JP6302731B2 - Polyethylene resin foam sheet - Google Patents
Polyethylene resin foam sheet Download PDFInfo
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- JP6302731B2 JP6302731B2 JP2014088087A JP2014088087A JP6302731B2 JP 6302731 B2 JP6302731 B2 JP 6302731B2 JP 2014088087 A JP2014088087 A JP 2014088087A JP 2014088087 A JP2014088087 A JP 2014088087A JP 6302731 B2 JP6302731 B2 JP 6302731B2
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- Prior art keywords
- polyethylene
- foam sheet
- weight
- polyethylene resin
- antistatic agent
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- 239000006260 foam Substances 0.000 title claims description 107
- 229920013716 polyethylene resin Polymers 0.000 title claims description 89
- 239000000463 material Substances 0.000 claims description 67
- 239000002216 antistatic agent Substances 0.000 claims description 60
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 45
- 229920005678 polyethylene based resin Polymers 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 229920001684 low density polyethylene Polymers 0.000 claims description 11
- 239000004702 low-density polyethylene Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 description 45
- 239000011347 resin Substances 0.000 description 45
- 239000000203 mixture Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 18
- 239000004088 foaming agent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000005022 packaging material Substances 0.000 description 13
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 13
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000001273 butane Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229920001477 hydrophilic polymer Polymers 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- -1 alicyclic hydrocarbons Chemical class 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229920001600 hydrophobic polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Buffer Packaging (AREA)
- Packaging Frangible Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリエチレン系樹脂発泡シートに関し、より詳しくは、包装材や間紙として好適に使用できるポリエチレン系樹脂発泡シートに関する。 The present invention relates to a polyethylene resin foam sheet, and more particularly to a polyethylene resin foam sheet that can be suitably used as a packaging material or a slip sheet.
従来、各種製品の包装材や間紙として、ポリエチレン系樹脂発泡シートが知られている。このポリエチレン系樹脂発泡シートは、柔軟性を有し、緩衝性に富み、被包装物表面を傷つけにくい等の特長を有する。一方で、ポリエチレン系樹脂発泡シートのような樹脂発泡体は、静電気の作用により帯電し易いため、樹脂発泡体表面に埃や塵が付着し易いという欠点があった。この欠点を補うために、帯電防止剤を用いて帯電防止性能を付与したポリエチレン系樹脂発泡シートが使用されている。 Conventionally, a polyethylene-based resin foam sheet is known as a packaging material or interleaf paper for various products. This polyethylene-based resin foam sheet is flexible, rich in shock-absorbing properties, and has features such as being hard to damage the surface of an object to be packaged. On the other hand, since a resin foam such as a polyethylene resin foam sheet is easily charged by the action of static electricity, there is a drawback in that dust and dust easily adhere to the surface of the resin foam. In order to compensate for this disadvantage, a polyethylene resin foam sheet imparted with antistatic performance using an antistatic agent is used.
帯電防止剤としては、例えば、界面活性剤が用いられている。界面活性剤は、通常、分子量が１０００程度もしくはそれ以下であり、帯電防止剤の中でも低分子型帯電防止剤として分類されている。このような低分子型帯電防止剤を用いた場合には、低分子型帯電防止剤がポリエチレン系樹脂発泡シート表面に浮き出てくること、所謂「ブリードアウト現象」により、ポリエチレン系樹脂発泡シートに帯電防止性能を付与することが可能となる。しかしながら、このようなポリエチレン系樹脂発泡シートをガラス板やガラス基板等の包装材や間紙として用いた場合には、ブリードアウトした低分子型帯電防止剤が被包装物表面に移行することに起因して、被包装物の表面が曇ってしまうという問題点があった。 As the antistatic agent, for example, a surfactant is used. Surfactants usually have a molecular weight of about 1000 or less and are classified as low molecular weight antistatic agents among antistatic agents. When such a low molecular weight antistatic agent is used, the low molecular weight antistatic agent floats on the surface of the polyethylene resin foam sheet, so that the polyethylene resin foam sheet is charged by the so-called “bleed out phenomenon”. It is possible to impart prevention performance. However, when such a polyethylene-based resin foam sheet is used as a packaging material such as a glass plate or a glass substrate or an interleaf, the bleed-out low molecular weight antistatic agent is transferred to the surface of the package. In addition, there is a problem that the surface of the packaged item becomes cloudy.
そこで、上記問題点を解消するために、これまでにも、低分子型帯電防止剤に替えて高分子型帯電防止剤を用いたポリエチレン系樹脂発泡シートが提案されている。例えば、特許文献１には、電子部品や薄型テレビ用ガラスなどの包装材を提供する目的で、高分子型帯電防止剤を含有するポリエチレン系樹脂発泡シートが提案されている。また、特許文献２には、高分子型帯電防止剤の使用量を低減させつつも求められる帯電防止効果を得る目的で、リチウムイオンを含む高分子型帯電防止剤を含有するポリエチレン系樹脂発泡シートが提案されている。 Therefore, in order to solve the above problems, a polyethylene resin foam sheet using a polymer type antistatic agent instead of a low molecular type antistatic agent has been proposed. For example, Patent Document 1 proposes a polyethylene resin foam sheet containing a polymer-type antistatic agent for the purpose of providing a packaging material such as an electronic component or a glass for a thin television. Patent Document 2 discloses a polyethylene resin foam sheet containing a polymer antistatic agent containing lithium ions for the purpose of obtaining the required antistatic effect while reducing the amount of the polymer antistatic agent used. Has been proposed.
しかしながら、高分子型帯電防止剤を含有するポリエチレン系樹脂発泡シートは十分な帯電防止性能を発現するが、該発泡シートをガラス板等の包装材や間紙として使用した場合に、被包装物表面の親水性を十分に維持することができていなかった。 However, a polyethylene resin foam sheet containing a polymeric antistatic agent exhibits sufficient antistatic performance, but when the foam sheet is used as a packaging material such as a glass plate or an interleaf, the surface of the package The hydrophilicity of was not able to be fully maintained.
本発明は、以上のとおりの事情に鑑みてなされたものであり、帯電防止性能に優れ、かつ、ガラス板等の包装材や間紙として使用した場合に、被包装物表面を曇らせにくいと共に、被包装物表面の親水性を維持できるような被包装物表面を汚染しにくい新規なポリエチレン系樹脂発泡シートを提供することを課題としている。 The present invention has been made in view of the circumstances as described above, is excellent in antistatic performance, and when used as a packaging material or interleaf paper such as a glass plate, it is difficult to fog the surface of the object to be packaged, It is an object of the present invention to provide a novel polyethylene-based resin foam sheet that can maintain the hydrophilicity of the surface of the package and hardly contaminates the surface of the package.
本発明者は、ポリエチレン系樹脂発泡シートを製造するにあたって、基材樹脂のポリエチレン系樹脂材料における有機物等の低分子量成分が少ない原料を用い、かつ高分子型帯電防止剤の配合量を特定範囲とすることによって、得られる発泡シート中の低分子量成分を特定範囲以下とし、帯電防止性能に優れ、かつ、被包装物表面の親水性を維持できると共に、被包装物表面を汚しにくいポリエチレン系樹脂発泡シートとなることを知見し、係る新規な知見に基づき、本発明を完成させるに至ったものである。 The present inventor uses a raw material with a small amount of low molecular weight components such as organic substances in the polyethylene resin material of the base resin in manufacturing the polyethylene resin foam sheet, and the blending amount of the polymer type antistatic agent is within a specific range. By making the low molecular weight component in the resulting foamed sheet below a specific range, it is excellent in antistatic performance, and can maintain the hydrophilicity of the surface of the package, and the polyethylene-based resin foam that does not easily contaminate the surface of the package The present inventors have found out that the sheet is a sheet, and have completed the present invention based on the new knowledge.
すなわち、本発明のポリエチレン系樹脂発泡シートは、高分子型帯電防止剤が配合されたポリエチレン系樹脂発泡シートであって、前記ポリエチレン系樹脂発泡シートのヘプタン抽出量が１．５重量％以下であり、前記高分子型帯電防止剤の配合量がポリエチレン系樹脂材料と高分子型帯電防止剤との合計１００重量％に対して１．５〜８重量％であることを特徴とする。 That is, the polyethylene resin foam sheet of the present invention is a polyethylene resin foam sheet containing a polymeric antistatic agent, and the amount of heptane extracted from the polyethylene resin foam sheet is 1.5% by weight or less. The blending amount of the polymer type antistatic agent is 1.5 to 8% by weight with respect to 100% by weight in total of the polyethylene resin material and the polymer type antistatic agent.
このポリエチレン系樹脂発泡シートにおいて、前記ポリエチレン系樹脂材料は、低密度ポリエチレンを含み、該ポリエチレン系樹脂材料のヘプタン抽出量が０．７重量％以下であることが好ましい。 In the polyethylene resin foam sheet, the polyethylene resin material preferably includes low-density polyethylene, and the amount of heptane extracted from the polyethylene resin material is preferably 0.7% by weight or less.
また、このポリエチレン系樹脂発泡シートにおいては、前記高分子型帯電防止剤の表面抵抗率が１×１０７Ω以下であることが好ましい。 In this polyethylene resin foam sheet, the polymer antistatic agent preferably has a surface resistivity of 1 × 10 7 Ω or less.
さらに、このポリエチレン系樹脂発泡シートにおいては、前記ポリエチレン系樹脂発泡シートの厚みが０．０５〜５ｍｍであり、見掛け密度が１８〜５００ｋｇ／ｍ３であることが好ましい。 Furthermore, in this polyethylene-based resin foam sheet, it is preferable that the thickness of the polyethylene-based resin foam sheet is 0.05 to 5 mm and the apparent density is 18 to 500 kg / m 3 .
このポリエチレン系樹脂発泡シートにおいては、高分子型帯電防止剤の配合量がポリエチレン系樹脂材料と高分子型帯電防止剤との合計１００重量％に対して２〜６重量％であることが好ましい。 In this polyethylene resin foam sheet, the blending amount of the polymer antistatic agent is preferably 2 to 6% by weight with respect to 100% by weight in total of the polyethylene resin material and the polymer antistatic agent.
そして、本発明のガラス板用間紙は、前記のポリエチレン系樹脂発泡シートからなることを特徴とする。 And the interleaf paper for glass plates of this invention consists of said polyethylene-type resin foam sheet, It is characterized by the above-mentioned.
本発明によれば、包装材や間紙として使用した場合に、帯電防止性能に優れ、かつ、被包装物表面の親水性を維持できると共に、被包装物表面を曇らせにくい新規なポリエチレン系樹脂発泡シートを提供することができる。 According to the present invention, when used as a packaging material or a slip sheet, a novel polyethylene-based resin foam that is excellent in antistatic performance, maintains the hydrophilicity of the surface of the package, and is difficult to fog the surface of the package Sheets can be provided.
以下、本発明のポリエチレン系樹脂発泡シートについて詳細に説明する。 Hereinafter, the polyethylene resin foam sheet of the present invention will be described in detail.
前記のとおり、本発明のポリエチレン系樹脂発泡シートは、高分子型帯電防止剤が配合されたポリエチレン系樹脂発泡シートであって、前記ポリエチレン系樹脂発泡シートのヘプタン抽出量が１．５重量％以下であり、前記高分子型帯電防止剤の配合量がポリエチレン系樹脂材料と高分子型帯電防止剤との合計１００重量％に対して１．５〜８重量％である。 As described above, the polyethylene resin foam sheet of the present invention is a polyethylene resin foam sheet in which a polymer antistatic agent is blended, and the heptane extraction amount of the polyethylene resin foam sheet is 1.5% by weight or less. The blending amount of the polymer type antistatic agent is 1.5 to 8% by weight with respect to 100% by weight in total of the polyethylene resin material and the polymer type antistatic agent.
＜ポリエチレン系樹脂材料＞
本発明で用いられるポリエチレン系樹脂材料は、ヘプタン抽出量が０．７重量％以下であることが好ましい。ポリエチレン系樹脂材料に含まれる低分子量成分としての有機物等の被包装物への移行をより抑制する観点からは、ポリエチレン系樹脂材料のヘプタン抽出量は、０．４重量％以下であることが好ましく、より好ましくは０．３重量％以下であり、さらに好ましくは０．２重量％以下である。
<Polyethylene resin material>
The polyethylene resin material used in the present invention preferably has a heptane extraction amount of 0.7% by weight or less. From the viewpoint of further suppressing the migration to an article to be packaged such as an organic substance as a low molecular weight component contained in the polyethylene resin material, the amount of heptane extracted from the polyethylene resin material is preferably 0.4% by weight or less. More preferably, it is 0.3 weight% or less, More preferably, it is 0.2 weight% or less.
本発明で用いられるポリエチレン系樹脂材料としては、例えば、スラリー法や溶液法を用いて製造されたポリエチレン系樹脂材料等が挙げられる。また、一般に入手可能なポリエチレン系樹脂材料から、ｎ−ヘプタン等の溶媒を用いて低分子量成分としての有機物等を抽出除去したポリエチレン系樹脂材料を用いてもよい。 Examples of the polyethylene resin material used in the present invention include a polyethylene resin material produced by using a slurry method or a solution method. Moreover, you may use the polyethylene-type resin material which extracted and removed the organic substance etc. as a low molecular-weight component from the generally available polyethylene-type resin material using solvents, such as n-heptane.
一般に入手可能なポリエチレン系樹脂材料としては、具体的には、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、エチレン−酢酸ビニル共重合体（ＥＶＡＣ）、エチレン−メタクリル酸メチル共重合体（ＥＭＭＡ）、エチレン−アクリル酸エチル（ＥＥＡＫ）や、これらの混合物等が挙げられる。包装材や間紙として用いる場合の緩衝性の観点からは、ポリエチレン系樹脂材料は、低密度ポリエチレン（ＬＤＰＥ）を主成分とすることが好ましい。なお、「主成分とする」とは、ポリエチレン系樹脂中に低密度ポリエチレン（ＬＤＰＥ）が５０重量％以上含まれることを意味し、同様の観点で、７０重量％以上含まれることが好ましく、より好ましくは９０重量％以上である。通常、低密度ポリエチレンの密度は９１０ｋｇ／ｍ３以上９３０ｋｇ／ｍ３未満である。 Examples of generally available polyethylene resin materials include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and ethylene-vinyl acetate copolymer (EVAC). , Ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate (EEAK), and a mixture thereof. From the viewpoint of buffering properties when used as a packaging material or interleaf paper, the polyethylene resin material preferably contains low-density polyethylene (LDPE) as a main component. The term “main component” means that the polyethylene resin contains 50% by weight or more of low density polyethylene (LDPE), and from the same viewpoint, 70% by weight or more is preferable. Preferably it is 90 weight% or more. Usually, the density of the low density polyethylene is less than 910 kg / m 3 or more 930 kg / m 3.
なお、経済的な観点や廃液処理等の環境面の観点からは、前記スラリー法や溶液法を用いて製造されたポリエチレン系樹脂材料等を用いることが好ましく考慮される。 Note that, from an economic viewpoint and an environmental viewpoint such as waste liquid treatment, it is preferable to use a polyethylene-based resin material or the like manufactured using the slurry method or the solution method.
また、ポリエチレン系樹脂材料は、必要に応じて２種以上を併用してもよい。２種以上のポリエチレン系樹脂材料を併用する場合には、ポリエチレン系樹脂材料全体として、ヘプタン抽出量が上記範囲を満足することが好ましい。 Moreover, two or more kinds of polyethylene resin materials may be used in combination as required. When using 2 or more types of polyethylene-type resin materials together, it is preferable that heptane extraction amount satisfies the said range as the whole polyethylene-type resin material.
本明細書において、ポリエチレン系樹脂材料の「ヘプタン抽出量」は、以下のとおりの手順に従って測定、算出される値をいう。ポリエチレン系樹脂材料（例えば、ペレット状のもの）を粉砕し、その２００メッシュパスの試料約２ｇをフラスコ内に投入し、ｎ−ヘプタン４００ｍｌを加え、５０℃にて４８時間加熱還流する。得られた溶液を濾過し、分取した残留物から溶媒を加熱真空下にて除去する。得られた残留物の重量と、前記ポリエチレン系樹脂材料の粉砕試料の重量との差を測定し、ポリエチレン系樹脂材料の粉砕試料の重量を基準として重量％に換算し、この値をポリエチレン系樹脂材料のヘプタン抽出量とする。なお、２種以上のポリエチレン系樹脂材料を併用する場合には、それぞれのポリエチレン系樹脂材料のヘプタン抽出量を測定し、その配合比に応じて、ヘプタン抽出量を算出すればよい。 In this specification, the “heptane extraction amount” of a polyethylene resin material refers to a value measured and calculated according to the following procedure. A polyethylene resin material (for example, pellets) is pulverized, about 2 g of a 200 mesh pass sample is put into the flask, 400 ml of n-heptane is added, and the mixture is heated to reflux at 50 ° C. for 48 hours. The resulting solution is filtered and the solvent is removed from the fractionated residue under heating vacuum. The difference between the weight of the obtained residue and the weight of the pulverized sample of the polyethylene-based resin material was measured, and converted to wt% based on the weight of the pulverized sample of the polyethylene-based resin material. The amount of heptane extracted from the material. In addition, when using together 2 or more types of polyethylene-type resin materials, the heptane extraction amount of each polyethylene-type resin material should be measured, and a heptane extraction amount should just be calculated according to the compounding ratio.
また、本発明で用いられるポリエチレン系樹脂材料は、発泡性の観点から、メルトマスフローレート（ＭＦＲ）が、１〜３０ｇ／１０分であることが好ましく、より好ましくは１．５〜２０ｇ／１０分、さらに好ましくは２〜１０ｇ／１０分である。ポリエチレン系樹脂材料のＭＦＲは、ＪＩＳ Ｋ７２１０（１９９９年）の条件Ｄに基づいて測定することができる。 The polyethylene resin material used in the present invention preferably has a melt mass flow rate (MFR) of 1 to 30 g / 10 minutes, more preferably 1.5 to 20 g / 10 minutes from the viewpoint of foamability. More preferably, it is 2 to 10 g / 10 min. The MFR of the polyethylene resin material can be measured based on the condition D of JIS K7210 (1999).
さらに、本発明で用いられるポリエチレン系樹脂材料は、発泡性の観点から、１９０℃での溶融張力が２０〜４００ｍＮであることが好ましく、より好ましくは３０〜３００ｍＮ、さらに好ましくは４０〜２５０ｍＮである。 Furthermore, from the viewpoint of foamability, the polyethylene resin material used in the present invention preferably has a melt tension at 190 ° C. of 20 to 400 mN, more preferably 30 to 300 mN, and even more preferably 40 to 250 mN. .
ポリエチレン系樹脂材料の溶融張力は、例えば、キャピログラフ１Ｄ（（株）東洋精機製作所製）を用いて測定することができる。具体的には、例えば、以下のようにして測定することができる。シリンダー径９．５５ｍｍ、長さ３５０ｍｍのシリンダーと、ノズル径２．０９５ｍｍ、長さ８．０ｍｍのオリフィスを用いて、シリンダーおよびオリフィスの設定温度を１９０℃とする。必要量の試料を、シリンダー内に入れ、４分間放置した後、ピストン速度を１０ｍｍ／分として、溶融樹脂をオリフィスから紐状に押し出す。この紐状物を、直径４５ｍｍの張力検出用プーリーに掛け、４分で引き取り速度が０ｍ／分から２００ｍ／分に達するように一定の増速で引取り速度を増加させながら引取りローラーで紐状物を引取って、紐状物が破断した際の直前の張力の極大値を得る。ここで、引取り速度が０ｍ／分から２００ｍ／分に達するまでの時間を４分とした理由は、樹脂の熱劣化を抑えるとともに得られる値の再現性を高めるためである。上記操作を異なる試料を使用して計１０回の測定を行い、得られた１０個の極大値のうち、最も大きな値から順に３つの値と、最も小さな値から順に３つの値を除外する。残った４つの値を相加平均して得られた値を溶融張力（ｃＮ）とする。 The melt tension of the polyethylene resin material can be measured using, for example, Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Specifically, for example, it can be measured as follows. Using a cylinder having a cylinder diameter of 9.55 mm and a length of 350 mm and an orifice having a nozzle diameter of 2.095 mm and a length of 8.0 mm, the set temperature of the cylinder and the orifice is set to 190 ° C. A necessary amount of the sample is put in a cylinder and left for 4 minutes, and then the piston speed is set to 10 mm / min, and the molten resin is extruded from the orifice into a string shape. This string is hung on a tension detection pulley with a diameter of 45 mm, and the string is formed with a pulling roller while increasing the pulling speed at a constant speed so that the pulling speed reaches 0 m / min to 200 m / min in 4 minutes. A thing is taken up and the maximum value of the tension just before a string-like thing breaks is obtained. Here, the reason why the time until the take-up speed reaches 0 m / min to 200 m / min is set to 4 minutes is to suppress the thermal deterioration of the resin and increase the reproducibility of the obtained value. The above operation is performed ten times using different samples, and among the ten maximum values obtained, three values are excluded from the largest value and three values are excluded from the smallest value. The value obtained by arithmetically averaging the remaining four values is taken as the melt tension (cN).
但し、上記の方法で溶融張力の測定を行った際に、引取り速度が２００ｍ／分に達しても紐状物が切れない場合には、引取り速度を２００ｍ／分の一定速度にして得られた値を溶融張力（ｃＮ）として採用することができる。より詳しくは、上記の方法と同様にして、溶融樹脂をオリフィスから紐状に押出して、この紐状物を張力検出用プーリーに掛け、４分間で０ｍ／分から２００ｍ／分に達するように一定の増速で引取り速度を増加させながら引取りローラーを回転させ、回転速度が２００ｍ／分に達するまで待つ。回転速度が２００ｍ／分に到達した後、張力のデータの取り込みを開始し、３０秒後にデータの取り込みを終了する。この３０秒の間に得られたテンション荷重曲線から得られたテンション最大値（Ｔｍａｘ）とテンション最小値（Ｔｍｉｎ）の平均値（Ｔａｖｅ）を、溶融張力とする。ここで、上記Ｔｍａｘとは、上記テンション荷重曲線において、検出されたピーク（山）値の合計値を検出された個数で除した値であり、上記Ｔｍｉｎとは、上記テンション荷重曲線において、検出されたディップ（谷）値の合計値を検出された個数で除した値である。なお、上記測定においては、溶融樹脂をオリフィスから紐状に押し出す際に、押し出される紐状物にできるだけ気泡が入らないようにすることが当然のことながら考慮される。 However, when the melt tension is measured by the above method and the string-like material does not break even when the take-up speed reaches 200 m / min, the take-up speed is obtained at a constant speed of 200 m / min. The obtained value can be adopted as the melt tension (cN). More specifically, in the same manner as in the above method, the molten resin is extruded into a string shape from the orifice, and the string object is hung on a pulley for tension detection, and it is constant so as to reach 0 m / min to 200 m / min in 4 minutes. The take-up roller is rotated while the take-up speed is increased at an increased speed, and the process waits until the rotation speed reaches 200 m / min. After the rotational speed reaches 200 m / min, the data acquisition of the tension is started, and the data acquisition is finished after 30 seconds. The average value (Tave) of the maximum tension value (Tmax) and the minimum tension value (Tmin) obtained from the tension load curve obtained during the 30 seconds is taken as the melt tension. Here, the Tmax is a value obtained by dividing the total value of detected peak (peak) values in the tension load curve by the detected number, and the Tmin is detected in the tension load curve. It is a value obtained by dividing the total value of the dip (valley) values by the detected number. In the above measurement, when extruding the molten resin from the orifice into a string shape, it is naturally taken into account that as much bubbles as possible do not enter the extruded string-like object.
＜高分子型帯電防止剤＞
本発明で用いられる高分子型帯電防止剤としては、例えば、体積抵抗率が１×１０５〜１×１０１１Ω・ｃｍの親水性ポリマー（以下、単に「親水性ポリマー」ともいう。）、親水性ポリマーブロックと疎水性ポリマーブロックとのブロックポリマー、アイオノマー等が挙げられる。親水性ポリマーとしては、例えば、ポリエーテル、カチオン性ポリマー、アニオン性ポリマー等が挙げられる。一方、疎水性ポリマーブロックとしては、例えば、ポリオレフィン、ポリアミド等が挙げられる。また、親水性ポリマーブロックと疎水性ポリマーブロックとの結合の種類としては、例えば、エステル結合、アミド結合、エーテル結合等が挙げられる。これらの中でも、帯電防止性能に優れるとともに、高分子型帯電防止剤を配合することによるポリエチレン系樹脂発泡シートの物性低下を抑制する観点からは、親水性ポリマーとしてポリエーテルブロックを有し、疎水性ポリマーブロックとしてポリオレフィンブロックを有するブロック共重合体が好ましい。
<Polymer type antistatic agent>
Examples of the polymer antistatic agent used in the present invention include a hydrophilic polymer having a volume resistivity of 1 × 10 5 to 1 × 10 11 Ω · cm (hereinafter also simply referred to as “hydrophilic polymer”), Examples include a block polymer of a hydrophilic polymer block and a hydrophobic polymer block, and an ionomer. Examples of the hydrophilic polymer include polyether, cationic polymer, anionic polymer and the like. On the other hand, examples of the hydrophobic polymer block include polyolefin and polyamide. Moreover, as a kind of coupling | bonding of a hydrophilic polymer block and a hydrophobic polymer block, an ester bond, an amide bond, an ether bond etc. are mentioned, for example. Among these, from the viewpoint of excellent antistatic performance and suppressing deterioration of physical properties of the polyethylene resin foam sheet by blending a polymer type antistatic agent, it has a polyether block as a hydrophilic polymer and is hydrophobic. A block copolymer having a polyolefin block as the polymer block is preferred.
また、ポリエチレン系樹脂発泡シートに所望の帯電防止性能を付与するとともに、高分子型帯電防止剤の配合量をより少なくすることによって高分子型帯電防止剤に含まれる低分子成分としての有機物等の移行をより抑制する観点からは、高分子型帯電防止剤は、表面抵抗率が１×１０７Ω以下であることが好ましい。高分子型帯電防止剤の表面抵抗率は、ＪＩＳ Ｋ６２７１（２００８年）に準拠して測定することができる。例えば、高分子型帯電防止剤の表面抵抗率は、試験片として、測定対象とする高分子型帯電防止剤を２００℃にて０．１ｍｍにヒートプレスしたものを用いて、ＪＩＳ Ｋ６２７１（２００８年）に準拠して測定することができる。 In addition to imparting desired antistatic performance to the polyethylene-based resin foam sheet, and reducing the blending amount of the polymer antistatic agent, organic substances as low molecular components contained in the polymer antistatic agent, etc. From the viewpoint of further suppressing migration, the polymer antistatic agent preferably has a surface resistivity of 1 × 10 7 Ω or less. The surface resistivity of the polymer antistatic agent can be measured in accordance with JIS K6271 (2008). For example, the surface resistivity of a polymer antistatic agent is determined by using JIS K6271 (2008) as a test piece obtained by heat-pressing a polymer antistatic agent to be measured at 200 ° C. to 0.1 mm. ) Can be measured.
高分子型帯電防止剤の配合量は、ポリエチレン系樹脂材料と高分子型帯電防止剤との合計１００重量％に対して１．５〜８重量％である。高分子型帯電防止剤の配合量が８重量％を超える場合には、高分子型帯電防止剤に含まれる低分子量成分が被包装物に移行しやすく、被包装物表面が曇りやすくなる場合や親水性が維持できなくなる場合がある。したがって、高分子型帯電防止剤の配合量は、ポリエチレン系樹脂発泡シートに所望の帯電防止性能を付与することが可能な範囲においてより少なくすることが好ましく考慮される。よって、好ましくは、高分子型帯電防止剤の配合量は６重量％以下であり、より好ましくは４重量％以下である。一方、高分子型帯電防止剤の配合量が１．５重量％未満の場合には、ポリエチレン系樹脂発泡シートに十分な帯電防止性能を付与することができない場合がある。よって、好ましくは、高分子型帯電防止剤の配合量は２重量％以上である。 The blending amount of the polymer type antistatic agent is 1.5 to 8% by weight with respect to 100% by weight of the total of the polyethylene resin material and the polymer type antistatic agent. When the amount of the polymer type antistatic agent exceeds 8% by weight, the low molecular weight component contained in the polymer type antistatic agent tends to migrate to the package, and the surface of the package tends to become cloudy. The hydrophilicity may not be maintained. Therefore, it is preferable to consider that the blending amount of the polymer type antistatic agent is less within a range in which desired antistatic performance can be imparted to the polyethylene resin foam sheet. Therefore, the blending amount of the polymer type antistatic agent is preferably 6% by weight or less, more preferably 4% by weight or less. On the other hand, when the blending amount of the polymer type antistatic agent is less than 1.5% by weight, sufficient antistatic performance may not be imparted to the polyethylene resin foam sheet. Therefore, the blending amount of the polymer type antistatic agent is preferably 2% by weight or more.
＜ポリエチレン系樹脂発泡シート＞
本発明のポリエチレン系樹脂発泡シート（以下、単に「発泡シート」ともいう。）は、ヘプタン抽出量が１．５重量％以下であることを特徴とする。ヘプタン抽出量が低いことによって、被包装物表面の親水性を維持しつつ、被包装物表面を曇らせにくくすることができる。かかる観点からは、発泡シートのヘプタン抽出量が１．３重量％以下であることが好ましく、より好ましくは１．０重量％以下である。
<Polyethylene resin foam sheet>
The polyethylene-based resin foam sheet of the present invention (hereinafter also simply referred to as “foam sheet”) is characterized in that the amount of heptane extracted is 1.5% by weight or less. When the amount of heptane extraction is low, the surface of the object to be packaged can be hardly fogged while maintaining the hydrophilicity of the surface of the object to be packaged. From this point of view, the heptane extraction amount of the foamed sheet is preferably 1.3% by weight or less, more preferably 1.0% by weight or less.
本明細書において、ポリエチレン系樹脂発泡シートの「ヘプタン抽出量」は、上記ポリエチレン系樹脂のヘプタン抽出と同様に行うことができ、以下のとおりの手順に従って測定、算出される。発泡シートを１０ｍｍ角に切断し、その切断物約２ｇをフラスコ内に投入し、ｎ−ヘプタン４００ｍｌを加え、５０℃にて４８時間加熱還流する。後はポリエチレン系樹脂材料と同様にしてヘプタン抽出量を求めることができる。 In the present specification, the “heptane extraction amount” of the polyethylene resin foam sheet can be performed in the same manner as the heptane extraction of the polyethylene resin, and is measured and calculated according to the following procedure. The foamed sheet is cut into 10 mm square, about 2 g of the cut product is put into the flask, 400 ml of n-heptane is added, and the mixture is heated to reflux at 50 ° C. for 48 hours. Thereafter, the amount of heptane extracted can be determined in the same manner as in the polyethylene resin material.
本発明の発泡シートの厚みは、所要の目的や用途、特性に応じて、選択することができる。例えば、包装材や間紙として用いる場合の緩衝性の観点からは、発泡シートの厚みは、０．０５ｍｍ以上が好ましく、より好ましくは０．１ｍｍ以上である。また、被包装物を梱包する際の取り扱いが容易である等の観点からは、発泡シートの厚みは、５ｍｍ以下が好ましく、より好ましくは３ｍｍ以下であり、さらに好ましくは２ｍｍ以下である。 The thickness of the foamed sheet of the present invention can be selected according to the required purpose, application and characteristics. For example, from the viewpoint of cushioning when used as a packaging material or an interleaf, the thickness of the foamed sheet is preferably 0.05 mm or more, and more preferably 0.1 mm or more. Further, from the viewpoint of easy handling when packing an article to be packaged, the thickness of the foamed sheet is preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less.
発泡シートの厚みは、以下のようにして算出することができる。まず、発泡シートを押出方向に直交する方向に垂直に切断し、この切断面の厚みを顕微鏡で拡大して幅方向全体に亘って略等間隔に１０点撮影を行う。次に、撮影した各点における発泡シートの厚みを測定する。そして、得られた値の算術平均値を、発泡シートの厚みとする。 The thickness of the foam sheet can be calculated as follows. First, the foamed sheet is cut perpendicularly to a direction orthogonal to the extrusion direction, and the thickness of the cut surface is enlarged with a microscope, and 10 points are photographed at substantially equal intervals over the entire width direction. Next, the thickness of the foam sheet at each photographed point is measured. And let the arithmetic mean value of the obtained value be the thickness of a foam sheet.
本発明の発泡シートの見掛け密度は、発泡シートの強度と緩衝性とのバランスを優れたものとする観点からは、１８〜５００ｋｇ／ｍ３の範囲内であることが好ましい。かかる観点からは、見掛け密度は、１８ｋｇ／ｍ３以上が好ましく、より好ましくは２０ｋｇ／ｍ３以上である。一方、見掛け密度は、３００ｋｇ／ｍ３以下が好ましく、より好ましくは２５０ｋｇ／ｍ３以下であり、さらに好ましくは２００ｋｇ／ｍ３以下である。 The apparent density of the foamed sheet of the present invention is preferably in the range of 18 to 500 kg / m 3 from the viewpoint of achieving an excellent balance between the strength and buffering properties of the foamed sheet. From this viewpoint, the apparent density is preferably 18 kg / m 3 or more, and more preferably 20 kg / m 3 or more. On the other hand, the apparent density is preferably 300 kg / m 3 or less, more preferably 250 kg / m 3 or less, and still more preferably 200 kg / m 3 or less.
発泡シートの見掛け密度は、以下のようにして算出することができる。まず、上記のとおり発泡シートの厚みを算出する。次に、以下のようにして坪量を算出する。発泡シートの坪量［ｇ／ｍ２］は、発泡シートの全幅にわたって、１０ｃｍ×発泡シートの幅×発泡シートの厚みのサイズの平面視矩形状の試験片を切り出し、試験片の質量［ｇ］を測定した後、この質量の値を試験片の面積［ｍ２：発泡シートの幅（ｍ）×０．１ｍ］で除することで得ることができる。このようにして得た坪量［ｇ／ｍ２］を、発泡シートの厚み［ｍｍ］で除し、単位換算することにより、発泡シートの見掛け密度［ｋｇ／ｍ３］とする。 The apparent density of the foam sheet can be calculated as follows. First, the thickness of the foam sheet is calculated as described above. Next, the basis weight is calculated as follows. The basis weight [g / m 2 ] of the foam sheet is 10 cm × the width of the foam sheet × the thickness of the foam sheet cut out a rectangular test piece in plan view over the entire width of the foam sheet, and the mass of the test piece [g] Then, the mass value can be obtained by dividing the value of the mass by the area of the test piece [m 2 : width (m) of foamed sheet × 0.1 m]. The basis weight [g / m 2 ] thus obtained is divided by the thickness [mm] of the foam sheet and converted into units to obtain the apparent density [kg / m 3 ] of the foam sheet.
本発明の発泡シートの独立気泡率は、好ましくは１０％以上であり、より好ましくは２０％以上である。発泡シートの独立気泡率：Ｓ（％）は、ＡＳＴＭ Ｄ２８５６−７０に記載されている手順Ｃに準拠し、空気比較式比重計（東芝ベックマン（株）製 ９３０型）を使用して測定した発泡シートの実容積（独立気泡の容積と樹脂部分の容積との和）：Ｖｘ（Ｌ）から、下記（１）式により算出することができる。
Ｓ（％）＝（Ｖｘ−Ｗ／ρ）×１００／（Ｖａ−Ｗ／ρ）・・・（１）
但し、上記式（１）中の、Ｖａ、Ｗ、ρはそれぞれ以下の通りである。
Ｖａ：測定に使用した発泡シートの見掛け容積（ｃｍ３）
Ｗ：試験片における発泡シートの質量（ｇ）
ρ：発泡シートを構成する樹脂の密度（ｇ／ｃｍ３）
The closed cell ratio of the foamed sheet of the present invention is preferably 10% or more, more preferably 20% or more. The closed cell ratio of the foam sheet: S (%) was measured by using an air-comparing hydrometer (model 930 manufactured by Toshiba Beckman Co., Ltd.) in accordance with Procedure C described in ASTM D2856-70. The actual volume of the sheet (the sum of the volume of closed cells and the volume of the resin portion): Vx (L) can be calculated by the following equation (1).
S (%) = (Vx−W / ρ) × 100 / (Va−W / ρ) (1)
However, Va, W, and ρ in the above formula (1) are as follows.
Va: Apparent volume of foam sheet used for measurement (cm 3 )
W: Mass of the foam sheet in the test piece (g)
ρ: Density of resin constituting the foam sheet (g / cm 3 )
本発明の発泡シートは帯電防止性能を有する。エレクトロニクス機器やその素材等の包装材や間紙として使用する観点からは、発泡シートの表面層側の初期帯電圧は、±２．５ｋＶの範囲内であることが好ましく、より好ましくは±２．０ｋＶの範囲内である。また、発泡シートは、この初期帯電圧が１／２に減衰するまでの時間、すなわち半減期（秒）が、６０秒以下であることが好ましく、より好ましくは３０秒以下である。発泡シートの半減期は、ＪＩＳ Ｌ１０９４（１９９７年）の半減期測定法に準拠して測定することができる。 The foam sheet of the present invention has antistatic performance. From the viewpoint of use as a packaging material or interleaf for electronic equipment and its materials, the initial voltage on the surface layer side of the foamed sheet is preferably within a range of ± 2.5 kV, more preferably ± 2. It is within the range of 0 kV. The foamed sheet preferably has a time until the initial charged voltage decays to ½, that is, a half-life (second) of 60 seconds or less, and more preferably 30 seconds or less. The half-life of the foamed sheet can be measured according to the half-life measurement method of JIS L1094 (1997).
また、エレクトロニクス機器やガラス板等の包装材や間紙として使用する観点からは、発泡シートの表面抵抗率は、１×１０１４Ω未満であることが好ましく、より好ましくは１×１０８〜１×１０１３Ωである。発泡シートの表面抵抗率は、ＪＩＳ Ｋ６２７１（２００８年）に準拠して測定することができる。 Further, from the viewpoint of use as a packaging material such as an electronic device or a glass plate or a slip sheet, the surface resistivity of the foamed sheet is preferably less than 1 × 10 14 Ω, more preferably 1 × 10 8 to 1. × 10 13 Ω. The surface resistivity of the foamed sheet can be measured according to JIS K6271 (2008).
＜ポリエチレン系樹脂発泡シートの製造方法＞
本発明のポリエチレン系樹脂発泡シートの製造方法について、好ましい実施形態を例示して説明する。本発明の発泡シートは、高分子型帯電防止剤を配合したポリエチレン系樹脂材料を押出成形することによって製造される。
<Method for producing polyethylene resin foam sheet>
About the manufacturing method of the polyethylene-type resin foam sheet of this invention, preferable embodiment is illustrated and demonstrated. The foam sheet of the present invention is produced by extruding a polyethylene resin material containing a polymer type antistatic agent.
まず、ポリエチレン系樹脂材料、高分子型帯電防止剤、および必要に応じて気泡調整剤等の添加剤を、押出機に供給し、加熱、混練した後、物理発泡剤を圧入して、更に混練して発泡シート成形用樹脂材料溶融物を得る。 First, an additive such as a polyethylene resin material, a polymer-type antistatic agent, and, if necessary, a bubble regulator, is supplied to an extruder, heated and kneaded, and then a physical foaming agent is injected and further kneaded. Thus, a resin material melt for forming a foam sheet is obtained.
次いで、押出機内で前記発泡シート成形用樹脂材料溶融物を発泡可能な温度に調整し、環状ダイを通して大気中に押出して、発泡シート成形用樹脂材料溶融物を発泡させて筒状発泡体を形成する。この筒状発泡体の内面を、拡幅しつつ円柱状冷却装置に沿わせて引取りながら切り開くことにより、発泡シートを得る。前記押出機、環状ダイ、円柱状冷却装置、筒状発泡体を切り開く装置等は、従来押出発泡の分野で用いられてきた一般に公知のものを用いることができる。なお、環状ダイの代わりにフラットダイを用いて押出発泡することもできる。 Next, the foamed sheet molding resin material melt is adjusted to a foamable temperature in an extruder and extruded into the atmosphere through an annular die to foam the foamed sheet molding resin material melt to form a cylindrical foam. To do. The foamed sheet is obtained by cutting the inner surface of the cylindrical foam while taking it up along the columnar cooling device while widening. As the extruder, the annular die, the columnar cooling device, the device for opening the cylindrical foam, etc., generally known ones that have been used in the field of extrusion foaming can be used. In addition, it is also possible to perform extrusion foaming using a flat die instead of the annular die.
前記物理発泡剤としては、例えば、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ノルマルヘキサン、イソヘキサン等の脂肪族炭化水素、シクロペンタン、シクロヘキサンなどの脂環式炭化水素、塩化メチル、塩化エチル等の塩化炭化水素、１，１，１，２−テトラフロロエタン、１，１−ジフロロエタン等のフッ化炭化水素、ジメチルエーテル、メチルエチルエーテル等のエーテル類、メタノール、エタノール等のアルコール類などの有機系物理発泡剤、酸素、窒素、二酸化炭素、空気、水等の無機系発泡剤が挙げられる。場合によっては、アゾジカルボンアミド等の分解型発泡剤を使用することもできる。これらの物理発泡剤は、２種以上を混合して使用することが可能である。これらのうち、発泡性の観点から有機系物理発泡剤が好ましく、中でもノルマルブタン、イソブタン、又はこれらの混合物を主成分とするものが好ましく、ノルマルブタン５０〜８０重量％、イソブタン２０〜５０重量％の比率であることがより好ましい（但し、ノルマルブタンとイソブタンの合計量を１００重量％とする）。 Examples of the physical blowing agent include aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, and isohexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, methyl chloride, and ethyl chloride. Organic hydrocarbons such as chlorohydrocarbons, fluorinated hydrocarbons such as 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane, ethers such as dimethyl ether and methyl ethyl ether, and alcohols such as methanol and ethanol Examples include physical foaming agents, inorganic foaming agents such as oxygen, nitrogen, carbon dioxide, air, and water. In some cases, a decomposable foaming agent such as azodicarbonamide can be used. These physical foaming agents can be used in combination of two or more. Among these, an organic physical foaming agent is preferable from the viewpoint of foaming properties, and among them, those having normal butane, isobutane, or a mixture thereof as a main component are preferable, and normal butane is 50 to 80% by weight, isobutane is 20 to 50% by weight. (The total amount of normal butane and isobutane is 100% by weight).
該発泡剤添加量は、発泡剤の種類、目的とする見かけ密度に応じて調整する。例えば、物理発泡剤としてイソブタン３０重量％とノルマルブタン７０重量％とのブタン混合物などの物理発泡剤を用いた場合、ポリエチレン系樹脂材料１００重量部に対して２〜３５重量部が好ましく、より好ましくは３〜３０重量部、さらに好ましくは４〜２５重量部である。 The amount of foaming agent added is adjusted according to the type of foaming agent and the desired apparent density. For example, when a physical foaming agent such as a butane mixture of 30% by weight of isobutane and 70% by weight of normal butane is used as the physical foaming agent, it is preferably 2 to 35 parts by weight, more preferably 100 parts by weight of the polyethylene resin material. Is 3 to 30 parts by weight, more preferably 4 to 25 parts by weight.
＜その他の添加剤＞
なお、本発明で用いられるポリエチレン系樹脂発泡シートには、ヘプタン抽出量が１．５重量％を超えない範囲において、必要に応じて一般的に用いられる気泡調整剤、安定剤、フィラー、収縮防止剤、界面活性剤等の各種添加剤を配合することができる。
<Other additives>
In addition, the polyethylene resin foam sheet used in the present invention has a foam regulator, stabilizer, filler, and shrinkage prevention generally used as needed within a range in which the amount of heptane extraction does not exceed 1.5% by weight. Various additives such as an agent and a surfactant can be blended.
前記気泡調整剤としては、例えば、有機系気泡調整剤、無機系気泡調整剤等が挙げられる。有機系気泡調整剤としては、例えば、リン酸−２，２−メチレンビス（４，６−ｔｅｒｔ−ブチルフェニル）ナトリウム、安息香酸ナトリウム、安息香酸カルシウム、安息香酸アルミニウム、ステアリン酸ナトリウム等が挙げられる。無機系気泡調整剤としては、例えば、ホウ酸亜鉛、ホウ酸マグネシウム、硼砂等のホウ酸金属塩、塩化ナトリウム、水酸化アルミニウム、タルク、ゼオライト、シリカ、炭酸カルシウム、重炭酸ナトリウム等が挙げられる。また、気泡調整剤として、クエン酸と重炭酸ナトリウム、クエン酸のモノアルカリ塩と重炭酸ナトリウムを組み合わせたもの等を用いてもよい。なお、気泡調整剤は、必要に応じて２種以上を併用してもよい。 Examples of the bubble regulator include organic bubble regulators and inorganic bubble regulators. Examples of the organic bubble regulator include sodium phosphate-2,2-methylenebis (4,6-tert-butylphenyl), sodium benzoate, calcium benzoate, aluminum benzoate, and sodium stearate. Examples of the inorganic foam regulator include boric acid metal salts such as zinc borate, magnesium borate, borax, sodium chloride, aluminum hydroxide, talc, zeolite, silica, calcium carbonate, sodium bicarbonate, and the like. Moreover, you may use what combined the citric acid and sodium bicarbonate, the monoalkali salt of citric acid, and sodium bicarbonate as a bubble regulator. In addition, you may use 2 or more types of bubble regulators together as needed.
前記収縮防止剤としては、従来使用されているステアリン酸モノグリセライド等が挙げられる。また、前記界面活性剤としては、アルキルスルホン酸塩やアルキルベンゼンスルホン酸塩等のアニオン系界面活性剤、ポリアルキレンオキシド等の非イオン系界面活性剤等が挙げられる。前記収縮防止剤や界面活性剤は、発泡シートの表面にブリードアウトしてガラス等の被包装物の曇りの原因となるおそれがある。上記観点から、前記収縮防止剤や界面活性剤の配合量は、発泡シートを構成する樹脂材料に対して０．３重量％以下が好ましく、より好ましくは０．２重量％以下、更に好ましくは０．１重量％以下であり、添加しないことが特に好ましい。 Examples of the shrinkage preventing agent include stearic acid monoglyceride conventionally used. Examples of the surfactant include anionic surfactants such as alkyl sulfonates and alkylbenzene sulfonates, and nonionic surfactants such as polyalkylene oxides. The shrinkage-preventing agent and the surfactant may bleed out on the surface of the foamed sheet and cause fogging of an object to be packaged such as glass. From the above viewpoint, the blending amount of the shrinkage inhibitor and the surfactant is preferably 0.3% by weight or less, more preferably 0.2% by weight or less, and still more preferably 0% with respect to the resin material constituting the foamed sheet. .1% by weight or less, and it is particularly preferable not to add.
本発明のポリエチレン系樹脂発泡シートは、帯電防止性能を有するとともに、発泡シートから被包装物への低分子量成分としての有機物等の移行が抑制されている。そのため、ガラス板用の間紙や包装材としてだけではなく、エレクトロニクス機器やその素材等の包装材や間紙としても好適に使用できるものである。 The polyethylene-based resin foam sheet of the present invention has antistatic performance and suppresses the transfer of organic substances and the like as low molecular weight components from the foam sheet to the package. Therefore, it can be suitably used not only as a slip sheet or packaging material for glass plates, but also as a packaging material or slip sheet for electronic equipment or its materials.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.
実施例、比較例において、以下に示すポリエチレン系樹脂材料、高分子型帯電防止剤および気泡調整剤を使用した。 In the examples and comparative examples, the following polyethylene-based resin materials, polymer antistatic agents and bubble regulators were used.
（１）ポリエチレン系樹脂材料
（ｉ）東ソー（株）製「低密度ポリエチレン：商品名１０Ｓ５４Ａ」（略称Ａ）（密度：９２５ｋｇ／ｍ３、ＭＦＲ：１．８ｇ／１０分、溶融張力：３２．６ｍＮ、融点：１１１℃、ヘプタン抽出量：０．１５重量％）
（ｉｉ）ダウ・ケミカル日本（株）製「低密度ポリエチレン：商品名ＮＵＣ８３２１」（略称Ｃ）（密度：９２２ｋｇ／ｍ３、ＭＦＲ：１．９ｇ／１０分、溶融張力：５２．２ｍＮ、融点：１１１℃、ヘプタン抽出量：１．１５重量％）
（ｉｉｉ）上記略称Ｃのポリエチレン系樹脂材料を、５０℃のｎ−ヘプタン中に２４時間浸漬し、低分子量成分を抽出除去したもの（略称Ｂ）（密度：９２２ｋｇ／ｍ３、ＭＦＲ：１．８ｇ／１０分、溶融張力：５４．５ｍＮ、融点：１１１℃、ヘプタン抽出量：０．３５重量％）
なお、ポリエチレン系樹脂材料のプロフィールをまとめたものを表１に示す。
(1) Polyethylene resin material (i) “Low-density polyethylene: Trade name 10S54A” (abbreviation A) (density: 925 kg / m 3 , MFR: 1.8 g / 10 min, melt tension: 32. manufactured by Tosoh Corporation. 6mN, melting point: 111 ° C., heptane extraction amount: 0.15% by weight)
(Ii) “Low Density Polyethylene: Trade Name NUC8321” (abbreviation C) (Density: 922 kg / m 3 , MFR: 1.9 g / 10 min, Melt Tension: 52.2 mN, Melting Point: (111 ° C., heptane extraction amount: 1.15% by weight)
(Iii) A polyethylene-based resin material of the above abbreviation C is immersed in n-heptane at 50 ° C. for 24 hours to extract and remove low molecular weight components (abbreviation B) (density: 922 kg / m 3 , MFR: 1. (8 g / 10 min, melt tension: 54.5 mN, melting point: 111 ° C., heptane extract: 0.35 wt%)
Table 1 summarizes the profiles of polyethylene resin materials.
（２）高分子型帯電防止剤
三洋化成工業（株）製「ポリエーテル−ポリプロピレンオレフィンブロック共重合体：ペレクトロンＨＳ」（略称「ＨＳ」）（融点：１３４℃、表面抵抗率：２．０×１０６Ω）
(2) Polymer type antistatic agent “Polyether-polypropylene olefin block copolymer: Peletron HS” (abbreviation “HS”) manufactured by Sanyo Chemical Industries, Ltd. (melting point: 134 ° C., surface resistivity: 2.0 × 10 6 Ω)
（３）気泡調整剤
松村産業（株）製「タルク：商品名ハイフィラー＃１２」
(3) Bubble regulator “Talc: Trade name High Filler # 12” manufactured by Matsumura Sangyo Co., Ltd.
＜実施例１＞
上記略称Ａのポリエチレン系樹脂材料に対し、上記略称ＨＳの高分子型帯電防止剤を４重量％となるよう配合し、これに気泡調製剤を１重量部配合した原料を、直径６５ｍｍの第一押出機の原料投入口に供給し、加熱混練し、温度を約２００℃に調整して溶融樹脂混合物を得た。この溶融樹脂混合物に、物理発泡剤として３．６重量部の混合ブタン（ノルマルブタン／イソブタン＝７０重量％／３０重量％）を圧入し、この混合物を、第一押出機の下流側に連結した直径９０ｍｍの第二押出機に送り、約１１５℃の樹脂温度のポリエチレン系樹脂発泡シート成形用樹脂溶融物を得た。
<Example 1>
The raw material in which the polymer type antistatic agent of the abbreviation HS is blended to 4% by weight with respect to the polyethylene resin material of the abbreviation A and 1 part by weight of a cell preparation agent is blended into The mixture was supplied to the raw material inlet of the extruder, heated and kneaded, and the temperature was adjusted to about 200 ° C. to obtain a molten resin mixture. To this molten resin mixture, 3.6 parts by weight of mixed butane (normal butane / isobutane = 70% by weight / 30% by weight) as a physical foaming agent was injected and this mixture was connected to the downstream side of the first extruder. It sent to the 90 mm diameter 2nd extruder, and obtained the resin melt for polyethylene-type resin foam sheet shaping | molding of the resin temperature of about 115 degreeC.
このポリエチレン系樹脂発泡シート成形用樹脂溶融物を、５０ｋｇ／ｈｒの吐出量で環状ダイ中へ導入して押出成形し、筒状発泡体を得た。この筒状発泡体を直径１５０ｍｍの筒状拡幅装置にて拡幅しながら、坪量が２３ｇ／ｍ２となるように引き取り、さらに筒状発泡体を押出方向に沿って切り開くことにより、ポリエチレン系樹脂発泡シートを得た。 The polyethylene resin foam sheet molding resin melt was introduced into an annular die at a discharge rate of 50 kg / hr and extruded to obtain a cylindrical foam. While expanding this cylindrical foam with a cylindrical widening apparatus having a diameter of 150 mm, the basis weight is taken up to 23 g / m 2 , and the cylindrical foam is further cut along the extrusion direction to obtain a polyethylene resin. A foam sheet was obtained.
＜実施例２＞
溶融樹脂混合物を作製する際に、高分子型帯電防止剤の配合量を２重量％とし、ポリエチレン系樹脂発泡シート成形用樹脂溶融物を作製する際に、実施例１で用いた物理発泡剤としての混合ブタンの圧入割合を９．４重量部としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Example 2>
As the physical foaming agent used in Example 1 when preparing the resin melt for forming a polyethylene-based resin foam sheet, the blending amount of the polymer type antistatic agent was 2% by weight when the molten resin mixture was prepared. A polyethylene-based resin foamed sheet was obtained in the same manner as in Example 1 except that the mixed butane pressure-in ratio was 9.4 parts by weight.
＜参考例＞
溶融樹脂混合物を作製する際に、高分子型帯電防止剤の配合量を６重量％としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
< Reference example >
A polyethylene-based resin foam sheet was obtained in the same manner as in Example 1 except that when the molten resin mixture was prepared, the blending amount of the polymer type antistatic agent was 6% by weight.
＜実施例４＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて上記略称Ｂのポリエチレン系樹脂を用い、ポリエチレン系樹脂発泡シート成形用樹脂溶融物を作製する際に、実施例１で用いた物理発泡剤としての混合ブタンの圧入割合を９．４重量部としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Example 4>
In preparing the resin melt for forming a polyethylene resin foamed sheet by using the polyethylene resin of the abbreviation B instead of the polyethylene resin material of the abbreviation A when preparing the molten resin mixture, A polyethylene-based resin foam sheet was obtained in the same manner as in Example 1 except that the press-in ratio of mixed butane as the physical foaming agent used was 9.4 parts by weight.
＜実施例５＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて、上記略称Ａのポリエチレン系樹脂５５重量％と上記略称Ｃのポリエチレン系樹脂４５重量％との混合樹脂（Ａ／Ｃ＝５５／４５）を用い、ポリエチレン系樹脂発泡シート成形用樹脂溶融物を作製する際に、実施例１で用いた物理発泡剤としての混合ブタンの圧入割合を９．４重量部としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Example 5>
In preparing the molten resin mixture, instead of the polyethylene resin material of the abbreviation A, a mixed resin (A / C) of 55 wt% of the polyethylene resin of the abbreviation A and 45 wt% of the polyethylene resin of the abbreviation C is used. = 55/45), when the resin melt for forming a polyethylene-based resin foam sheet is produced, the press-in ratio of the mixed butane used as the physical foaming agent used in Example 1 is 9.4 parts by weight Obtained a polyethylene resin foam sheet in the same manner as in Example 1.
＜実施例６＞
ポリエチレン系樹脂発泡シート成形用樹脂溶融物を作製する際に、実施例１で用いた物理発泡剤としての混合ブタンの圧入割合を９．４重量部としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Example 6>
When producing a resin melt for forming a polyethylene-based resin foam sheet, the same procedure as in Example 1 was conducted except that the press-in ratio of the mixed butane as the physical foaming agent used in Example 1 was 9.4 parts by weight. A polyethylene resin foam sheet was obtained.
＜実施例７＞
ポリエチレン系樹脂発泡シート成形用樹脂溶融物を作製する際に、実施例１で用いた物理発泡剤としての混合ブタンの圧入割合を１７．６重量部としたこと、および筒状発泡体を筒状拡幅装置にて拡幅する際に、坪量が３１ｇ／ｍ２となるように引き取り速度を調整したこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Example 7>
When producing the resin melt for forming a polyethylene-based resin foam sheet, the press-in ratio of the mixed butane used as the physical foaming agent used in Example 1 was 17.6 parts by weight, and the tubular foam was formed into a tubular shape. A polyethylene-based resin foam sheet was obtained in the same manner as in Example 1 except that the take-up speed was adjusted so that the basis weight was 31 g / m 2 when widening with a widening device.
＜比較例１＞
溶融樹脂混合物を作製する際に、高分子型帯電防止剤の配合量を１重量％としたこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative Example 1>
A polyethylene-based resin foam sheet was obtained in the same manner as in Example 1 except that when the molten resin mixture was prepared, the blending amount of the polymer type antistatic agent was 1% by weight.
＜比較例２＞
溶融樹脂混合物を作製する際に、高分子型帯電防止剤の配合量を１５重量％としたこと以外は実施例２と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative example 2>
A polyethylene-based resin foam sheet was obtained in the same manner as in Example 2 except that when the molten resin mixture was prepared, the blending amount of the polymer-type antistatic agent was 15% by weight.
＜比較例３＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて、上記略称Ｃのポリエチレン系樹脂材料を使用したこと以外は実施例２と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative Example 3>
When preparing the molten resin mixture, a polyethylene resin foam sheet was obtained in the same manner as in Example 2 except that the polyethylene resin material of the abbreviation C was used instead of the polyethylene resin material of the abbreviation A. It was.
＜比較例４＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて、上記略称Ａのポリエチレン系樹脂材料３０重量％と上記略称Ｃのポリエチレン系樹脂材料７０重量％の混合樹脂材料（Ａ／Ｃ＝３０／７０）を用いたこと以外は実施例７と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative Example 4>
When preparing the molten resin mixture, instead of the polyethylene resin material of the abbreviation A, a mixed resin material (A of 30 wt% of the polyethylene resin material of the abbreviation A and 70 wt% of the polyethylene resin material of the abbreviation C is used. A polyethylene-based resin foam sheet was obtained in the same manner as in Example 7 except that / C = 30/70) was used.
＜比較例５＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて、上記略称Ｃのポリエチレン系樹脂材料を使用し、高分子型帯電防止剤の配合量を９重量％、界面活性剤としてポリエチレングリコール（三洋化成工業（株）製、商品名：ＰＥＧ−３００、数平均分子量：３００）を４．２重量％添加したこと以外は実施例２と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative Example 5>
When preparing the molten resin mixture, the polyethylene resin material of the abbreviation C is used instead of the polyethylene resin material of the abbreviation A, the blending amount of the polymer antistatic agent is 9% by weight, and the surfactant. As in Example 2, except that polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG-300, number average molecular weight: 300) was added in an amount of 4.2% by weight, a polyethylene resin foam sheet was obtained. Obtained.
＜比較例６＞
溶融樹脂混合物を作製する際に、上記略称Ａのポリエチレン系樹脂材料に代えて、上記略称Ｃのポリエチレン系樹脂材料を使用し、帯電防止剤を配合しなかったこと以外は実施例１と同様にして、ポリエチレン系樹脂発泡シートを得た。
<Comparative Example 6>
When preparing the molten resin mixture, the same procedure as in Example 1 was used except that the polyethylene resin material of the abbreviation C was used instead of the polyethylene resin material of the abbreviation A and no antistatic agent was added. Thus, a polyethylene resin foam sheet was obtained.
実施例１〜２、参考例、実施例４〜７および比較例１〜６で用いたポリエチレン系樹脂材料、高分子型帯電防止剤、および物理発泡剤の組み合わせを表２に示す。 Table 2 shows combinations of the polyethylene resin materials, polymer antistatic agents, and physical foaming agents used in Examples 1-2, Reference Examples, Examples 4-7, and Comparative Examples 1-6.
このようにして得られた実施例１〜２、参考例、実施例４〜７および比較例１〜６のポリエチレン系樹脂発泡シートについて、下記のとおりの各種物性の測定および評価を行った。 About the polyethylene-type resin foam sheet of Examples 1-2 obtained in this way , a reference example, Examples 4-7, and Comparative Examples 1-6, various physical properties were measured and evaluated as follows.
（１）ヘプタン抽出量
上記のとおりに測定、算出した。
(1) Extracted amount of heptane Measured and calculated as described above.
（２）厚み、坪量および見掛け密度の測定
上記のとおりに測定、算出した。
(2) Measurement of thickness, basis weight, and apparent density Measurement and calculation were performed as described above.
（３）初期帯電圧、一分後残存帯電圧および半減期の測定
試験片として、発泡シートから無作為に、縦４５ｍｍ×横４５ｍｍのサイズ（厚みは発泡シートの厚みである）のシートを５枚切り出した。
［初期帯電圧］
上記の試験片を、温度２３℃、相対湿度５０％環境下にて、２４時間状態調節した後、スタティックオネストメーター（シシド静電気株式会社製 ＴＩＰＥ Ｓ−５１０９）を使用して、温度２３℃、相対湿度５０％環境下にて、ＪＩＳ Ｌ１０９４（１９９７年）Ａ法に従って、ターンテーブルの回転速度を１３００ｒｐｍとし、試験片の表面層側に（−）１０ｋＶの電圧を３０秒間印加し、印加を停止したときの帯電圧を測定した。
［一分後残存帯電圧］
上記初期帯電圧の測定から１分後の帯電圧を、上記に準じて測定した。
［半減期］
上記初期帯電圧の値が１／２となるまでの時間を測定した。
これらの測定を各試験片の両面について行い（発泡シート１枚あたり試験片５枚×２面＝計１０回）、得られた結果の算術平均値を、初期帯電圧、一分後残存帯電圧および半減期として採用した。
(3) Measurement of initial charged voltage, remaining charged voltage after 1 minute and half-life As a test piece, a sheet of a size of 45 mm in length and 45 mm in width (thickness is the thickness of the foamed sheet) is randomly selected from the foamed sheet. Cut out.
[Initial voltage]
The above test piece was conditioned at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then, using a static Honest meter (TIPE S-5109, manufactured by Sicid Electrostatic Co., Ltd.) Under a 50% humidity environment, according to JIS L1094 (1997) A method, the rotation speed of the turntable was set to 1300 rpm, a voltage of (−) 10 kV was applied to the surface layer side of the test piece for 30 seconds, and the application was stopped. The charging voltage was measured.
[Remaining charged voltage after 1 minute]
The charged voltage after 1 minute from the measurement of the initial charged voltage was measured according to the above.
[Half-life]
The time until the value of the initial charging voltage became 1/2 was measured.
These measurements were performed on both sides of each test piece (5 test pieces per foam sheet × 2 surfaces = 10 times in total), and the arithmetic average value of the obtained results was determined as the initial charged voltage and the remaining charged voltage after 1 minute. And adopted as half-life.
（４）表面抵抗率の測定
試験片として、発泡シートから無作為に、縦１００ｍｍ×横１００ｍｍのサイズ（厚みは発泡シートの厚みである）のシートを３枚切り出した。ＪＩＳ Ｋ６２７１（２００１年）に準拠して、５００Ｖの電圧を印加してから１分後の表面抵抗値を、タケダ理研工業（株）製「ＴＲ８６０１」を用いて測定した。この測定を各試験片の両面について行い（発泡シート１枚あたり試験片３枚×２面＝計６回）、得られた結果の算術平均値を表面抵抗率として採用した。
(4) Measurement of surface resistivity As a test piece, three sheets having a size of 100 mm in length and 100 mm in width (thickness is the thickness of the foam sheet) were cut out from the foam sheet. Based on JIS K6271 (2001), the surface resistance value 1 minute after applying a voltage of 500 V was measured using “TR8601” manufactured by Takeda Riken Kogyo Co., Ltd. This measurement was performed on both surfaces of each test piece (3 test pieces per foam sheet × 2 surfaces = total 6 times), and the arithmetic average value of the obtained results was adopted as the surface resistivity.
（５）接触角の測定
プレクリンスライドガラス（松浪ガラス工業（株）製）に、発泡シートを３．８ｇ／ｃｍ２の圧力で密着させ、６０℃下で２４時間静置した。その後、発泡シートをガラスから除去し、発泡シートが接触していた面について、ＪＩＳ Ｒ３２５７（１９９９年）に記載の静滴法に従って、接触角を測定した。
(5) Measurement of contact angle A foam sheet was adhered to a preclinic slide glass (manufactured by Matsunami Glass Industry Co., Ltd.) at a pressure of 3.8 g / cm 2 , and allowed to stand at 60 ° C. for 24 hours. Thereafter, the foam sheet was removed from the glass, and the contact angle of the surface with which the foam sheet was in contact was measured according to the sessile drop method described in JIS R3257 (1999).
（６）帯電防止性能評価
上記半減期の有無に基づいて評価を行った。下記表３および表４では、半減期が６０秒以内であるものを○、半減期が６０秒を超えるものを×とした。
(6) Evaluation of antistatic performance Evaluation was performed based on the presence or absence of the above half-life. In Tables 3 and 4 below, those having a half-life of 60 seconds or less were marked with ◯, and those with a half-life exceeding 60 seconds were marked with ×.
（７）被包装物の表面の親水性評価
上記接触角の値に基づいて評価を行った。下記表３および表４では、接触角が２０°未満のものを○、２０°以上のものを×とした。
(7) Evaluation of hydrophilicity of surface of packaged object Evaluation was performed based on the value of the contact angle. In Table 3 and Table 4 below, those having a contact angle of less than 20 ° are indicated as “◯”, and those having a contact angle of 20 ° or more as “X”.
（８）ヘーズ評価
ＪＩＳ Ｋ７１３６（２０００年）に従って、濁度計（日本電飾工業（株）製；形式ＮＤＨ２０００）を用いて測定し、試験前後のヘーズ値の差をヘーズ上昇値（Ｈｚ）とした。なお、発泡シートの圧着条件は、上記接触角の測定と同様とした。下記表３および表４では、ヘーズ上昇値が１．０未満のものを◎、ヘーズ上昇値が１以上〜２未満のものを○、ヘーズ上昇値が２以上〜５未満のものを△、ヘーズ上昇値が５以上のものを×とした。
(8) Haze evaluation Measured using a turbidimeter (manufactured by Nippon Denshoku Kogyo Co., Ltd .; model NDH2000) according to JIS K7136 (2000), and the difference between haze values before and after the test was compared with the haze increase value (Hz) did. Note that the pressure-bonding conditions of the foam sheet were the same as the measurement of the contact angle. In Tables 3 and 4 below, the haze increase value is less than 1.0, the haze increase value is 1 or more and less than 2 ○, the haze increase value is 2 or more and less than 5 Δ, and the haze An increase value of 5 or more was rated as x.
以上のポリエチレン系樹脂発泡シートの物性測定結果および評価結果を、表３および表４に示す。 Tables 3 and 4 show the physical property measurement results and evaluation results of the above polyethylene-based resin foam sheets.
実施例１〜２、参考例、実施例４〜７の発泡シートは、帯電防止性能に優れ、かつ、被包装物表面を曇らせにくいと共に、被包装物表面の親水性を維持できるような被包装物表面を汚染しにくいものであり、いずれの物性・評価項目についても優れた特性を示した。一方、実施例１〜２、参考例、実施例４〜７の条件よりも高分子型帯電防止剤の配合量を減らした比較例１の発泡シートは、実施例１〜２、参考例、実施例４〜７の発泡シートと比較して帯電防止性能が有意に劣っていた。また、実施例１〜２、参考例、実施例４〜７の条件よりも高分子型帯電防止剤の配合量を増やした比較例２の発泡シートは、実施例１〜２、参考例、実施例４〜７の発泡シートと比較して被包装物表面の親水性が有意に劣っており、ヘーズ上昇値が大きかった。比較例３および４の発泡シートは、実施例１〜２、参考例、実施例４〜７の発泡シートと比較して、主にポリエチレン系樹脂材料に含まれる低分子量成分の被包装物への移行が多いためか、被包装物表面の親水性が有意に劣っていた。実施例１〜２、参考例、実施例４〜７の条件よりも高分子型帯電防止剤の配合量を増やし、かつ界面活性剤を添加した比較例５の発泡シートは、主にブリードアウトした界面活性剤が被包装物表面へ移行するためか、ヘーズ上昇値が最も大きかった。帯電防止剤を配合しなかった比較例６の発泡シートは、主にポリエチレン系樹脂材料に含まれる低分子量成分の被包装物への移行が多いためか、被包装物表面の親水性が有意に劣っており、帯電防止性能も有意に劣っていた。 The foamed sheets of Examples 1 to 2, Reference Example, and Examples 4 to 7 have excellent antistatic performance, are difficult to fog the surface of the packaged object, and can maintain the hydrophilicity of the surface of the packaged object. It is difficult to contaminate the surface of the material, and showed excellent properties for all physical properties and evaluation items. On the other hand, the foamed sheet of Comparative Example 1 in which the blending amount of the polymer type antistatic agent was reduced as compared with the conditions of Examples 1 and 2, Reference Examples and Examples 4 to 7, was the same as that of Examples 1 and 2, Reference Examples, and Examples. Compared with the foamed sheets of Examples 4 to 7, the antistatic performance was significantly inferior. In Examples 21 to Reference Example, the foam sheet of Example 4-7 conditions Comparative Example 2 increased the amount of the polymeric antistatic agent than is Example 21 to Reference Example, performed Compared with the foamed sheets of Examples 4 to 7, the hydrophilicity of the surface of the package was significantly inferior, and the haze increase value was large. Compared with the foamed sheets of Comparative Examples 3 and 4, the foamed sheets of Examples 1 and 2, Reference Examples and Examples 4 to 7, the low molecular weight component mainly contained in the polyethylene resin material was applied to the package. The hydrophilicity of the surface of the object to be packaged was significantly inferior because of a lot of migration. The foamed sheet of Comparative Example 5 in which the compounding amount of the polymer type antistatic agent was increased in comparison with the conditions of Examples 1 and 2, Reference Examples and Examples 4 to 7 and the surfactant was added was mainly bleeded out. The haze increase value was the largest because the surfactant was transferred to the surface of the package. The foamed sheet of Comparative Example 6 that does not contain an antistatic agent is significantly improved in hydrophilicity on the surface of the packaged object, probably because the low molecular weight component contained in the polyethylene resin material is often transferred to the packaged object. It was inferior and the antistatic performance was also significantly inferior.
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