JP5561762B2 - Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles - Google Patents
Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles Download PDFInfo
- Publication number
- JP5561762B2 JP5561762B2 JP2009292596A JP2009292596A JP5561762B2 JP 5561762 B2 JP5561762 B2 JP 5561762B2 JP 2009292596 A JP2009292596 A JP 2009292596A JP 2009292596 A JP2009292596 A JP 2009292596A JP 5561762 B2 JP5561762 B2 JP 5561762B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- particles
- resin
- polyolefin resin
- mineral oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims description 277
- 229920005672 polyolefin resin Polymers 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title description 38
- 229920005989 resin Polymers 0.000 claims description 105
- 239000011347 resin Substances 0.000 claims description 105
- 239000002480 mineral oil Substances 0.000 claims description 85
- 235000010446 mineral oil Nutrition 0.000 claims description 85
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 60
- 239000004088 foaming agent Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 29
- 239000011342 resin composition Substances 0.000 claims description 16
- 239000002612 dispersion medium Substances 0.000 claims description 14
- 238000007906 compression Methods 0.000 claims description 12
- 230000006835 compression Effects 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 39
- 238000005470 impregnation Methods 0.000 description 38
- 238000005187 foaming Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000012188 paraffin wax Chemical group 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000000126 substance Substances 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
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004996 alkyl benzenes 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 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
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、ポリオレフィン系樹脂発泡粒子、ポリオレフィン系樹脂発泡粒子成形体、及びポリオレフィン系樹脂発泡粒子の製造方法に関する。 The present invention relates to a polyolefin resin expanded particle, a polyolefin resin expanded particle molded body, and a method for producing a polyolefin resin expanded particle.
ポリオレフィン系樹脂発泡粒子は用途に合わせて様々な形状に成形可能である。そして、該発泡粒子から型内成形により得られるポリオレフィン系樹脂発泡粒子成形体は、各種包装緩衝材、自動車の衝撃吸収材など、広範な用途に用いられている。しかし、柔軟性が要求される精密な被梱包物の包装資材や、触感や圧縮後の形状の回復性が要求されるシートクッション材などの用途に用いられる発泡粒子成形体としては、より軽量で、柔軟な成形体、さらには圧縮永久歪の小さな、回復性に優れる成形体が求められる。
例えば、特許文献1には、ポリオレフィン系樹脂と非晶性ゴム質重合体との樹脂組成物からなる型内発泡成形用発泡ビーズが記載されている。また、特許文献2には、ポリオレフィン系樹脂とポリオレフィン系ゴムからなる組成物を基材樹脂とするポリオレフィン系樹脂発泡粒子が記載されている。
The polyolefin resin expanded particles can be molded into various shapes according to the application. The polyolefin resin foamed particle molded body obtained from the foamed particles by in-mold molding is used in a wide range of applications such as various packaging cushioning materials and automobile impact absorbing materials. However, it is lighter in weight as a foamed particle molded body used for applications such as precision packaging materials that require flexibility, and seat cushion materials that require tactile sensation and shape recovery after compression. Therefore, there is a demand for a flexible molded body, and further a molded body having a small compression set and excellent recoverability.
For example, Patent Literature 1 describes foam beads for in-mold foam molding made of a resin composition of a polyolefin resin and an amorphous rubber polymer. Patent Document 2 describes polyolefin resin expanded particles in which a base resin is a composition comprising a polyolefin resin and a polyolefin rubber.
従来より、柔軟性と軽量性に優れる発泡粒子成形体を得る手段として、ポリオレフィン系樹脂にエラストマー成分を多量に含有させることが行なわれている。しかし、この方法では、十分な柔軟性や回復性を有する発泡粒子成形体を得ることはできなかった。 Conventionally, as a means for obtaining a foamed particle molded body excellent in flexibility and lightness, a polyolefin resin is made to contain a large amount of an elastomer component. However, with this method, a foamed particle molded body having sufficient flexibility and recoverability could not be obtained.
特許文献1には発泡倍率4倍の発泡粒子が得られたことが記載されているだけであり、柔軟性としては不十分なものであり、軽量性にも課題を残すものであった。
また、特許文献2により得られた発泡粒子を型内成形して得られた発泡粒子成形体は、圧縮強度が2kg/cm2程度のものであり、柔軟性に課題を残すものであった。
Patent Document 1 only describes that foamed particles having a foaming ratio of 4 times were obtained, which was insufficient as flexibility and left a problem in lightness.
In addition, the foamed particle molded body obtained by in-mold molding of the foamed particles obtained in Patent Document 2 has a compressive strength of about 2 kg / cm 2 , leaving a problem in flexibility.
一方、ポリオレフィン系樹脂に可塑剤を添加すると、樹脂の柔軟性が向上することが知られている。しかし、柔軟性を向上させるために発泡粒子を形成する基材樹脂に多量の可塑剤を添加する場合には基材樹脂を押出機にて溶融、混練してストランド状に押出し、ペレタイザーなどにてカットして樹脂粒子を製造する際に、基材樹脂が可塑化し過ぎていることにより、安定して樹脂粒子を得ることができなかった。
また、樹脂粒子を発泡する際には、加圧下の密閉容器中から、発泡剤を含有する樹脂粒子を分散媒と共に大気圧中に放出しようとすると、発泡した粒子同士が融着して、ブロッキングが起こり、安定して発泡粒子を得ることが困難であった。更に、型内成形する際には、発泡粒子の充填性が低下するという問題が生じるなど、可塑剤を用いる方法では、発泡粒子や、発泡粒子成形体を製造する際に起きる特有の問題により、柔軟性、軽量性と回復性に優れる発泡粒子成形体を得ることは困難であった。
On the other hand, adding a plasticizer to a polyolefin resin is known to improve the flexibility of the resin. However, when adding a large amount of plasticizer to the base resin that forms expanded particles in order to improve flexibility, the base resin is melted and kneaded with an extruder and extruded into a strand, and then with a pelletizer, etc. When producing resin particles by cutting, the resin particles could not be stably obtained because the base resin was too plasticized.
Further, when foaming resin particles, if the resin particles containing a foaming agent are released into the atmospheric pressure together with the dispersion medium from a sealed container under pressure, the foamed particles are fused together to block. It was difficult to stably obtain expanded particles. Furthermore, when molding in-mold, there is a problem that the filling property of the foamed particles is reduced, and in the method using a plasticizer, due to the specific problems that occur when producing foamed particles and foamed particle molded bodies, It was difficult to obtain a foamed particle molded body excellent in flexibility, light weight and recoverability.
本発明は、前記問題点に鑑み、柔軟性や回復性に優れると共に、見かけ密度が低い(高発泡倍率の)発泡粒子成形体を得ることができるポリオレフィン系樹脂発泡粒子、該発泡粒子の製造方法、更に該発泡粒子から型内成形によって得られる、柔軟性、回復性に優れたポリオレフィン系樹脂発泡粒子成形体を提供することを目的とする。 In view of the above-mentioned problems, the present invention provides a polyolefin resin foamed particle capable of obtaining a foamed particle molded article having excellent flexibility and recoverability and having a low apparent density (high foaming ratio), and a method for producing the foamed particle Another object of the present invention is to provide a polyolefin-based resin foam particle molded body that is obtained from the foamed particles by in-mold molding and has excellent flexibility and recoverability.
本発明によれば、以下に示すポリオレフィン系樹脂発泡粒子、ポリオレフィン系樹脂発泡粒子成形体、ポリオレフィン系樹脂発泡粒子の製造方法が提供される。
[1] ポリオレフィン系樹脂80〜30重量%と、熱可塑性エラストマー20〜70重量%とからなる樹脂組成物(ただし、前記ポリオレフィン系樹脂と熱可塑性エラストマーの合計は100重量%である)と、
前記樹脂組成物100重量部に対して15〜95重量部の鉱物性油とからなり、
前記熱可塑性エラストマーの配合量に対する前記鉱物性油の配合量の重量比率が0.4〜3であり、
見かけ密度が15〜150g/Lであることを特徴とするポリオレフィン系樹脂発泡粒子。
[2] 前記1に記載のポリオレフィン系樹脂発泡粒子を型内成形して得られる成形体であって、前記成形体の見かけ密度が10〜100g/Lであり、圧縮永久歪(JIS K6767)が6%以下であることを特徴とするポリオレフィン系樹脂発泡粒子成形体。
[3] ポリオレフィン系樹脂80〜30重量%と、熱可塑性エラストマー20〜70重量%と(前記ポリオレフィン系樹脂と熱可塑性エラストマーの合計は100重量%である)、0〜70重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部である)の鉱物性油とを配合し、溶融混練して得られる溶融混練物を、造粒して樹脂粒子とし、
前記樹脂粒子と、発泡剤と、0〜70重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部である)の鉱物性油とを密閉容器中で分散媒に分散させて、前記樹脂粒子に発泡剤と前記鉱物性油とを含浸させ、
次いで、発泡剤と鉱物性油とを含有する樹脂粒子を発泡させて、15〜95重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部である)の鉱物性油を含有し、前記熱可塑性エラストマーの配合量に対する前記鉱物性油の配合量の重量比率が0.4〜3である発泡粒子を得ることを特徴とするポリオレフィン系樹脂発泡粒子の製造方法。
According to the present invention, the following polyolefin resin expanded particles, polyolefin resin expanded particle molded bodies, and methods for producing polyolefin resin expanded particles are provided.
[1] A resin composition comprising 80 to 30% by weight of a polyolefin resin and 20 to 70% by weight of a thermoplastic elastomer (however, the total of the polyolefin resin and the thermoplastic elastomer is 100% by weight);
Comprising 15 to 95 parts by weight of mineral oil with respect to 100 parts by weight of the resin composition,
The weight ratio of the blending amount of the mineral oil to the blending amount of the thermoplastic elastomer is 0.4 to 3,
Polyolefin resin foamed particles having an apparent density of 15 to 150 g / L.
[2] A molded body obtained by in-mold molding of the polyolefin-based resin expanded particles according to 1 above, wherein the molded body has an apparent density of 10 to 100 g / L, and has a compression set (JIS K6767). A polyolefin-based resin foamed particle molded body characterized by being 6% or less.
[3] 80-30% by weight of a polyolefin resin, 20-70% by weight of a thermoplastic elastomer (the total of the polyolefin resin and the thermoplastic elastomer is 100% by weight), 0-70 parts by weight (the polyolefin system) A blended mineral oil) and a melt-kneaded product obtained by melt-kneading to form resin particles,
Using the resin particles, the foaming agent, and mineral oil of 0 to 70 parts by weight (parts by weight relative to 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer) as a dispersion medium in a closed container Disperse, impregnate the resin particles with a foaming agent and the mineral oil,
Subsequently, the resin particles containing the foaming agent and the mineral oil are foamed, and 15 to 95 parts by weight (which is a part by weight based on 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer). A process for producing foamed polyolefin-based resin particles, comprising foamed particles containing oil and having a weight ratio of the blended amount of the mineral oil to the blended amount of the thermoplastic elastomer of 0.4 to 3 .
本発明のポリオレフィン系樹脂発泡粒子(以下、単に発泡粒子ともいう。)は、特定量のポリオレフィン系樹脂と熱可塑性エラストマーとからなる樹脂組成物と、特定量の鉱物性油とからなることから、鉱物性油が添加されているにもかかわらず、べたつきがなく、型内成形時の発泡粒子の充填性や、発泡粒子間の融着不足といった問題のない、型内成形性に優れる発泡粒子である。
また、本発明の発泡粒子の製造方法によれば、本発明の発泡粒子の前駆体となる樹脂粒子を製造する樹脂粒子製造工程においては、前記熱可塑性エラストマーが鉱物性油との相溶性に優れることから、樹脂粒子製造時のペレタイズ工程における生産安定性の低下やストランドのカット性が悪化するといった問題が防止される。また、発泡剤と鉱物性油とを密閉容器中で含浸させる含浸工程においては、前記熱可塑性エラストマーが鉱物性油との相溶性に優れることから、含浸工程で添加される鉱物性油を効果的に樹脂粒子に含浸させることが可能となる。更に、発泡剤と鉱物性油とを含有する樹脂粒子を発泡させる発泡工程においては、発泡した粒子同士の融着が防止される。
さらに、樹脂粒子製造工程における鉱物性油の配合と、含浸工程における鉱物性油の配合とを組み合わせることにより、鉱物性油の配合量を調整して、柔軟性の程度を幅広く調整することができる。しかも、樹脂粒子製造工程と含浸工程の2段階に分けて鉱物性油を配合することにより、より多量の鉱物性油を発泡粒子に含有させることが可能となる。また、鉱物性油の配合量が同じである場合においても、全量の鉱物性油を1工程で配合するよりも、樹脂粒子製造時の製造安定性を維持しつつ、含浸工程での含浸時間を短縮することが可能となる。
また、本発明のポリオレフィン系樹脂発泡粒子成形体(以下、発泡粒子成形体、成形体ともいう。)は、前記発泡粒子を型内成形して得られる見かけ密度の低い成形体である。従って、圧縮永久歪が小さく回復性に優れ、軽量であり、さらには柔軟性に優れる成形体であることから、柔軟性が要求される精密な被梱包物の包装資材や、触感や回復性が要求されるシートクッション材などの用途に好適に用いることができる。
The polyolefin resin expanded particles of the present invention (hereinafter also simply referred to as expanded particles) are composed of a resin composition comprising a specific amount of a polyolefin resin and a thermoplastic elastomer, and a specific amount of mineral oil. Despite the addition of mineral oil, it is a foam particle with excellent in-moldability that has no stickiness and has no problems such as filling of the foam particles during molding and insufficient fusion between the foam particles. is there.
Further, according to the method for producing foamed particles of the present invention, in the resin particle production process for producing resin particles that are precursors of the foamed particles of the present invention, the thermoplastic elastomer is excellent in compatibility with mineral oil. Therefore, problems such as a decrease in production stability in the pelletizing process at the time of producing resin particles and a deterioration in the cut property of the strand are prevented. In addition, in the impregnation step of impregnating the foaming agent and mineral oil in a closed container, the thermoplastic elastomer is excellent in compatibility with the mineral oil, so the mineral oil added in the impregnation step is effective. It is possible to impregnate the resin particles. Furthermore, in the foaming process in which the resin particles containing the foaming agent and mineral oil are foamed, fusion between the foamed particles is prevented.
Furthermore, by combining the blending of mineral oil in the resin particle manufacturing process and the blending of mineral oil in the impregnation process, the amount of mineral oil can be adjusted and the degree of flexibility can be widely adjusted. . In addition, by blending the mineral oil in two steps, a resin particle manufacturing process and an impregnation process, a larger amount of mineral oil can be contained in the expanded particles. Further, even when the blending amount of the mineral oil is the same, the impregnation time in the impregnation step is maintained while maintaining the production stability during the production of the resin particles, rather than blending the entire amount of the mineral oil in one step. It can be shortened.
The polyolefin resin expanded particle molded body of the present invention (hereinafter also referred to as expanded particle molded body or molded body) is a molded body having a low apparent density obtained by molding the expanded particles in a mold. Therefore, since it is a compact with a small compression set, excellent recoverability, light weight, and excellent flexibility, it has high precision packaging materials for packaging, tactile sensation and recoverability that require flexibility. It can be suitably used for required uses such as a seat cushion material.
以下、本発明のポリオレフィン系樹脂発泡粒子、その製造方法及び該発泡粒子から得られるポリオレフィン系樹脂発泡粒子成形体について詳細に説明する。
本発明のポリオレフィン系樹脂発泡粒子は、ポリオレフィン系樹脂と熱可塑性エラストマーとからなる樹脂組成物を含有するものである。該樹脂組成物が熱可塑性エラストマーを含有することにより、前記発泡粒子を得る際の前駆体である樹脂粒子に、後述する鉱物性油を多量に含有させることが可能となる。
Hereinafter, the polyolefin resin expanded particles of the present invention, the production method thereof, and the polyolefin resin expanded particles molded body obtained from the expanded particles will be described in detail.
The polyolefin resin expanded particles of the present invention contain a resin composition comprising a polyolefin resin and a thermoplastic elastomer. When the resin composition contains a thermoplastic elastomer, the resin particles that are precursors for obtaining the foamed particles can contain a large amount of mineral oil described later.
本発明で用いられるポリオレフィン系樹脂としては、その重合用単量体がオレフィンを含有するものであれば、その組成、合成法に特に制限はないが、好ましくはオレフィン成分が50重量%以上、より好ましくは70重量%以上、含有するものがよい。上記ポリオレフィン系樹脂としては、例えば、プロピレン単独重合体、プロピレンランダム共重合体、プロピレンブロック共重合体、プロピレングラフト共重合体などのポリプロピレン系樹脂、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、直鎖状超低密度ポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体などのポリエチレン系樹脂、ポリブテン、及びこれらの混合物などを使用することができる。なかでもポリプロピレン系樹脂が好ましい。 The polyolefin resin used in the present invention is not particularly limited in its composition and synthesis method as long as the monomer for polymerization contains olefin, but preferably contains 50% by weight or more of olefin component. It is preferable to contain 70% by weight or more. Examples of the polyolefin resin include polypropylene resins such as propylene homopolymer, propylene random copolymer, propylene block copolymer, propylene graft copolymer, high density polyethylene, medium density polyethylene, low density polyethylene, Polyethylene resins such as chain ultra-low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polybutene, and mixtures thereof can be used. Of these, polypropylene resins are preferred.
ポリオレフィン系樹脂のメルトフローレイト(MFR)は0.1〜20g/10分であることが好ましい。MFRが上記範囲内である場合には、樹脂粒子製造工程時における押出機への負荷が過大となったり、樹脂の混合状態が悪化することなく、また、溶融混練物の張力が低下して連続気泡となることがなく、より良好な発泡粒子が得られる。かかる観点から、MFRの下限は0.5g/10分が好ましく、1.0g/10分がより好ましい。一方、その上限は、15g/10分が好ましく、10g/10分がより好ましい。 The melt flow rate (MFR) of the polyolefin resin is preferably 0.1 to 20 g / 10 minutes. When the MFR is within the above range, the load on the extruder during the resin particle production process is not excessive, the mixed state of the resin is not deteriorated, and the tension of the melt-kneaded product is continuously reduced. Better foamed particles can be obtained without bubbles. From this viewpoint, the lower limit of MFR is preferably 0.5 g / 10 minutes, and more preferably 1.0 g / 10 minutes. On the other hand, the upper limit is preferably 15 g / 10 min, and more preferably 10 g / 10 min.
メルトフローレイト(MFR)の測定は、ポリプロピレン系樹脂についてはJIS K7210(1999年)の試験条件M(温度230℃、荷重2.16kg)に基づいて行い、ポリエチレン系樹脂についてはJIS K7210(1999年)の試験条件D(温度190℃、荷重2.16kg)に基づいて測定を行なう。
Melt flow rate (MFR) is measured based on test conditions M (temperature 230 ° C., load 2.16 kg) of JIS K7210 (1999) for polypropylene resins, and JIS K7210 (1999) for polyethylene resins. ) And the test condition D (temperature 190 ° C., load 2.16 kg).
本発明で用いられる熱可塑性エラストマーとしては、ポリブタジエン、ポリイソプレン、エチレン−プロピレン共重合体、エチレン−プロピレン−ジエン共重合体、スチレン−ブタジエン共重合体、スチレン−ブタジエン、スチレン−イソプレン、スチレン−ブタジエン−スチレン、スチレン−イソプレン−スチレンのブロック共重合体と、それらの水添ポリマーであるスチレン−エチレン−エチレン−プロピレンのブロック共重合体(SEP)、スチレン−エチレン−ブチレン−スチレンのブロック共重合体(HEBS)、スチレン−エチレン−ブチレン−スチレンのブロック共重合体(SEBS)、スチレン−エチレン−プロピレン−スチレンのブロック共重合体(SEPS)、水添スチレンブタジエンゴム(HSBR)、スチレン−エチレン−エチレン−プロピレン−スチレンのブロック共重合体(SEEPS)などが挙げられる。また、エチレン−プロピレンゴム(EPM)、エチレン−プロピレン−ジエンの三元共重合体(EPDM)といった、いわゆる動的架橋型のエラストマーも使用可能である。その中でも、ポリオレフィン系樹脂との相溶性に優れる観点から、前記共重合体の水添物やSEEPS、動的架橋型エラストマーが好ましく、HSBRが特に好ましい。
Examples of the thermoplastic elastomer used in the present invention include polybutadiene, polyisoprene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene, styrene-isoprene, and styrene-butadiene. -Styrene, Styrene-Isoprene-Styrene Block Copolymer, and Hydrogenated Polymers Styrene-Ethylene-Ethylene-Propylene Block Copolymer (SEP), Styrene-Ethylene-Butylene-Styrene Block Copolymer (HEBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), hydrogenated styrene butadiene rubber (HSBR), styrene-ethylene Len - ethylene - propylene - like block copolymer of styrene (SEEPS). Also, so-called dynamically crosslinked elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene terpolymer (EPDM) can be used. Among these, from the viewpoint of excellent compatibility with the polyolefin-based resin, hydrogenated products, SEEPS, and dynamically cross-linked elastomers are preferable, and HSBR is particularly preferable.
本発明の発泡粒子は、前記ポリオレフィン系樹脂と前記熱可塑性エラストマーとからなる樹脂組成物を含有するものである。前記樹脂組成物の配合比率は、ポリオレフィン系樹脂の配合比率が80〜30重量%であり、熱可塑性エラストマーの配合比率が20〜70重量%である(ただし、前記ポリオレフィン系樹脂と熱可塑性エラストマーの合計は100重量%である)。
熱可塑性エラストマーの配合量が少なすぎる(ポリオレフィン系樹脂の配合量が多すぎる)場合には、発泡粒子や、該発泡粒子から得られる発泡粒子成形体の柔軟性が低下する虞がある。また、熱可塑性エラストマーに対して鉱物性油の配合量が相対的に多くなるため、樹脂粒子製造工程でのペレタイズが不安定になる虞や、含浸工程時には分散不良を生じ、樹脂粒子同士が融着して発泡粒子が得られなくなる虞がある。また、発泡した粒子同士が融着してしまい、型内成形が不可能なものとなる虞がある。更には、発泡粒子に含浸しきれない鉱物性油がブリードアウト若しくは発泡粒子表面を被い、発泡粒子がべたついて、発泡粒子を金型に充填することが困難となり、成形性が低下して、発泡粒子成形体を得ることができなくなる虞がある。かかる観点から、熱可塑性エラストマーの配合比率は25重量%以上が好ましい。
一方、熱可塑性エラストマーの配合量が多すぎる(ポリオレフィン系樹脂の配合量が少なすぎる)場合には、発泡粒子が連続気泡になり易くなる虞がある。また、前記樹脂組成物が軟質化しすぎて、成形可能な発泡粒子を得ることが困難となるおそれがある。かかる観点から、熱可塑性エラストマーの配合比率は65重量%以下であることが好ましく、より好ましくは60重量%以下である。
The expanded particles of the present invention contain a resin composition composed of the polyolefin resin and the thermoplastic elastomer. The blending ratio of the resin composition is such that the blending ratio of the polyolefin resin is 80 to 30% by weight and the blending ratio of the thermoplastic elastomer is 20 to 70% by weight (however, the blending ratio of the polyolefin resin and the thermoplastic elastomer is The total is 100% by weight).
When the amount of the thermoplastic elastomer is too small (the amount of the polyolefin resin is too large), the flexibility of the foamed particles and the foamed particle molded body obtained from the foamed particles may be lowered. In addition, since the blending amount of mineral oil is relatively large with respect to the thermoplastic elastomer, pelletization in the resin particle manufacturing process may become unstable, and dispersion may occur during the impregnation process, causing the resin particles to melt. There is a risk that foamed particles may not be obtained. In addition, the foamed particles may be fused together, making it impossible to perform in-mold molding. Furthermore, the mineral oil that cannot fully impregnate the expanded particles bleeds out or covers the expanded particle surface, the expanded particles become sticky, and it becomes difficult to fill the expanded particles with the mold, and the moldability decreases. There is a possibility that a foamed particle molded body cannot be obtained. From this viewpoint, the blending ratio of the thermoplastic elastomer is preferably 25% by weight or more.
On the other hand, when the blending amount of the thermoplastic elastomer is too large (the blending amount of the polyolefin resin is too small), there is a possibility that the foamed particles are likely to become open cells. In addition, the resin composition may be too soft and it may be difficult to obtain moldable foam particles. From this viewpoint, the blending ratio of the thermoplastic elastomer is preferably 65% by weight or less, more preferably 60% by weight or less.
前記樹脂組成物には、所望に応じて各種添加剤を添加することができる。このような添加剤としては、たとえば、酸化防止剤、紫外線防止剤、帯電防止剤、難燃剤、金属不活性剤、核剤、あるいは気泡調整剤等を挙げることができる。気泡調整剤としては、たとえばホウ酸亜鉛、タルク、炭酸カルシウム、ホウ砂、水酸化アルミニウムなどの無機粉体が例示される。これらの添加剤は、合計で前記樹脂組成物100重量部当り20重量部以下で使用されることが好ましく、5重量部以下で使用されることがより好ましい。これらの添加剤は、通常、必要最小限の量で使用される。また、これらの添加剤は、例えば、樹脂粒子製造工程において、前記樹脂組成物を押出機内で溶融した溶融混練物に添加、混練することによって、樹脂粒子中に含有させることができる。 Various additives can be added to the resin composition as desired. Examples of such additives include antioxidants, ultraviolet light inhibitors, antistatic agents, flame retardants, metal deactivators, nucleating agents, and bubble regulators. Examples of the air conditioner include inorganic powders such as zinc borate, talc, calcium carbonate, borax, and aluminum hydroxide. These additives are preferably used in a total amount of 20 parts by weight or less per 100 parts by weight of the resin composition, and more preferably 5 parts by weight or less. These additives are usually used in the minimum necessary amount. Moreover, these additives can be contained in the resin particles by, for example, adding and kneading the resin composition to a melt-kneaded material melted in an extruder in the resin particle manufacturing process.
本発明で用いられる鉱物性油とは、原油や石油などから分離、蒸留、精製されるものであり、芳香族環、ナフテン環、パラフィン鎖などを含む混合物である。特に、アロマ系鉱物性油、ナフテン系鉱物性油、パラフィン系鉱物性油などの流動点が0℃以下のものが好ましく、これらの中でもパラフィン系鉱物性油が特に好ましい。本発明においては、鉱物性油と前記熱可塑性エラストマーとの相溶性が良好であることから、ポリオレフィン系樹脂に多量の鉱物性油を含有させることができる。 The mineral oil used in the present invention is one that is separated, distilled and refined from crude oil or petroleum, and is a mixture containing aromatic rings, naphthene rings, paraffin chains and the like. In particular, those having a pour point of 0 ° C. or less such as aroma mineral oil, naphthenic mineral oil, paraffin mineral oil and the like are preferable, and paraffin mineral oil is particularly preferable among these. In the present invention, since the compatibility between the mineral oil and the thermoplastic elastomer is good, the polyolefin resin can contain a large amount of mineral oil.
鉱物性油の含有量は、前記ポリオレフィン系樹脂と前記熱可塑性エラストマーとからなる樹脂組成物100重量部に対して15〜95重量部である。その下限は、20重量部が好ましく、より好ましくは22重量部である。一方、その上限は、90重量部が好ましく、より好ましくは80重量部、更に好ましくは70重量部である。
鉱物性油の含有量が少なすぎる場合には、得られる発泡粒子、更には発泡粒子成形体の柔軟性や回復性が不十分となる虞がある。一方、該含有量が多すぎる場合には、含浸工程時の樹脂粒子の分散が悪化して樹脂粒子間の凝結を生じる虞がある。尚、含浸工程時の分散性が悪化して樹脂粒子が凝結を生じた場合には、発泡後の発泡した粒子においても凝結が見られるものとなる。また、発泡工程においても、発泡した粒子同士が凝結する虞がある。金型充填時には発泡粒子同士が凝固して発泡粒子の型内充填が不可能となったり、型内成形時に二次発泡不良が生じる虞がある。発泡粒子成形体においては、成形後の発泡粒子成形体の収縮が過大となったり、発泡粒子成形体の耐熱性が低下したり、鉱物性油がブリードアウトしてべたつきやほこりの吸着による汚損が発生し易くなるなどの不具合が生じる虞がある。
Content of mineral oil is 15-95 weight part with respect to 100 weight part of resin compositions which consist of the said polyolefin resin and the said thermoplastic elastomer. The lower limit is preferably 20 parts by weight, more preferably 22 parts by weight. On the other hand, the upper limit is preferably 90 parts by weight, more preferably 80 parts by weight, and still more preferably 70 parts by weight.
If the content of mineral oil is too small, the foamed particles obtained, and the foamed particle molded body, may have insufficient flexibility and recoverability. On the other hand, when the content is too large, dispersion of the resin particles during the impregnation step may be deteriorated to cause condensation between the resin particles. In addition, when the dispersibility at the time of an impregnation process deteriorates and a resin particle produces condensation, condensation will be seen also in the foamed particle after foaming. In the foaming process, the foamed particles may condense. When the mold is filled, the foamed particles may be solidified to make it impossible to fill the foamed particles in the mold, or a secondary foaming failure may occur during in-mold molding. In the foamed particle molded body, the shrinkage of the foamed particle molded body after molding is excessive, the heat resistance of the foamed particle molded body is reduced, or mineral oil bleeds out, causing contamination due to stickiness and dust adsorption There is a possibility that problems such as being likely to occur occur.
なお、過剰量の鉱物性油を配合した場合、過剰分の鉱物性油は、樹脂粒子及び/又は発泡粒子表面のべたつきとなって現れる。従って、べたつきのない樹脂粒子及び/又は発泡粒子であれば、配合した鉱物性油の全量が樹脂粒子及び/又は発泡粒子に含浸されていると考えられる。故に、べたつきのない樹脂粒子及び/又は発泡粒子が得られている場合には、樹脂粒子製造工程と含浸工程で樹脂粒子及び/又は発泡粒子に添加した鉱物性油の配合量と、発泡粒子、更に発泡粒子成形体中の鉱物性油の含有量とが大きく変わることはない。 When an excessive amount of mineral oil is blended, the excessive amount of mineral oil appears as stickiness on the surface of the resin particles and / or the expanded particles. Therefore, if the resin particles and / or the expanded particles are not sticky, it is considered that the total amount of the blended mineral oil is impregnated in the resin particles and / or the expanded particles. Therefore, when resin particles and / or expanded particles without stickiness are obtained, the blending amount of mineral oil added to the resin particles and / or expanded particles in the resin particle production process and the impregnation process, Furthermore, the content of the mineral oil in the foamed particle molded body does not change greatly.
前記熱可塑性エラストマーの配合量に対する前記鉱物性油の配合量の重量比率は、0.4〜3である。上記範囲内であれば、前記熱可塑性エラストマーと前記鉱物性油との相溶性が良好であり、ポリオレフィン系樹脂に多量の鉱物性油を含有させることができることから、発泡性や型内成形性が良好な発泡粒子を得ることができ、柔軟性や回復性に優れる発泡粒子成形体が得られる発泡粒子となる。上記重量比率は、好ましくは0.5〜2である。
Weight ratio of the amount of the mineral oil to the amount of the thermoplastic elastomer, Ru 0.4 to 3 der. Within the above range, the thermoplastic elastomer and the mineral oil have good compatibility, and a large amount of mineral oil can be contained in the polyolefin-based resin. Good foamed particles can be obtained, and the foamed particles can be obtained as a foamed particle molded body having excellent flexibility and recoverability. The weight ratio, good Mashiku is 0.5-2.
本発明の発泡粒子の見かけ密度は15〜150g/Lである。発泡粒子の見かけ密度が小さすぎると、最終的に得られる発泡粒子成形体の圧縮強度、引張強度などの機械的強度が低くなったり、型内成形後の発泡粒子成形体の収縮が大きくなり、目的とする形状を保つことが困難となる虞がある。かかる観点から、見かけ密度の下限は、20g/Lが好ましく、より好ましくは25g/L、更に好ましくは30g/Lである。一方、該見かけ密度が大きすぎると、該発泡粒子を型内成形して得られる発泡粒子成形体の柔軟性や軽量性が低下する虞がある。かかる観点から、その上限は、120g/Lが好ましく、より好ましくは100g/Lである、更に好ましくは90g/Lである。 The apparent density of the expanded particles of the present invention is 15 to 150 g / L. If the apparent density of the expanded particles is too small, the mechanical strength such as the compressive strength and tensile strength of the finally obtained expanded particle molded product is reduced, or the expanded expanded particle molded product after in-mold molding is increased, There is a risk that it is difficult to maintain the target shape. From this viewpoint, the lower limit of the apparent density is preferably 20 g / L, more preferably 25 g / L, and still more preferably 30 g / L. On the other hand, when the apparent density is too large, the flexibility and lightness of the foamed particle molded body obtained by molding the foamed particles in a mold may be reduced. From this viewpoint, the upper limit is preferably 120 g / L, more preferably 100 g / L, and still more preferably 90 g / L.
発泡粒子の見かけ密度の測定は、23℃の水の入ったメスシリンダーを用意し、該メスシリンダーに、相対湿度50%、23℃、1atmの条件にて2日放置した約50mlの発泡粒子(発泡粒子群の重量W)を金網などを使用して沈めて、水位上昇分より発泡粒子群の容積V(L)を読み取る。該容積V(L)と該メスシリンダーに入れた発泡粒子群の重量W(g)とから、割り算(W/V)することにより求めることができる。 The apparent density of the expanded particles was measured by preparing a graduated cylinder containing water at 23 ° C., and leaving the graduated cylinder for about 50 ml of expanded particles (relative humidity 50%, 23 ° C., 1 atm for 2 days). The weight W) of the expanded particle group is sunk using a wire mesh or the like, and the volume V (L) of the expanded particle group is read from the rise in water level. It can be determined by dividing (W / V) from the volume V (L) and the weight W (g) of the expanded particles in the graduated cylinder.
次に、本発明のポリオレフィン系樹脂発泡粒子の製造方法について説明する。
該発泡粒子は、樹脂粒子製造工程と含浸工程と発泡工程とを少なくとも含む製造工程を経ることにより製造される。
前記樹脂粒子製造工程においては、前記ポリオレフィン系樹脂80〜30重量%と、前記熱可塑性エラストマー20〜70重量%と、(ただし、前記ポリオレフィン系樹脂と熱可塑性エラストマーの合計は100重量%である)と、前記鉱物性油0〜70重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部)を配合し、押出機に供給し溶融混練して溶融混練物とし、該溶融混練物を押出機からストランド状に押出し、該ストランドを発泡粒子とするのに適した大きさに切断する方法など、公知の造粒方法より、樹脂粒子が製造される。
Next, the manufacturing method of the polyolefin-type resin expanded particle of this invention is demonstrated.
The expanded particles are manufactured through a manufacturing process including at least a resin particle manufacturing process, an impregnation process, and a foaming process.
In the resin particle production process, the polyolefin resin 80 to 30% by weight and the thermoplastic elastomer 20 to 70% by weight (however, the total of the polyolefin resin and the thermoplastic elastomer is 100% by weight). And 0 to 70 parts by weight of the mineral oil (parts by weight relative to 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer), supplied to an extruder and melt-kneaded to obtain a melt-kneaded product, Resin particles are produced by a known granulation method such as a method of extruding the melt-kneaded material from an extruder into a strand shape and cutting the strand into a size suitable for forming expanded particles.
前述の方法において、ストランドを水冷により冷却した後、所定の長さに切断する際には、ストランドカット法を採用することができる。その他に、前記ストランドを所定の長さに切断後または切断と同時に、冷却して、樹脂粒子を得るアンダーウォーターカット法などにより、樹脂粒子を得ることができる。特に、装置が安価で簡便に実施することができることからストランドカット法が好ましい。 In the above-described method, the strand cutting method can be adopted when the strand is cooled by water cooling and then cut into a predetermined length. In addition, resin particles can be obtained by an underwater cut method in which the strands are cooled to a predetermined length or simultaneously with the cutting to obtain resin particles. In particular, the strand cutting method is preferable because the apparatus is inexpensive and can be easily implemented.
本発明で用いる樹脂粒子は、前述の通り、鉱物性油を含有する場合には、前記熱可塑性エラストマーを特定量含有していることにより、食い込み不良によるサージング(押出時の吐出の微妙な変動)の発生や、ストランド状の押出物が柔軟になりすぎることでストランドカットが困難となる等の不都合が防止され、樹脂粒子製造工程を安定して行なうことが可能となる。 As described above, when the resin particles used in the present invention contain mineral oil, by containing a specific amount of the thermoplastic elastomer, surging due to poor biting (subtle variations in ejection during extrusion) And inconveniences such as strand cutting becomes difficult due to the strand-shaped extrudate becoming too flexible, and the resin particle production process can be performed stably.
樹脂粒子製造工程においては、前記ポリオレフィン系樹脂と前記熱可塑性エラストマーを個別のフィーダーにて投入することもできれば、予めこれらをタンブラーなどにて予備混合した後に、一括してホッパーに投入することも出来る。鉱物性油は、その一部を前記タンブラーなどにて前記ポリオレフィン系樹脂や熱可塑性エラストマーと共に予備混合してから投入することもできれば、ポンプなどにて押出機に直接圧入したりすることも出来る。投入順序に特に制限はなく、前記ポリオレフィン系樹脂と熱可塑性エラストマーと鉱物性油とが溶融混練され、溶融混練物となり、造粒されて、樹脂粒子が形成されればよい。 In the resin particle production process, the polyolefin resin and the thermoplastic elastomer can be charged with separate feeders, or they can be preliminarily mixed with a tumbler or the like and then charged into the hopper at once. . A part of the mineral oil can be added after being premixed together with the polyolefin resin and thermoplastic elastomer by the tumbler or the like, or can be directly injected into the extruder by a pump or the like. There is no restriction | limiting in particular in an injection | throwing-in order, The said polyolefin resin, a thermoplastic elastomer, and mineral oil should just be melt-kneaded, it may become a melt-kneaded material, it granulates, and a resin particle may be formed.
樹脂粒子製造工程で配合される鉱物性油の配合量は、前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対し、0〜70重量部(0重量部、即ち、樹脂粒子製造工程で鉱物性油を添加しない場合を含む。)である。その下限は、5重量部が好ましく、より好ましくは10重量部である。一方、その上限は、50重量部が好ましく、より好ましくは40重量部である。配合量が前記範囲内である場合には、押出時の食い込み不良によるサージングの発生や、柔軟になりすぎることでストランドカットが困難となることがなく、より安定して、樹脂粒子を得ることができる。 The blending amount of the mineral oil blended in the resin particle manufacturing process is 0 to 70 parts by weight (0 parts by weight, ie, resin particle manufacturing) with respect to 100 parts by weight of the total blending amount of the polyolefin resin and the thermoplastic elastomer. Including the case where no mineral oil is added in the process). The lower limit is preferably 5 parts by weight, more preferably 10 parts by weight. On the other hand, the upper limit is preferably 50 parts by weight, more preferably 40 parts by weight. When the blending amount is within the above range, the occurrence of surging due to poor biting at the time of extrusion, and strand cutting does not become difficult due to being too flexible, and it is possible to obtain resin particles more stably. it can.
樹脂粒子の1個当たりの平均重量は、通常0.01〜10.0mgが好ましく、0.1〜5.0mgがより好ましい。尚、樹脂粒子の平均重量は、無作為に選んだ200個の樹脂粒子の重量(mg)を200で除した値である。 The average weight per resin particle is usually preferably 0.01 to 10.0 mg, more preferably 0.1 to 5.0 mg. The average weight of the resin particles is a value obtained by dividing the weight (mg) of 200 randomly selected resin particles by 200.
前記含浸工程においては、前述のようにして得られた樹脂粒子と発泡剤とを、密閉容器内で水等の分散媒体に分散させ、撹拌下で加熱して樹脂粒子を軟化させて、発泡剤が樹脂粒子へ含浸される。更に、鉱物性油を加えた場合には鉱物性油も樹脂粒子へ含浸される。 In the impregnation step, the resin particles and the foaming agent obtained as described above are dispersed in a dispersion medium such as water in a sealed container, and heated under stirring to soften the resin particles, and then the foaming agent. Is impregnated into the resin particles. Furthermore, when mineral oil is added, the mineral oil is also impregnated into the resin particles.
前記発泡剤としては、有機系物理発泡剤や無機系物理発泡剤、又はこれらの混合物等を用いることができる。有機系物理発泡剤としてはプロパン、ブタン、ヘキサン、ペンタン、ヘプタン等の脂肪族炭化水素類、シクロブタン、シクロヘキサン等の脂環式炭化水素類、クロロフロロメタン、トリフロロメタン、1,1−ジフロロエタン、1,1,1,2−テトラフロロエタン、メチルクロライド、エチルクロライド、メチレンクロライド等のハロゲン化炭化水素、ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル等のジアルキルエーテル等が挙げられ、これらの2種以上を混合して用いることができる。前記無機系物理発泡剤としては、窒素、二酸化炭素、アルゴン、空気、水等が挙げられ、これらの2種以上を混合して用いることができる。有機系物理発泡剤と無機系物理発泡剤とを混合して用いる場合、上記した有機系物理発泡剤と無機系物理発泡剤より任意に選択したものを組合せて用いることができる。なお、無機系物理発泡剤と有機系物理発泡剤とを併用する場合には無機系物理発泡剤が少なくとも30重量%以上含有されることが好ましい。 As the foaming agent, an organic physical foaming agent, an inorganic physical foaming agent, or a mixture thereof can be used. Examples of organic physical blowing agents include aliphatic hydrocarbons such as propane, butane, hexane, pentane and heptane, alicyclic hydrocarbons such as cyclobutane and cyclohexane, chlorofluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, halogenated hydrocarbons such as methyl chloride, ethyl chloride, and methylene chloride, and dialkyl ethers such as dimethyl ether, diethyl ether, and methyl ethyl ether, and the like. It can be used by mixing. Examples of the inorganic physical foaming agent include nitrogen, carbon dioxide, argon, air, water, and the like, and two or more of these can be used in combination. When an organic physical foaming agent and an inorganic physical foaming agent are mixed and used, those arbitrarily selected from the above-mentioned organic physical foaming agent and inorganic physical foaming agent can be used in combination. In addition, when using together an inorganic type physical foaming agent and an organic type physical foaming agent, it is preferable that an inorganic type physical foaming agent contains at least 30 weight% or more.
前記発泡剤のうち、特に環境対応の点から、無機系物理発泡剤が好ましく、中でも窒素、空気、二酸化炭素、水が好ましい。なお、含浸工程において、分散媒として水を使用する場合には、該樹脂粒子に吸水性樹脂などを混錬したものを使用することにより分散媒である水を発泡剤として使用することもできる。
発泡剤の使用量は、目的とする発泡粒子の見かけ密度、樹脂組成物の種類、または発泡剤の種類等を考慮して決定されるが、通常、樹脂粒子100重量部当たり、有機系物理発泡剤で5〜50重量部、無機系物理発泡剤で0.5〜30重量部を用いることが好ましい。
Among the foaming agents, an inorganic physical foaming agent is particularly preferable from the viewpoint of environmental friendliness, and nitrogen, air, carbon dioxide, and water are particularly preferable. In addition, when water is used as a dispersion medium in the impregnation step, water as a dispersion medium can be used as a foaming agent by using a mixture of the resin particles with a water absorbent resin.
The amount of the foaming agent used is determined in consideration of the apparent density of the target foamed particles, the type of the resin composition, or the type of the foaming agent. Usually, the organic physical foaming per 100 parts by weight of the resin particles. It is preferable to use 5 to 50 parts by weight of the agent and 0.5 to 30 parts by weight of the inorganic physical foaming agent.
含浸工程において樹脂粒子を分散させる分散媒としては、上記した水に限らず、樹脂粒子を溶解させない溶媒であれば使用することができる。水以外の分散媒としては、例えばエチレングリコール、グリセリン、メタノール、エタノール等が挙げられるが、通常は水が用いられる。 The dispersion medium for dispersing the resin particles in the impregnation step is not limited to the above-described water, and any solvent that does not dissolve the resin particles can be used. Examples of the dispersion medium other than water include ethylene glycol, glycerin, methanol, ethanol and the like, but usually water is used.
上記方法において、分散媒中には、必要に応じて、樹脂粒子が分散媒中に均一に分散するように、酸化アルミニウム、第三リン酸カルシウム、ピロリン酸マグネシウム、酸化亜鉛、カオリンなどの難水溶性無機物質等の分散剤、ドデシルベンゼンスルホン酸ナトリウム、アルカンスルホン酸ナトリウムなどのアニオン系界面活性剤等の分散助剤を分散させることが好ましい。含浸工程において分散媒中に添加される分散剤の量は、樹脂粒子の重量を基準として、樹脂粒子の重量と分散剤の重量との比率(樹脂粒子の重量/分散剤の重量)を20〜2000、更に30〜1000とすることが好ましい。また、分散剤の重量と分散助剤の重量(有効成分量として)との比率(分散剤の重量/分散助剤の重量)を0.1〜500、更に1〜100とすることが好ましい。 In the above method, in the dispersion medium, a poorly water-soluble inorganic substance such as aluminum oxide, tricalcium phosphate, magnesium pyrophosphate, zinc oxide, kaolin or the like is provided in the dispersion medium as necessary so that the resin particles are uniformly dispersed in the dispersion medium. It is preferable to disperse a dispersing aid such as a dispersing agent such as a substance and an anionic surfactant such as sodium dodecylbenzenesulfonate and sodium alkanesulfonate. The amount of the dispersant added to the dispersion medium in the impregnation step is a ratio of the weight of the resin particles to the weight of the dispersant (the weight of the resin particles / the weight of the dispersant) based on the weight of the resin particles. 2000, more preferably 30 to 1000. The ratio of the weight of the dispersant to the weight of the dispersion aid (as the amount of active ingredient) (the weight of the dispersant / the weight of the dispersion aid) is preferably 0.1 to 500, and more preferably 1 to 100.
含浸工程においては、発泡剤と共に鉱物性油を含浸させることができる。その配合量は前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対して、0〜70重量部(0重量部、即ち、含浸工程で鉱物性油を添加しない場合を含む。)である。その下限は、10重量部が好ましく、より好ましくは20重量部である。一方、その上限は、60重量部が好ましく、より好ましくは50重量部である。 In the impregnation step, mineral oil can be impregnated with the foaming agent. The blending amount is 0 to 70 parts by weight with respect to the total blending amount of the polyolefin resin and the thermoplastic elastomer (0 part by weight, that is, including the case where no mineral oil is added in the impregnation step). It is. The lower limit is preferably 10 parts by weight, more preferably 20 parts by weight. On the other hand, the upper limit is preferably 60 parts by weight, more preferably 50 parts by weight.
また、前記樹脂粒子製造工程で配合した鉱物性油と含浸工程で配合した鉱物性油の配合量の合計は、前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対して、15〜95重量部である。
上述のように、鉱物性油の配合量が少ない場合には樹脂粒子製造工程又は含浸工程のいずれかの工程でのみ、鉱物性油を配合することもできる。しかし、1工程で全量の鉱物性油を配合するよりも、樹脂粒子製造工程と含浸工程の2段階に分けて鉱物性油を配合することにより、樹脂粒子の造粒時の製造安定性を向上し、含浸工程での含浸時間を短縮することが可能となる。更には、樹脂粒子製造工程と含浸工程の2段階に分けて鉱物性油を配合することにより、より多量の鉱物性油を発泡粒子に含有させることが可能となる。
前記配合量の下限は、20重量部が好ましく、より好ましくは22重量部である。一方、その上限は、90重量部が好ましく、より好ましくは80重量部、更に好ましくは70重量部である。また、前記樹脂粒子製造工程と含浸工程では、含浸工程の配合量を多く配合する方が、特に樹脂粒子製造時の安定性が向上することから好ましい。
The total amount of the mineral oil blended in the resin particle manufacturing step and the mineral oil blended in the impregnation step is 15 parts by weight with respect to a total of 100 parts by weight of the polyolefin resin and the thermoplastic elastomer. -95 parts by weight.
As described above, when the blending amount of the mineral oil is small, the mineral oil can be blended only in either the resin particle manufacturing process or the impregnation process. However, the production stability during granulation of resin particles is improved by blending the mineral oil in two stages, the resin particle production process and the impregnation process, rather than blending the entire amount of mineral oil in one process. In addition, the impregnation time in the impregnation step can be shortened. Furthermore, by blending the mineral oil in two stages of the resin particle manufacturing process and the impregnation process, a larger amount of the mineral oil can be contained in the expanded particles.
The lower limit of the amount is preferably 20 parts by weight, more preferably 22 parts by weight. On the other hand, the upper limit is preferably 90 parts by weight, more preferably 80 parts by weight, and still more preferably 70 parts by weight. Further, in the resin particle production step and the impregnation step, it is preferable to add a larger amount of the impregnation step because stability during production of the resin particles is improved.
前記発泡工程においては、樹脂粒子の軟化温度以上の温度で密閉容器内から低圧下(通常大気圧下)に、発泡剤と鉱物性油とを含有する樹脂粒子を放出して、発泡が行なわれる。この場合、密閉容器内の内容物を密閉容器から低圧域に放出する際には、使用した発泡剤あるいは窒素、空気等の無機ガスで密閉容器内に背圧をかけて、該容器内の圧力が急激に低下しないようにして、内容物を放出することが好ましい。このような操作により、得られる発泡粒子の見かけ密度が更に均一なものとなる。得られた発泡粒子は、鉱物性油を15〜95重量部含有したものとなる。 In the foaming step, foaming is performed by releasing resin particles containing the foaming agent and mineral oil from the inside of the sealed container at a temperature equal to or higher than the softening temperature of the resin particles under a low pressure (usually atmospheric pressure). . In this case, when the contents in the sealed container are discharged from the sealed container to the low pressure region, back pressure is applied to the sealed container with the used foaming agent or an inorganic gas such as nitrogen, air, etc. It is preferable to release the contents in such a manner that the content does not drop rapidly. By such an operation, the apparent density of the obtained expanded particles becomes more uniform. The obtained expanded particles contain 15 to 95 parts by weight of mineral oil.
なお、含浸工程と発泡工程とは、同一の密閉容器中で連続して行なうことが生産効率向上の観点から好ましい。なお、含浸工程及び発泡工程については、特公昭49−2183号公報、特公昭56−1344号公報、特公昭62−61227号公報などに記載の公知の発泡方法を採用することができる。 The impregnation step and the foaming step are preferably performed continuously in the same sealed container from the viewpoint of improving production efficiency. For the impregnation step and the foaming step, known foaming methods described in JP-B-49-2183, JP-B-56-1344, JP-B-62-61227 and the like can be employed.
次に、本発明のポリオレフィン系樹脂発泡粒子成形体について説明する。
本発明の発泡粒子成形体は、前記発泡粒子を用いて型内成形方法により製造されるものである。該型内成形方法としては、公知の方法を採用することができる。
例えば、従来の発泡粒子の型内成形で用いられる雌雄一対の成形型を用い、大気圧下又は減圧下で発泡粒子を成形型キャビティー内に充填し、型閉めして成形型キャビティー体積を5〜70%減少するように圧縮し、次いで型内にスチーム等の熱媒を供給して加熱を行い、発泡粒子を加熱融着させる減圧成形法による方法(例えば、特公昭46−38359号公報)。また、発泡粒子を加圧気体により、予め加圧処理して発泡粒子内の圧力を高めることにより、発泡粒子の二次発泡性を高め、二次発泡性を維持しつつ大気圧下又は減圧下に発泡粒子を成形型キャビティー内に充填して型閉めし、次いで型内にスチーム等の熱媒を供給して加熱を行い、発泡粒子を加熱融着させる加圧成形法(例えば、特公昭51−22951号公報)などの成形法により成形することができる。また、圧縮ガスにより大気圧以上に加圧したキャビティー内に、当該圧力以上に加圧した発泡粒子を充填した後、キャビティー内にスチーム等の熱媒を供給して加熱を行い、発泡粒子を加熱融着させる圧縮充填成型法(特公平4−46217号公報)により成形することもできる。その他に、特殊な条件にて得られる二次発泡力の高い発泡粒子を、大気圧下又は減圧下で雌雄一対の成形型のキャビティー内に充填した後、次いでスチーム等の熱媒を供給して加熱を行い、発泡粒子を加熱融着させる常圧充填成型法(特公平6−49795号公報)又は上記の方法を組み合わせた方法(特公平6−22919号公報)などによっても成形することができる。
Next, the polyolefin resin foamed particle molded body of the present invention will be described.
The foamed particle molded body of the present invention is produced by an in-mold molding method using the foamed particles. As the in-mold forming method, a known method can be employed.
For example, using a pair of male and female molding dies used in conventional molding of foamed particles, the foamed particles are filled into the mold cavity under atmospheric pressure or reduced pressure, and the mold is closed to increase the mold cavity volume. A method using a reduced pressure molding method (for example, Japanese Examined Patent Publication No. 46-38359) in which compression is performed so as to decrease by 5 to 70%, and then a heating medium such as steam is supplied into the mold and heating is performed, and the expanded particles are heated and fused ). In addition, the foamed particles are pre-pressurized with a pressurized gas to increase the pressure in the foamed particles, thereby increasing the secondary foamability of the foamed particles and maintaining the secondary foamability under atmospheric pressure or reduced pressure. Filled with foam particles in the mold cavity and closed, and then heated by supplying a heat medium such as steam into the mold and heated to melt the foam particles (for example, Shokosho) No. 51-2951) and the like. In addition, after filling the cavities pressurized above the atmospheric pressure with compressed gas with foamed particles pressurized above the pressure, a heating medium such as steam is supplied into the cavities and heated to produce the foamed particles. It is also possible to mold by a compression filling molding method (Japanese Patent Publication No. 4-46217). In addition, after filling foam particles with high secondary foaming power obtained under special conditions into a cavity of a pair of male and female molds under atmospheric pressure or reduced pressure, a heating medium such as steam is then supplied. It can also be molded by an atmospheric pressure filling molding method (Japanese Patent Publication No. 6-49795) or a method combining the above methods (Japanese Patent Publication No. 6-22919) or the like. it can.
このようにして得られる、本発明の発泡粒子成形体の見かけ密度は10〜100g/Lである。該発泡粒子成形体は、従来よりも高発泡倍率の成形体であることから、優れた柔軟性や回復性、軽量性、緩衝特性を有し、精密な被梱包物の包装資材や、シートクッション材として好適に用いることができる。 The apparent density of the foamed particle molded body of the present invention thus obtained is 10 to 100 g / L. Since the foamed particle molded body is a molded body having a higher expansion ratio than before, it has excellent flexibility, recoverability, light weight, and cushioning characteristics. It can be suitably used as a material.
前記発泡粒子成形体の見かけ密度が低すぎる場合には、圧縮強度、引張強度などの機械的強度が低くなり、精密な被梱包物の梱包資材やクッション材として用いた場合、荷重に耐え切れず、底付きする虞がある。かかる観点から、発泡粒子成形体の見かけ密度の下限は、15g/Lが好ましく、より好ましくは20g/Lである。一方、該見かけ密度が高すぎる場合には、柔軟性や軽量性が低くなる虞がある。かかる観点から、その上限は、90g/Lが好ましく、より好ましくは85g/L、更に好ましくは70g/Lである。 If the apparent density of the foamed particle molded body is too low, the mechanical strength such as compressive strength and tensile strength will be low, and when used as a packaging material or cushioning material for precise packaging, it cannot withstand the load. There is a risk of bottoming out. From this viewpoint, the lower limit of the apparent density of the foamed particle molded body is preferably 15 g / L, and more preferably 20 g / L. On the other hand, when the apparent density is too high, flexibility and lightness may be lowered. From this viewpoint, the upper limit is preferably 90 g / L, more preferably 85 g / L, and still more preferably 70 g / L.
前記発泡粒子成形体の見かけ密度d(g/L)の測定は、直方体の成形体であればそのままの、異形の成形体であれば直方体に切り出して試験片とする。該試験片の縦、横、高さの寸法計測し、これを乗じて体積V(L)を算出し、該試験片の重量W(g)を除することで求められる。 The apparent density d (g / L) of the foamed particle molded body is measured as it is if it is a rectangular parallelepiped molded body, and cut into a rectangular parallelepiped if it is an irregular shaped molded body. This is obtained by measuring the vertical, horizontal, and height dimensions of the test piece, multiplying it to calculate the volume V (L), and dividing the weight W (g) of the test piece.
本発明の発泡粒子成形体は、前記ポリオレフィン系樹脂と前記熱可塑性エラストマーと前記鉱物性油とを含有することから、柔軟性、特に圧縮後の回復性が飛躍的に向上しているものである。特に、本発明の発泡粒子成形体は、柔軟性だけでなく、圧縮後の回復性に優れる発泡粒子成形体である。 Since the foamed particle molded body of the present invention contains the polyolefin-based resin, the thermoplastic elastomer, and the mineral oil, the flexibility, particularly the recoverability after compression is dramatically improved. . In particular, the foamed particle molded body of the present invention is a foamed particle molded body excellent not only in flexibility but also in recoverability after compression.
本発明の発泡粒子成形体は、JIS K 6767により測定される圧縮永久歪が6%以下であり、優れた圧縮後の形状の回復性を示し、精密な被梱包物に対する包装資材や、クッション材として好適な発泡粒子成形体である。上記のような用途に用いる場合には、圧縮永久歪は、数値が低いほど好ましく、好ましくは5%以下、より好ましくは4%以下である。 The foamed particle molded body of the present invention has a compression set measured by JIS K 6767 of 6% or less, exhibits excellent recoverability of the shape after compression, and is a packaging material or cushion material for a precise packaged article. It is a suitable foamed particle molded body. When used in the above applications, the compression set is preferably as low as possible, preferably 5% or less, more preferably 4% or less.
本発明の発泡粒子成形体の50%ひずみ時における圧縮応力の測定は、JIS K6767により求められる値である。50%ひずみ時の圧縮応力が低いほど、柔軟性に優れるものとなり、精密な被梱包物に対する包装資材や、クッション材として好適な成形体となる。上記のような用途に用いる場合には、発泡粒子成形体としては、180kPa以下であることが好ましく、より好ましくは150kPa以下、さらに好ましくは120kPa以下である。 The measurement of the compressive stress at the time of 50% strain of the foamed particle molded body of the present invention is a value determined according to JIS K6767. The lower the compressive stress at the time of 50% strain, the better the flexibility, and the molded article suitable as a packaging material or cushioning material for a precise packaged object. When used in the above applications, the foamed particle molded body is preferably 180 kPa or less, more preferably 150 kPa or less, and still more preferably 120 kPa or less.
以下、実施例及び比較例を挙げて本発明をより詳細に説明する。
下記表1に、実施例、比較例で用いた熱可塑性エラストマーの種類、物性等を示す。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Table 1 below shows the types and physical properties of the thermoplastic elastomers used in the examples and comparative examples.
実施例1
(樹脂粒子製造工程)
ポリオレフィン系樹脂として、エチレンコンテント2.7重量%、MFR5g/10分、融点143℃のエチレンプロピレンランダムコポリマー(以下、PP1ともいう。)50重量%と、表1に示す熱可塑性エラストマー(E1)50重量%と、鉱物性油25重量部(パラフィン系プロセス油、出光興産製ダイナオイルPW90;前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計を100重量部とした重量部)とを、タンブラーにて予備混合した後、これらを押出機に投入し、溶融混練してストランド状に押出し、粒子重量約2mgとなる様に、ペレタイザーにてカットして造粒し、樹脂粒子を得た。
Example 1
(Resin particle manufacturing process)
As the polyolefin resin, ethylene content 2.7 wt%, MFR 5 g / 10 min, melting point 143 ° C. ethylene propylene random copolymer (hereinafter also referred to as PP1) 50 wt%, and thermoplastic elastomer (E1) 50 shown in Table 1 % By weight and 25 parts by weight of mineral oil (paraffinic process oil, Idemitsu Kosan Dyna Oil PW90; parts by weight with the total amount of the polyolefin resin and the thermoplastic elastomer as 100 parts by weight) in a tumbler After premixing, these were put into an extruder, melt-kneaded and extruded into strands, and cut and granulated with a pelletizer to obtain a particle weight of about 2 mg to obtain resin particles.
(含浸工程)
得られた樹脂粒子1kgと鉱物性油300g(パラフィン系プロセス油、出光興産製ダイナオイルPW90;前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対して30重量部)とを、分散媒である水3リットル(L)と共に、撹拌機を備えた5Lの密閉容器内に仕込み、更に分散媒中に、分散剤としてカオリンを3g、分散助剤としてアルキルベンゼンスルホン酸ナトリウム0.04g、及び硫酸アルミニウム0.1gを添加し、密閉容器内に発泡剤としてCO280g(前記樹脂粒子の重量100重量部に対して8重量部)を圧入した。
(発泡工程)
その後、撹拌下で発泡温度にまで昇温し、同温度に15分間保持した後、内容物を大気圧下に放出して発泡粒子を得た。
(Impregnation process)
1 kg of the obtained resin particles and 300 g of mineral oil (paraffinic process oil, Idemitsu Kosan Dyna Oil PW90; 30 parts by weight with respect to a total of 100 parts by weight of the polyolefin resin and the thermoplastic elastomer), Along with 3 liters (L) of water as a dispersion medium, the mixture is charged into a 5 L sealed container equipped with a stirrer, and further 3 g of kaolin as a dispersant and 0.04 g of sodium alkylbenzene sulfonate as a dispersion aid in the dispersion medium, And 0.1 g of aluminum sulfate was added, and 80 g of CO 2 (8 parts by weight with respect to 100 parts by weight of the resin particles) was injected as a foaming agent into the sealed container.
(Foaming process)
Thereafter, the temperature was raised to the foaming temperature under stirring and maintained at that temperature for 15 minutes, and then the contents were released under atmospheric pressure to obtain foamed particles.
得られた発泡粒子を加圧タンクに投入し、0.3MPa(G)の圧力で12時間加圧して内圧を付与し、取り出した後、縦250mm×横250mm×厚み100mmの平板が得られる金型に該発泡粒子を充填し、水蒸気加熱による型内成形を行い、更に、該発泡粒子成形体を80℃のオーブン中にて、12時間養生して発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。 The obtained expanded particles are put into a pressurized tank, pressurized for 12 hours at a pressure of 0.3 MPa (G) to give an internal pressure, and after taking out, a gold plate is obtained that is 250 mm long × 250 mm wide × 100 mm thick. The foamed particles were filled into the mold, molded in the mold by heating with steam, and the foamed particle molded body was cured in an oven at 80 ° C. for 12 hours to obtain a foamed particle molded body. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例2
樹脂粒子製造工程においては実施例1と同様の操作で樹脂粒子を得た。次に、含浸工程における前記鉱物性油(PW90)の量を、前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対して65重量部とした以外は、実施例1と同様の操作で発泡粒子を得た。更に、実施例1と同様に型内成形を行い、発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Example 2
In the resin particle production process, resin particles were obtained in the same manner as in Example 1. Next, the amount of the mineral oil (PW90) in the impregnation step was the same as in Example 1 except that the amount was 65 parts by weight with respect to a total of 100 parts by weight of the polyolefin resin and the thermoplastic elastomer. Foamed particles were obtained by the operation. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例3
樹脂粒子製造工程において、熱可塑性エラストマーの配合量を29重量%(PP1が71重量%)にすると共に鉱物性油を配合しないこと以外は、実施例1と同様に樹脂粒子を得た。次に、含浸工程における鉱物性油(PW90)を40重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部)添加した以外は、実施例1と同様の操作で発泡粒子を得た。更に、実施例1と同様に型内成形を行い、発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Example 3
In the resin particle production process, resin particles were obtained in the same manner as in Example 1 except that the amount of the thermoplastic elastomer was 29% by weight (PP1 was 71% by weight) and no mineral oil was added. Next, the same operation as in Example 1 was carried out except that 40 parts by weight of mineral oil (PW90) in the impregnation step was added (parts by weight relative to 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer). Expanded particles were obtained. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例4〜6
熱可塑性エラストマーの種類を変えた以外は実施例3と同様の操作で樹脂粒子、発泡粒子を製造し、更に発泡粒子成形体を得た。
得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Examples 4-6
Resin particles and foamed particles were produced in the same manner as in Example 3 except that the type of thermoplastic elastomer was changed, and a foamed particle molded body was obtained.
Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例7
樹脂粒子製造工程においては、実施例1と同様の操作で樹脂粒子を得た。次に、含浸工程においては、鉱物性油を添加しない以外は、実施例1と同様に発泡粒子を得た。更に、実施例1と同様に型内成形を行い、発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Example 7
In the resin particle production process, resin particles were obtained in the same manner as in Example 1. Next, in the impregnation step, expanded particles were obtained in the same manner as in Example 1 except that mineral oil was not added. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例8
樹脂粒子製造工程においては、表1に示すE2の熱可塑性エラストマーを使用し、鉱物性油を添加しない以外は、実施例1と同様に樹脂粒子を得た。次に、含浸工程で、鉱物性油(PW90)を表2に示す量添加した以外は、実施例1と同様にして発泡粒子を得た。更に、実施例1と同様に発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Example 8
In the resin particle production process, resin particles were obtained in the same manner as in Example 1 except that the thermoplastic elastomer E2 shown in Table 1 was used and no mineral oil was added. Next, expanded particles were obtained in the same manner as in Example 1 except that mineral oil (PW90) was added in the impregnation step in the amount shown in Table 2. Further, a foamed particle molded body was obtained in the same manner as in Example 1. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
実施例9
樹脂粒子製造工程では鉱物性油を添加しない以外、実施例1と同様に樹脂粒子を得た。次に、含浸工程でのみ、表2に示す量の鉱物性油(PW90)を添加したこと以外は、実施例1と同様に発泡粒子を得た。更に、実施例1と同様に型内成形を行い、発泡粒子成形体を得た。得られた発泡粒子、発泡粒子成形体の物性等を表2に示した。
Example 9
Resin particles were obtained in the same manner as in Example 1 except that mineral oil was not added in the resin particle production process. Next, expanded particles were obtained in the same manner as in Example 1 except that the mineral oil (PW90) in the amount shown in Table 2 was added only in the impregnation step. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Table 2 shows the physical properties and the like of the obtained expanded particles and the expanded molded article.
比較例1
実施例3の樹脂粒子を用い、含浸工程で鉱物性油を配合しない以外、実施例3と同様に発泡粒子を得た。さらに、実施例1と同様に型内成形を行い発泡粒子成形体を得た。鉱物性油を含有していないことから、含浸工程での分散性、型内成形性には優れるものの、得られた発泡粒子成形体は、柔軟性や回復性が不足していた。
Comparative Example 1
Expanded particles were obtained in the same manner as in Example 3 except that the resin particles of Example 3 were used and no mineral oil was added in the impregnation step. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Since it does not contain mineral oil, it has excellent dispersibility in the impregnation step and in-mold moldability, but the obtained foamed particle molded body lacks flexibility and recoverability.
比較例2
熱可塑性エラストマーの種類を変えた以外は、比較例1と同様に樹脂粒子、発泡粒子を得た。更に、実施例1と同様に型内成形を行い、発泡粒子成形体を得た。含浸工程での分散性、型内成形性には問題は無かったものの、得られた発泡粒子成形体は回復性が不足したものであった。
Comparative Example 2
Resin particles and expanded particles were obtained in the same manner as in Comparative Example 1 except that the type of thermoplastic elastomer was changed. Further, in-mold molding was performed in the same manner as in Example 1 to obtain a foamed particle molded body. Although there was no problem in dispersibility and in-mold moldability in the impregnation step, the obtained foamed particle molded body was insufficient in recoverability.
比較例3
樹脂粒子製造工程の鉱物性油の配合量を、100重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部)とした以外は、実施例3と同様に樹脂粒子を製造した。しかし、ストランドが柔軟になりすぎたために、造粒ができず、樹脂粒子を得ることができなかった。また、押出時の食い込み不良によるサージングも発生した。
Comparative Example 3
Resin particles in the same manner as in Example 3 except that the blending amount of the mineral oil in the resin particle manufacturing process was 100 parts by weight (parts by weight relative to 100 parts by weight of the total blending amount of the polyolefin resin and the thermoplastic elastomer). Manufactured. However, since the strand became too flexible, granulation could not be performed and resin particles could not be obtained. In addition, surging due to poor biting during extrusion also occurred.
比較例4
実施例3で得られた樹脂粒子を使用し、含浸工程の鉱物性油の配合量を、120重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの合計量100重量部に対する重量部)とした以外は、実施例3と同様に発泡粒子を製造した。含浸工程での分散性が低下し、樹脂粒子が凝結し、発泡した粒子同士が凝結しており、型内成形に使用できるような発泡粒子を得ることが出来なかった。
Comparative Example 4
Except for using the resin particles obtained in Example 3, the blending amount of the mineral oil in the impregnation step was 120 parts by weight (parts by weight relative to 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer). In the same manner as in Example 3, foamed particles were produced. The dispersibility in the impregnation step was lowered, the resin particles were agglomerated, and the foamed particles were agglomerated, and it was not possible to obtain foamed particles that could be used for in-mold molding.
比較例5
ポリオレフィン系樹脂を、表2に示す割合で配合した以外、実施例3と同様にして、樹脂粒子、発泡粒子を得た。熱可塑性エラストマーの配合量が少ないため、発泡粒子がべたついて、成形金型に発泡粒子を充填することができず、発泡粒子成形体を得ることができなかった。
Comparative Example 5
Resin particles and foamed particles were obtained in the same manner as in Example 3 except that the polyolefin resin was blended in the ratio shown in Table 2. Since the blended amount of the thermoplastic elastomer was small, the foamed particles were sticky, and the foamed particles could not be filled in the molding die, and a foamed particle molded body could not be obtained.
比較例6
熱可塑性エラストマーを、表2に示す割合で配合した以外、実施例3と同様にして、樹脂粒子、発泡粒子を得た。熱可塑性エラストマーの配合量が多すぎるため、発泡粒子が連続気泡化してしまい、型内成形時に二次発泡せず、発泡粒子成形体を得ることができなかった。
Comparative Example 6
Resin particles and foamed particles were obtained in the same manner as in Example 3 except that the thermoplastic elastomer was blended in the ratio shown in Table 2. Since the blended amount of the thermoplastic elastomer was too large, the foamed particles became open-celled, and secondary foaming did not occur during in-mold molding, and a foamed particle molded body could not be obtained.
分散安定性の評価
○:発泡工程において発泡後、発泡した粒子同士間での凝結が生じなかった。
×:発泡工程において発泡後、発泡した粒子同士間での凝結が生じていた。
Evaluation of dispersion stability ○: After foaming in the foaming step, no condensation occurred between the foamed particles.
X: Condensation between the foamed particles occurred after foaming in the foaming process.
型内成形性の評価
◎:発泡粒子成形体の表面がべたつかず、発泡粒子成形体の収縮率が10%以下である。
○:発泡粒子成形体の表面が多少べたついているが、発泡粒子成形体が得られる。
×:発泡粒子の表面がべたついて、発泡粒子を成形金型に充填できず、発泡粒子成形体を得ることができない。
Evaluation of in-mold moldability A: The surface of the foamed particle molded body is not sticky, and the shrinkage ratio of the foamed particle molded body is 10% or less.
○: Although the surface of the foamed particle molded body is somewhat sticky, a foamed particle molded body can be obtained.
X: The surface of the foamed particles is sticky, the foamed particles cannot be filled into the molding die, and the foamed particle molded body cannot be obtained.
Claims (3)
前記樹脂組成物100重量部に対して15〜95重量部の鉱物性油とからなり、
前記熱可塑性エラストマーの配合量に対する前記鉱物性油の配合量の重量比率が0.4〜3であり、
見かけ密度が15〜150g/Lであることを特徴とするポリオレフィン系樹脂発泡粒子。
A resin composition comprising 80 to 30% by weight of a polyolefin resin and 20 to 70% by weight of a thermoplastic elastomer (however, the total of the polyolefin resin and the thermoplastic elastomer is 100% by weight);
Comprising 15 to 95 parts by weight of mineral oil with respect to 100 parts by weight of the resin composition,
The weight ratio of the blending amount of the mineral oil to the blending amount of the thermoplastic elastomer is 0.4 to 3,
Polyolefin resin foamed particles having an apparent density of 15 to 150 g / L.
A molded product obtained by in-mold molding of the polyolefin resin expanded particles according to claim 1, wherein the molded product has an apparent density of 10 to 100 g / L and a compression set (JIS K 6767) of 6 % Molded polyolefin resin foam particles, characterized by being less than or equal to%.
前記樹脂粒子と、発泡剤と、0〜70重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部である)の鉱物性油とを密閉容器中で分散媒に分散させて、前記樹脂粒子に発泡剤と前記鉱物性油とを含浸させ、
次いで、発泡剤と鉱物性油とを含有する樹脂粒子を発泡させて15〜95重量部(前記ポリオレフィン系樹脂と熱可塑性エラストマーの配合量の合計100重量部に対する重量部である)の鉱物性油を含有し、前記熱可塑性エラストマーの配合量に対する前記鉱物性油の配合量の重量比率が0.4〜3である発泡粒子を得ることを特徴とするポリオレフィン系樹脂発泡粒子の製造方法。
80 to 30% by weight of a polyolefin resin, 20 to 70% by weight of a thermoplastic elastomer (the total of the polyolefin resin and the thermoplastic elastomer is 100% by weight), 0 to 70 parts by weight (the polyolefin resin and heat The blended amount of the plastic elastomer is 100 parts by weight with respect to a total of 100 parts by weight of mineral oil), and the melt-kneaded product obtained by melt-kneading is granulated into resin particles,
Using the resin particles, the foaming agent, and mineral oil of 0 to 70 parts by weight (parts by weight relative to 100 parts by weight of the total amount of the polyolefin resin and the thermoplastic elastomer) as a dispersion medium in a closed container Disperse, impregnate the resin particles with a foaming agent and the mineral oil,
Next, 15 to 95 parts by weight of a mineral oil containing foaming agent and mineral oil is foamed (the amount is 100 parts by weight with respect to the total amount of the polyolefin resin and the thermoplastic elastomer). And a foamed particle having a weight ratio of the blended amount of the mineral oil to the blended amount of the thermoplastic elastomer of 0.4 to 3 is obtained.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009292596A JP5561762B2 (en) | 2009-12-24 | 2009-12-24 | Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009292596A JP5561762B2 (en) | 2009-12-24 | 2009-12-24 | Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011132356A JP2011132356A (en) | 2011-07-07 |
JP5561762B2 true JP5561762B2 (en) | 2014-07-30 |
Family
ID=44345458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009292596A Active JP5561762B2 (en) | 2009-12-24 | 2009-12-24 | Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5561762B2 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3202833B1 (en) | 2014-09-30 | 2020-01-01 | Sekisui Plastics Co., Ltd. | Expanded article |
JP6441120B2 (en) * | 2015-02-27 | 2018-12-19 | 株式会社ジェイエスピー | Cross-linked polyethylene resin expanded particles and expanded molded article |
JP6643814B2 (en) | 2015-05-14 | 2020-02-12 | 株式会社ジェイエスピー | Crosslinked expanded particles and expanded particle molding |
JP2017185771A (en) * | 2016-03-30 | 2017-10-12 | 積水化成品工業株式会社 | Interior material for vehicle |
JP6836866B2 (en) | 2016-09-16 | 2021-03-03 | 株式会社ジェイエスピー | Crosslinked foamed particles and their molded product |
JP6519813B2 (en) | 2016-11-11 | 2019-05-29 | 株式会社ジェイエスピー | Expanded particles and their compacts |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6277916B1 (en) * | 1999-02-25 | 2001-08-21 | The Dow Chemical Company | Process for preparing thermoplastic vulcanizates |
JP2003147116A (en) * | 2001-11-19 | 2003-05-21 | Sumitomo Chem Co Ltd | Expandable bead, in-mold expansion molded product, method for manufacturing in-molded expansion molded product, and multi-layered molded product |
JP2009161741A (en) * | 2007-12-12 | 2009-07-23 | Sumitomo Chemical Co Ltd | Process for producing thermoplastic elastomer composition foam |
JP5167900B2 (en) * | 2008-03-27 | 2013-03-21 | Jsr株式会社 | Thermoplastic elastomer composition, foam, and method for producing foam |
-
2009
- 2009-12-24 JP JP2009292596A patent/JP5561762B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2011132356A (en) | 2011-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5561762B2 (en) | Polyolefin resin expanded particles, polyolefin resin expanded particles molded body, and method for producing polyolefin resin expanded particles | |
JP5498162B2 (en) | Polypropylene resin foamed particles and molded articles thereof | |
JP5351433B2 (en) | Polypropylene resin pre-expanded particles and a polypropylene resin in-mold foam molded product obtained from the polypropylene resin pre-expanded particles | |
JP6441120B2 (en) | Cross-linked polyethylene resin expanded particles and expanded molded article | |
CN103347942B (en) | Process for producing expandable thermoplastic beads with improved expandability | |
JP5116448B2 (en) | Open cell foam and method for producing the same | |
JPWO2018016399A1 (en) | Polypropylene-based resin pre-expanded particles and method for producing the pre-expanded particles | |
KR20110110281A (en) | Elastic particle foam based on polyolefin/styrene polymer mixtures | |
WO2018066505A1 (en) | Expanded particle molded article | |
JP5314411B2 (en) | Method for producing polypropylene resin expanded particle molded body, and molded body | |
WO2018088429A1 (en) | Foam particle moulded article and sole member | |
KR102562308B1 (en) | Olefin-based thermoplastic elastomer expanded particles | |
JP6961607B2 (en) | Foamed particle molded product | |
JP5324967B2 (en) | Thermoplastic resin expanded particles and method for producing the same | |
JP4023911B2 (en) | Cylindrical polyolefin resin foam particles having through holes and a method for producing a polyolefin resin foam molded body having continuous voids | |
WO2018052125A1 (en) | Expanded beads and molded object thereof | |
US8410187B2 (en) | Polyvinylidene fluoride resin expanded beads, and molded articles of polyvinylidene fluoride resin expanded beads | |
JP6845426B2 (en) | Foam molding resin, foam molding and its manufacturing method | |
JP2018070735A (en) | Foamed particle and method for producing foamed particle molding | |
JP2021070713A (en) | Foamable resin particle and method for producing foamable resin particle | |
JP4017535B2 (en) | Styrene-olefin mixed resin foamable particles, production method thereof, and styrene-olefin mixed resin foam molded article | |
WO2020090335A1 (en) | Foam particles | |
JP6993601B1 (en) | Polyolefin-based resin foamed particles, their manufacturing method, and polyolefin-based resin foamed particle molded body | |
KR101732759B1 (en) | Expandable composite resin particle, method for preparing the same, and foamed molded article | |
KR101674610B1 (en) | Polymer foam particle and preparation method of the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121025 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131004 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131010 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131206 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140605 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140605 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5561762 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |