferably 40 kPa or more. preferable.
The 25% compressive strength can be adjusted by the type of resin, the bubble diameter, the foaming ratio, and the like. For example, when the foaming ratio is increased, the value of the 25% compressive strength can be lowered.
The 25% compressive strength refers to a foam sheet measured in accordance with JIS K6767.
＜架橋度＞
発泡体シートは架橋されていることが好ましい。また、発泡体シートの架橋度は１５質量％以上が好ましい。架橋度を前記下限値以上とすると平均気泡径を上記範囲内に調整しやすくなると共に、発泡体シートの気泡を微細化しやすくなる。さらに、各気泡の大きさのばらつきも少なくなるため、最大気泡径が小さくなり、耐衝撃性や機械強度を向上させやすくなる。そのような観点から、発泡体シートの架橋度は、２５質量％以上がより好ましく、３０質量％以上が更に好ましい。また、発泡体シートの柔軟性、耐衝撃性、衝撃吸収性などを向上させる観点から、架橋度は、６５質量％以下が好ましく、６０質量％以下がさらに好ましく、５５質量％以下がさらに好ましい。<Crosslink degree>
The foam sheet is preferably crosslinked. The degree of cross-linking of the foam sheet is preferably 15% by mass or more. When the degree of cross-linking is set to the lower limit value or more, the average bubble diameter can be easily adjusted within the above range, and the bubbles in the foam sheet can be easily made finer. Further, since the variation in the size of each bubble is reduced, the maximum bubble diameter is reduced, and it becomes easy to improve the impact resistance and the mechanical strength. From such a viewpoint, the degree of cross-linking of the foam sheet is more preferably 25% by mass or more, further preferably 30% by mass or more. Further, from the viewpoint of improving the flexibility, impact resistance, impact absorption and the like of the foam sheet, the degree of cross-linking is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less.
発泡体シートは、上記樹脂と発泡剤を含む樹脂組成物を発泡してなるものである。また、発泡体シートには、さらに添加剤が配合されていてもよく、したがって、発泡体シートは、上記樹脂と発泡剤に加えて添加剤を含む樹脂組成物を発泡してなるものでもよい。 The foam sheet is formed by foaming a resin composition containing the above resin and a foaming agent. Further, the foam sheet may further contain an additive, and therefore, the foam sheet may be formed by foaming a resin composition containing an additive in addition to the above resin and the foaming agent.
〔発泡剤〕
発泡剤としては熱分解型発泡剤が好ましい。熱分解型発泡剤の具体例としては、分解温度が１４０℃〜２７０℃程度の有機系又は無機系の化学発泡剤が挙げられる。
有機系発泡剤としては、アゾジカルボンアミド、アゾジカルボン酸金属塩（アゾジカルボン酸バリウム等）、アゾビスイソブチロニトリル等のアゾ化合物、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミン等のニトロソ化合物、ヒドラゾジカルボンアミド、４，４’−オキシビス（ベンゼンスルホニルヒドラジド）、トルエンスルホニルヒドラジド等のヒドラジン誘導体、トルエンスルホニルセミカルバジド等のセミカルバジド化合物等が挙げられる。
無機系発泡剤としては、炭酸アンモニウム、炭酸ナトリウム、炭酸水素アンモニウム、炭酸水素ナトリウム、亜硝酸アンモニウム、水素化ホウ素ナトリウム、無水クエン酸モノソーダ等が挙げられる。
これらの中では、微細な気泡を得る観点、及び経済性、安全面の観点から、アゾ化合物、ニトロソ化合物が好ましく、アゾジカルボンアミド、アゾビスイソブチロニトリル、Ｎ，Ｎ’−ジニトロソペンタメチレンテトラミンがより好ましく、アゾジカルボンアミドが特に好ましい。これらの熱分解型発泡剤は、単独で又は２以上を組み合わせて使用することができる。
熱分解型発泡剤の配合量は、樹脂成分１００質量部に対して１〜３０質量部が好ましい。このような配合量とすることで、シートの気泡が破裂せずに適切に発泡ができる。また、熱分解型発泡剤の配合量を多くすると、発泡倍率が高くなり、柔軟性を向上させることが可能である。そのため、熱分解型発泡剤の配合量は、３〜２５質量部がより好ましく、５〜１８質量部がさらに好ましい。[Effervescent agent]
As the foaming agent, a pyrolysis type foaming agent is preferable. Specific examples of the thermally decomposable foaming agent include organic or inorganic chemical foaming agents having a decomposition temperature of about 140 ° C. to 270 ° C.
Examples of the organic foaming agent include azodicarbonamides, azodicarboxylic acid metal salts (azodicarboxylic acid barium and the like), azo compounds such as azobisisobutyronitrile, and nitroso compounds such as N, N'-dinitrosopentamethylenetetramine. Examples thereof include hydrazodicarbonamides, 4,4'-oxybis (benzenesulfonyl hydrazide), hydrazine derivatives such as toluenesulfonyl hydrazide, and semicarbazide compounds such as toluenesulfonyl semicarbazide.
Examples of the inorganic foaming agent include ammonium carbonate, sodium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium boron hydride, anhydrous monosoda citrate and the like.
Among these, azo compounds and nitroso compounds are preferable from the viewpoint of obtaining fine bubbles, and from the viewpoint of economy and safety, azodicarbonamide, azobisisobutyronitrile, N, N'-dinitrosopentamethylene. Tetramine is more preferred, and azodicarbonamide is particularly preferred. These pyrolyzable foaming agents can be used alone or in combination of two or more.
The blending amount of the pyrolysis foaming agent is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin component. With such a blending amount, air bubbles in the sheet do not burst and foaming can be appropriately performed. Further, when the blending amount of the pyrolysis type foaming agent is increased, the foaming ratio becomes high and the flexibility can be improved. Therefore, the blending amount of the pyrolysis type foaming agent is more preferably 3 to 25 parts by mass, further preferably 5 to 18 parts by mass.
〔添加剤〕
発泡体シートには、添加剤として気泡核調整剤が配合されることが好ましい。気泡核調整剤としては、酸化亜鉛、ステアリン酸亜鉛等の亜鉛化合物、クエン酸、尿素の有機化合物等が挙げられる。これらの中では、酸化亜鉛、ステアリン酸亜鉛がより好ましく、これらは一方のみ使用してもよいし、両方を使用してもよい。発泡剤に加えて気泡核調整剤を使用することで、平均気泡径、及び気泡径のばらつきを小さくしやすくなる。
気泡核調整剤の配合量は、樹脂成分１００質量部に対して、好ましくは０．１〜８質量部、より好ましくは０．２〜５質量部、更に好ましくは０．３〜２．５質量部である。〔Additive〕
It is preferable that the foam sheet contains a bubble nucleating agent as an additive. Examples of the bubble nucleating agent include zinc compounds such as zinc oxide and zinc stearate, and organic compounds such as citric acid and urea. Among these, zinc oxide and zinc stearate are more preferable, and these may be used alone or both may be used. By using the bubble nucleating agent in addition to the foaming agent, it becomes easy to reduce the variation in the average bubble diameter and the bubble diameter.
The blending amount of the bubble nucleating agent is preferably 0.1 to 8 parts by mass, more preferably 0.2 to 5 parts by mass, and further preferably 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the resin component. It is a department.
発泡体シートには、添加剤として酸化防止剤が配合されてもよい。酸化防止剤としては、リン系酸化防止剤、フェノール系酸化防止剤、イオウ系酸化防止剤、アミン系酸化防止剤等が挙げられる。酸化防止剤は、例えば樹脂成分１００質量部に対して０．０１〜５質量部配合される。
また、発泡体シートには、添加剤として着色剤が配合されていてもよい。着色剤は、発泡体シートの色を調整するものとして配合される。着色剤としては、具体的には、顔料、染料等が挙げられる。着色剤は、例えば樹脂成分１００質量部に対して０．５〜５質量部配合される。
発泡体シートには、添加剤として、必要に応じて、上記以外にも、熱安定剤、難燃剤、帯電防止剤、充填材等の発泡体シートに一般的に使用する添加剤が配合されていてもよい。The foam sheet may contain an antioxidant as an additive. Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like. For example, the antioxidant is blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin component.
Further, the foam sheet may contain a colorant as an additive. The colorant is formulated to adjust the color of the foam sheet. Specific examples of the colorant include pigments and dyes. For example, the colorant is blended in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin component.
In addition to the above, the foam sheet contains, if necessary, additives generally used for foam sheets such as heat stabilizers, flame retardants, antistatic agents, and fillers. May be.
＜発泡体シートの製造方法＞
発泡体シートは、樹脂、発泡剤及び必要に応じてその他添加剤を配合し、混練することで得られた樹脂組成物をシート状に成形することにより発泡性樹脂シートを準備し、次いで電離放射線等により架橋した後、加熱炉、オーブン等の加熱装置内にて加熱して発泡させる方法により製造することが好ましい。<Manufacturing method of foam sheet>
For the foam sheet, a foamable resin sheet is prepared by molding a resin composition obtained by blending a resin, a foaming agent and other additives as necessary and kneading into a sheet, and then ionizing radiation. It is preferable to carry out the production by a method of foaming by heating in a heating device such as a heating furnace or an oven after cross-linking with or the like.
上記発泡性樹脂シートは、例えば、バンバリーミキサーや加圧ニーダ等の混練り機を用いて各種成分を混練して得た樹脂組成物を、押出機、カレンダ、コンベアベルトキャスティング等により連続的に押し出すことにより得るとよい。
発泡性樹脂シートの架橋方法としては、電離性放射線による架橋、有機過酸化物による架橋等が挙げられるが、電離性放射線による架橋が好ましい。
電離性放射線により架橋する場合、電離性放射線としては、例えば、紫外光、γ線、電子線等が挙げられる。電離性放射線の照射量は、０．５〜１０Ｍｒａｄが好ましく、１．５〜８Ｍｒａｄがより好ましい。電離性放射線により架橋を行った場合、径が小さく均一な気泡径を有する発泡体シートを得ることができる。The foamable resin sheet is obtained by continuously extruding a resin composition obtained by kneading various components using a kneader such as a Banbury mixer or a pressure kneader by an extruder, a calendar, a conveyor belt casting or the like. It is good to get it by.
Examples of the method for cross-linking the foamable resin sheet include cross-linking with ionizing radiation and cross-linking with an organic peroxide, and cross-linking with ionizing radiation is preferable.
When cross-linking with ionizing radiation, examples of the ionizing radiation include ultraviolet light, γ-rays, electron beams and the like. The irradiation amount of ionizing radiation is preferably 0.5 to 10 Mrad, more preferably 1.5 to 8 Mrad. When cross-linking is performed by ionizing radiation, a foam sheet having a small diameter and a uniform bubble diameter can be obtained.
有機過酸化物により架橋する場合、有機過酸化物としては、例えば、ジイソプロピルベンゼンヒドロパーオキサイド、２,４−ジクロロベンゾイルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブチルパーベンゾエート、クミルハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、１,１−ジ（ｔ−ブチルパーオキシ）−３,３,５−トリメチルヘキサン、ｎ−ブチル−４,４−ジ（ｔ−ブチルパーオキシ）バレレート、α,α'−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、２,５−ジメチル−２,５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ｔ−ブチルパーオキシクメン等が挙げられる。
有機過酸化物の配合量は、樹脂成分１００質量部に対して０．０５〜１０質量部が好ましく、０．１〜７質量部がより好ましい。When cross-linking with an organic peroxide, examples of the organic peroxide include diisopropylbenzene hydroperoxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl perbenzoate, cumyl hydroperoxide, and t. -Butyl Hydroperoxide, 1,1-di (t-Butyl Peroxy) -3,3,5-trimethylhexane, n-Butyl-4,4-di (t-Butyl Peroxy) Valerate, α, α' -Bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, t-butylperoxycumene and the like can be mentioned.
The blending amount of the organic peroxide is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the resin component.
発泡性樹脂シートを発泡させる方法としては、オーブンのようなバッチ方式や、発泡性樹脂シートを長尺のシート状とし、連続的に加熱炉内を通す連続発泡方式を挙げることができる。加熱温度は、好ましくは２００〜３２０℃、より好ましくは２５０〜３００℃である。 Examples of the method for foaming the effervescent resin sheet include a batch method such as an oven, and a continuous effervescent method in which the effervescent resin sheet is formed into a long sheet and continuously passed through a heating furnace. The heating temperature is preferably 200 to 320 ° C, more preferably 250 to 300 ° C.
発泡性樹脂シートは、発泡させる際にＭＤ方向及びＴＤ方向の少なくとも一方、好ましくはこれらの両方に延伸させるとよい。ＭＤ方向及びＴＤ方向に延伸させることで、平均気泡径、平均気泡径の比を上記した範囲内に調整しやすくなる。また、発泡性樹脂シートは、発泡した後にＭＤ方向及びＴＤ方向の少なくとも一方、好ましくはこれらの両方に延伸させてもよい。なお、発泡性樹脂シートを発泡させた後に延伸する場合には、発泡後に冷却することなく発泡時の溶融状態を維持したまま続けて延伸してもよく、冷却した後、再度加熱して溶融又は軟化状態とした上で延伸してもよい。 The effervescent resin sheet may be stretched in at least one of the MD direction and the TD direction, preferably both of them when foaming. By stretching in the MD direction and the TD direction, it becomes easy to adjust the ratio of the average cell diameter and the average cell diameter within the above range. Further, the foamable resin sheet may be stretched after foaming in at least one of the MD direction and the TD direction, preferably both of them. When the foamable resin sheet is foamed and then stretched, it may be continuously stretched while maintaining the molten state at the time of foaming without cooling after foaming, and after cooling, it may be heated again to melt or melt. It may be stretched after being in a softened state.
＜用途＞
本発明の発泡体シートは、電子機器用途に好適に使用される。すなわち、本発明の発泡体シートは、例えば、スマートフォン等の携帯電話、カメラ、ゲーム機器、電子手帳、タブレット端末、ノート型パーソナルコンピューター等の電子機器の内部、好ましくはスマートフォン等の携帯電話の内部において好適に使用されるものである。発泡体シートは、電子機器内部において、例えば、シール材、衝撃吸収材などとして使用される。<Use>
The foam sheet of the present invention is suitably used for electronic device applications. That is, the foam sheet of the present invention is, for example, inside a mobile phone such as a smartphone, a camera, a game device, an electronic organizer, a tablet terminal, a notebook personal computer, or the like, preferably inside a mobile phone such as a smartphone. It is preferably used. The foam sheet is used inside an electronic device as, for example, a sealing material, a shock absorbing material, or the like.
［粘着テープ］
本発明の発泡体シートは、発泡体シートを基材とする粘着テープに使用してもよい。粘着テープは、例えば、発泡体シートと、発泡体シートの少なくとも一方の面に設けた粘着材とを備えるものである。粘着テープは、粘着材を介して他の部材に接着することが可能になる。粘着テープは、発泡体シートの両面に粘着材を設けたものでもよいし、片面に粘着材を設けたものでもよい。[Adhesive tape]
The foam sheet of the present invention may be used for an adhesive tape using the foam sheet as a base material. The adhesive tape includes, for example, a foam sheet and an adhesive material provided on at least one surface of the foam sheet. The adhesive tape can be adhered to other members via the adhesive material. The adhesive tape may be a foam sheet provided with an adhesive material on both sides, or may be provided with an adhesive material on one side.
粘着材は、感圧接着性を有する部材であって、少なくとも粘着剤層を備えるものであればよく、発泡体シートの表面に積層された粘着剤層単体であってもよいし、発泡体シートの表面に貼付された両面粘着シートであってもよいが、粘着剤層単体であることが好ましい。なお、両面粘着シートは、基材と、基材の両面に設けられた粘着剤層とを備えるものである。両面粘着シートは、一方の粘着剤層を発泡体シートに接着させるとともに、他方の粘着剤層を他の部材に接着させるために使用する。
粘着剤層を構成する粘着剤としては、特に制限はなく、例えば、アクリル系粘着剤、ウレタン系粘着剤、ゴム系粘着剤等を用いることができる。また、粘着材の上には、さらに離型紙等の剥離シートが貼り合わされてもよい。
粘着材の厚さは、５〜２００μｍであることが好ましく、より好ましくは７〜１５０μｍであり、更に好ましくは１０〜１００μｍである。The pressure-sensitive adhesive material may be a member having pressure-sensitive adhesiveness and may have at least a pressure-sensitive adhesive layer, and may be a single pressure-sensitive adhesive layer laminated on the surface of the foam sheet, or may be a foam sheet. Although it may be a double-sided pressure-sensitive adhesive sheet attached to the surface of the pressure-sensitive adhesive layer, it is preferably a single pressure-sensitive adhesive layer. The double-sided pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer provided on both sides of the base material. The double-sided pressure-sensitive adhesive sheet is used to adhere one pressure-sensitive adhesive layer to the foam sheet and the other pressure-sensitive adhesive layer to another member.
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or the like can be used. Further, a release sheet such as a release paper may be further bonded on the adhesive material.
The thickness of the pressure-sensitive adhesive is preferably 5 to 200 μm, more preferably 7 to 150 μm, and even more preferably 10 to 100 μm.
本発明を実施例により更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。 The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
［実施例１］
バイオ樹脂（１）及びポリエチレン系樹脂（１）と、熱分解型発泡剤としてアゾジカルボンアミドと、気泡核調整剤としてステアリン酸亜鉛及び酸化亜鉛と、酸化防止剤と、黒顔料とを、表２に記載の配合で押出機に供給して１３０℃で溶融混練して、樹脂組成物を得た。その樹脂組成物を押し出して長尺状の発泡性樹脂シートを得た。
次に、上記長尺状の発泡性樹脂シートの両面に加速電圧５００ｋＶの電子線を４．５Ｍｒａｄ照射して樹脂シートを架橋した。架橋した発泡性樹脂シートを熱風及び赤外線ヒーターにより２５０℃に保持された発泡炉内に連続的に送り込んで、ＭＤ及びＴＤ方向に延伸させながら発泡させて、表１に記載の厚みの発泡体シートを得た。[Example 1]
Table 2 shows the bioresin (1) and polyethylene resin (1), azodicarbonamide as a pyrolysis foaming agent, zinc stearate and zinc oxide as bubble nucleating agents, antioxidants, and black pigments. The resin composition was obtained by supplying to an extruder with the formulation described in 1 and melt-kneading at 130 ° C. The resin composition was extruded to obtain a long foamable resin sheet.
Next, the resin sheet was crosslinked by irradiating both sides of the long foamable resin sheet with an electron beam having an acceleration voltage of 500 kV for 4.5 Mrad. The crosslinked foamable resin sheet is continuously sent into a foaming furnace held at 250 ° C. by hot air and an infrared heater, and foamed while being stretched in the MD and TD directions to form a foam sheet having the thickness shown in Table 1. Got
［実施例２〜１７及び比較例１〜２］
押出機に供給される各成分を表２に記載のように調整して、樹脂組成物を実施例１と同様に得た。その後、架橋度が表２に記載されるとおりになるように電子線の照射量を調整し、かつ（ＭＤ＋ＴＤ）／２ＺＤが表２に記載されるとおりになるように、延伸の程度を調整したことを除いて実施例１と同様に実施した。[Examples 2 to 17 and Comparative Examples 1 to 2]
Each component supplied to the extruder was adjusted as shown in Table 2 to obtain a resin composition in the same manner as in Example 1. After that, the irradiation amount of the electron beam was adjusted so that the degree of cross-linking was as shown in Table 2, and the degree of stretching was adjusted so that (MD + TD) / 2ZD was as shown in Table 2. Except for this, it was carried out in the same manner as in Example 1.
実施例、比較例において得られた発泡体シートを以下のように評価した。
＜架橋度＞
発泡体シートから約１００ｍｇの試験片を採取し、試験片の重量Ａ（ｍｇ）を精秤する。次に、この試験片を１２０℃のキシレン３０ｃｍ３中に浸漬して２４時間放置した後、２００メッシュの金網で濾過して金網上の不溶解分を採取、真空乾燥し、不溶解分の重量Ｂ（ｍｇ）を精秤する。得られた値から、下記式により架橋度（質量％）を算出した。
架橋度（質量％）＝（Ｂ／Ａ）×１００
＜発泡倍率＞
発泡前と発泡後の比容積（単位：ｃｃ／ｇ）を測定し、発泡後の比容積／発泡前の比容積によって算出した。
＜発泡体シートにおけるバイオ率＞
明細書記載の方法で算出した。
＜平均気泡径及び最大気泡径＞
発泡体シートの平均気泡径及び最大気泡径は、明細書記載の方法で測定した。
＜２５％圧縮強度＞
発泡体シートについてＪＩＳ Ｋ６７６７に準拠して２５％圧縮強度を測定した。The foam sheets obtained in Examples and Comparative Examples were evaluated as follows.
<Crosslink degree>
Approximately 100 mg of the test piece is collected from the foam sheet, and the weight A (mg) of the test piece is precisely weighed. Next, this test piece was immersed in xylene 30 cm 3 at 120 ° C. and left for 24 hours, then filtered through a 200 mesh wire mesh to collect the insoluble matter on the wire mesh, vacuum dried, and the weight of the insoluble matter. Weigh B (mg) precisely. From the obtained values, the degree of cross-linking (mass%) was calculated by the following formula.
Degree of cross-linking (% by mass) = (B / A) x 100
<Effervescence magnification>
The specific volume before and after foaming (unit: cc / g) was measured and calculated by the specific volume after foaming / the specific volume before foaming.
<Bio-rate in foam sheet>
Calculated by the method described in the specification.
<Average bubble diameter and maximum bubble diameter>
The average cell diameter and the maximum cell diameter of the foam sheet were measured by the method described in the specification.
<25% compressive strength>
The 25% compressive strength of the foam sheet was measured according to JIS K6767.
表２の結果から明らかなように、各実施例の発泡体シートはバイオ率が高く、かつ厚みが薄いにもかかわらず、最大気泡径を小さくでき、耐衝撃性などの各種性能が良好になることが理解できる。 As is clear from the results in Table 2, although the foam sheet of each example has a high biorate and a thin thickness, the maximum bubble diameter can be reduced and various performances such as impact resistance are improved. Can be understood.
Claims (12)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019035550 | 2019-02-28 | ||
| JP2019035550 | 2019-02-28 | ||
| PCT/JP2020/008518 WO2020175699A1 (en) | 2019-02-28 | 2020-02-28 | Foam sheet and adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2020175699A1 true JPWO2020175699A1 (en) | 2021-12-23 |
| JPWO2020175699A5 JPWO2020175699A5 (en) | 2022-10-26 |
Family
ID=72239822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020516486A Pending JPWO2020175699A1 (en) | 2019-02-28 | 2020-02-28 | Foam sheet and adhesive tape |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2020175699A1 (en) |
| KR (1) | KR20210135228A (en) |
| CN (1) | CN113490707A (en) |
| WO (1) | WO2020175699A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013060528A (en) * | 2011-09-13 | 2013-04-04 | Sekisui Plastics Co Ltd | Polyethylene-based resin foamed sheet, expanded molding, and method for producing polyethylene-based resin foamed sheet |
| JP2018053186A (en) * | 2016-09-30 | 2018-04-05 | 積水化学工業株式会社 | Closed-cell resin foam and method for producing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1449869A4 (en) * | 2001-11-29 | 2005-01-19 | Toray Industries | Crosslinked biodegradable resin continuous foamed sheet and method for production thereof |
| JP5919841B2 (en) | 2012-01-27 | 2016-05-18 | 東レ株式会社 | Foam |
| JP2018065898A (en) | 2016-10-18 | 2018-04-26 | 東レ株式会社 | Foamed body |
| CN110475812A (en) * | 2017-03-30 | 2019-11-19 | 积水化学工业株式会社 | Resin foamed sheet, the manufacturing method of resin foamed sheet and adhesive tape |
-
2020
- 2020-02-28 WO PCT/JP2020/008518 patent/WO2020175699A1/en active Application Filing
- 2020-02-28 JP JP2020516486A patent/JPWO2020175699A1/en active Pending
- 2020-02-28 CN CN202080016728.7A patent/CN113490707A/en active Pending
- 2020-02-28 KR KR1020217026915A patent/KR20210135228A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013060528A (en) * | 2011-09-13 | 2013-04-04 | Sekisui Plastics Co Ltd | Polyethylene-based resin foamed sheet, expanded molding, and method for producing polyethylene-based resin foamed sheet |
| JP2018053186A (en) * | 2016-09-30 | 2018-04-05 | 積水化学工業株式会社 | Closed-cell resin foam and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113490707A (en) | 2021-10-08 |
| KR20210135228A (en) | 2021-11-12 |
| WO2020175699A1 (en) | 2020-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6987178B2 (en) | Polyolefin resin foam sheet and adhesive tape | |
| US10125201B2 (en) | Polyolefin resin foam sheet and adhesive tape | |
| JP6207009B2 (en) | Cross-linked polyolefin resin foam sheet | |
| CN108291047B (en) | Polyolefin resin foamed sheet and adhesive tape | |
| WO2015046526A1 (en) | Crosslinked polyolefin resin foam sheet | |
| JP6773816B2 (en) | Polyolefin resin foam sheet and adhesive tape | |
| JP7071836B2 (en) | Foam sheet and adhesive tape | |
| CN108026310B (en) | Polyolefin resin foam sheet and adhesive tape | |
| JP7071848B2 (en) | Foam sheet and adhesive tape | |
| JP7295623B2 (en) | Polyolefin resin foam sheet and adhesive tape using the same | |
| JP6625032B2 (en) | Closed-cell resin foam and method for producing the same | |
| JP6901476B2 (en) | Crosslinked resin foam sheet, its manufacturing method, and adhesive tape | |
| WO2018181498A1 (en) | Polyolefin-based foamed sheet, production method therefor, and pressure-sensitive adhesive tape | |
| JP2021031608A (en) | Foam sheet, and adhesive tape | |
| JPWO2020175699A1 (en) | Foam sheet and adhesive tape | |
| JP2021152103A (en) | Foam sheet and adhesive tape | |
| JP2021152099A (en) | Foam sheet and adhesive tape | |
| JP2019178210A (en) | Resin foam sheet and adhesive tape | |
| JP2018135473A (en) | Resin foam sheet and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221018 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20221018 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230627 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20231219 |