JP3962936B2 - Expandable styrenic resin particles and foam molded products - Google Patents
Expandable styrenic resin particles and foam molded products Download PDFInfo
- Publication number
- JP3962936B2 JP3962936B2 JP06641798A JP6641798A JP3962936B2 JP 3962936 B2 JP3962936 B2 JP 3962936B2 JP 06641798 A JP06641798 A JP 06641798A JP 6641798 A JP6641798 A JP 6641798A JP 3962936 B2 JP3962936 B2 JP 3962936B2
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- JP
- Japan
- Prior art keywords
- resin particles
- expandable styrene
- weight
- polyvinyl alcohol
- expandable
- 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.)
- Expired - Fee Related
Links
- 239000002245 particle Substances 0.000 title claims description 93
- 229920001890 Novodur Polymers 0.000 title claims description 13
- 239000006260 foam Substances 0.000 title description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 130
- 229920005989 resin Polymers 0.000 claims description 102
- 239000011347 resin Substances 0.000 claims description 102
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 239000011737 fluorine Substances 0.000 claims description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 16
- 229920006163 vinyl copolymer Polymers 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000010097 foam moulding Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 17
- 238000000465 moulding Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000004088 foaming agent Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000035515 penetration Effects 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000003925 fat Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 sucrose ester Chemical class 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
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- 239000012466 permeate Substances 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-M Pentobarbital sodium Chemical compound [Na+].CCCC(C)C1(CC)C(=O)NC(=O)[N-]C1=O QGMRQYFBGABWDR-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 235000021549 curry roux Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 235000021149 fatty food Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006298 saran Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、得られる発泡成形品が乳化剤成分と油脂成分が混在する内容物用の容器として好適な発泡性スチレン系樹脂粒子及び発泡成形品に関する。
【０００２】
【従来の技術】
一般に発泡性スチレン系樹脂粒子は、スチーム等によって予め予備発泡させて予備発泡粒子となし、この予備発泡粒子を小孔を有する金型に充填し再度加熱し成形することができる。こうして得られた成形品は経済性，軽量性，衛生性などに優れた特性を示し包装材料，断熱材料，容器等として多くの分野で使用されている。
【０００３】
ここで、発泡性スチレン系樹脂粒子は、発泡剤（一般に常温で液体または気体の脂肪族炭化水素，例えばプロパン、ブタン、ペンタン、ヘキサン等）をスチレン系樹脂粒子と共に水性媒体中に分散させて、粒子に発泡剤を含浸させる方法、またはスチレン系樹脂粒子に対して溶解性を有するトルエン、シクロヘキサン等の溶剤を少量含有する水性懸濁液中で発泡剤を含浸させる方法等により製造される。そして、こうして得られた発泡性スチレン系樹脂粒子は前述の工程を経て成形される。
【０００４】
しかしながら、得られた成形品は発泡性スチレン系樹脂粒子を石垣上に積み重ね、これを発泡圧と熱によって融着させたものであるため、樹脂粒子同士が一体化されていない場合がある。その結果、容器として使用するとき、収納される内容物の種類によっては、内容物が容器外壁または成形品内部に浸透してくるおそれがある。
このような浸透性を防止するためには、浸透する内容物が容器内部を浸透する際、道となる成形品内部の空隙を最小限にする方法，およびこの粒子表面の表面エネルギーを小さくすることにより、浸透する内容物に対し成形品表面の接触角を大きくする方法を一般的に採ることができる。
【０００５】
前者の方法として一般に行なわれているのは成形時の加熱条件を強化することであり、より欠陥の少ない成形品とするためには成形温度を低めに設定し、発泡性スチレン系樹脂粒子を長時間加熱する方法がとられている。
しかしながら、この方法は発泡性スチレン系樹脂粒子の成形加熱に長時間を要し、成形工業的には生産性を著しく低下させるため有用な方法とは言い難い。
【０００６】
一方、後者の方法としては、予備発泡において発泡性スチレン系樹脂粒子の集塊化防止のために一般的に使用されている金属石鹸（カルボン酸塩）の量を、より多くすることが行なわれている。
しかしながら、この方法においても金属石鹸に起因した発泡性スチレン系樹脂粒子の融着阻害の性質を発現させないために、成形加熱時間を長くする必要があり、やはり工業的に有用な方法とはいい難い。
【０００７】
そこで、より短い成形加熱時間で以て、内容物の浸透性の少ない発泡性スチレン系樹脂粒子が種々提案されている。
例えば特公昭５６−３４１７２号公報では、表面を蔗糖エステルまたはその誘導体で被覆した発泡性スチレン系樹脂粒子が、特開平２−８８６５２号公報では特定のパーフルオロアルキル基含有共重合体等を被覆層として用いた発泡性熱可塑性樹脂粒子組成物が、特開平２−１１５２４２号公報ではリシノール酸の金属塩等を含む被覆層を有する発泡性スチレン系樹脂粒子が、および特開平３−１９０９４１号公報では特定の含フッ素ビニル系単量体と親油性単量体との共重合体で被覆した発泡性スチレン系樹脂粒子がそれぞれ開示されている。
また、特開昭６２−１５８７３０号公報には、含フッ素ビニル型重合体部分と親水性ビニル型重合体部分とからなる共重合体が被覆または含有されている発泡性熱可塑性樹脂粒子が開示されている。
【０００８】
【発明が解決しようとする課題】
しかしながら、特公昭５６−３４１７２号公報、特開平２−８８６５２号公報、特開平２−１１５２４２号公報および特開平３−１９０９４１号公報に開示された発泡性スチレン系樹脂粒子あるいは発泡性熱可塑性樹脂粒子組成物は、一般の水性（乳化系を含む。）あるいは油性の内容物については優れた遮蔽性（浸透防止性）を示すことができるものの、成形品に加工した際の当該成形品に収容する内容物の種類によっては浸透防止性能が不十分となるおそれがあった。
すなわち、上述した発泡性スチレン系樹脂粒子によって成形された容器はその経済性、保温性等により、幅広い用途を持つが、一部の浸透性が高い内容物の容器等として長期間使用した場合に、当該内容物が浸透してくるおそれがあった。
【０００９】
もちろん、特公昭５６−３４１７２号公報等に開示された発泡性スチレン系樹脂粒子は、一部の浸透性が高い油性の内容物（例えば、乳化剤成分と油脂成分が混在するカレールウ、機械油等）についても、比較的長時間加熱成形することにより、優れた遮蔽性（浸透防止性）を示すことができる。しかしながら、長時間加熱成形することによる生産性の低下については否めない。
【００１０】
また、特開昭６２−１５８７３０号公報に開示された発泡性熱可塑性樹脂粒子は、含フッ素ビニル型重合体部分と親水性ビニル型重合体部分とからなる共重合体を用いているが、当該共重合体の原料である含フッ素ビニル型単量体および親水性ビニル系単量体の相溶性に乏しく、当該共重合体の特性がばらつきやすいという問題が見られた。
【００１１】
したがって、特開昭６２−１５８７３０号公報に開示された発泡性熱可塑性樹脂粒子を即席ラーメン等の容器（カップ）に加熱成形した場合には、流通在庫中に乳化剤成分と油脂成分が混在する油脂分、カレー成分あるいはスープ成分等の内容物が温度や湿度の影響をうけて、容器（カップ）の外壁へにじみ出てくるおそれがあった。また、機械部品の通い箱として加熱成形した場合には、当該通い箱に機械部品を機械油につけた状態で用いるため、当該通い箱を何度も繰り返して使用するうちに、機械油が通い箱の外壁へ浸透してくる場合があった。
【００１２】
すなわち、前述したいずれの特許公報に開示された発泡性スチレン系樹脂粒子等においても、浸透性が高い内容物に対する遮蔽性（浸透防止性）と、成形加熱時間に代表される生産性との兼ね合い（バランス）において必ずしも満足のいくものではなかった。
本発明は上述の問題に鑑みなされたのであり、特定の一部の浸透性が高い内容物における容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部に浸透することが少なく、かつ短時間で成形可能なこれらの特性のバランスに優れた発泡性スチレン系樹脂粒子及びこれを用いた発泡成形品を提供することを目的とする。
【００１３】
【課題を解決するための手段】
本発明は、下記の一般式（Ｉ）で表される含フッ素ビニル系単量体４０〜９５重量％および下記の一般式（ＩＩ）で表されるビニル系単量体５〜６０重量％を重合させて得られた含フッ素ビニル系共重合体と、ポリビニルアルコール系樹脂とを含む被覆物を、発泡性スチレン系樹脂粒子本体の表面に被覆した発泡性スチレン系樹脂粒子に関する。
【００１４】
【化３】
【００１５】
【化４】
【００１６】
このように一部に親水性高分子を含んで発泡性スチレン系樹脂粒子を構成することにより、親水性高分子であるポリビニルアルコール系樹脂が接着剤の役目を果たしているためと推定されるが、優れた内容物の遮蔽性を保持したまま、浸透性が高い油性の内容物における容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部へ浸透するおそれが著しく少なくなる。
【００１７】
本発明においては、含フッ素ビニル系共重合体の被覆物が発泡性スチレン系樹脂粒子本体１００重量部に対して、０．００５〜０．３重量部の範囲内の値とすることが好ましい。
【００１８】
また本発明においては、ポリビニルアルコール系樹脂の被覆物が発泡性スチレン系樹脂粒子本体１００重量部に対して、０．００１〜０．１重量部の範囲内の値とすることが好ましい。
【００１９】
このような範囲でポリビニルアルコール系樹脂を被覆物中に含むことにより、親水性成分や油成分の浸透をより効率的に防止することができる。したがって、発泡性スチレン系樹脂粒子を、浸透性が高い油性の内容物あるいは乳化剤成分と油脂成分が混在する油性の内容物に対する容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部へ浸透するおそれが少ない。
また、このようなポリビニルアルコール系樹脂の使用量であれば、予備加熱時には、発泡性スチレン系樹脂粒子同士が凝集して集塊化するおそれが少ない一方、成形加熱時には、ポリビニルアルコール系樹脂が接着剤としての役目を果たし、優れた融着性を示すことが可能となる。
【００２０】
【発明の実施の形態】
次に本発明の実施の形態を具体的に説明する。
１．発泡性スチレン系樹脂粒子
本発明の発泡性スチレン系樹脂粒子は、発泡性スチレン系樹脂粒子本体の表面に所定の含フッ素ビニル系重合体を被覆することにより得られるものである。
（１）発泡性スチレン系樹脂粒子本体
発泡性スチレン系樹脂粒子本体は、上述のように、スチレン系樹脂粒子に、発泡剤を含浸させることにより調製することができる。
【００２１】
（ａ）スチレン系樹脂粒子
スチレン系樹脂粒子としては、特に制限はないが、例えばスチレンホモポリマー、またはスチレンモノマーと共重合可能な成分，例えばアクリロニトリル，メタクリル酸メチル，メタクリル酸ブチル等のメタクリル酸エステル類、アクリル酸メチル，アクリル酸エチル，アクリル酸ブチル等のアクリル酸エステル類、α−メチルスチレン，クロルスチレン，ビニルトルエン等のスチレン誘導体のモノマーなどとの一種または二種以上の共重合体を挙げることができる。
【００２２】
（ｂ）発泡剤
発泡剤としては、特に制限はないが、例えばプロパン，ブタン，ペンタン，ヘキサン等の脂肪族炭化水素，またはフレオン１１，フレオン１２等のフロン系化合物などの常温で液体または気体状の化合物を挙げることができる。
【００２３】
（ｃ）発泡剤の含浸
発泡剤の含浸方法としては、特に制限はない。発泡剤の含浸量はスチレン系樹脂粒子本体に対して3〜10重量％が好ましい。
【００２４】
（２）含フッ素ビニル系共重合体
下記一般式（Ｉ）表される含フッ素ビニル系単量体と、下記一般式（ＩＩ）で表されるビニル系単量体とを重合して得られるものが用いられる。
（ｄ）含フッ素ビニル系単量体
含フッ素ビニル系単量体は、下記一般式（Ｉ）で表される化合物が用いられる。
【００２５】
【化５】
【００２６】
このような含フッ素ビニル系単量体の例としては具体的に以下のものが挙げられる。
Ｃ8F17ＳＯ2-Ｎ（ＣＨ3）−ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2
Ｃ8F17ＳＯ2-Ｎ（ＣＨ3）−ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2
Ｃ8F17ＳＯ2-Ｎ（Ｃ2Ｈ5）−ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2
Ｃ8F17ＳＯ2-Ｎ（Ｃ2Ｈ5）−ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）＝ＣＨ2
【００２７】
（ｅ）ビニル系単量体
ビニル系単量体は、下記一般式（ＩＩ）で表される化合物が用いられる。
【００２８】
【化６】
【００２９】
このようなビニル系単量体の例としては、具体的に以下のものを挙げることができる。
ＣＨ2=ＣＨ−ＣＯＯＣ11Ｈ23
ＣＨ2=Ｃ（ＣＨ3）−ＣＯＯＣ15Ｈ31
ＣＨ2=ＣＨ−ＣＯＯＣ17Ｈ35
ＣＨ2=Ｃ（ＣＨ3）−ＣＯＯＣ17Ｈ35
【００３０】
（ｆ）重合割合
一般式（Ｉ）で表される含フッ素ビニル系単量体及び一般式（ＩＩ）で表されるビニル系単量体との重合割合は、含フッ素ビニル系単量体４０〜９５重量％、ビニル系単量体５〜６０重量％とされる。含フッ素ビニル系単量体の重合割合が４０重量％未満であると成形品としたときに十分な撥水，撥油性を付与することは困難となり、また９５重量％を越えると、成形における熱融着を阻害することになる。
【００３１】
（ｇ）重合方法
本発明における含フッ素ビニル系共重合体の重合方法としては、特に制限はないが、例えば溶液重合、乳化重合等を挙げることができる。重合に用いられる重合開始剤としては、溶液重合においては過酸化ラウロイル、過酸化ベンゾイル，ｔｅｒｔ−ブチルパーオキシイソブチレート、ｔｅｒｔ−ブチルパ−オキシピバレート等を挙げることができる。また、乳化重合に於いては、過硫酸カリウム，過硫酸アンモニウム等を挙げることができる。
【００３２】
（ｈ）含フッ素ビニル系共重合体の使用量
本発明における含フッ素ビニル系共重合体の被服物は発泡性スチレン系樹脂粒子本体１００重量部に対して、０．００５〜０．３重量部の範囲内の値とすることが好ましく、より好ましくは０．０１〜０．２重量部である。含フッ素ビニル系共重合体の被覆物が０．００５重量部未満では十分な撥油性が得られない傾向があり、また０．３重量部を超えても得られる発泡成形品の特性が向上しない傾向がある。
【００３３】
（３）ポリビニルアルコール系樹脂
（ｉ）ポリビニルアルコール系樹脂の種類
本発明に使用するポリビニルアルコール系樹脂の鹸化度（ＪＩＳ Ｋ ６７２６に準拠）は、７０〜９９．９ｍｏｌ％の範囲内の値とするのが好ましい。
ポリビニルアルコール系樹脂の鹸化度がこのような範囲内の値であれば、より効率的に油成分等の浸透を防止して、浸透性が高い油性の内容物における容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部へ浸透するおそれがより少なくなる。また、このような範囲の鹸化度であれば、優れた内容物の遮蔽性を保持したまま、短時間で成形可能な発泡性スチレン系樹脂粒子及び発泡成形品を提供することが可能となる。さらに、ポリビニルアルコール系樹脂の鹸化度がこのような範囲内の値であれば、発泡性スチレン系樹脂粒子本体との密着力をより向上させることもできる。
したがって、内容物の遮蔽性および生産性の効率とのバランスにより優れている観点から、ポリビニルアルコール系樹脂の鹸化度を、７５〜９５ｍｏｌ％の範囲内の値とするのがより好ましく、８０〜９０ｍｏｌ％の範囲内の値とすることがさらに好ましい。
【００３４】
また、発泡性スチレン系樹脂粒子を被覆するにあたり、使用するポリビニルアルコール系樹脂の重合度（ＪＩＳ Ｋ ６７２６に準拠）を、３００〜６００００の範囲内の値とするのが好ましい。
ポリビニルアルコール系樹脂の重合度がこのような範囲内の値であれば、発泡性スチレン系樹脂粒子本体との密着力がより向上するためである。したがって、浸透性が高い、比較的高温の油性の内容物における容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部へ浸透することがより少なくなる。さらには、ポリビニルアルコール系樹脂の重合度がこのような範囲内の値であれば、成形加熱時に、発泡性スチレン系樹脂粒子の融着を阻害するおそれもより少ないためである。
したがって、内容物の遮蔽性および生産性の効率とのバランスがより優れている観点から、ポリビニルアルコール系樹脂の重合度を、４００〜１０００の範囲内の値とするのがより好ましく、５００〜８００の範囲内の値とすることがさらに好ましい。
【００３５】
また、発泡性スチレン系樹脂粒子を被覆するにあたり、ポリビニルアルコール系樹脂が、ポリビニルアルコール、ポリビニルホルマールおよびポリビニルブチラールからなる群から選択された少なくとも一つの樹脂であるのが好ましい。
かかるポリビニルアルコール系樹脂は、一定量の水酸基やビニル基を有しており、浸透性が高い油性の内容物における容器等に使用した場合であっても、収容される内容物が容器外壁または成形品内部へ浸透することが少なく、かつ短時間で成形可能な発泡性スチレン系樹脂粒子及び発泡成形品を提供することが可能となる。
【００３６】
また、発泡性スチレン系樹脂粒子を被覆するにあたり、使用する含フッ素ビニル系共重合体が、水系エマルション（水系エマルジョンと称する場合もある。）であることが好ましい。
また、発泡性スチレン系樹脂粒子を構成するにあたり、使用するポリビニルアルコール系樹脂が、水溶液であることが好ましい。
それぞれ被覆物を構成する含フッ素ビニル系共重合体は、油性であり、親水性のポリビニルアルコール系樹脂とは一般に相溶性に乏しい。したがって、それぞれをそのまま混合しても時間が経過すると分離してしまうおそれがある。しかるに、使用する含フッ素ビニル系共重合体およびポリビニルアルコール系樹脂あるいはいずれか一方が、水系エマルションあるいは水溶液であれば、かかる混合分離の問題が生じず、任意の量で以て、含フッ素ビニル系共重合体とポリビニルアルコール系樹脂とを均一に混合することができる。
【００３７】
本発明に使用できるポリビニルアルコールは、商業的に入手できるものをそのまま使用できるが、作業性の点から、４重量％水溶液粘度が１〜１００センチポイズ（ｃｐ）の範囲内の値を有するものが好ましく、１０〜８０センチポイズ（ｃｐ）の範囲内の値がより好ましい。
また、加熱成形時の発泡性スチレン系樹脂粒子同士の融着性がより良好な観点から、ポリビニルアルコール系樹脂のガラス転移点を、３０〜１００℃の範囲内の値とするのが好ましく、４０〜８０℃の範囲内の値がより好ましい。。
【００３８】
なお、ポリビニルアルコール系樹脂のガラス転移点を調整したり、柔軟性を改良したり、あるいは含フッ素ビニル系単量体との混合性をより良好とするために、添加剤として、グリセリン、エチレングリコール、ＤＢＰ（ジブチルフタレート）、ＤＯＰ（ジオクチルフタレート）、アルギン酸アミド、アクリルアミド、澱粉、ＣＭＣ、メチルセルロース、グリオキサゾール、ジメチロール尿素等の一つまたは二つ以上を添加することができる。
さらに、ポリビニルアルコール系樹脂の耐熱性を向上させたり、発泡性スチレン系樹脂粒子本体との密着性を向上させるために、イソシアネート等の架橋剤を添加することも好ましい。
【００３９】
（ｊ）ポリビニルアルコール系樹脂の使用方法
ポリビニルアルコール系樹脂は、含フッ素ビニル系単量体と混合後に発泡性スチレン系樹脂粒子本体に対して被覆処理することも可能であるし、また、含フッ素ビニル系単量体とは別に、単独で発泡性スチレン系樹脂粒子本体に対して被覆処理することも好ましい。含フッ素ビニル系単量体と混合後に被覆処理することにより、一度の操作で発泡性スチレン系樹脂粒子本体に対して被覆処理することができる点で好ましく、一方、単独で発泡性スチレン系樹脂粒子本体に対して被覆処理することにより、含フッ素ビニル系単量体との分離による濃度むらが生じるおそれが少なくなる点で好ましい。
【００４０】
（ｋ）ポリビニルアルコールの使用量
本発明におけるポリビニルアルコールの使用量は、発泡性スチレン系樹脂粒子本体１００重量部に対して好ましくは０．００１〜０．１重量部、より好ましくは０．００５〜０．０５重量部とされる。ポリビニルアルコールの使用量が０．００１重量部未満では、成形品としたときの乳化剤成分や油脂成分の遮蔽能力が不十分な傾向があり、また０．１重量部を越えても得られる発泡成形品の特性が向上しない傾向がある。
【００４１】
（４）その他の被覆剤
発泡性スチレン系樹脂粒子本体の被覆においては、前述の共重合体のほかに従来公知の被覆剤を併用することができる。例えば、一次発泡における集塊化防止のため使用されるステアリン酸亜鉛、ステアリン酸カルシウムなどの金属石鹸、エチレンビスアミド、ステアリン酸アミドのような高級脂肪酸アミドを挙げることができる。これらの集塊化防止剤は発泡性スチレン系樹脂粒子本体１００重量部に対し０．０５〜０．５重量部の範囲内で使用することが好ましい。中でも集塊化防止効果に特に優れており、また安価で経済的観点からステアリン酸亜鉛が好ましい。
【００４２】
また成形工程においてこの発泡性スチレン系樹脂粒子本体の融着促進効果のある添加剤も使用可能である。かかる物質としては従来公知のものが使用できる。例えばステアリン酸グリセライド、オレイン酸グリセライドなどの高級脂肪酸のトリエステル、ジエステル、モノエステル類、蔗糖エステル類等の１種または２種以上が使用できる。
【００４３】
さらに、一次発泡性スチレン系樹脂粒子本体の静電防止剤として使用されるグリセリン、ソルビトール、ポリエチレングリコール、ポリプロピレングリコール等の多価アルコール類、ソルビタンエステル、高級脂肪酸のエチレングリコール付加物等のノニオン系界面活性剤の、１種または２種以上の併用も可能である。これら静電防止剤は発泡性スチレン系樹脂粒子本体１００重量部に対し０．００５〜０．２重量部の範囲内で使用することが好ましい。
【００４４】
（５）被覆の形成
本発明における発泡性スチレン系樹脂粒子本体の表面への含フッ素ビニル系共重合体およびポリビニルアルコール系樹脂の被覆物の形成方法は、特に制限はなく従来既知の手段で行なうことができる。
例えば、リボンブレンダー、Ｖ形ブレンダー、ヘンシェルミキサー、レディゲミキサー等の混合機を用い、室温、１００〜１０、０００ｒｐｍの回転数、および１０秒〜１時間の撹拌時間の条件で、発泡性スチレン系樹脂粒子本体、含フッ素ビニル系共重合体、ポリビニルアルコール系樹脂及び前述の被覆剤各成分等をそれぞれ混合することによって被覆形成することができる。
但し、発泡性スチレン系樹脂粒子本体、含フッ素ビニル系共重合体、ポリビニルアルコール系樹脂及び前述の被覆剤各成分等をそれぞれ個別に層状に被覆形成することもできる。
【００４５】
２．発泡成形品
本発明の発泡成形品は、前述の発泡性スチレン系樹脂粒子を成形することによって得ることができる。すなわち、上述した発泡性スチレン系樹脂粒子を使用することにより、短い成形加熱時間で以て、発泡粒子同士が強固に融着しかつその粒子界面が優れた撥油性を有する発泡成形品を得ることができる。
ここで、具体的な成形加熱条件は特に制限されるものではないが、前述したとおり、金型等を用いて、加熱温度が９０〜１５０℃、加熱時間が１〜６０秒の条件で発泡成形するのが好ましい。従って、このように本発明の発泡成形品を製造すれば、例えば発泡成形品（容器）内に、ラ−ド、即席ラ−メン類、カレ−ルウ、マヨネ−ズ、マ−ガリン等の浸透性の高い油性及び脂肪性の食品あるいは機械油等を直接包装あるいは収容しても、当該発泡成形品を構成する発泡性スチレン系樹脂粒子間から容器外へ油脂等が浸透するのを有効に防止することができ、発泡成形品の製品寿命を長くすることも可能となる。
【００４６】
【実施例】
次に実施例によって本発明を詳細に説明するが、本発明はこれらにより制限されるものではない。
［実施例１］
(a) 試料の作製
発泡剤として5.5重量％のペンタン（isoーペンタン／nーペンタンの重量比＝30／70）を含む直径0.35〜0.60mmの発泡性ポリスチレン粒子（日立化成工業社製ハイビーズ５ＳＧ）2000ｇをヘンシェルミキサーに入れ、攪拌しながらステアリン酸亜鉛6ｇ，シュガーエステル（第一工業製薬社製Ａ−１０Ｅ）0.4ｇ，グリセリン0.4ｇ，および、鹸化度が80モル％であって、４重量％溶液粘度が5センチポイズであるポリビニルアルコール0.2ｇを溶解した、含フッ素ビニル系共重合体の20％エマルジョンであって重合体を構成する単量体割合が、
Ｃ8F17ＳＯ2-Ｎ（ＣＨ3)−ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2 ６５重量％
ＣＨ2=Ｃ（ＣＨ3）−ＣＯＯＣ17Ｈ35 ３５重量％
である共重合体エマルジョン2.2ｇ（含フッ素ビニル系共重合体の固形分0.4ｇ）を順次加え被覆された発泡性スチレン系樹脂粒子を得た。
【００４７】
これをバッチ式一次発泡装置で熱風とスチームの混合気を熱媒として嵩密度10ｍｌ／ｇになるよう発泡させ、一次発泡樹脂粒子を得た。常温常圧下で16時間熟成したのち内容積500CC，肉厚2.0mmの成形品を得るための金型に充填し表１に示す加熱時間で加熱成形した。このとき加熱時間以外に原料充填，冷却，その他で８秒を要した。
【００４８】
(b) 性能評価
得られたカップに、1)油脂の遮蔽性の確認として、カレールウ200ｇを入れたのち、サランラップで包装し、60℃雰囲気下で浸出テスト 2)乳化剤の遮蔽性の確認として、界面活性剤水溶液（花王社製スコアロール７００：0.1重量％）を約300ｇ入れ、カップ外壁に浸透を開始する時間を測定した結果を表１に示す。
【００４９】
［比較例１］
実施例１において、含フッ素共重合体のみを除いて発泡性スチレン系樹脂粒子としたこと以外は実施例１と同様にしてカップ状成形品を得た。評価結果を表１に示す。
【００５０】
［比較例２］
実施例１において、ポリビニルアルコールのみを除いて発泡性スチレン系樹脂粒子としたこと以外は実施例１と同様にしてカップ状成形品を得た。評価結果を表１に示す。
【００５１】
［比較例３］
実施例１において、含フッ素共重合体およびポリビニルアルコールを除いて発泡性スチレン系樹脂粒子としたこと以外は実施例１と同様にしてカップ状成形品を得た。評価結果を表１に示す。
【００５２】
【表１】
【発明の効果】
本発明により、発泡成形品（カップ）を成形した場合に、浸透性の高い内容物であっても、当該内容物が発泡成形品の外壁まで浸透する時間（浸透時間）を著しく長くすることができるようになった。そして、特にカレールウのような浸透性の高い内容物に対しても優れた遮蔽性を示し、当該内容物を著しく長い間保持することができるようになった。
また、このように発泡性スチレン系樹脂粒子を構成することにより、上記の優れた遮蔽性を有しながら、当該発泡性スチレン系樹脂粒子の生産性を損なうことがない。
本発明により、浸透性の高い内容物の遮蔽性と加熱成形性とのバランスに優れた発泡性スチレン系樹脂粒子及び発泡成形品を提供することが出来るようになった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an expandable styrenic resin particle and a foam molded product suitable as a container for contents in which the obtained foam molded product contains an emulsifier component and an oil and fat component.
[0002]
[Prior art]
In general, expandable styrene resin particles can be pre-expanded with steam or the like to form pre-expanded particles, and the pre-expanded particles can be filled in a mold having small holes and heated again to be molded. The molded product thus obtained exhibits excellent properties such as economy, light weight, and hygiene, and is used in many fields as a packaging material, a heat insulating material, a container and the like.
[0003]
Here, the expandable styrenic resin particles are obtained by dispersing a foaming agent (generally a liquid or gaseous aliphatic hydrocarbon such as propane, butane, pentane, hexane, etc. at room temperature together with styrene resin particles in an aqueous medium, It is produced by a method of impregnating a foaming agent into particles or a method of impregnating a foaming agent in an aqueous suspension containing a small amount of a solvent such as toluene or cyclohexane having solubility in styrene resin particles. And the expandable styrene resin particle obtained in this way is shape | molded through the above-mentioned process.
[0004]
However, since the obtained molded product is obtained by stacking expandable styrene resin particles on a stone wall and fusing them with foaming pressure and heat, the resin particles may not be integrated. As a result, when used as a container, the contents may permeate into the outer wall of the container or the inside of the molded product depending on the type of contents stored.
In order to prevent such penetration, a method of minimizing the voids inside the molded article that becomes the path when the contents to penetrate penetrate the inside of the container, and the surface energy of the particle surface should be reduced. Thus, it is possible to generally adopt a method of increasing the contact angle of the surface of the molded product with respect to the contents to penetrate.
[0005]
In general, the former method is to strengthen the heating conditions during molding. In order to obtain a molded product with fewer defects, the molding temperature is set lower and the expandable styrene resin particles are longer. The method of heating for hours is taken.
However, this method requires a long time for molding and heating the expandable styrenic resin particles, and it is difficult to say that it is a useful method in the molding industry because the productivity is significantly reduced.
[0006]
On the other hand, as the latter method, the amount of metal soap (carboxylate) generally used for preventing agglomeration of expandable styrene resin particles in the pre-foaming is increased. ing.
However, even in this method, it is necessary to lengthen the molding heating time in order not to exhibit the property of inhibiting the fusion of the expandable styrene resin particles due to the metal soap, and it is difficult to say that this is an industrially useful method. .
[0007]
Accordingly, various foamable styrene resin particles with less permeability of the contents have been proposed with a shorter molding heating time.
For example, in Japanese Examined Patent Publication No. 56-34172, expandable styrenic resin particles whose surface is coated with sucrose ester or a derivative thereof are used. In JP-A-2-88652, a specific perfluoroalkyl group-containing copolymer is coated. The foamable thermoplastic resin particle composition used as a foamed styrenic resin particle having a coating layer containing a metal salt of ricinoleic acid in JP-A-2-115242 and in JP-A-3-190941 Expandable styrene resin particles coated with a copolymer of a specific fluorine-containing vinyl monomer and a lipophilic monomer are disclosed.
Japanese Patent Application Laid-Open No. 62-158730 discloses expandable thermoplastic resin particles coated or contained with a copolymer comprising a fluorine-containing vinyl polymer portion and a hydrophilic vinyl polymer portion. ing.
[0008]
[Problems to be solved by the invention]
However, expandable styrenic resin particles or expandable thermoplastic resin particles disclosed in JP-B-56-34172, JP-A-2-88652, JP-A-2-115242 and JP-A-3-190941. Although the composition can exhibit excellent shielding (penetration prevention) for general aqueous (including emulsifying systems) or oily contents, it is contained in the molded product when processed into a molded product. Depending on the type of contents, there was a risk that the permeation prevention performance would be insufficient.
That is, the container molded with the above-mentioned expandable styrene resin particles has a wide range of uses due to its economic efficiency, heat retention, etc., but when used for a long time as a container of some highly permeable contents, etc. There was a risk that the contents would permeate.
[0009]
Of course, the expandable styrenic resin particles disclosed in Japanese Examined Patent Publication No. 56-34172, etc. are partly oily contents having high permeability (for example, curry roux, machine oil, etc. in which an emulsifier component and an oil component are mixed). In addition, by performing heat molding for a relatively long time, excellent shielding properties (permeation preventing properties) can be exhibited. However, it cannot be denied about the decrease in productivity due to long-time heat forming.
[0010]
The expandable thermoplastic resin particles disclosed in JP-A-62-158730 use a copolymer comprising a fluorine-containing vinyl polymer portion and a hydrophilic vinyl polymer portion. There has been a problem that the compatibility of the fluorine-containing vinyl monomer and the hydrophilic vinyl monomer, which are raw materials of the copolymer, is poor and the characteristics of the copolymer are likely to vary.
[0011]
Therefore, when the foamable thermoplastic resin particles disclosed in Japanese Patent Application Laid-Open No. Sho 62-158730 are thermoformed into containers (cups) such as instant noodles, fats and oils in which emulsifier components and fat components are mixed in the distribution stock The contents such as the ingredients, curry ingredients or soup ingredients may be affected by the temperature and humidity and ooze out to the outer wall of the container (cup). In addition, when thermoformed as a returnable box for machine parts, the machine parts are used in a state where the machine parts are attached to machine oil in the returnable box. In some cases, it penetrated into the outer wall.
[0012]
That is, in the expandable styrene resin particles and the like disclosed in any of the aforementioned patent publications, there is a balance between the shielding property (penetration prevention property) for the highly permeable content and the productivity represented by the molding heating time. (Balance) was not always satisfactory.
The present invention has been made in view of the above-described problems, and even when a specific part of the highly permeable contents is used for a container or the like, the contents to be stored penetrate into the outer wall of the container or the inside of the molded product. It is an object of the present invention to provide an expandable styrene resin particle excellent in the balance of these properties that can be molded in a short time and a foam molded product using the same.
[0013]
[Means for Solving the Problems]
The present invention comprises 40 to 95% by weight of a fluorine-containing vinyl monomer represented by the following general formula (I) and 5 to 60% by weight of a vinyl monomer represented by the following general formula (II). The present invention relates to expandable styrene resin particles obtained by coating a surface of a foamable styrene resin particle body with a coating containing a fluorine-containing vinyl copolymer obtained by polymerization and a polyvinyl alcohol resin.
[0014]
[Chemical 3]
[0015]
[Formula 4]
[0016]
It is presumed that the polyvinyl alcohol resin, which is a hydrophilic polymer, plays the role of an adhesive by constituting the expandable styrene resin particles partially containing a hydrophilic polymer in this way, Even when it is used for containers with oily contents with high permeability while maintaining excellent shielding of the contents, there is a significant risk that the contents to be stored will penetrate into the outer wall of the container or the inside of the molded product. Less.
[0017]
In this invention, it is preferable that the coating of a fluorine-containing vinyl-type copolymer shall be a value within the range of 0.005-0.3 weight part with respect to 100 weight part of expandable styrene-type resin particle bodies.
[0018]
Moreover, in this invention, it is preferable that the coating of a polyvinyl alcohol-type resin shall be a value within the range of 0.001-0.1 weight part with respect to 100 weight part of expandable styrene-type resin particle bodies.
[0019]
By including the polyvinyl alcohol resin in the coating within such a range, it is possible to more efficiently prevent the penetration of the hydrophilic component and the oil component. Therefore, even when the expandable styrene resin particles are used in a container for an oily content having high permeability or an oily content in which an emulsifier component and an oil and fat component are mixed, the content to be stored is the container. There is little risk of penetration into the outer wall or inside the molded product.
In addition, with such a usage amount of the polyvinyl alcohol resin, the foamable styrene resin particles are less likely to aggregate and agglomerate during preheating, while the polyvinyl alcohol resin adheres during molding heating. It serves as an agent and can exhibit excellent fusion properties.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the present invention will be specifically described.
1. Expandable Styrenic Resin Particles The expandable styrene resin particles of the present invention are obtained by coating the surface of the expandable styrene resin particle main body with a predetermined fluorine-containing vinyl polymer.
(1) Expandable styrene resin particle body The expandable styrene resin particle body can be prepared by impregnating a styrene resin particle with a foaming agent as described above.
[0021]
(A) Styrenic resin particles The styrene resin particles are not particularly limited. For example, styrene homopolymers or components copolymerizable with styrene monomers, for example, methacrylic acid esters such as acrylonitrile, methyl methacrylate, butyl methacrylate, etc. , Acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate, and one or more copolymers with monomers of styrene derivatives such as α-methylstyrene, chlorostyrene, and vinyltoluene. be able to.
[0022]
(B) Foaming agent The foaming agent is not particularly limited, but is liquid or gaseous at room temperature, such as aliphatic hydrocarbons such as propane, butane, pentane, and hexane, or fluorocarbon compounds such as Freon 11 and Freon 12. Can be mentioned.
[0023]
(C) Impregnation of foaming agent The method for impregnating the foaming agent is not particularly limited. The impregnation amount of the foaming agent is preferably 3 to 10% by weight based on the styrene resin particle body.
[0024]
(2) Fluorinated vinyl copolymer obtained by polymerizing a fluorinated vinyl monomer represented by the following general formula (I) and a vinyl monomer represented by the following general formula (II) Things are used.
(D) Fluorine-containing vinyl monomer As the fluorine-containing vinyl monomer, a compound represented by the following general formula (I) is used.
[0025]
[Chemical formula 5]
[0026]
Specific examples of such fluorine-containing vinyl monomers include the following.
C 8 F 17 SO 2 -N ( CH 3) -CH 2 CH 2 OCOCH = CH 2
C 8 F 17 SO 2 -N ( CH 3) -CH 2 CH 2 OCOC (CH 3) = CH 2
C 8 F 17 SO 2 -N ( C 2 H 5) -CH 2 CH 2 OCOCH = CH 2
C 8 F 17 SO 2 -N ( C 2 H 5) -CH 2 CH 2 OCOC (CH 3) = CH 2
[0027]
(E) Vinyl monomer As the vinyl monomer, a compound represented by the following general formula (II) is used.
[0028]
[Chemical 6]
[0029]
Specific examples of such vinyl monomers include the following.
CH 2 = CH-COOC 11 H 23
CH 2 = C (CH 3) -COOC 15 H 31
CH 2 = CH-COOC 17 H 35
CH 2 = C (CH 3) -COOC 17 H 35
[0030]
(F) Polymerization ratio The polymerization ratio of the fluorine-containing vinyl monomer represented by the general formula (I) and the vinyl monomer represented by the general formula (II) is as follows. ˜95 wt%, vinyl monomer 5˜60 wt%. When the polymerization ratio of the fluorine-containing vinyl monomer is less than 40% by weight, it becomes difficult to give sufficient water and oil repellency when it is formed into a molded product. It will inhibit fusion.
[0031]
(G) Polymerization method Although there is no restriction | limiting in particular as a polymerization method of the fluorine-containing vinyl-type copolymer in this invention, For example, solution polymerization, emulsion polymerization, etc. can be mentioned. Examples of the polymerization initiator used for the polymerization include lauroyl peroxide, benzoyl peroxide, tert-butyl peroxyisobutyrate, and tert-butyl peroxypivalate in solution polymerization. Examples of emulsion polymerization include potassium persulfate and ammonium persulfate.
[0032]
(H) Amount of fluorine-containing vinyl copolymer used In the present invention, the fluorine-containing vinyl copolymer clothing is 0.005 to 0.3 parts by weight with respect to 100 parts by weight of the expandable styrene resin particle body. It is preferable to set it as the value within the range, More preferably, it is 0.01-0.2 weight part. If the coating of the fluorine-containing vinyl copolymer is less than 0.005 parts by weight, sufficient oil repellency tends not to be obtained, and if it exceeds 0.3 parts by weight, the properties of the foamed molded product obtained do not improve. Tend.
[0033]
(3) Polyvinyl alcohol-based resin (i) Kind of polyvinyl alcohol-based resin The saponification degree (based on JIS K 6726) of the polyvinyl alcohol-based resin used in the present invention is set to a value within the range of 70 to 99.9 mol%. Is preferred.
If the saponification degree of the polyvinyl alcohol resin is within such a range, it is a case where the penetration of oil components and the like is more effectively prevented and the saponification degree is used for a container or the like in a highly permeable oily content. However, there is less risk that the contents to be stored will penetrate into the outer wall of the container or the inside of the molded product. In addition, when the degree of saponification is in such a range, it is possible to provide expandable styrene resin particles and a foam molded product that can be molded in a short time while maintaining excellent shielding of the contents. Furthermore, if the saponification degree of the polyvinyl alcohol-based resin is a value within such a range, the adhesion with the expandable styrene-based resin particle body can be further improved.
Therefore, it is more preferable to set the saponification degree of the polyvinyl alcohol-based resin to a value within the range of 75 to 95 mol%, from the viewpoint of being more excellent in balance between the shielding properties of the contents and the efficiency of productivity. More preferably, the value is within the range of%.
[0034]
Further, when coating the expandable styrene resin particles, the degree of polymerization of the polyvinyl alcohol resin used (based on JIS K 6726) is preferably set to a value in the range of 300 to 60000.
This is because if the degree of polymerization of the polyvinyl alcohol-based resin is a value within such a range, the adhesion with the expandable styrene-based resin particle body is further improved. Therefore, even when it is used for a container or the like of oily contents having a high permeability and a relatively high temperature, the contained contents are less likely to penetrate into the outer wall of the container or the inside of the molded product. Furthermore, if the polymerization degree of the polyvinyl alcohol-based resin is a value within such a range, it is less likely to inhibit the fusion of the expandable styrene-based resin particles during molding and heating.
Therefore, it is more preferable to set the polymerization degree of the polyvinyl alcohol-based resin to a value within the range of 400 to 1000 from the viewpoint that the balance between the shielding properties of the contents and the efficiency of productivity is more excellent. It is more preferable to set the value within the range.
[0035]
In covering the expandable styrene resin particles, the polyvinyl alcohol resin is preferably at least one resin selected from the group consisting of polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral.
Such a polyvinyl alcohol-based resin has a certain amount of hydroxyl group or vinyl group, and even when it is used for a container or the like in a highly permeable oily content, the content to be stored is the outer wall of the container or molded It is possible to provide expandable styrenic resin particles and a foam-molded product that hardly penetrate into the product and can be molded in a short time.
[0036]
Moreover, it is preferable that the fluorine-containing vinyl copolymer to be used for coating the expandable styrene resin particles is an aqueous emulsion (sometimes referred to as an aqueous emulsion).
Moreover, when comprising expandable styrene-type resin particles, it is preferable that the polyvinyl alcohol-type resin to be used is aqueous solution.
Each of the fluorine-containing vinyl copolymers constituting the coating is oily and generally poor in compatibility with hydrophilic polyvinyl alcohol resins. Therefore, even if they are mixed as they are, they may be separated after a lapse of time. However, if the fluorine-containing vinyl copolymer and / or polyvinyl alcohol resin to be used is either an aqueous emulsion or an aqueous solution, the problem of such mixing / separation does not occur. A copolymer and a polyvinyl alcohol-type resin can be mixed uniformly.
[0037]
As the polyvinyl alcohol that can be used in the present invention, commercially available ones can be used as they are, but from the viewpoint of workability, it is preferable that the viscosity of a 4% by weight aqueous solution has a value in the range of 1 to 100 centipoise (cp). A value within the range of 10 to 80 centipoise (cp) is more preferable.
In addition, from the viewpoint of better fusion between the expandable styrene resin particles at the time of heat molding, the glass transition point of the polyvinyl alcohol resin is preferably set to a value within the range of 30 to 100 ° C. A value in the range of ˜80 ° C. is more preferable. .
[0038]
In order to adjust the glass transition point of the polyvinyl alcohol resin, improve the flexibility, or improve the mixing property with the fluorine-containing vinyl monomer, glycerol, ethylene glycol are used as additives. One or two or more of DBP (dibutyl phthalate), DOP (dioctyl phthalate), alginic acid amide, acrylamide, starch, CMC, methylcellulose, glyoxazole, dimethylol urea and the like can be added.
Furthermore, it is also preferable to add a crosslinking agent such as isocyanate in order to improve the heat resistance of the polyvinyl alcohol-based resin or improve the adhesion to the foamable styrene-based resin particle body.
[0039]
(J) Usage method of polyvinyl alcohol resin Polyvinyl alcohol resin can be coated on the expandable styrene resin particle main body after mixing with fluorine-containing vinyl monomer, and fluorine-containing resin can also be used. Apart from the vinyl monomer, it is also preferable to coat the foamable styrene resin particle main body alone. It is preferable in that it can be coated on the expandable styrenic resin particle main body by a single operation by coating after mixing with the fluorine-containing vinyl monomer. On the other hand, the expandable styrene resin particle alone By subjecting the main body to a coating treatment, it is preferable in that the possibility of uneven density due to separation from the fluorine-containing vinyl monomer is reduced.
[0040]
(K) Amount of Polyvinyl Alcohol The amount of polyvinyl alcohol used in the present invention is preferably 0.001 to 0.1 parts by weight, more preferably 0.005 to 100 parts by weight of the expandable styrene resin particle body. 0.05 parts by weight. When the amount of polyvinyl alcohol used is less than 0.001 part by weight, the foaming molding tends to be insufficient in the shielding ability of the emulsifier component and the oil and fat component when formed into a molded product. Product characteristics tend not to improve.
[0041]
(4) Other coating agents In the coating of the foamable styrene resin particle main body, conventionally known coating agents can be used in addition to the above-mentioned copolymer. Examples thereof include metal soaps such as zinc stearate and calcium stearate used for preventing agglomeration in primary foaming, and higher fatty acid amides such as ethylenebisamide and stearamide. These agglomeration inhibitors are preferably used in the range of 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the expandable styrene resin particle body. Of these, zinc stearate is particularly preferred from the viewpoint of agglomeration prevention and is inexpensive and economical.
[0042]
In the molding step, an additive having an effect of promoting fusion of the expandable styrene resin particle main body can be used. A conventionally well-known thing can be used as this substance. For example, one or more of higher fatty acid triesters, diesters, monoesters, sucrose esters such as stearic acid glyceride and oleic acid glyceride can be used.
[0043]
Further, nonionic interfaces such as polyhydric alcohols such as glycerin, sorbitol, polyethylene glycol and polypropylene glycol, sorbitan esters, and ethylene glycol adducts of higher fatty acids used as antistatic agents for the primary foamable styrene resin particles. One or more active agents may be used in combination. These antistatic agents are preferably used in the range of 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the expandable styrene resin particle body.
[0044]
(5) Formation of coating The method for forming a coating of a fluorinated vinyl copolymer and a polyvinyl alcohol resin on the surface of the expandable styrene resin particle main body in the present invention is not particularly limited and is carried out by a conventionally known means. be able to.
For example, using a blender such as a ribbon blender, V-shaped blender, Henschel mixer, Redige mixer, etc., at room temperature, at a rotational speed of 100 to 10,000 rpm, and at a stirring time of 10 seconds to 1 hour, a foaming styrene type The coating can be formed by mixing the resin particle main body, the fluorine-containing vinyl-based copolymer, the polyvinyl alcohol-based resin, each component of the above-described coating agent, and the like.
However, the foamable styrene resin particle main body, the fluorine-containing vinyl copolymer, the polyvinyl alcohol resin, the respective components of the above-mentioned coating agent, and the like can be individually coated in layers.
[0045]
2. Foam Molded Article The foam molded article of the present invention can be obtained by molding the aforementioned expandable styrene resin particles. That is, by using the above-mentioned expandable styrene resin particles, it is possible to obtain a foam-molded article having excellent oil repellency in which the foam particles are firmly fused and the particle interface is excellent with a short molding heating time. Can do.
Here, specific molding heating conditions are not particularly limited, but as described above, foam molding is performed using a mold or the like under the conditions of a heating temperature of 90 to 150 ° C. and a heating time of 1 to 60 seconds. It is preferable to do this. Accordingly, when the foamed molded product of the present invention is produced in this way, for example, the penetration of lard, instant ramen, kareulu, mayonnaise, margarine, etc. into the foamed molded product (container). Even if highly oily and fatty foods or machine oils are directly packaged or contained, it is possible to effectively prevent oils and fats from penetrating from between the expandable styrene resin particles constituting the foamed molded product to the outside of the container. It is also possible to extend the product life of the foam molded product.
[0046]
【Example】
EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these.
[Example 1]
(a) Preparation of sample Expandable polystyrene particles having a diameter of 0.35 to 0.60 mm containing 5.5% by weight of pentane (iso-pentane / n-pentane weight ratio = 30/70) as a foaming agent (High Beads 5SG manufactured by Hitachi Chemical Co., Ltd.) 2000 g In a Henschel mixer, while stirring, 6 g of zinc stearate, 0.4 g of sugar ester (A-10E manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.4 g of glycerin, and a saponification degree of 80 mol%, a 4 wt% solution A 20% emulsion of a fluorine-containing vinyl copolymer in which 0.2 g of polyvinyl alcohol having a viscosity of 5 centipoise is dissolved, and the ratio of monomers constituting the polymer is
C 8 F 17 SO 2 —N (CH 3 ) —CH 2 CH 2 OCOCH═CH 2 65 wt%
CH 2 = C (CH 3) -COOC 17 H 35 35 wt%
Copolymer emulsion 2.2 g (solid content of fluorine-containing vinyl copolymer 0.4 g) was sequentially added to obtain expandable styrene resin particles coated.
[0047]
This was foamed with a batch type primary foaming apparatus using a mixture of hot air and steam as a heat medium to a bulk density of 10 ml / g to obtain primary foamed resin particles. After aging at room temperature and normal pressure for 16 hours, it was filled in a mold for obtaining a molded product having an inner volume of 500 CC and a wall thickness of 2.0 mm, followed by heat molding as shown in Table 1. At this time, in addition to the heating time, 8 seconds were required for filling the raw material, cooling, etc.
[0048]
(b) Performance evaluation In the obtained cup, 1) As a confirmation of the oil shielding property, 200 g of Carreau was added and then wrapped with Saran wrap and leached in an atmosphere of 60 ° C. 2) As a confirmation of the emulsifier shielding property, Table 1 shows the results of measuring about 300 g of an aqueous surfactant solution (score roll 700: 0.1% by weight manufactured by Kao Co., Ltd.) and measuring the time for infiltration into the outer wall of the cup.
[0049]
[Comparative Example 1]
A cup-shaped molded product was obtained in the same manner as in Example 1 except that only the fluorinated copolymer was used to obtain expandable styrene resin particles. The evaluation results are shown in Table 1.
[0050]
[Comparative Example 2]
In Example 1, a cup-shaped molded article was obtained in the same manner as in Example 1 except that only the polyvinyl alcohol was used to obtain expandable styrene resin particles. The evaluation results are shown in Table 1.
[0051]
[Comparative Example 3]
In Example 1, a cup-shaped molded article was obtained in the same manner as in Example 1 except that the fluorinated copolymer and polyvinyl alcohol were excluded to obtain expandable styrene resin particles. The evaluation results are shown in Table 1.
[0052]
[Table 1]
【The invention's effect】
According to the present invention, when a foam molded product (cup) is molded, even if the content is highly permeable, the time (permeation time) for the content to permeate to the outer wall of the foam molded product can be significantly increased. I can do it now. And the shielding property which was excellent also with respect to the content with especially high permeability | transmittance, such as Kalerou, was able to be hold | maintained for the said remarkably long time.
In addition, by configuring the expandable styrene resin particles in this way, the productivity of the expandable styrene resin particles is not impaired while having the above-described excellent shielding properties.
According to the present invention, it is possible to provide expandable styrene-based resin particles and a foam-molded product excellent in the balance between the shielding property of the highly penetrating contents and the heat moldability.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06641798A JP3962936B2 (en) | 1998-03-17 | 1998-03-17 | Expandable styrenic resin particles and foam molded products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06641798A JP3962936B2 (en) | 1998-03-17 | 1998-03-17 | Expandable styrenic resin particles and foam molded products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11263868A JPH11263868A (en) | 1999-09-28 |
| JP3962936B2 true JP3962936B2 (en) | 2007-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06641798A Expired - Fee Related JP3962936B2 (en) | 1998-03-17 | 1998-03-17 | Expandable styrenic resin particles and foam molded products |
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| JP4576267B2 (en) * | 2005-03-23 | 2010-11-04 | 積水化成品工業株式会社 | Surface-modified expandable polystyrene resin particles and method for producing the same, polystyrene resin expanded particles for manufacturing expanded molded articles, and polystyrene resin expanded molded articles |
| ITRM20130410A1 (en) * | 2013-07-12 | 2015-01-13 | Maio Ernesto Di | METHOD FOR THE PREPARATION OF MICROMETRIC OR NANOMETRIC CAVE PARTICLES |
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| JPH11263868A (en) | 1999-09-28 |
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