JP2019065191A - Resin foam sheet, manufacturing method of resin foam sheet, and adhesive tape - Google Patents
Resin foam sheet, manufacturing method of resin foam sheet, and adhesive tape Download PDFInfo
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- JP2019065191A JP2019065191A JP2017192259A JP2017192259A JP2019065191A JP 2019065191 A JP2019065191 A JP 2019065191A JP 2017192259 A JP2017192259 A JP 2017192259A JP 2017192259 A JP2017192259 A JP 2017192259A JP 2019065191 A JP2019065191 A JP 2019065191A
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- Prior art keywords
- foam sheet
- resin foam
- resin
- less
- ratio
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 237
- 239000011347 resin Substances 0.000 title claims abstract description 237
- 239000006260 foam Substances 0.000 title claims abstract description 198
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims description 25
- 229920005672 polyolefin resin Polymers 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229920013716 polyethylene resin Polymers 0.000 claims description 14
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 12
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 92
- 239000003566 sealing material Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 17
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000005187 foaming Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- 239000003446 ligand Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 210000003855 cell nucleus Anatomy 0.000 description 5
- 238000005979 thermal decomposition reaction 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000005865 ionizing radiation Effects 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 239000004156 Azodicarbonamide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003963 antioxidant agent 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
- 235000019399 azodicarbonamide Nutrition 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
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 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
- 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
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- RXVMKCWWKQUKDI-UHFFFAOYSA-N (sulfonylamino)urea;toluene Chemical compound CC1=CC=CC=C1.NC(=O)NN=S(=O)=O RXVMKCWWKQUKDI-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XZGCGBCJTNRXPB-UHFFFAOYSA-N C[Ti](N(C)C)(N(C)C)(N(C)C)C1C=CC=C1 Chemical compound C[Ti](N(C)C)(N(C)C)(N(C)C)C1C=CC=C1 XZGCGBCJTNRXPB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001408 amides 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
- 125000005604 azodicarboxylate group Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-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
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 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
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 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
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 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
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 1
- 235000018342 monosodium citrate Nutrition 0.000 description 1
- 239000002524 monosodium citrate Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 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
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本発明は、樹脂発泡シート、樹脂発泡シートの製造方法、及び粘着テープに関する。 The present invention relates to a resin foam sheet, a method for producing a resin foam sheet, and an adhesive tape.
従来、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等の電子機器では、樹脂発泡シートからなるシール材又は衝撃吸収材が使用されている。これらシール材又は衝撃吸収材は、樹脂発泡シートを基材とした粘着テープ等にして使用されることがある。例えば、上記電子機器における表示装置は、一般的に、ＬＣＤ等の表示パネルの上に保護パネルを設置した構造を有するが、その保護パネルを、表示パネル外側の額縁部分と貼り合わせるために、樹脂発泡シートを基材とした粘着テープが使用される。
電子機器内部に使用される樹脂発泡シートとしては、熱分解型発泡剤を含む発泡性ポリオレフィン系樹脂シートを発泡且つ架橋させて得られる架橋ポリオレフィン系樹脂発泡シートが知られている（例えば、特許文献１参照）。
Conventionally, in electronic devices such as mobile phones, cameras, game machines, electronic notebooks, tablet terminals, notebook personal computers and the like, sealing materials or impact absorbing materials made of resin foam sheets are used. These sealing materials or impact absorbing materials may be used as an adhesive tape etc. which used the resin foam sheet as a base material. For example, the display device in the electronic device generally has a structure in which a protection panel is installed on a display panel such as an LCD, but in order to bond the protection panel to a frame portion outside the display panel, An adhesive tape based on a foamed sheet is used.
As a resin foam sheet used inside an electronic device, a crosslinked polyolefin resin foam sheet obtained by foaming and crosslinking a foamable polyolefin resin sheet containing a thermal decomposition-type foaming agent is known (for example, patent documents 1).
ところで、昨今、電子機器は小型化が進む一方で各種部品の高機能化も進み、電子機器内部のスペースの制約が大きくなるだけでなく、機器の内部構造が複雑化している。内部構造の複雑化に伴い、大小さまざまな段差をもった筐体が増えると想定される。その際、樹脂発泡シートを基材とするシール材と筐体との間に隙間があいてしまうと防水性が失われ、そこを起点にして剥がれやすくなる。
したがって、樹脂発泡シートを基材とするシール材を電子機器等に貼り付ける際、防水性や接着強度の観点から、段差追従性が求められる。また、これと共に部品を再利用する観点で、シール材が千切れることなく容易に剥離できるリワーク性が求められる。
By the way, recently, while the miniaturization of electronic devices is progressing, the functionalization of various parts is also advanced, and not only the restriction of the space inside the electronic device becomes large but also the internal structure of the device is complicated. It is assumed that with the complexity of the internal structure, the number of cases with various steps will increase. At that time, if there is a gap between the sealing material based on the resin foam sheet and the casing, the waterproof property is lost, and it becomes easy to be peeled off from there.
Therefore, when sticking the sealing material which uses a resin foam sheet as a substrate to electronic equipment etc., level difference flattery nature is called for from waterproofness and a viewpoint of adhesive strength. In addition, from the viewpoint of reusing parts together with this, a rework property that can be easily peeled off without breaking the sealing material is required.
本発明は、以上の事情に鑑みてなされたものであり、段差に追従して良好な接着性を示すと共に、リワーク性が良好なシール材の基材として用いることができる樹脂発泡シート、該樹脂発泡シートの製造方法、及び該樹脂発泡シートを備える粘着テープを提供することを課題とする。 The present invention has been made in view of the above-mentioned circumstances, and it is possible to use a resin foam sheet which can be used as a base material of a sealing material having good reworkability while showing good adhesion following steps. An object of the present invention is to provide a method for producing a foam sheet and an adhesive tape provided with the resin foam sheet.
発明者らは、鋭意検討の結果、比較的小さい気泡径の存在割合を特定の範囲に調整した樹脂発泡シートであれば、段差に追従して良好な接着性を示し、且つ良好なリワーク性を示すシール材の基材として用いることができることを見出し、本発明を完成させた。すなわち、本発明は下記のとおりである。 The inventors of the present invention, as a result of intensive studies, show that if the resin foam sheet has a relatively small cell diameter adjusted to a specific range, it exhibits good adhesion following the step and good reworkability. The inventors have found that the present invention can be used as a base material of the sealing material shown and complete the present invention. That is, the present invention is as follows.
［１］樹脂発泡シート中の全気泡の数に対し、ＭＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上であり、ＴＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上であり、ＭＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が５０％以上であり、ＴＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が４５％以上である、樹脂発泡シート。
［２］前記樹脂発泡シートのＭＤ方向及びＴＤ方向のそれぞれの平均気泡径が１００μｍ以下である、上記［１］に記載の樹脂発泡シート。
［３］前記樹脂発泡シートの厚さが１．２ｍｍ以下である、上記［１］又は［２］に記載の樹脂発泡シート。
[1] The ratio of the number of cells having a cell diameter of more than 20 μm and 40 μm or less in the MD direction to the number of all cells in the resin foam sheet is 12% or more, and the cell diameter in the TD direction is more than 20 μm and 40 μm or less The ratio of the number of certain bubbles is 12% or more, the ratio of the number of bubbles having a bubble diameter of more than 20 μm and 80 μm or less in the MD direction is 50% or more, and the bubbles of 20 μm and 80 μm or less in the TD direction The resin foam sheet whose ratio of the number of is 45% or more.
[2] The resin foam sheet according to the above [1], wherein the average cell diameter in each of the MD direction and the TD direction of the resin foam sheet is 100 μm or less.
[3] The resin foam sheet as described in the above [1] or [2], wherein the thickness of the resin foam sheet is 1.2 mm or less.
［４］前記樹脂発泡シートのＭＤ方向の破断点強度が７〜３０ＭＰａであり、ＴＤ方向の破断点強度が５〜３０ＭＰａである、上記［１］〜［３］のいずれか１項に記載の樹脂発泡シート。
［５］前記樹脂発泡シートの２５％圧縮強度が４０〜６００ｋＰａである、上記［１］〜［４］のいずれか１項に記載の樹脂発泡シート。
［６］前記樹脂発泡シートの発泡倍率が１．２〜１１ｃｍ３／ｇである、上記［１］〜［５］のいずれか１項に記載の樹脂発泡シート。
［７］前記樹脂発泡シートはポリオレフィン樹脂を含む、上記［１］〜［６］のいずれか１項に記載の樹脂発泡シート。
[4] The breaking point strength in the MD direction of the resin foam sheet is 7 to 30 MPa, and the breaking point strength in the TD direction is 5 to 30 MPa according to any one of the above [1] to [3] Resin foam sheet.
[5] The resin foam sheet according to any one of the above [1] to [4], wherein the 25% compressive strength of the resin foam sheet is 40 to 600 kPa.
[6] The resin foam sheet according to any one of the above [1] to [5], wherein the expansion ratio of the resin foam sheet is 1.2 to 11 cm 3 / g.
[7] The resin foam sheet according to any one of the above [1] to [6], wherein the resin foam sheet contains a polyolefin resin.
［８］前記ポリオレフィン樹脂がポリエチレン樹脂である、上記［７］に記載の樹脂発泡シート。
［９］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直鎖状低密度ポリエチレンである、上記［８］に記載の樹脂発泡シート。
［１０］上記［１］〜［９］のいずれか１項に記載の樹脂発泡シートの製造方法であって、
樹脂及び熱分解型発泡剤を含むシート状の発泡性組成物を架橋し、加熱して前記熱分解型発泡剤を発泡させ、延伸倍率１．１倍以上でＴＤ方向及びＭＤ方向の少なくともいずれか一方に延伸する、樹脂発泡シートの製造方法。
［１１］上記［１］〜［９］のいずれか１項に記載の樹脂発泡シートと、該樹脂発泡シートの少なくともいずれか一方の面に設けた粘着剤層とを備える粘着テープ。
[8] The resin foam sheet according to the above [7], wherein the polyolefin resin is a polyethylene resin.
[9] The resin foam sheet according to the above [8], wherein the polyethylene resin is a linear low density polyethylene polymerized with a polymerization catalyst of a metallocene compound.
[10] A method for producing a resin foam sheet according to any one of [1] to [9] above,
A sheet-like foamable composition containing a resin and a thermal decomposition-type foaming agent is crosslinked and heated to foam the thermal decomposition-type foaming agent, and at least one of TD direction and MD direction at a draw ratio of 1.1 times or more The manufacturing method of the resin foam sheet stretched to one side.
[11] A pressure-sensitive adhesive tape comprising the resin foam sheet according to any one of the above [1] to [9] and a pressure-sensitive adhesive layer provided on at least one surface of the resin foam sheet.
本発明によれば、段差に追従して良好な接着性を示すと共に、リワーク性が良好なシール材の基材として用いることができる樹脂発泡シート、該樹脂発泡シートの製造方法、及び該樹脂発泡シートを備える粘着テープを提供することができる。 According to the present invention, a resin foam sheet which can be used as a base material of a sealing material which exhibits good adhesion following a level difference and has a good rework property, a method for producing the resin foam sheet, and the resin foam An adhesive tape comprising a sheet can be provided.
以下、本発明について実施形態を用いて詳細に説明する。
［樹脂発泡シート］
本発明の実施形態に係る樹脂発泡シートは、樹脂発泡シート中の全気泡の数に対し、ＭＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上であり、ＴＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上であり、ＭＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が５０％以上であり、ＴＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が４５％以上である、樹脂発泡シートである。
なお、ＭＤ方向は、Machine directionを意味し、押出方向等と一致する方向であるとともに、ＴＤ方向は、Transverse directionを意味し、ＭＤ方向に直交する方向であり、樹脂発泡シートのシート面に平行な方向である。
Hereinafter, the present invention will be described in detail using embodiments.
[Resin foam sheet]
In the resin foam sheet according to the embodiment of the present invention, the ratio of the number of cells having a cell diameter in the MD direction of more than 20 μm and 40 μm or less to the number of all cells in the resin foam sheet is 12% or more. The ratio of the number of air bubbles having a diameter of more than 20 μm and 40 μm or less is 12% or more, and the ratio of the number of air bubbles having a cell diameter of 20 μm to 80 μm or less in the MD direction is 50% or more It is a resin foam sheet whose ratio of the number of air bubbles whose diameter is more than 20 micrometers and 80 micrometers or less is 45% or more.
In addition, MD direction means Machine direction, and is a direction coinciding with extrusion direction etc., and TD direction means Transverse direction, is a direction orthogonal to MD direction, and is parallel to the sheet surface of the resin foam sheet. Direction.
＜ＭＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートは、ＭＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上である。前記気泡の数の割合が１２％未満であると、必然的に気泡径が大きな気泡が発泡樹脂シート中に多くなるため、該気泡を起点として樹脂発泡シートが千切れたり破れたりしやすくなり、樹脂発泡シートを基材として有するシール材のリワーク性が低下する。そのような観点から、ＭＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合は、１５％以上が好ましく、１８％以上がより好ましく、そして、上限値に制限はないが、７０％以下が好ましく、６５％以下がより好ましく、６０％以下が更に好ましい。
<Proportion of the number of bubbles having a bubble diameter of more than 20 μm and 40 μm or less in the MD direction>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 20 μm and 40 μm or less in the MD direction is 12% or more. When the ratio of the number of the bubbles is less than 12%, the bubbles having a large cell diameter inevitably increase in the foamed resin sheet, so the resin foam sheet is easily broken or broken starting from the bubbles. The rework property of the sealing material which has a resin foam sheet as a base material falls. From such a point of view, the ratio of the number of bubbles having a bubble diameter of more than 20 μm and 40 μm or less in the MD direction is preferably 15% or more, more preferably 18% or more, and the upper limit is not limited. The following is preferable, 65% or less is more preferable, and 60% or less is more preferable.
＜ＴＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートは、ＴＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合が１２％以上である。前記気泡の数の割合が１２％未満であると、前述のＭＤ方向における理由と同様に、気泡径が大きな気泡が発泡樹脂シート中に多くなるため、該気泡を起点として樹脂発泡シートが千切れたり破れたりしやすくなる。そのような観点から、ＴＤ方向における気泡径が２０μｍ超４０μｍ以下である気泡の数の割合は、１５％以上が好ましく、１８％以上がより好ましく、そして、上限値に制限はないが、７０％以下が好ましく、６０％以下がより好ましく、５５％以下が更に好ましく、５０％以下がより更に好ましい。
<Proportion of the number of bubbles having a bubble diameter of more than 20 μm and 40 μm or less in the TD direction>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 20 μm and 40 μm or less in the TD direction is 12% or more. If the ratio of the number of the bubbles is less than 12%, the bubbles having a large cell diameter increase in the foamed resin sheet as in the case of the above-mentioned MD direction, so the resin foam sheet is broken starting from the bubbles. It becomes easy to break. From such a point of view, the ratio of the number of bubbles having a bubble diameter of more than 20 μm and 40 μm or less in the TD direction is preferably 15% or more, more preferably 18% or more, and the upper limit is not limited. The following is preferable, 60% or less is more preferable, 55% or less is more preferable, and 50% or less is still more preferable.
＜ＭＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートは、ＭＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が５０％以上である。前記気泡の数の割合が５０％未満であると、必然的に気泡径が大きな気泡が発泡樹脂シート中に極端に多くなるため、該気泡を起点として樹脂発泡シートが千切れたり破れたりしやすくなる。また、発泡樹脂シート中の気泡径の大きさのバラツキが多くなるため、この樹脂発泡シートを用いたシール材のリワーク性が低下する。そのような観点から、ＭＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合は、５５％以上が好ましく、６０％以上がより好ましく、６４％以上が更に好ましく、６８％以上がより更に好ましい。そして、上限値に制限はないが、９５％以下が好ましく、９０％以下がより好ましく、８５％以下が更に好ましく、８０％以下がより更に好ましく、７５％以下がより更に好ましい。
<Proportion of the Number of Bubbles Having a Bubble Diameter of More Than 20 μm and 80 μm or Less in the MD Direction>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 20 μm and 80 μm or less in the MD direction is 50% or more. If the ratio of the number of cells is less than 50%, the cells having a large cell diameter inevitably become extremely large in the foamed resin sheet, so the resin foam sheet is likely to be broken or broken starting from the cells. Become. In addition, since the variation in the size of the cell diameter in the foamed resin sheet is increased, the reworkability of the sealing material using the foamed resin sheet is reduced. From such a viewpoint, the ratio of the number of cells having a cell diameter in the MD direction of more than 20 μm and 80 μm is preferably 55% or more, more preferably 60% or more, still more preferably 64% or more, and 68% or more More preferable. And although there is no restriction | limiting in an upper limit, 95% or less is preferable, 90% or less is more preferable, 85% or less is still more preferable, 80% or less is still more preferable, 75% or less is still more preferable.
＜ＴＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートは、ＴＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合が４５％以上である。前記気泡の数の割合が４５％未満であると、前記ＭＤ方向における理由と同様の理由から、樹脂発泡シートが千切れたり破れたりしやすくなる。また、発泡樹脂シート中の気泡径の大きさのバラツキが多くなるため、この樹脂発泡シートを基材として有するシール材のリワーク性が低下する。そのような観点から、ＴＤ方向における気泡径が２０μｍ超８０μｍ以下である気泡の数の割合は、４８％以上が好ましく、５０％以上がより好ましく、５２％以上が更に好ましく、そして、上限値に制限はないが、８０％以下が好ましく、７５％以下がより好ましく、７０％以下が更に好ましく、６５％以下がより更に好ましい。
<Proportion of the number of bubbles having a bubble diameter of more than 20 μm and 80 μm or less in the TD direction>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 20 μm and 80 μm or less in the TD direction is 45% or more. If the ratio of the number of the bubbles is less than 45%, the resin foam sheet is likely to be broken or torn for the same reason as the reason in the MD direction. In addition, since the variation in the size of the cell diameter in the foamed resin sheet is increased, the reworkability of the sealing material having the foamed resin sheet as a base is lowered. From such a point of view, the ratio of the number of cells having a cell diameter of more than 20 μm and 80 μm or less in the TD direction is preferably 48% or more, more preferably 50% or more, and still more preferably 52% or more. Although there is no limitation, 80% or less is preferable, 75% or less is more preferable, 70% or less is more preferable, and 65% or less is still more preferable.
＜気泡径が２０μｍ以下である気泡の数の割合＞
全気泡の数に対し、ＭＤ方向における気泡径が２０μｍ以下である気泡の数の割合は、１０％以下であることが好ましい。発泡樹脂シートを基材とするシール材のリワーク性を向上させることを考慮すると気泡径が２０μｍ以下である気泡が多く存在しても問題はないが、気泡径が２０μｍ以下である気泡を多く有する樹脂発泡シートは、コストの点で製造が困難である。よって、ＭＤ方向における気泡径が２０μｍ以下である気泡の数の割合は、好ましくは８％以下、より好ましくは７％以下、更に好ましくは６％以下である。
また、ＴＤ方向における気泡径が２０μｍ以下である気泡の数の割合は、同様に製造コストの観点から、好ましくは１０％以下、より好ましくは８％以下、更に好ましくは７％以下、より更に好ましくは６％以下である。
気泡径が２０μｍ以下である気泡の数の割合の下限値は、ＭＤ方向及びＴＤ方向のいずれも制限はないが、好ましくは１％以上、より好ましくは２％以上である。
<Proportion of the number of bubbles having a bubble diameter of 20 μm or less>
The ratio of the number of cells having a cell diameter of 20 μm or less in the MD direction to the number of all cells is preferably 10% or less. Considering improving the reworkability of the sealing material using a foamed resin sheet as a base, there is no problem even if there are many air bubbles with a cell diameter of 20 μm or less, but it has many air bubbles with a cell diameter of 20 μm or less A resin foam sheet is difficult to manufacture in terms of cost. Therefore, the ratio of the number of cells having a cell diameter of 20 μm or less in the MD direction is preferably 8% or less, more preferably 7% or less, and still more preferably 6% or less.
Also, the ratio of the number of cells having a cell diameter of 20 μm or less in the TD direction is preferably 10% or less, more preferably 8% or less, still more preferably 7% or less, still more preferably from the viewpoint of production cost. Is less than 6%.
The lower limit of the ratio of the number of bubbles having a bubble diameter of 20 μm or less is not limited in either the MD direction or the TD direction, but is preferably 1% or more, more preferably 2% or more.
＜気泡径が４０μｍ超６０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートにおいて、ＭＤ方向における気泡径が４０μｍ超６０μｍ以下である気泡の数の割合は１５〜５０％が好ましい。前記気泡の数の割合が前記範囲内であると発泡樹脂シート中の気泡径の大きさのバラツキが少なくなるため、この樹脂発泡シートを基材とするシール材のリワーク性が向上する。そのような観点から、ＭＤ方向における気泡径が４０μｍ超６０μｍ以下である気泡の数の割合は、２０〜４５％がより好ましく、２３〜４０％が更に好ましく、２３〜３８％がより更に好ましい。また、同様の理由から、ＴＤ方向における気泡径が４０μｍ超６０μｍ以下である気泡の数の割合は、１０〜４０％が好ましく、１２〜３５％がより好ましく、１５〜３０％が更に好ましい。
<Proportion of the number of bubbles having a bubble diameter of more than 40 μm and 60 μm or less>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 40 μm and 60 μm or less in the MD direction is preferably 15 to 50%. When the ratio of the number of the bubbles is within the above range, the variation in the size of the bubble diameter in the foamed resin sheet is reduced, so that the reworkability of the sealing material based on this foamed resin sheet is improved. From such a point of view, the ratio of the number of cells having a cell diameter of more than 40 μm and 60 μm or less in the MD direction is more preferably 20 to 45%, still more preferably 23 to 40%, and still more preferably 23 to 38%. Further, for the same reason, the ratio of the number of bubbles having a bubble diameter of more than 40 μm and 60 μm or less in the TD direction is preferably 10 to 40%, more preferably 12 to 35%, and still more preferably 15 to 30%.
＜気泡径が６０μｍ超８０μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートにおいて、ＭＤ方向における気泡径が６０μｍ超８０μｍ以下である気泡の数の割合は１〜３０％が好ましい。前記気泡の数の割合が前記範囲内であると発泡樹脂シート中の気泡径の大きさのバラツキが少なくなるため、この樹脂発泡シートを基材とするシール材のリワーク性が向上する。そのような観点から、ＭＤ方向における気泡径が６０μｍ超８０μｍ以下である気泡の数の割合は、１〜２８％が好ましく、１〜２５％がより好ましく、１〜２２％が更に好ましい。また、同様の理由から、ＴＤ方向における気泡径が６０μｍ超８０μｍ以下である気泡の数の割合は、１〜３０％が好ましく、１〜２５％がより好ましく、１〜２０％が更に好ましい。
<Proportion of the number of bubbles having a bubble diameter of more than 60 μm and 80 μm or less>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter in the MD direction of more than 60 μm and 80 μm or less is preferably 1 to 30%. When the ratio of the number of the bubbles is within the above range, the variation in the size of the bubble diameter in the foamed resin sheet is reduced, so that the reworkability of the sealing material based on this foamed resin sheet is improved. From such a point of view, the ratio of the number of cells having a cell diameter of 60 μm to 80 μm or less in the MD direction is preferably 1 to 28%, more preferably 1 to 25%, and still more preferably 1 to 22%. In addition, for the same reason, the ratio of the number of cells having a cell diameter of 60 μm to 80 μm or less in the TD direction is preferably 1 to 30%, more preferably 1 to 25%, and still more preferably 1 to 20%.
＜気泡径が８０μｍ超１００μｍ以下である気泡の数の割合＞
本発明の樹脂発泡シートにおいて、ＭＤ方向における気泡径が８０μｍ超１００μｍ以下である気泡の数の割合は、３０％以下であることが好ましい。樹脂発泡シートにおいては、８０μｍ超の気泡径を有する気泡が多いと、それらの気泡を起点として樹脂発泡シートが千切れたり破れたりしやすくなる。この樹脂発泡シートを用いた発泡樹脂シートのリワーク性が低下する。そのような観点から、ＭＤ方向における気泡径が８０μｍ超１００μｍ以下である気泡の数の割合は、１〜２５％が好ましく、１〜２０％がより好ましく、１〜１５％が更に好ましい。また、同様の理由から、ＴＤ方向における気泡径が８０μｍ超１００μｍ以下である気泡の数の割合は、１〜３０％が好ましく、１〜２５％がより好ましく、１〜２０％が更に好ましい。
<Proportion of Number of Bubbles Having Bubble Diameter of More Than 80 μm and 100 μm or Less>
In the resin foam sheet of the present invention, the ratio of the number of cells having a cell diameter of more than 80 μm and 100 μm or less in the MD direction is preferably 30% or less. In the resin foam sheet, when there are many cells having a cell diameter of more than 80 μm, the resin foam sheet tends to be broken or torn from those cells. The reworkability of the foamed resin sheet using this foamed resin sheet is reduced. From such a point of view, the ratio of the number of cells having a cell diameter of 80 μm to 100 μm or less in the MD direction is preferably 1 to 25%, more preferably 1 to 20%, and still more preferably 1 to 15%. In addition, for the same reason, the ratio of the number of cells having a cell diameter of 80 μm to 100 μm or less in the TD direction is preferably 1 to 30%, more preferably 1 to 25%, and still more preferably 1 to 20%.
ＭＤ方向及びＴＤ方向における気泡径を上記範囲とするには、例えば、後述する発泡剤を用いて製造したり、樹脂発泡シート作製時の延伸率を高くすればよい。また、架橋度、平均気泡径、発泡倍率等を適宜後述する範囲内等に設定することで調整することができる。
なお、ＭＤ方向における気泡径が１００μｍ超である気泡の数の割合は、実質的に存在しないことが好ましいが、この樹脂発泡シートを基材として用いたシール材のリワーク性を向上させる観点から、１０％以下が好ましく、５％以下がより好ましく、４％以下が更に好ましい。
In order to make the cell diameter in the MD direction and the TD direction be in the above range, for example, it may be manufactured using a foaming agent to be described later, or the stretching ratio at the time of resin foam sheet preparation may be increased. In addition, the degree of crosslinking, the average cell diameter, the expansion ratio and the like can be appropriately adjusted by setting them in the ranges described later and the like.
In addition, although it is preferable that the ratio of the number of cells having a cell diameter of more than 100 μm in the MD direction does not substantially exist, from the viewpoint of improving the reworkability of the sealing material using this resin foam sheet as a substrate, 10% or less is preferable, 5% or less is more preferable, and 4% or less is more preferable.
＜平均気泡径＞
樹脂発泡シートは、ＭＤ及びＴＤ方向の平均気泡径のいずれもが、好ましくは１００μｍ以下、より好ましくは９５μｍ以下、更に好ましくは９０μｍ以下、より更に好ましくは８５μｍ以下である。このような平均気泡径の気泡は一般的に微細気泡と呼ばれる。樹脂発泡シートの２５％圧縮強度が小さいと層間強度が低下してテープ強度が損なわれることがあるが、平均気泡径が１００μｍ以下であることで強度を補填することができる。また、樹脂発泡シートは、微細気泡を有することでシート幅を狭くしたような場合でも、その狭い幅の間に独立気泡が多数存在することになる。そのため、幅を狭くした場合でも、適度な圧縮強度、破断点強度が確保できる。
また、ＭＤ及びＴＤの平均気泡径それぞれは、製造容易性の観点から、好ましくは１０μｍ以上、より好ましくは２０μｍ以上、更に好ましくは３０μｍ以上である。
<Average bubble diameter>
The foamed resin sheet has an average cell diameter in the MD and TD directions of preferably 100 μm or less, more preferably 95 μm or less, still more preferably 90 μm or less, still more preferably 85 μm or less. Bubbles of such an average bubble diameter are generally called fine bubbles. If the 25% compressive strength of the resin foam sheet is low, the interlayer strength may be reduced and the tape strength may be impaired, but the strength can be compensated by the average cell diameter being 100 μm or less. In addition, even when the sheet width of the resin foam sheet is narrowed by having fine cells, a large number of closed cells exist in the narrow width. Therefore, even when the width is narrowed, appropriate compressive strength and breaking point strength can be secured.
The average cell diameter of each of MD and TD is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more from the viewpoint of ease of production.
なお、気泡の数の割合、及び平均気泡径は下記の要領で測定したものをいう。
樹脂発泡シートを５０ｍｍ四方にカットしたものを測定用の発泡体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、ＴＤ方向に沿ってそれぞれ厚さ方向に切断した。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、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、前記各範囲に存在する気泡の数の割合を算出し気泡の数の割合とすると共に、全ての気泡の平均値をＭＤ方向、ＴＤ方向の平均気泡径とした。
In addition, the ratio of the number of air bubbles and the average air bubble diameter mean what was measured in the following way.
What cut the resin foam sheet to 50 mm around was prepared as a foam sample for measurement. This was immersed in liquid nitrogen for 1 minute, and then cut in the thickness direction along the MD and TD directions with a razor blade. This cross section is taken a 200x magnification with a digital microscope ("VHX-900" manufactured by KEYENCE CORPORATION), and all bubbles present in the cut surface for 2 mm in length in the MD direction and TD direction respectively The bubble diameter was measured, and the operation was repeated five times. And while calculating the ratio of the number of air bubbles which exists in each said range and setting it as the ratio of the number of air bubbles, the average value of all the air bubbles was made into the average air bubble diameter of MD direction and TD direction.
＜破断点強度＞
本発明の樹脂発泡シートのＭＤ方向における破断点強度は、７〜３０ＭＰａが好ましく、１０〜２５ＭＰａがより好ましく、１０〜２０ＭＰａが更に好ましい。
一方、本発明の樹脂発泡シートのＴＤ方向における破断点強度は、５〜３０ＭＰａが好ましく、５〜２５ＭＰａがより好ましく５〜２０ＭＰａが更に好ましい。
ＭＤ方向及びＴＤ方向の破断点強度が前記範囲内であると、樹脂発泡シートを細く打ち抜いたものを基材として用いたシール材のリワーク時に、ＭＤ方向及びＴＤ方向のいずれの方向に力が加わっても千切れることなく容易に剥離することができる。
<Breaking point strength>
7-30 Mpa is preferable, 10-25 Mpa is more preferable, and 10-20 Mpa of the resin foam sheet of this invention is more preferable.
On the other hand, 5-30 Mpa is preferable, as for the breaking point strength in the TD direction of the resin foam sheet of this invention, 5-25 Mpa is more preferable, and 5-20 Mpa is still more preferable.
When the strength at break in the MD direction and the TD direction is within the above range, a force is applied in either the MD direction or the TD direction when the seal material is reworked using a thin punched resin foam sheet as a substrate However, it can be easily peeled off without breaking.
＜破断までの伸び率＞
本発明の樹脂発泡シートのＭＤ方向における破断までの伸び率は、１００〜６００％が好ましく、１５０〜５５０％がより好ましく、２００〜５００％が更に好ましく、２５０〜５００％がより更に好ましい。
一方、本発明の樹脂発泡シートのＴＤ方向における破断までの伸び率は、１００〜６００％が好ましく、１２０〜４００％がより好ましく１４０〜３５０％が更に好ましく、１６０〜３２０％がより更に好ましい。ＭＤ方向及びＴＤ方向の伸び率が６００％以下であると、樹脂発泡シートを基材として用いたシール材を引っ張って剥離する際に、伸びにくく容易に剥離することができる。
<Elongation to break>
100 to 600% is preferable, 150 to 550% is more preferable, 200 to 500% is still more preferable, and 250 to 500% of the elongation rate to the fracture | rupture in MD direction of the resin foam sheet of this invention is still more preferable.
On the other hand, the elongation to fracture in the TD direction of the resin foam sheet of the present invention is preferably 100 to 600%, more preferably 120 to 400%, still more preferably 140 to 350%, and still more preferably 160 to 320%. When the elongation percentage in the MD direction and the TD direction is 600% or less, when the sealing material using the resin foam sheet as a base material is pulled and peeled off, it is difficult to stretch and can be easily peeled off.
＜２５％圧縮強度＞
本発明の樹脂発泡シートの２５％圧縮強度は４０〜６００ｋＰａが好ましく、４５〜６００ｋＰａがより好ましく、１４０〜５５０ｋＰａがさらに好ましく、１５０〜５００ｋＰａがより更に好ましく、なかでも１６０〜４５０ｋＰａがより更に好ましい。２５％圧縮強度が前記範囲内であると、段差のある被着体に対して樹脂発泡シートを基材として有するシール材を隙間なく貼り付けることが可能になり防水性を担保することができる。
なお、２５％圧縮強度は、樹脂発泡シートを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 resin foam sheet of the present invention is preferably 40 to 600 kPa, more preferably 45 to 600 kPa, still more preferably 140 to 550 kPa, still more preferably 150 to 500 kPa, and even more preferably 160 to 450 kPa. When the 25% compressive strength is within the above range, it is possible to attach a sealing material having a resin foam sheet as a base to an adherend having a level difference without gaps, and waterproofness can be secured.
In addition, 25% compressive strength means what measured the resin foam sheet based on JISK6767.
＜架橋度＞
本発明に係る樹脂発泡シートは架橋されていることがこのましく、架橋度は３５質量％以上が好ましい。架橋度が３５質量％未満では、樹脂発泡シート中の気泡径の大きさを一定の範囲に制御することが難しくなる。架橋度を３５質量％以上とすることで樹脂シートの気泡を微細化しやすくなり、また各気泡の大きさのバラツキも少なくしやすくなり、この樹脂発泡シートを基材として有するシール材のリワーク性、及び機械強度を向上させることができる。そのような観点から、架橋度は４０〜６５質量％が好ましく、４５〜６０質量％がより好ましく、４５〜５５質量％が更に好ましい。これら上限値以下とすることで気泡径のバラツキを小さくなるように発泡させやすくなり、発泡倍率を高めやすくなる。樹脂発泡シートは、発泡倍率を高めることで柔軟性を高めやすくなり、圧縮強度を適切な値としやすくなる。
<Crosslinking degree>
The foamed resin sheet according to the present invention is preferably crosslinked, and the degree of crosslinking is preferably 35% by mass or more. When the degree of crosslinking is less than 35% by mass, it becomes difficult to control the size of the cell diameter in the resin foam sheet within a certain range. By setting the degree of cross-linking to 35% by mass or more, it becomes easy to make the cells of the resin sheet finer, and it becomes easy to reduce the variation in the size of each cell, and the reworkability of the sealing material having this resin foam sheet as a substrate, And mechanical strength can be improved. From such a viewpoint, the crosslinking degree is preferably 40 to 65% by mass, more preferably 45 to 60% by mass, and still more preferably 45 to 55% by mass. By setting the upper limit value or less, it becomes easy to foam so as to reduce the variation of the cell diameter, and it becomes easy to increase the foaming ratio. By increasing the expansion ratio of the resin foam sheet, the flexibility can be easily improved, and the compressive strength can be easily adjusted to an appropriate value.
＜独立気泡率＞
本発明の樹脂発泡シートは、独立気泡を有するものであることが好ましい。独立気泡を有するとは、全気泡に対する独立気泡の割合（「独立気泡率」という）が７０％以上となることを意味する。独立気泡率は、好ましくは７５％以上、より好ましくは８０％以上、更に好ましくは８５％以上、より更に好ましくは９０％以上、より更に好ましくは９５％以上である。樹脂発泡シートの独立気泡率が７０％以上であると、樹脂発泡シートの防水性が向上する。
独立気泡率は、ＡＳＴＭ Ｄ２８５６（１９９８）に準拠して求めることができる。市販の測定器では、乾式自動密度計アキュピック１３３０等が挙げられる。
<Closed cell rate>
It is preferable that the resin foam sheet of this invention is a thing which has a closed cell. Having a closed cell means that the ratio of the closed cell to all the cells (referred to as the “closed cell rate”) is 70% or more. The closed cell rate is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, still more preferably 90% or more, still more preferably 95% or more. The waterproofness of a resin foam sheet improves that the closed cell rate of a resin foam sheet is 70% or more.
The closed cell rate can be determined in accordance with ASTM D2856 (1998). In a commercially available measuring device, a dry automatic densimeter Accupyc 1330 and the like can be mentioned.
独立気泡率は、より具体的には下記の要領で測定される。樹脂発泡シートから一辺が５ｃｍの平面正方形状で、且つ一定厚さの試験片を切り出す。試験片の厚さを測定し、試験片の見掛け体積Ｖ１を算出するとともに試験片の重量Ｗ１を測定する。次に、気泡の占める見掛け体積Ｖ２を下記式に基づいて算出する。なお、試験片を構成している樹脂の密度は、１ｇ／ｃｍ３とする。
気泡の占める見掛け体積Ｖ２＝Ｖ１−Ｗ１
続いて、試験片を２３℃の蒸留水中に水面から１００ｍｍの深さに沈めて、試験片に１５ｋＰａの圧力を３分間に亘って加える。しかる後、試験片を水中から取り出して試験片の表面に付着した水分を除去し、試験片の重量Ｗ２を測定し、下記式に基づいて連続気泡率Ｆ１及び独立気泡率Ｆ２を算出する。
連続気泡率Ｆ１（％）＝｛（Ｗ２−Ｗ１）／Ｖ２｝×１００
独立気泡率Ｆ２（％）＝１００−Ｆ１
The closed cell rate is more specifically measured in the following manner. From the resin foam sheet, a test piece of a flat square shape with a side of 5 cm and a constant thickness is cut out. The thickness of the test piece was measured, to measure the weight W 1 of the specimen to calculate the apparent volume V 1 of the test piece. Next, the apparent volume V 2 occupied by the air bubbles is calculated based on the following equation. In addition, the density of the resin which comprises the test piece shall be 1 g / cm < 3 >.
Apparent volume occupied by air bubbles V 2 = V 1 -W 1
Subsequently, the test piece is immersed in distilled water at 23 ° C. to a depth of 100 mm from the water surface, and a pressure of 15 kPa is applied to the test piece for 3 minutes. Calculating Thereafter, the test piece was to remove moisture adhered to the surface of the removed from the water specimen, the weight W 2 of the test piece was measured, the open cell ratio F 1 and the closed cell ratio F 2 based on the following formula Do.
Open cell rate F 1 (%) = {(W 2 −W 1 ) / V 2 } × 100
Closed cell rate F 2 (%) = 100-F 1
＜樹脂発泡シートの寸法＞
樹脂発泡シートの厚さは１．２ｍｍ以下であることが好ましい。厚さが１．２ｍｍ以下であると薄型化が可能になり、小型化した電子機器に好適に使用できる。そのような観点から、樹脂発泡シートの厚さは、０．０１ｍｍ〜１．０ｍｍが好ましく、０．０１ｍｍ〜０．７ｍｍが好ましく、０．０１ｍｍ〜０．２８ｍｍがより好ましく、０．０３〜０．２５ｍｍが更に好ましく、０．０５〜０．２ｍｍがより更に好ましい。樹脂発泡シートの厚さが０．０１ｍ以上であると、樹脂発泡シートの耐衝撃性及び柔軟性の確保が容易になる。
<Dimension of resin foam sheet>
The thickness of the resin foam sheet is preferably 1.2 mm or less. If the thickness is 1.2 mm or less, it is possible to reduce the thickness, and it can be suitably used for a miniaturized electronic device. From such a viewpoint, the thickness of the resin foam sheet is preferably 0.01 mm to 1.0 mm, preferably 0.01 mm to 0.7 mm, and more preferably 0.01 mm to 0.28 mm, 0.03 to 0. .25 mm is more preferable, and 0.05 to 0.2 mm is still more preferable. When the thickness of the resin foam sheet is 0.01 m or more, it is easy to ensure the impact resistance and the flexibility of the resin foam sheet.
樹脂発泡シートは、その幅が狭いものが好ましく、具体的には、細線状に加工したものが好ましい。例えば樹脂発泡シートの幅を５ｍｍ以下にして使用してもよく、好ましくは３ｍｍ以下、より好ましくは１ｍｍ以下で使用する。樹脂発泡シートの幅を狭くすると、小型化された電子機器内部において好適に使用することが可能である。
樹脂発泡シートの幅の下限値は特に限定されないが、例えば０．１ｍｍ以上のものであってもよいし、０．２ｍｍ以上のものであってもよい。なお、樹脂発泡シートの平面形状は、特に限定されないが、細長矩形状、枠状、Ｌ字状、コの字状等とするとよい。ただし、これらの形状以外でも、通常の四角形、円形等の他のいかなる形状であってもよい。
The foamed resin sheet preferably has a narrow width, and specifically, it is preferably processed into a thin line shape. For example, the width of the resin foam sheet may be 5 mm or less, preferably 3 mm or less, more preferably 1 mm or less. By narrowing the width of the resin foam sheet, it can be suitably used inside a miniaturized electronic device.
The lower limit value of the width of the resin foam sheet is not particularly limited, but may be, for example, 0.1 mm or more, or 0.2 mm or more. The planar shape of the resin foam sheet is not particularly limited, but it may be an elongated rectangular shape, a frame shape, an L shape, a U shape, or the like. However, other than these shapes, it may be any other shape such as a regular square or a circle.
＜発泡倍率＞
樹脂発泡シートの発泡倍率は、１．２〜１１ｃｍ３／ｇであることが好ましい。発泡倍率をこれらの範囲内とすることで圧縮強度を上記範囲内に調整しやすくすることができる。また、発泡倍率を１．２ｃｍ３／ｇ以上とすることで、圧縮強度、柔軟性が良好となり、樹脂発泡シートの衝撃吸収性、シール性が良好となりやすい。一方で、１１ｃｍ３／ｇ以下とすることで、機械強度が高くなり、耐衝撃性等を向上させやすくなる。
以上の観点から、発泡倍率は、１．２〜１０ｃｍ３／ｇが好ましく、１．２〜８ｃｍ３／ｇがより好ましく、１．３〜７ｃｍ３／ｇが更に好ましく、１．３〜６ｃｍ３／ｇがより更に好ましく、１．３〜５ｃｍ３／ｇがより更に好ましく、１．３〜３．５ｃｍ３／ｇがより更に好ましく、１．５〜３．０ｃｍ３／ｇがより更に好ましい。なお、本発明では、ＪＩＳ Ｋ７２２２に従い樹脂発泡シートの密度を求め、その逆数を発泡倍率とする。
<Expansion ratio>
The expansion ratio of the resin foam sheet is preferably 1.2 to 11 cm 3 / g. By setting the expansion ratio within these ranges, the compressive strength can be easily adjusted within the above range. In addition, by setting the expansion ratio to 1.2 cm 3 / g or more, the compressive strength and the flexibility become good, and the impact absorptivity of the resin foam sheet and the sealability tend to be good. On the other hand, by setting it as 11 cm < 3 > / g or less, mechanical strength becomes high and it becomes easy to improve impact resistance etc.
In view of the above, the expansion ratio is preferably 1.2~10cm 3 / g, more preferably 1.2~8cm 3 / g, more preferably 1.3~7cm 3 / g, 1.3~6cm 3 / G is more preferable, 1.3 to 5 cm 3 / g is more preferable, 1.3 to 3.5 cm 3 / g is further more preferable, and 1.5 to 3.0 cm 3 / g is further more preferable. In the present invention, the density of the resin foam sheet is determined in accordance with JIS K7222, and the reciprocal thereof is defined as the expansion ratio.
＜ポリオレフィン樹脂＞
樹脂発泡シートに使用される樹脂としては、各種の樹脂を使用すればよいが、中でもポリオレフィン樹脂を使用することが好ましい。ポリオレフィン樹脂を使用することで、樹脂発泡シートの適度な柔軟性を確保しつつ、平均気泡径を小さくすることが可能である。
ポリオレフィン樹脂としては、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等が挙げられ、これらの中ではポリエチレン樹脂が好ましい。
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。
<Polyolefin resin>
As resin used for a resin foam sheet, although various resin may be used, it is preferable to use polyolefin resin among them. By using a polyolefin resin, it is possible to reduce the average cell diameter while securing appropriate flexibility of the resin foam sheet.
As a polyolefin resin, a polyethylene resin, a polypropylene resin, an ethylene-vinyl acetate copolymer etc. are mentioned, Among these, a polyethylene resin is preferable.
The polyethylene resin may, for example, be a polyethylene resin polymerized with a polymerization catalyst such as a Ziegler-Natta compound, a metallocene compound or a chromium oxide compound, and preferably a polyethylene resin polymerized with a polymerization catalyst of a metallocene compound.
また、ポリエチレン樹脂としては、直鎖状低密度ポリエチレンが好ましい。直鎖状低密度ポリエチレンを用いることにより、樹脂発泡シートに柔軟性を付与するとともに、樹脂発泡シートの薄型化が可能になる。この直鎖状低密度ポリエチレンは、メタロセン化合物等の重合触媒を用いて得たものがより好ましい。また、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、具体的には、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。
ポリエチレン樹脂、例えば上記した直鎖状低密度ポリエチレンの密度は、０．８７０〜０．９１０ｇ／ｃｍ３が好ましく、０．８７５〜０．９０７ｇ／ｃｍ３がより好ましく、０．８８０〜０．９０５ｇ／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。
Moreover, as a polyethylene resin, linear low density polyethylene is preferable. By using linear low density polyethylene, it is possible to make the resin foam sheet flexible and to make the resin foam sheet thinner. The linear low density polyethylene is more preferably one obtained by using a polymerization catalyst such as a metallocene compound. In addition, 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. Linear low density polyethylene is more preferred.
Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. Especially, a C4-C10 alpha-olefin is preferable.
Polyethylene resin, for example the density of the linear low density polyethylene as described above is preferably 0.870~0.910g / cm 3, more preferably 0.875~0.907g / cm 3, 0.880~0.905g / Cm 3 is more preferred. As a polyethylene resin, a plurality of polyethylene resins can also be used, and polyethylene resins other than the above-described density range may be added.
（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、樹脂発泡シートを薄くしてもその厚さを均一にしやすくなる。
(Metallocene compounds)
As a metallocene compound, compounds, such as a bis (cyclopentadienyl) metal complex which has a structure which pinched | interposed the transition metal between the π electron system unsaturated compounds, can be mentioned. More specifically, one or more cyclopentadienyl rings or their analogs exist as ligands (ligands) in tetravalent transition metals such as titanium, zirconium, nickel, palladium, hafnium, and platinum. Compounds can be mentioned.
Such metallocene compounds are uniform in the nature of the active site, and each active site has the same activity. A polymer synthesized using a metallocene compound has high uniformity in molecular weight, molecular weight distribution, composition, composition distribution, etc. Therefore, when a sheet containing a polymer synthesized using a metallocene compound is crosslinked, the crosslinking becomes uniform. Proceed to As a result, since it can extend | stretch uniformly, even if it thins a resin foam sheet, it becomes easy to make the thickness uniform.
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。
As a ligand, a cyclopentadienyl ring, an indenyl ring, etc. can be mentioned, for example. These cyclic compounds may be substituted by a hydrocarbon group, a substituted hydrocarbon group or a hydrocarbon-substituted metalloid group. As a hydrocarbon group, for example, methyl group, 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, various decyl groups And various cetyl groups, phenyl groups and the like. "Various" means various isomers including n-, sec-, tert- and iso-.
Also, a polymer obtained by polymerizing a cyclic compound as an oligomer may be used as a ligand.
Furthermore, in addition to unsaturated compounds of π electron system, monovalent anion ligands or divalent anion chelate ligands such as chlorine and bromine, hydrocarbons, alkoxides, arylamides, aryloxides, aryloxides, amides, arylamides, phosphides, aryls Phosphide or the like may be used.
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。
樹脂発泡シートに含まれるポリオレフィン樹脂は、上記した直鎖状低密度ポリエチレンを使用する場合、上記の直鎖状低密度ポリエチレンを単独で使用してもよいが、他のポリオレフィン樹脂と併用してもよく、例えば、以下に述べる他のポリオレフィン樹脂と併用してもよい。他のポリオレフィン樹脂を含有する場合、直鎖状低密度ポリエチレン（１００質量％）に対する他のポリオレフィン樹脂の割合は、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましい。
Examples of metallocene compounds containing tetravalent transition metals and ligands include cyclopentadienyl titanium tris (dimethylamide), methyl cyclopentadienyl titanium tris (dimethyl amide), bis (cyclopentadienyl) titanium dichloride, dimethyl And silyl tetramethyl cyclopentadienyl-t-butylamido zirconium dichloride and the like.
The metallocene compound acts as a catalyst in the polymerization of various olefins in combination with a specific co-catalyst (co-catalyst). Specific examples of the cocatalyst include methylaluminoxane (MAO) and boron compounds. The molar ratio of the cocatalyst to the metallocene compound is preferably 10 to 1,000,000 mol, and more preferably 50 to 5,000 mol.
As the polyolefin resin contained in the resin foam sheet, when using the above-described linear low density polyethylene, the above linear low density polyethylene may be used alone, but it may be used in combination with other polyolefin resins. For example, it may be used in combination with other polyolefin resins described below. When it contains other polyolefin resin, 40 mass% or less is preferable, as for the ratio of the other polyolefin resin with respect to linear low density polyethylene (100 mass%), 30 mass% or less is more preferable, and 20 mass% or less is further preferable.
ポリオレフィン樹脂として使用するエチレン−酢酸ビニル共重合体は、例えば、エチレンを５０質量％以上含有するエチレン−酢酸ビニル共重合体が挙げられる。
また、ポリプロピレン樹脂としては、例えば、ポリプロピレン、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、エチレン、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、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。
Examples of the ethylene-vinyl acetate copolymer used as the polyolefin resin include an ethylene-vinyl acetate copolymer containing 50% by mass or more of ethylene.
Moreover, as a polypropylene resin, the propylene-alpha-olefin copolymer etc. which contain 50 mass% or more of polypropylene and propylene etc. are mentioned, for example. One of these may be used alone, or two or more may be used in combination.
Specific examples of the α-olefin constituting the propylene-α-olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1- An octene etc. can be mentioned, Among these, a C6-C12 alpha-olefin is preferable.
また、樹脂発泡シートは、樹脂としてポリオレフィン樹脂を使用する場合、樹脂発泡シートに含有される樹脂は、ポリオレフィン樹脂を単独で使用してもよいが、ポリオレフィン樹脂以外の樹脂を含んでもよい。樹脂発泡シートにおいて、ポリオレフィン樹脂の樹脂全量に対する割合は、６０質量％以上が好ましく、７０質量％以上がより好ましく、８０質量％以上が更に好ましい。
また、樹脂発泡シートに使用するポリオレフィン樹脂以外の樹脂としては、スチレン系熱可塑性エラストマー、ＥＰＤＭ等のエチレンプロピレン系熱可塑性エラストマー等の各種のエラストマー、ゴム成分等が挙げられる。
Moreover, when using a polyolefin resin as resin, a resin foam sheet may use polyolefin resin independently, but resin contained in a resin foam sheet may also contain resin other than polyolefin resin. In the resin foam sheet, 60 mass% or more is preferable, as for the ratio with respect to resin whole quantity of polyolefin resin, 70 mass% or more is more preferable, and 80 mass% or more is still more preferable.
Moreover, as resins other than polyolefin resin used for a resin foam sheet, various elastomers, such as a styrene-type thermoplastic elastomer, ethylene propylene-type thermoplastic elastomers, such as EPDM, a rubber component, etc. are mentioned.
（熱分解型発泡剤）
本発明の樹脂発泡シートは、上記樹脂と熱分解型発泡剤とを含む発泡性組成物を発泡してなることが好ましい。また、熱分解型発泡剤としては、粒径が１５μｍ未満のものを使用することが好ましい。本発明においては、粒径が１５μｍ未満のものを使用し、また、架橋度を特定の範囲に調整することによって、樹脂発泡シート中の気泡径の分布を制御することができ、その結果、この樹脂発泡シートを基材として有するシール材のリワーク性を向上させることができる。そのような観点から、熱分解型発泡剤の粒径は、２〜１４μｍが好ましく、５〜１３μｍがより好ましい。
なお、熱分解型発泡剤の粒径は、レーザー回折法により測定した値であって、累積頻度５０％に相当する粒径（Ｄ５０）を意味する。
(Pyrolytic foam)
It is preferable that the resin foam sheet of this invention foams the foamable composition containing the said resin and a thermal decomposition-type foaming agent. Moreover, as a thermal decomposition type foaming agent, it is preferable to use that whose particle size is less than 15 micrometers. In the present invention, by using the one having a particle size of less than 15 μm and adjusting the degree of crosslinking to a specific range, it is possible to control the distribution of the cell diameter in the resin foam sheet, and as a result, The rework property of the sealing material which has a resin foam sheet as a base material can be improved. From such a viewpoint, the particle size of the thermal decomposition-type foaming agent is preferably 2 to 14 μm, and more preferably 5 to 13 μm.
The particle size of the thermal decomposition type foaming agent is a value measured by a laser diffraction method, and means a particle size (D50) corresponding to a cumulative frequency of 50%.
熱分解型発泡剤としては、有機発泡剤、無機発泡剤が使用可能である。有機発泡剤としては、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、アゾ化合物が好ましく、アゾジカルボンアミドがより好ましい。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。
発泡性組成物における熱分解型発泡剤の配合量は、樹脂１００質量部に対して、１〜１０質量部が好ましく、１〜８質量部がより好ましく、１．５〜７質量部が更に好ましい。
As a thermal decomposition type foaming agent, an organic foaming agent and an inorganic foaming agent can be used. As an organic foaming agent, azo compounds such as azodicarbonamide, metal salts of azodicarboxylate (such as barium azodicarboxylate), azobisisobutyronitrile and the like, nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, and hydra Examples thereof include hydrazine derivatives such as zodicarbonamide, 4,4'-oxybis (benzenesulfonyl hydrazide), toluene sulfonyl hydrazide, and semicarbazide compounds such as toluene sulfonyl semicarbazide.
As the inorganic foaming agent, ammonium carbonate, sodium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate and the like can be mentioned.
Among these, an azo compound is preferable, and azodicarbonamide is more preferable, from the viewpoint of obtaining fine bubbles and from the viewpoint of economy and safety. One of these may be used alone, or two or more may be used in combination.
The blending amount of the thermal decomposition-type foaming agent in the foamable composition is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and still more preferably 1.5 to 7 parts by mass with respect to 100 parts by mass of the resin. .
また、発泡性組成物は、上記樹脂と熱分解型発泡剤に加えて、気泡核調整剤を含有することが好ましい。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が、これらの中では、酸化亜鉛が好ましい。上記した小粒径の発泡剤に加えて気泡核調整剤を使用することで、気泡径及び標準偏差をより小さくしやすくなる。気泡核調整剤の配合量は、樹脂１００質量部に対して、０．４〜８質量部が好ましく、０．５〜５質量部がより好ましく、０．８〜２．５質量部が更に好ましい。
発泡性組成物は、必要に応じて、上記以外にも、酸化防止剤、熱安定剤、着色剤、難燃剤、帯電防止剤、充填材等の発泡体に一般的に使用する添加剤を含有していてもよい。
In addition to the resin and the thermal decomposition type foaming agent, the foamable composition preferably contains a cell nucleus modifier. Examples of the cell nucleus modifier include zinc compounds such as zinc oxide and zinc stearate, and organic compounds of citric acid and urea. Among these, zinc oxide is preferable. The use of the cell nucleus modifier in addition to the above-described small particle size foaming agent makes it easier to reduce the cell diameter and the standard deviation. 0.4-8 mass parts is preferable with respect to 100 mass parts of resin, 0.5-5 mass parts is more preferable, and, as for the compounding quantity of a cell nucleus regulator, 0.8-2.5 mass parts is still more preferable. .
The foamable composition optionally contains, in addition to the above, additives generally used for foams such as an antioxidant, a heat stabilizer, a colorant, a flame retardant, an antistatic agent, and a filler. It may be done.
［樹脂発泡シートの製造方法］
樹脂発泡シートの製造方法は、特に制限はないが、例えば、樹脂及び熱分解型発泡剤を含むシート状の発泡性組成物を架橋し、加熱して熱分解型発泡剤を発泡させ、延伸倍率１．１倍以上でＴＤ方向及びＭＤ方向の少なくとも一方に延伸することで製造する。その製造方法は、より具体的には、以下の工程（１）〜（４）を含む。
工程（１）：樹脂、及び熱分解型発泡剤を含む添加剤を混合して、シート状の発泡性組成物（樹脂シート）に成形する工程
工程（２）：シート状の発泡性組成物に電離性放射線を照射して発泡性組成物を架橋させる工程
工程（３）：架橋させた発泡性組成物を加熱し、熱分解型発泡剤を発泡させて、樹脂発泡シートを得る工程
工程（４）：延伸倍率１．１倍以上で、ＭＤ方向又はＴＤ方向のいずれか一方又は双方の方向に樹脂発泡シートを延伸する工程
[Method for producing resin foam sheet]
Although the manufacturing method of a resin foam sheet does not have a restriction | limiting in particular, For example, it crosslinks the sheet-like foamable composition containing resin and a thermal decomposition-type foaming agent, It heats, foams a thermal decomposition-type foaming agent, Stretching ratio It manufactures by extending | stretching to at least one of TD direction and MD direction by 1.1 times or more. More specifically, the manufacturing method includes the following steps (1) to (4).
Step (1): A step of mixing a resin and an additive containing a thermal decomposition-type foaming agent to form a sheet-like foamable composition (resin sheet) Step (2): Sheet-like foamable composition Step (3) of Crosslinking the Foamable Composition by Irradiation with Ionizing Radiation: Step of Heating the Crosslinked Foamable Composition to Foam the Thermally Decomposable Foaming Agent to Obtain a Resin Foam Sheet (4 ): A step of stretching a resin foam sheet in one or both of the MD direction and the TD direction at a draw ratio of 1.1 times or more
工程（１）において、樹脂シートを成形する方法は、特に限定されないが、例えば、樹脂及び添加剤を押出機に供給して溶融混練し、押出機から発泡性組成物をシート状に押出すことによって樹脂シートを成形すればよい。
工程（２）において発泡性組成物を架橋する方法としては、樹脂シートに電子線、α線、β線、γ線等の電離性放射線を照射する方法を用いる。上記電離放射線の照射量は、得られる樹脂発泡シートの架橋度が上記した所望の範囲となるように調整すればよいが、５〜１５Ｍｒａｄであることが好ましく、６〜１３Ｍｒａｄであることがより好ましい。
工程（３）において、発泡性組成物を加熱し熱分解型発泡剤を発泡させるときの加熱温度は、熱分解型発泡剤の発泡温度以上であればよいが、好ましくは２００〜３００℃、より好ましくは２２０〜２８０℃である。
Although the method to shape | mold a resin sheet in a process (1) is not specifically limited, For example, resin and an additive are supplied to an extruder, melt-kneading, and extruding a foamable composition from an extruder in a sheet form The resin sheet may be formed by
As a method of crosslinking the foamable composition in the step (2), a method of irradiating the resin sheet with ionizing radiation such as an electron beam, an alpha ray, a beta ray, and a gamma ray is used. The irradiation dose of the ionizing radiation may be adjusted so that the degree of crosslinking of the resulting resin foam sheet falls within the above-described desired range, but it is preferably 5 to 15 Mrad, and more preferably 6 to 13 Mrad. .
In the step (3), the heating temperature when heating the foamable composition to foam the thermal decomposition-type foaming agent may be at least the foaming temperature of the thermal decomposition-type foaming agent, preferably 200 to 300 ° C., Preferably it is 220-280 degreeC.
工程（４）における樹脂発泡シートの延伸は、ＭＤ及びＴＤ方向の両方に行ってもよいし、一方のみに行ってもよいが、両方に行うことが好ましい。また樹脂発泡シートの延伸は、樹脂シートを発泡させて樹脂発泡シートを得た後に行ってもよいし、樹脂シートを発泡させつつ行ってもよい。なお、樹脂シートを発泡させて樹脂発泡シートを得た後、樹脂発泡シートを延伸する場合には、樹脂発泡シートを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樹脂発泡シートを延伸してもよく、樹脂発泡シートを冷却した後、再度、樹脂発泡シートを加熱して溶融又は軟化状態とした上で樹脂発泡シートを延伸してもよい。樹脂発泡シートは延伸することで薄厚にしやすくなる。
工程（４）において、樹脂発泡シートのＭＤ方向及びＴＤ方向の一方又は両方への延伸倍率は、１．２〜４．０倍が好ましく、１．５〜３．３倍がより好ましい。なかでも、両方への延伸倍率をこれら範囲内にすることが特に好ましい。かかる範囲とすることで、破断圧縮パラメータを所望の範囲としやすくなる。
また、延伸倍率を上記下限値以上とすると、樹脂発泡シートの柔軟性及び引張強度が良好になりやすくなる。一方、上限値以下とすると、樹脂発泡シートが延伸中に破断したり、発泡中の樹脂発泡シートから発泡ガスが抜けて発泡倍率が著しく低下したりすることが防止され、樹脂発泡シートの柔軟性や引張強度が良好になり、品質も均一なものとしやすくなる。
また、延伸時に樹脂発泡シートは、例えば１００〜２８０℃、好ましくは１５０〜２６０℃に加熱すればよい。
以上のようにして得られた樹脂発泡シートは、抜き加工等の周知の方法により切断して、所望の形状に加工してもよい。
The stretching of the resin foam sheet in the step (4) may be performed in both the MD and TD directions, or may be performed in only one direction, but is preferably performed in both directions. In addition, the resin foam sheet may be stretched after the resin sheet is foamed to obtain the resin foam sheet, or the resin sheet may be foamed. When the resin foam sheet is stretched after the resin sheet is foamed to obtain the resin foam sheet, the resin foam sheet is stretched without cooling the resin foam sheet while maintaining the molten state at the time of foaming. After cooling the resin foam sheet, the resin foam sheet may be heated again to be in a molten or softened state, and then the resin foam sheet may be stretched. The resin foam sheet can be easily made thin by stretching.
In a process (4), 1.2 to 4.0 times are preferable and, as for the draw ratio to one or both of MD direction and TD direction of a resin foam sheet, 1.5 to 3.3 times are more preferable. Among them, it is particularly preferable to set the draw ratio to both in these ranges. By setting it as this range, it becomes easy to make a breaking compression parameter into a desired range.
Moreover, when a draw ratio is made more than the said lower limit, the softness | flexibility and tensile strength of a resin foam sheet will become favorable easily. On the other hand, when the upper limit value is set, it is prevented that the resin foam sheet is broken during stretching or that the foaming gas is removed from the resin foam sheet being foamed and the expansion ratio is significantly reduced, and the flexibility of the resin foam sheet Also, the tensile strength is improved and the quality is easily made uniform.
In addition, the resin foam sheet may be heated to, for example, 100 to 280 ° C., preferably 150 to 260 ° C. at the time of stretching.
The resin foam sheet obtained as described above may be cut into a desired shape by cutting using a known method such as punching.
ただし、本製造方法は、上記に限定されずに、上記以外の方法により、樹脂発泡シートを得てもよい。例えば、電離性放射線を照射する代わりに、発泡性組成物に予め有機過酸化物を配合しておき、発泡性組成物を加熱して有機過酸化物を分解させる方法等により架橋を行ってもよい。 However, the present manufacturing method is not limited to the above, and a resin foam sheet may be obtained by a method other than the above. For example, instead of irradiating ionizing radiation, crosslinking may be carried out by a method in which an organic peroxide is blended in advance with the foamable composition and the foamable composition is heated to decompose the organic peroxide. Good.
樹脂発泡シートの用途は、特に限定されないが、例えば電子機器内部でシール材として使用することが好ましい。本発明の樹脂発泡シートを基材として有するシール材は、薄くしても良好なリワーク性を有するので、配置するスペースが小さい各種の携帯電子機器内部で好適に使用できる。携帯電子機器としては、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等が挙げられる。樹脂発泡シートは、電子機器内部において、衝撃吸収材としても使用可能である。
また、樹脂発泡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、段差追従性及びリワーク性の良好な本発明の樹脂発泡シートを基材とすることで、貼り付け不良等が生じにくくなる。
Although the use of a resin foam sheet is not specifically limited, For example, it is preferable to use as a sealing material inside electronic devices. Since the sealing material having the resin foam sheet of the present invention as a base has good reworkability even if it is thin, it can be suitably used inside various portable electronic devices in which the space to be arranged is small. Examples of portable electronic devices include cellular phones, cameras, game devices, electronic organizers, tablet terminals, notebook personal computers, and the like. The resin foam sheet can also be used as an impact absorbing material inside the electronic device.
Moreover, you may use for the adhesive tape which makes a resin foam sheet a base material. An adhesive tape becomes difficult to produce sticking defect etc. by using as a base material the resin foam sheet of this invention favorable in level | step difference follow-up property and rework property.
［粘着テープ］
粘着テープは、例えば、本発明に係る樹脂発泡シートと、当該樹脂発泡シートの少なくともいずれか一方の面に設けた粘着剤層とを備えるものであるが、両面に粘着剤層を設けた両面粘着テープが好ましい。
粘着テープを構成する粘着剤層の厚さは、５〜２００μｍであることが好ましい。粘着剤層の厚さは、より好ましくは７〜１５０μｍであり、更に好ましくは１０〜１００μｍである。粘着剤層の厚さが５〜２００μｍの範囲であると、粘着テープを用いて固定した構成体の厚さを薄くできる。
粘着剤層に使用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、粘着剤層の上には、更に離型紙等の剥離シートが貼り合わされてもよい。
樹脂発泡シートの少なくとも一面に粘着剤層を形成する方法は、特に限定されないが、例えば、樹脂発泡シートの少なくとも一面にコーター等の塗工機を用いて粘着剤を塗布する方法がある。また、樹脂発泡シートの少なくとも一面にスプレーを用いて粘着剤を噴霧、塗布する方法、樹脂発泡シートの少なくとも一面に刷毛を用いて粘着剤を塗布する方法、剥離シート上に形成した粘着剤層を樹脂発泡シートの少なくとも一面に転写する方法等が挙げられる。
[Adhesive tape]
The pressure-sensitive adhesive tape comprises, for example, a resin foam sheet according to the present invention and a pressure-sensitive adhesive layer provided on at least one surface of the resin foam sheet, but a double-sided pressure-sensitive adhesive on both sides Tape is preferred.
It is preferable that the thickness of the adhesive layer which comprises an adhesive tape is 5-200 micrometers. The thickness of the pressure-sensitive adhesive layer is more preferably 7 to 150 μm, still more preferably 10 to 100 μm. When the thickness of the pressure-sensitive adhesive layer is in the range of 5 to 200 μm, the thickness of the structure fixed using the pressure-sensitive adhesive tape can be reduced.
There is no restriction | limiting in particular as an adhesive used for an adhesive layer, For example, an acrylic adhesive, a urethane adhesive, a rubber adhesive etc. can be used.
Moreover, on the pressure-sensitive adhesive layer, a release sheet such as release paper may be further bonded.
Although the method of forming an adhesive layer in at least one surface of a resin foam sheet is not specifically limited, For example, there exists a method of apply | coating an adhesive using at least one surface of a resin foam sheet using coating machines, such as a coater. Also, a method of spraying and applying an adhesive on at least one side of a resin foam sheet, a method of applying an adhesive on at least one side of a resin foam sheet using a brush, and an adhesive layer formed on a release sheet The method etc. of transferring to at least one surface of a resin foam sheet are mentioned.
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 by these examples.
［測定方法］
各物性の測定方法及び評価方法は、次の通りである。
＜見かけ密度及び発泡倍率＞
樹脂発泡シートについてＪＩＳ Ｋ７２２２に準拠して見かけ密度を測定し、その逆数を発泡倍率とした。
[Measuring method]
The measuring method and evaluation method of each physical property are as follows.
<Apparent density and expansion ratio>
The apparent density of the resin foam sheet was measured in accordance with JIS K7222, and the reciprocal thereof was taken as the expansion ratio.
＜架橋度＞
樹脂発泡シートから約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
<Crosslinking degree>
About 100 mg of a test piece is taken from the resin foam sheet, and the weight A (mg) of the test piece is precisely weighed. Next, the test piece is immersed in 30 cm 3 of xylene at 120 ° C. and left for 24 hours, and then filtered through a 200 mesh wire mesh to collect insolubles on the wire net, vacuum-dried, and the weight of the insoluble portion Carefully weigh B (mg). The degree of crosslinking (% by mass) was calculated from the obtained value by the following equation.
Degree of crosslinking (mass%) = (B / A) × 100
＜独立気泡率＞
樹脂発泡シートの独立気泡率は、明細書記載の方法で測定した。
<Closed cell rate>
The closed cell rate of the resin foam sheet was measured by the method described in the specification.
＜平均気泡径、気泡の数の割合＞
樹脂発泡シートの平均気泡径及び気泡の数の割合は、明細書記載の方法で測定した。
<Average bubble diameter, ratio of number of bubbles>
The average cell diameter of the resin foam sheet and the ratio of the number of cells were measured by the method described in the specification.
＜破断点強度及び伸び率＞
樹脂発泡シートをＪＩＳ Ｋ６２５１ ４．１に規定されるダンベル状１号形にカットした。これを試料として用い、測定温度２３℃で、ＭＤ方向及びＴＤ方向の破断点強度とそのときの伸び率をＪＩＳ Ｋ６７６７に準拠して測定した。
<Breaking point strength and elongation rate>
The resin foam sheet was cut into a dumbbell-shaped No. 1 shape defined in JIS K6251 4.1. Using this as a sample, the breaking point strength in the MD direction and the TD direction and the elongation at that time were measured according to JIS K6767 at a measurement temperature of 23 ° C.
＜２５％圧縮強度＞
樹脂発泡シートについてＪＩＳ Ｋ６７６７に準拠して２５％圧縮強度を測定した。
<25% compressive strength>
The 25% compressive strength of the resin foam sheet was measured according to JIS K6767.
＜リワーク性評価試験＞
実施例又は比較例で作成した樹脂発泡シートの片面にアクリル系粘着剤層を設けた粘着テープを用意した。室温２３℃、相対湿度５０％の環境下にて、２ｍｍ×１００ｍｍのサイズにカットした粘着テープをステンレス板に貼り付け、２４時間放置した。その後、粘着テープを剥がして、剥がれ状態を目視で評価した。貼り付け前と同じ状態に剥がせればリワーク性良好として“Ａ”、シートがちぎれたり、引伸ばされてステンレス板に糊が残ったりするとリワーク性不良として“Ｂ”と評価した。
<Reworkability evaluation test>
The adhesive tape which provided the acrylic adhesive layer on the single side | surface of the resin foam sheet created by the Example or the comparative example was prepared. A pressure-sensitive adhesive tape cut into a size of 2 mm × 100 mm was attached to a stainless steel plate and allowed to stand for 24 hours under an environment of a room temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the adhesive tape was peeled off, and the peeled state was visually evaluated. If it can be peeled off in the same state as before attachment, it is evaluated as "A" as good rework property, "B" as poor rework property if the sheet is torn or stretched and the adhesive remains on the stainless steel plate.
＜段差追従性＞
（両面粘着テープの作製）
実施例及び比較例で作製した樹脂発泡シートの両面に下記方法により得られた粘着剤層を積層し、樹脂発泡シートを基材とする両面粘着テープを以下の要領で作製した。
<Step followability>
(Preparation of double-sided adhesive tape)
The adhesive layer obtained by the following method was laminated | stacked on both surfaces of the resin foam sheet produced by the Example and the comparative example, and the double-sided adhesive tape which uses a resin foam sheet as a base material was produced in the following ways.
温度計、攪拌機、冷却管を備えた反応器にブチルアクリレート７５質量部、２−エチルヘキシルアクリレート２２質量部、アクリル酸３質量部、２−ヒドロキシエチルアクリレート０．２質量部、及び酢酸エチル８０質量部を加え、窒素置換した後、反応器を加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１質量部を添加した。５時間還流させて、アクリル共重合体（ｚ）の溶液を得た。得られたアクリル共重合体（ｚ）について、カラムとしてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｅｌ」を用いてＧＰＣ法により重量平均分子量を測定したところ、６０万であった。
得られたアクリル共重合体（ｚ）の溶液に含まれるアクリル共重合体（ｚ）の固形分１００質量部に対して、軟化点１３５℃の重合ロジンエステル１５質量部、酢酸エチル（不二化学薬品株式会社製）１２５質量部、イソシアネート系架橋剤（東ソー株式会社製、コロネートＬ４５）２質量部を添加し、攪拌することにより粘着剤（Ｚ）を得た。なお、アクリル系粘着剤の架橋度は３３質量％であった。
厚さ１５０μｍの離型紙を用意し、この離型紙の離型処理面に粘着剤（Ｚ）を塗布し、１００℃で５分間乾燥させることにより、厚さ５０μｍのアクリル系粘着剤層を形成した。このアクリル系粘着剤層を、発泡シートからなる基材の表面と貼り合わせた。次いで、同様の要領で、基材の反対の表面にも上記と同じアクリル系粘着剤層を貼り合わせた。これにより、厚さ１５０μｍの離型紙で両面が覆われた両面粘着テープを得た。
In a reactor equipped with a thermometer, a stirrer and a condenser, 75 parts by mass of butyl acrylate, 22 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of acrylic acid, 0.2 parts by mass of 2-hydroxyethyl acrylate, and 80 parts by mass of ethyl acetate The reaction vessel was heated to start refluxing. Subsequently, 0.1 parts by mass of azobisisobutyronitrile as a polymerization initiator was added into the reactor. Refluxing for 5 hours gave a solution of acrylic copolymer (z). The weight average molecular weight of the obtained acrylic copolymer (z) was measured by GPC using “2690 Separations Model” manufactured by Water as a column, and was 600,000.
15 parts by mass of polymerized rosin ester having a softening point of 135 ° C., based on 100 parts by mass of the solid content of the acrylic copolymer (z) contained in the obtained solution of the acrylic copolymer (z), ethyl acetate A pressure-sensitive adhesive (Z) was obtained by adding 125 parts by mass of Chemical Co., Ltd., and 2 parts by mass of an isocyanate-based crosslinking agent (Tosoh Co., Ltd., Coronate L 45) and stirring. In addition, the crosslinking degree of the acrylic adhesive was 33 mass%.
A release paper having a thickness of 150 μm was prepared, an adhesive (Z) was applied to the release-treated surface of the release paper, and dried at 100 ° C. for 5 minutes to form an acrylic pressure-sensitive adhesive layer having a thickness of 50 μm. . The acrylic pressure-sensitive adhesive layer was bonded to the surface of a base material made of a foam sheet. Then, in the same manner, the same acrylic pressure-sensitive adhesive layer as described above was bonded to the opposite surface of the substrate. In this way, a double-sided pressure-sensitive adhesive tape in which both sides were covered with a 150 μm-thick release paper was obtained.
（試験装置の作製）
（１）試験装置Ａ：ＰＣ／Ｇｌａｓｓ
図１に、両面粘着テープのプッシュ試験の模式図を示す。得られた両面粘着テープを外径が幅４６ｍｍ、長さ６１ｍｍ、内径が幅４４ｍｍ、長さ５９ｍｍに打ち抜き、幅１ｍｍの額縁状の試験片１を作製した。次いで、図１（ａ）に示すように、中央部分に幅３８ｍｍ、長さ５０ｍｍの四角い穴のあいた厚さ２ｍｍのポリカーボネート板３に対して離型紙を剥がした試験片１を四角い穴がほぼ中央に位置するように貼り付けた。その後、試験片１の上面から幅５５ｍｍ、長さ６５ｍｍ、厚さ２ｍｍのガラス板５を試験片１がほぼ中央に位置するように貼り付け、試験装置Ａを組み立てた。
その後、試験装置Ａの上面に位置するガラス板５側から７０℃で３０ｋｇｆの圧力を１０秒間加えて上下に位置するガラス板及びポリカーボネート板と試験片とを加熱圧着し、常温で２４時間放置した。
(Preparation of test equipment)
(1) Test equipment A: PC / Glass
The schematic diagram of the push test of a double-sided adhesive tape is shown in FIG. The obtained double-sided pressure-sensitive adhesive tape was punched into an outer diameter of 46 mm, a length of 61 mm, an inner diameter of 44 mm, and a length of 59 mm, to produce a frame-shaped test piece 1 of 1 mm in width. Next, as shown in FIG. 1 (a), a square 2 hole of the test piece 1 in which the release paper was peeled off from a 2 mm thick polycarbonate plate 3 having a square hole of 38 mm wide and 50 mm long at the central portion Sticked to be located in Thereafter, a glass plate 5 having a width of 55 mm, a length of 65 mm, and a thickness of 2 mm was attached from the upper surface of the test piece 1 so that the test piece 1 was positioned approximately at the center, and the test device A was assembled.
Thereafter, a pressure of 30 kgf was applied for 10 seconds at 70 ° C. from the glass plate 5 side located on the upper surface of the test apparatus A, and the glass plate and polycarbonate plate positioned above and below and the test piece were heat-pressed and left at room temperature for 24 hours .
（２）試験装置Ｂ：ＳＵＳ／Ｇｌａｓｓ
ポリカーボネート板３をステンレス板（ＳＵＳ３０４、厚さ：２ｍｍ）とした以外は、試験装置Ａの場合と同様にして、試験装置Ｂを組み立てた。その後、試験装置Ａの場合と同様にして、加熱圧着し、常温で２４時間放置した。
(2) Test device B: SUS / Glass
A test device B was assembled in the same manner as the test device A except that the polycarbonate plate 3 was changed to a stainless steel plate (SUS 304, thickness: 2 mm). Thereafter, in the same manner as in the case of the test apparatus A, heat compression was applied, and left at normal temperature for 24 hours.
（プッシュ試験）
図１（ｂ）に示すように、作製した試験装置Ａ又は試験装置Ｂを裏返して（ガラス板５を下方に向けて）支持台に固定し、開口部側から１０ｍｍ／ｍｉｎの速度で下面のガラス板５を押していき、ガラス板５が剥がれたときの荷重（Ｎ）〔ＰＵＳＨ粘着力〕を測定した。測定は２３℃にて行った。
なお、ＰＣ／ＧｌａｓｓにおいてＰＵＳＨ粘着力が７０〜９０Ｎであり、かつ、ＳＵＳ／ＧｌａｓｓにおいてＰＵＳＨ粘着力が１５０〜１９０Ｎであれば、やわらかさに起因する貼り付けやすさが優れる（段差追従性が優れる）として“Ａ”とした。また、いずれか一方が上記範囲内であれば良好である（段差追従性が良好）として“Ｂ”、それ以外の場合を“Ｃ”とした。
(Push test)
As shown in FIG. 1 (b), the manufactured test device A or test device B is turned over (with the glass plate 5 facing downward) and fixed to the support base, and the lower surface at a speed of 10 mm / min from the opening side. The load (N) [PUSH adhesive force] when the glass plate 5 was pushed and the glass plate 5 peeled was measured. The measurement was performed at 23 ° C.
In addition, if the PUSH adhesion is 70 to 90 N in PC / Glass and the PUSH adhesion is 150 to 190 N in SUS / Glass, the ease of adhesion due to softness is excellent (step followability is excellent) As "A". In addition, if either one is within the above range, it is considered as "B" if it is good (step followability is good), and "C" otherwise.
［ポリオレフィン系樹脂］
本実施例で使用したポリオレフィン系樹脂を以下に示す。
・樹脂Ａ：直鎖状低密度ポリエチレン樹脂（ダウケミカル社製、商品名「アフィニティーＰＬ１８５０」、密度０．９０２ｇ／ｃｍ３）
[Polyolefin resin]
The polyolefin resins used in this example are shown below.
Resin A: Linear low density polyethylene resin (manufactured by Dow Chemical Co., trade name "Affinity PL 1850", density 0.902 g / cm 3 )
［実施例１］
樹脂Ａを１００質量部と、熱分解型発泡剤として粒径１３μｍのアゾジカルボンアミド３質量部と、気泡核調整剤として酸化亜鉛（堺化学工業株式会社製、商品名「ＯＷ−２１２Ｆ」）１．０質量部と、酸化防止剤（酸防）０．５質量部とを押出機に供給して１３０℃で溶融混練し、厚さが３００μｍの長尺状の樹脂シートに押出した。
次に、上記長尺状の樹脂シートの両面に加速電圧５００ｋＶの電子線を７Ｍｒａｄ照射して樹脂シートを架橋した後、架橋した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加熱して発泡させて、厚さ５００μｍの樹脂発泡シートを得た。
Example 1
100 parts by mass of resin A, 3 parts by mass of azodicarbonamide having a particle diameter of 13 μm as a thermal decomposition type foaming agent, zinc oxide as a cell nucleus regulator (trade name “OW-212F” manufactured by Sakai Chemical Industry Co., Ltd.) 1 0 parts by mass and 0.5 parts by mass of an antioxidant (antioxidant) were supplied to an extruder, and the mixture was melt-kneaded at 130 ° C. and extruded into a long resin sheet of 300 μm in thickness.
Next, 7 Mrad of electron beam with an accelerating voltage of 500 kV is irradiated on both sides of the above long resin sheet for 7 Mrad to crosslink the resin sheet, and then the crosslinked resin sheet is held in a foaming furnace maintained at 250 ° C. by hot air and infrared heater. The mixture was continuously fed, heated and foamed to obtain a 500 μm thick resin foam sheet.
次いで、得られた樹脂発泡シートを発泡炉から連続的に送り出した後、この樹脂発泡シートをその両面の温度が２００〜２５０℃となるように維持した。その状態で、樹脂発泡シートをそのＴＤ方向に２．５倍の延伸倍率で延伸させると共に、樹脂発泡シートの発泡炉への送り込み速度（供給速度）よりも速い巻取速度でもって樹脂発泡シートを巻き取ることによって樹脂発泡シートをＭＤ方向にも２．０倍に延伸させて、樹脂発泡シート（厚さ：０．０６ｍｍ）を得た。なお、上記樹脂発泡シートの巻取速度は、樹脂シート自身の発泡によるＭＤ方向への膨張分を考慮しつつ調整した。得られた樹脂発泡シートを上記評価方法に従って評価し、その結果を表１に示す。 Next, the obtained resin foam sheet was continuously fed out from the foaming furnace, and the resin foam sheet was maintained so that the temperature on both sides thereof was 200 to 250 ° C. In that state, the resin foam sheet is stretched in the TD direction at a draw ratio of 2.5 times, and the resin foam sheet is drawn at a winding speed faster than the feeding speed (supply speed) of the resin foam sheet into the foaming furnace. The resin foam sheet was stretched 2.0 times also in the MD direction by winding up to obtain a resin foam sheet (thickness: 0.06 mm). In addition, the winding speed of the said resin foam sheet was adjusted considering the expansion part to MD direction by foaming of resin sheet itself. The resulting resin foam sheet was evaluated according to the above evaluation method, and the results are shown in Table 1.
［実施例２〜６及び比較例１〜２］
樹脂、添加剤、樹脂発泡シートの厚さを下記表１に示すように変更したこと以外は、実施例１と同様にして樹脂発泡シートを得た。ＭＤ及びＴＤの延伸倍率は１．５〜３．５の範囲内で調整した。得られた樹脂発泡シートを上記評価方法に従って評価し、その結果を表１に示す。
[Examples 2 to 6 and Comparative Examples 1 to 2]
A resin foam sheet was obtained in the same manner as in Example 1 except that the thickness of the resin, the additive and the resin foam sheet was changed as shown in Table 1 below. The draw ratio of MD and TD was adjusted within the range of 1.5-3.5. The resulting resin foam sheet was evaluated according to the above evaluation method, and the results are shown in Table 1.
表１より明らかなように、本発明によれば、段差に追従して良好な接着性を示すと共に、リワーク性が良好なシール材の基材として好適に用いることができる樹脂発泡シートを得ることができる。 As is clear from Table 1, according to the present invention, it is possible to obtain a resin foam sheet that can be suitably used as a base material of a sealing material that exhibits good adhesion following a level difference and that has good reworkability. Can.
１ 試験片
３ ポリカーボネート板
５ ガラス板
1 Test piece 3 Polycarbonate plate 5 Glass plate
Claims (11)
樹脂及び熱分解型発泡剤を含むシート状の発泡性組成物を架橋し、加熱して前記熱分解型発泡剤を発泡させ、延伸倍率１．１倍以上でＴＤ方向及びＭＤ方向の少なくともいずれか一方に延伸する、樹脂発泡シートの製造方法。 It is a manufacturing method of the resin foam sheet of any one of Claims 1-9, Comprising:
A sheet-like foamable composition containing a resin and a thermal decomposition-type foaming agent is crosslinked and heated to foam the thermal decomposition-type foaming agent, and at least one of TD direction and MD direction at a draw ratio of 1.1 times or more The manufacturing method of the resin foam sheet stretched to one side.
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| JP2009258274A (en) * | 2008-04-15 | 2009-11-05 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive sheet for front plate of display device |
| WO2016052556A1 (en) * | 2014-09-30 | 2016-04-07 | 積水化学工業株式会社 | Polyolefin resin foam sheet and adhesive tape |
| WO2016052557A1 (en) * | 2014-09-30 | 2016-04-07 | 積水化学工業株式会社 | Polyolefin resin foam sheet and adhesive tape |
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