JPH04180941A - Foamable thermoplastic resin particle and molded foam - Google Patents
Foamable thermoplastic resin particle and molded foamInfo
- Publication number
- JPH04180941A JPH04180941A JP31003990A JP31003990A JPH04180941A JP H04180941 A JPH04180941 A JP H04180941A JP 31003990 A JP31003990 A JP 31003990A JP 31003990 A JP31003990 A JP 31003990A JP H04180941 A JPH04180941 A JP H04180941A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- acid
- resin particles
- particles
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 77
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 35
- 239000013518 molded foam Substances 0.000 title abstract 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 8
- 238000010097 foam moulding Methods 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 abstract description 14
- 230000004927 fusion Effects 0.000 abstract description 11
- 239000001736 Calcium glycerylphosphate Substances 0.000 abstract description 10
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 abstract description 10
- 229940095618 calcium glycerophosphate Drugs 0.000 abstract description 10
- 235000019299 calcium glycerylphosphate Nutrition 0.000 abstract description 10
- -1 phlopylene gellicol Chemical compound 0.000 description 41
- 238000000465 moulding Methods 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000005187 foaming Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920006248 expandable polystyrene Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- 239000004604 Blowing Agent Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000004904 shortening Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical class CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical class CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229960002901 sodium glycerophosphate Drugs 0.000 description 2
- REULQIKBNNDNDX-UHFFFAOYSA-M sodium;2,3-dihydroxypropyl hydrogen phosphate Chemical compound [Na+].OCC(O)COP(O)([O-])=O REULQIKBNNDNDX-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- APAUNQLFVGBQQW-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1(C)C APAUNQLFVGBQQW-UHFFFAOYSA-N 0.000 description 1
- LBHPSYROQDMVBS-UHFFFAOYSA-N (1-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1 LBHPSYROQDMVBS-UHFFFAOYSA-N 0.000 description 1
- CJCGDEYGAIPAEN-UHFFFAOYSA-N (1-methylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C)CCCCC1 CJCGDEYGAIPAEN-UHFFFAOYSA-N 0.000 description 1
- URWUDHFIOMIXCX-UHFFFAOYSA-N (2,2-dimethyl-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2C(C)(C)C1(OC(=O)C(=C)C)C3 URWUDHFIOMIXCX-UHFFFAOYSA-N 0.000 description 1
- OEZWIIUNRMEKGW-UHFFFAOYSA-N (2-bromophenyl) 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1=CC=CC=C1Br OEZWIIUNRMEKGW-UHFFFAOYSA-N 0.000 description 1
- VNYTWDAWZSFABS-UHFFFAOYSA-N (2-bromophenyl) prop-2-enoate Chemical compound BrC1=CC=CC=C1OC(=O)C=C VNYTWDAWZSFABS-UHFFFAOYSA-N 0.000 description 1
- YKZMWXJHPKWFLS-UHFFFAOYSA-N (2-chlorophenyl) 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1=CC=CC=C1Cl YKZMWXJHPKWFLS-UHFFFAOYSA-N 0.000 description 1
- GOUZWCLULXUQSR-UHFFFAOYSA-N (2-chlorophenyl) prop-2-enoate Chemical compound ClC1=CC=CC=C1OC(=O)C=C GOUZWCLULXUQSR-UHFFFAOYSA-N 0.000 description 1
- KBHSYCDRICCRMQ-UHFFFAOYSA-N (2-fluorophenyl) 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1=CC=CC=C1F KBHSYCDRICCRMQ-UHFFFAOYSA-N 0.000 description 1
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- PNNHLULHRSZWPG-UHFFFAOYSA-J 1,5-dihydroxypentan-3-yl phosphate;2,3-dihydroxypropyl phosphate;manganese(2+) Chemical compound [Mn+2].[Mn+2].OCC(O)COP([O-])([O-])=O.OCCC(CCO)OP([O-])([O-])=O PNNHLULHRSZWPG-UHFFFAOYSA-J 0.000 description 1
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- CCHRVFZBKRIKIX-UHFFFAOYSA-N 1-nitro-3-(3-nitrophenyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C=2C=C(C=CC=2)[N+]([O-])=O)=C1 CCHRVFZBKRIKIX-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YQDJMFFVPVZWNK-UHFFFAOYSA-N 2,3-dihexadecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCCCOCC(CO)OCCCCCCCCCCCCCCCC YQDJMFFVPVZWNK-UHFFFAOYSA-N 0.000 description 1
- UVGWFJJQDYURET-UHFFFAOYSA-L 2,3-dihydroxypropyl phosphate;nickel(2+) Chemical compound [Ni+2].OCC(O)COP([O-])([O-])=O UVGWFJJQDYURET-UHFFFAOYSA-L 0.000 description 1
- QEHCYTDFERPPPU-UHFFFAOYSA-N 2,3-dioctadecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCOCC(CO)OCCCCCCCCCCCCCCCCCC QEHCYTDFERPPPU-UHFFFAOYSA-N 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
- XDJFUWIQZPRDDG-UHFFFAOYSA-J prop-2-enoate;tin(4+) Chemical compound [Sn+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C XDJFUWIQZPRDDG-UHFFFAOYSA-J 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XLMCDAMBOROREP-UHFFFAOYSA-N zinc;3-phosphonooxypropane-1,2-diolate Chemical compound [Zn+2].OP(O)(=O)OCC([O-])C[O-] XLMCDAMBOROREP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な発泡性熱可塑性樹脂粒子及び発泡成形品
に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to novel expandable thermoplastic resin particles and foam molded articles.
（従来の技術）
ビニル系樹脂等の熱可塑性樹脂発泡体の製造に広く用い
られている方法は、まず発泡性熱可塑性樹脂粒子を予備
発泡装置で攪拌しながらスチームで加熱し、所望の嵩密
Ｉｆまで発泡膨張（１次発泡）させ９次いで膨張によっ
て発現し九発泡粒子内の減圧状態を常圧あるいは常圧付
近まで回復させることを目的とした熟成工種を１１まえ
、最後に小孔１間隙を有する金型中に充填したのち、ス
チームによって加熱（２次発泡）シ、金型を冷却して成
形体内部の発泡圧を減少させ２発泡成形体を取り出すと
いうものである。近年、生産性の向上や材料費の低減を
目的として、成形時間の短縮化や低密度化が指向されて
いる。(Prior art) A widely used method for manufacturing thermoplastic resin foams such as vinyl resins is to first heat expandable thermoplastic resin particles with steam while stirring them in a pre-foaming device to achieve the desired bulk density. After foaming and expanding (primary foaming) up to If, 11 stages of aging are carried out with the aim of restoring the reduced pressure inside the foamed particles to normal pressure or around normal pressure. After filling the foam into a mold having a foam, the foam is heated (secondary foaming) with steam, the mold is cooled to reduce the foaming pressure inside the molded product, and the two-foamed molded product is taken out. In recent years, efforts have been made to shorten molding time and lower density in order to improve productivity and reduce material costs.
成形時間を短縮する方法として９例えば１％公昭５３−
９７０６０号公報や特公昭５８−５６５６８号公報には
９発泡性スチレン系樹脂粒子の表面に融点５０〜１１０
℃のベヘニン酸、ステアリン酸、パルミチン酸、ミリス
チン酸およびラウリン酸からなる群から選ばれた少なく
とも一種の脂肪族カルボン酸とグリセリン、エチレング
リコール、フロピレンゲリコール、ステアリルアルコー
ルおよびセチルアルコールからなる群から選ばれた少な
くとも一種の脂肪族アルコールとのエステルと微粉滑剤
との混合物を被覆する方法が記載されている。発泡性ビ
ニル系樹脂粒子の表面に微粉状の飽和脂肪酸のトリグリ
セライドなどを被覆する方法は、成形時間の短縮にとっ
て非常に有効な手段である。しかし、予備発泡の際、ブ
ロッキングが起き易いという弊害もある。ブロッキング
は、予備発泡された粒子の熟成や風乾を行うための熟成
槽への移送や成形装置への移送などを妨害する原因とな
る。このような理由から予備発泡し九際にブロッキング
しない発泡性ビニル系樹脂粒子が求められる。このため
、特公昭５３−９７０６０号公報や特公昭５８−５６５
６８号公報など！ＩＣ＃′ｉ金属石ケンや脂肪酸アミド
などの併用が例示される。As a method of shortening molding time, for example, 1% Kosho 53-
No. 97060 and Japanese Patent Publication No. 58-56568 disclose that the surface of expandable styrene resin particles has a melting point of 50 to 110.
at least one aliphatic carboxylic acid selected from the group consisting of behenic acid, stearic acid, palmitic acid, myristic acid and lauric acid and the group consisting of glycerin, ethylene glycol, phlopylene gellicol, stearyl alcohol and cetyl alcohol. A method of coating a mixture of an ester with at least one selected aliphatic alcohol and a finely divided lubricant is described. A method of coating the surface of expandable vinyl resin particles with finely divided saturated fatty acid triglyceride is a very effective means for shortening molding time. However, it also has the disadvantage that blocking tends to occur during pre-foaming. Blocking becomes a cause of interfering with the transportation of pre-foamed particles to a maturing tank for ripening and air drying, or to a molding device. For these reasons, there is a need for expandable vinyl resin particles that are pre-foamed and do not block at the last stage. For this reason, Japanese Patent Publication No. 53-97060 and Special Publication No. 58-565
Publication No. 68 and more! Examples include the combined use of IC#'i metal soap and fatty acid amide.
しかし、この方法では予備発泡時のブロッキングの発生
は充分に抑制できない。特に、脂肪族カルボン酸とグリ
セリンなどの脂肪族アルコールとのエステル類と併用す
る場合、その欠点は顕著となる。However, this method cannot sufficiently suppress the occurrence of blocking during pre-foaming. In particular, when used in combination with esters of aliphatic carboxylic acids and aliphatic alcohols such as glycerin, the disadvantage becomes remarkable.
（発明が解決しようとする課題）
本発明は、これらの欠点を解決するものであ見ブロッキ
ングの生成がなく、シかも成形品の融着。(Problems to be Solved by the Invention) The present invention solves these drawbacks, and eliminates the formation of visual blocking and prevents the fusion of molded products.
外観共に優れる発泡性熱可塑性樹脂粒子及び発泡成形品
を提供するものである。The present invention provides expandable thermoplastic resin particles and foam molded products that have excellent appearance.
（課題を解決するための手段）
すなわち本発明は、グリセロリン酸の金属塩が被覆され
ていることを特徴とする発泡性熱可塑性樹脂粒子及びこ
れを発泡成形して得られる発泡成形品に関する。(Means for Solving the Problems) That is, the present invention relates to expandable thermoplastic resin particles characterized by being coated with a metal salt of glycerophosphoric acid, and a foam molded article obtained by foam molding the particles.
本発明において使用されるグリセロリン酸の金属塩とし
ては、グリセロリン酸ナトリウム、グリセロリン酸カリ
ウム、グリセロリン酸マグネシウム、グリセロリン酸カ
ルシウム、グリセロリン酸マンガン、グリセロリン酸鉄
、グリ七ロリン酸フパルト、グリセロリン酸ニッケル、
グリセロリン酸鋼、グリセロリン酸銀、グリセロリン酸
亜鉛などが挙げられる。これらの中でも、グリセロリン
酸ナトリウム及びグリセロリン酸カルシウムが特にブロ
ッキング防止の効果が高く好ましい。The metal salts of glycerophosphate used in the present invention include sodium glycerophosphate, potassium glycerophosphate, magnesium glycerophosphate, calcium glycerophosphate, manganese glycerophosphate, iron glycerophosphate, fuparto glycerophosphate, nickel glycerophosphate,
Examples include glycerophosphate steel, silver glycerophosphate, and zinc glycerophosphate. Among these, sodium glycerophosphate and calcium glycerophosphate are particularly preferred since they have a particularly high blocking prevention effect.
グリセロリン酸の金属塩の樹脂粒子表面の被覆量は、未
被覆の熱可塑性樹脂粒子に対して０．０５重量Ｘ〜α５
重量Ｘが好ましく、％ｌＣ０，１〜０，３重量％が好ま
しい。ここで被覆量が０．０５５重量％満では、ブロッ
キング防止効果が充分でない。The coating amount of the metal salt of glycerophosphoric acid on the resin particle surface is 0.05 weight X to α5 with respect to the uncoated thermoplastic resin particle.
Weight X is preferred, and %lC0.1 to 0.3% by weight is preferred. If the coating amount is less than 0.055% by weight, the anti-blocking effect is not sufficient.
一方、α５重量％を超えるとブロッキング防止の面から
のみ評価すれば満足する結果が得られるが。On the other hand, if α exceeds 5% by weight, satisfactory results can be obtained if evaluated only from the viewpoint of preventing blocking.
発泡成形品の融着度が低下すると共に過剰のグリセ〇
１７７酸の金属塩が予備発泡機や成形機のスチーム孔を
閉塞したり、予備発泡された粒子の熟成時、風乾を行う
ための熟成槽への移送時、成形機への時などに大気中に
拡散し９作業環境の悪化や機械類の故障を引き起こすな
どの弊害が誘発する。The degree of fusion of foamed molded products decreases and excessive grease
Metal salts of 177 acid may clog the steam holes of pre-foaming machines and molding machines, or may be released into the atmosphere during ripening of pre-foamed particles, when transferred to a maturing tank for air drying, and when transferred to a molding machine. This can lead to harmful effects such as deterioration of the working environment and breakdown of machinery.
これらのグリセロリン酸の金属塩を樹脂粒子表面に被覆
するには１例えばこれらを粉末のまま加え、ヘンシェル
ミキサー、スーパーミキサー等の容器固定式高速流動型
混合機、ダブルコーン型ミキサー、ナツタ−型ミキサー
、■−ブレンダー。To coat the surface of resin particles with these metal salts of glycerophosphoric acid, 1. For example, add them in powder form and use a fixed-container high-speed fluid mixer such as a Henschel mixer or a super mixer, a double cone mixer, or a Natsuta mixer. , ■ - Blender.
ローラー等を用いて混合し、処理する。また、少量の発
泡性熱可塑性樹脂粒子を被覆処理する場合。Mix and process using a roller or the like. Also, when coating a small amount of expandable thermoplastic resin particles.
ビニール袋など身近にある袋、容器などに樹脂粒子とグ
リセロリン酸の金属塩粉末とを加えて混合処理すること
本できる。It is possible to mix resin particles and glycerophosphoric acid metal salt powder by adding them to a commonly available bag or container such as a plastic bag.
被覆する際に用いるグリセｃｘ ＩＪン醗の金属塩の量
（添加量）は、所望の被覆量よシも多く用いられるのが
好ましい。これは被覆に使用する装置の容器内にも該金
属塩が付着し、被覆量は添加量よシ約２０〜４０重量Ｘ
少なくなる為である。従って、これらの減少分を踏まえ
て、添加量が決定される。It is preferable that the amount (addition amount) of the metal salt used in coating is greater than the desired coating amount. This is because the metal salt also adheres to the inside of the container of the equipment used for coating, and the amount of coating is approximately 20 to 40 times the weight of the added amount.
This is because it becomes less. Therefore, the addition amount is determined based on these decreases.
得られる被覆された発泡性熱可塑性樹脂粒子の実際のグ
リセロリン酸の被覆量は、原子吸光分析や高速液体クロ
マトグラフィー等の公知の方法により定量することがで
きる。The actual amount of glycerophosphoric acid coated on the obtained coated expandable thermoplastic resin particles can be determined by a known method such as atomic absorption spectrometry or high performance liquid chromatography.
発泡性熱可塑性樹脂粒子にグリセロリン酸の金属塩を被
覆する場合、必要に応じて冷却時間の短縮剤、融着改良
剤、帯電防止剤、汎用のブロッキング防止剤等を同時に
併用できる。When coating the expandable thermoplastic resin particles with a metal salt of glycerophosphoric acid, a cooling time shortening agent, a fusion improver, an antistatic agent, a general-purpose antiblocking agent, etc. can be used in combination, if necessary.
冷却時間の短縮剤としては、ベヘニン酸、ステアリン酸
、パルミチン酸、ラウリン酸、ミリスチン酸、オレイン
散、リノール酸、リルン酸、オクチル駿、ノニル駿、カ
プリン酸、１２−とドロキシステアリン識、バルミトン
駿、大豆硬化油。Cooling time shortening agents include behenic acid, stearic acid, palmitic acid, lauric acid, myristic acid, olein powder, linoleic acid, lylinic acid, octyl-shun, nonyl-shun, capric acid, 12- and droxystearin, and balmitone. Shun, hydrogenated soybean oil.
エルカ酸、リケステリル酸、リシノステアロール酸、ウ
ンデカン酸、テトラコサン酸等からなる群から選ばれた
少なくとも一種の脂肪族カルボン酸とグリセリン、エチ
レングリコール、プロピレングリコール、ステアリルア
ルコールおよびセチルアルコール等からなる群から選ば
れた少なくと４一種の脂肪族アルコールとのエステル、
パラフィンロウ、流動パラフィン、やし油、オリーブ油
。At least one aliphatic carboxylic acid selected from the group consisting of erucic acid, liquesteric acid, ricinostearic acid, undecanoic acid, tetracosanoic acid, etc., and a group consisting of glycerin, ethylene glycol, propylene glycol, stearyl alcohol, cetyl alcohol, etc. esters with at least four aliphatic alcohols selected from
Paraffin wax, liquid paraffin, coconut oil, olive oil.
パーム油などの食用油、フタル駿ジステアリルアミド、
フタル酸ジラウリルアミドなどのフタル酸アミド化合物
、グリセリンジステアリルエーテルグリセリンジヘキサ
デシルエーテルナトのグリセリンジアルキルエーテルな
どが挙げられる。Edible oils such as palm oil, phthalate distearylamide,
Examples include phthalic acid amide compounds such as phthalic acid dilaurylamide, glycerin dialkyl ethers such as glycerin distearyl ether and glycerin dihexadecyl ether.
融着改良剤としては、ジペンタエリスリトール高級脂肪
酸エステル、ンルビタン高級脂肪醗エステル、オレイン
酸アミド、ステアリン陵アミドなどの脂肪酸アミド、ス
テアリルアミン、硬化牛脂アミンなどの脂肪族アミン、
エチレンビスステアリルアミド、エチレンビスステアリ
ルアミドなどの高級脂肪酸ビスアミドなどが挙げられる
。As the adhesion improver, fatty acid amides such as dipentaerythritol higher fatty acid ester, nrubitan higher fatty acid ester, oleic acid amide, and stearinamide, aliphatic amines such as stearylamine and hardened beef tallow amine,
Examples include higher fatty acid bisamides such as ethylene bis stearylamide and ethylene bis stearyl amide.
帯電防止剤としては、エチレングリコール、テトラエチ
レンクリコールジメチルエーテル、フロピレンゲリコー
ル、グリセリン、ポリエチレングリコール、ポリプロピ
レングリコール、あるいはカチオン系、アニオン系、ノ
ニオン系９両性系の界面活性剤が挙げられる。Examples of the antistatic agent include ethylene glycol, tetraethylene glycol dimethyl ether, propylene gelicol, glycerin, polyethylene glycol, polypropylene glycol, and cationic, anionic, nonionic, and amphoteric surfactants.
ブロッキング防止剤としては、ステアリン酸亜鉛、ステ
アリン酸カルシウム、ステアリン識アルミニウム、ステ
アリン酸カドミウム等の金属石ケン、ロジン、ロジンの
カルシウム塩、炭酸カルシウム、タルク、カオリン、硫
酸バリウム等の無機物粉末等が挙げられる。Examples of anti-blocking agents include metal soaps such as zinc stearate, calcium stearate, aluminum stearate, and cadmium stearate, rosin, calcium salts of rosin, and inorganic powders such as calcium carbonate, talc, kaolin, and barium sulfate. .
本発明において、グリセロリン酸の金属塩を被覆される
発泡性熱可塑性樹脂粒子の樹脂成分そのものとしてはビ
ニル系単量体の単独重合体、２種類以上のビニル系単量
体からなる共重合体、または、これらビニル系重合体を
ブレンドしてなるビニル系樹脂が好ましく用いられる。In the present invention, the resin component itself of the expandable thermoplastic resin particles coated with the metal salt of glycerophosphoric acid is a homopolymer of vinyl monomers, a copolymer consisting of two or more types of vinyl monomers, Alternatively, a vinyl resin obtained by blending these vinyl polymers is preferably used.
具体的には。in particular.
ビニル芳香族炭化水素化合物、不飽和脂肪酸エステル、
シアンビニル化合物、不飽和２塩基酸、不飽和脂肪酸等
の単独重合体、これらの共重合体。Vinyl aromatic hydrocarbon compounds, unsaturated fatty acid esters,
Homopolymers of cyanvinyl compounds, unsaturated dibasic acids, unsaturated fatty acids, etc., and copolymers thereof.
これらの重合体をブレンドしてなる樹脂、エチレン単独
重合体、エチレン−酢酸ビニルの如きエチレン共重合体
、プロピレン単独重合体等が挙げられる。Examples include resins obtained by blending these polymers, ethylene homopolymers, ethylene copolymers such as ethylene-vinyl acetate, propylene homopolymers, and the like.
これらの中でも特に本発明においてはスチレン１などの
ビニル芳香族炭化水素化合物の単独、これらの２種類以
上の単量体との共重合体、ビニル芳香族炭化水素化合物
と共重合可能なその他の単量体を共重合し念共重合体、
これら重合体のブレンド物等のスチレン系樹脂が好まし
い。Among these, the present invention particularly uses vinyl aromatic hydrocarbon compounds such as styrene 1 alone, copolymers with two or more of these monomers, and other monomers copolymerizable with vinyl aromatic hydrocarbon compounds. copolymerized by copolymerizing polymers,
Styrenic resins such as blends of these polymers are preferred.
ビニル芳香族炭化水素化合物としては、スチレン、α−
メチルスチレン、０−メチルスチレン。Examples of vinyl aromatic hydrocarbon compounds include styrene, α-
Methylstyrene, 0-methylstyrene.
ｍ −メチルスチレン、ｐ−メチルスチレン、ｐ−シク
ロへキシルスチレンｅ ｐ−１−ブチルスチレン、ジメ
チルスチレン、α−ビニルナフタレン。m-methylstyrene, p-methylstyrene, p-cyclohexylstyrene e p-1-butylstyrene, dimethylstyrene, α-vinylnaphthalene.
β−ビニルナフタレン、α−インプロペニルナフタレン
、β−イソプロペニルナフタレン、メトオキシスチレン
、ヒドロオキシスチレン、カルボメトキシスチレン、ア
セトキシスチレン、シアノスチレ７等が挙げられる。Examples include β-vinylnaphthalene, α-impropenylnaphthalene, β-isopropenylnaphthalene, methoxystyrene, hydroxystyrene, carbomethoxystyrene, acetoxystyrene, and cyanostyrene 7.
この中では特にスチレンが好ましい。Among these, styrene is particularly preferred.
不飽和脂肪酸エステルとしては、アクリル酸メチル、ア
クリル酸エチル、アクリル酸メチル、アクリル酸２−エ
チルヘキシル等のアクリル酸アルキルエステル、アクリ
ル醗シクロヘキシル、アクリル酸メチルシクロヘキシル
、アクリル酸ボルニル、アクリル酸インボルニル、アク
リル酸アダマフ５−ル等のアクリル酸シクロアルキルエ
ステル７１１Ｊ ル酸フェニル、アクリル酸ベンジル、
アクリル駿ナフチル等のアクリル酸芳香族エステル。Examples of unsaturated fatty acid esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, methyl acrylate, and 2-ethylhexyl acrylate, acrylic cyclohexyl, methylcyclohexyl acrylate, bornyl acrylate, inbornyl acrylate, and acrylic acid. 711J Acrylic acid cycloalkyl esters such as Adamaf 5-ru, phenyl fluorate, benzyl acrylate,
Aromatic acrylic esters such as acrylic naphthyl.
アクリル酸フルオロフェニル、アクリル酸クロロフェニ
ル、アクリル酸ブロモフェニル、アクリル酸フルオロベ
ンジル、アクリル酸クロロベンジル。Fluorophenyl acrylate, chlorophenyl acrylate, bromophenyl acrylate, fluorobenzyl acrylate, chlorobenzyl acrylate.
アクリル酸ブロモベンジル等のアクリル酸置換芳香族エ
ステル、アクリル酸フルオロエチル、アクリル酸フルオ
ロエチル、アクリル酸クロロエチル。Acrylic acid substituted aromatic esters such as bromobenzyl acrylate, fluoroethyl acrylate, fluoroethyl acrylate, chloroethyl acrylate.
アクリル酸ブロモエチル等のアクリル醗ノーロゲン化ア
ルキルエステル、アクリル醗ヒドロキシアルキルエステ
ル、アクリル酸グリシジル、アクリル酸エチレングリコ
ールエステル、アクリル酸ポリエチレングリコールエス
テル、アクリル酸アルキルアミノアルキルエステル、ア
クリル酸シアノアルキルエステル等のアクリル酸エステ
ル、α−フルオロアクリル酸エステル、α−クロロアク
リル酸エステル、ａ−シアノアクリル酸エステル等のα
−置換アクリル酸エステル、メタクリル酸エチル、メタ
クリル酸エチル、メタクリル酸ブチル。Acrylic acids such as acrylic acid norogenated alkyl esters such as bromoethyl acrylate, acrylic hydroxyalkyl esters, glycidyl acrylates, ethylene glycol acrylate esters, polyethylene glycol acrylates, alkylaminoalkyl acrylates, and cyanoalkyl acrylates. α such as ester, α-fluoroacrylate, α-chloroacrylate, a-cyanoacrylate, etc.
-Substituted acrylic esters, ethyl methacrylate, ethyl methacrylate, butyl methacrylate.
メタクリルＷ１２−エチルヘキシル等のメタクリル酸ア
ルキルエステル、メタクリル酸フェニル、メタクリル酸
ベンジル、メタクリル酸ナフチル等のメタクリル酸芳香
族エステル、メタクリル酸フルオロフェニル、メタクリ
ル酸クロロフェニル、メタクリル酸ブロモフェニル、メ
タクリル酸フルオロベンジル、メタクリル酸クロロベン
ジル、メタクリル酸ブロモベンジル等のメタクリル酸置
換芳香族エステル、メタクリル酸フルオロメチル、メタ
クリル酸フルオロエチル、メタクリル酸クロロエチル、
メタクリル酸ブロモエチル等のメタクリル酸ハロゲン化
アルキルエステル、メタクリル酸ヒドロキシアルキルエ
ステル、メタクリル酸グリシジル、メタクリル酸エチレ
ングリコールエステル、メタクリル酸ポリエチレングリ
コールエステル、メタクリル酸アルキルアミノアルキル
エステル、メタクリル酸シアノアルキルエステル等のメ
タクリル酸エステル、メタクリル酸シクロペンチル、メ
タクリル酸シクロヘキシル、メタクリル酸メチルシクロ
ヘキシル、メタクリル酸トリメチルシクロヘキシル、メ
タクリル酸ノルボルニル、メタクリル酸ノルボルニルメ
チル、メタクリル酸イブボルニル、メタクリル酸ボルニ
ル、メタクリル酸メ／チル、メタクリル酸７エンチル、
メタクリル酸アダマンチル、メタクリル酸ジメチルアダ
マンチル、メタクリル酸トリシクロ［：５１ＬＯ”）デ
カ−８−イル、メタクリル酸トリシクロ〔１２１，０”
’：ｌデカー９−イル、メタクリル酸トリシクロ［５１
１，０”１デカ−３−メチル、メタクリル酸トリシクロ
Ｃ５４１０″６〕デカ−４−メチル。Methacrylic acid alkyl esters such as methacrylic W12-ethylhexyl, methacrylic acid aromatic esters such as phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, fluorophenyl methacrylate, chlorophenyl methacrylate, bromophenyl methacrylate, fluorobenzyl methacrylate, methacryl Substituted aromatic esters of methacrylic acid such as chlorobenzyl methacrylate, bromobenzyl methacrylate, fluoromethyl methacrylate, fluoroethyl methacrylate, chloroethyl methacrylate,
Methacrylic acids such as halogenated alkyl methacrylates such as bromoethyl methacrylate, hydroxyalkyl methacrylates, glycidyl methacrylates, ethylene glycol methacrylates, polyethylene glycol methacrylates, alkylaminoalkyl methacrylates, and cyanoalkyl methacrylates. Ester, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, norbornyl methacrylate, norbornylmethyl methacrylate, ibubornyl methacrylate, bornyl methacrylate, methyl methacrylate, 7-ethyl methacrylate,
Adamantyl methacrylate, dimethyladamantyl methacrylate, tricyclo[:51LO”)dec-8-yl methacrylate, tricyclo[121,0” methacrylate]
': l decal-9-yl, tricyclo methacrylate [51
1,0"1 deca-3-methyl, tricycloC5410"6]deca-4-methyl methacrylate.
メタクリル酸シクロドデシル等のメタクリル識脂環式エ
ステルなどを挙げることができる。Examples include methacrylic alicyclic esters such as cyclododecyl methacrylate.
シアノビニル化合物の例としては、アクリロニトリル、
メタクリレートリル等を挙げることが出来る。Examples of cyanovinyl compounds include acrylonitrile,
Methacrylate trile and the like can be mentioned.
不飽和２塩基酸、その誘導体としては、Ｎ−メチルマレ
イミド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミ
ド、Ｎ−ブチルマレイミド、Ｎ−シクロヘキシルマレイ
ミド、Ｎ−フェニルｉレイξド、Ｎ−メチルフェニルマ
レイミド、Ｎ−メトキシフェニルマレイミド、Ｎ−カル
ボキシフェニルマレイミドなどＯＮ−置換マレイミド、
マレイン酸、フマル酸等を挙げることが出来る。不飽和
脂肪酸、その誘導体としては前述の不飽和脂肪酸エステ
ルの外、アクリルアミド、メタクリルアミド、Ｎ−ジメ
チルアクリルアミド、Ｎ−ジエチルアクリルアミド、Ｎ
−ジメチルメタクリルアミド。Unsaturated dibasic acids and their derivatives include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenyl iray ξ, N-methylphenylmaleimide, ON-substituted maleimides such as N-methoxyphenylmaleimide, N-carboxyphenylmaleimide,
Examples include maleic acid and fumaric acid. Unsaturated fatty acids and their derivatives include, in addition to the unsaturated fatty acid esters mentioned above, acrylamide, methacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-diethylacrylamide,
-dimethyl methacrylamide.
Ｎ−ジエチルメタクリルアミドなどのアクリル酸アミド
もしくはメタクリル酸アミド類、アクリル酸カルシウム
、メタクリル酸カルシウム、アクリル識バリウム、メタ
クリル酸バリウム、アクリル酸鉛、メタクリル酸鉛、ア
クリル醗スズ、メタクリル酸スズ、アクリル酸亜鉛、メ
タクリル酸亜鉛等のアクリル酸もしくはメタクリル酸の
金属塩。Acrylic acid amide or methacrylic acid amide such as N-diethylmethacrylamide, calcium acrylate, calcium methacrylate, barium acrylate, barium methacrylate, lead acrylate, lead methacrylate, tin acrylate, tin methacrylate, acrylic acid Metal salts of acrylic acid or methacrylic acid such as zinc and zinc methacrylate.
アクリル酸、メタクリル酸などを挙げることが出来る。Examples include acrylic acid and methacrylic acid.
スチレン系樹脂を用いる場合、ビニル芳香族炭化水素化
合物と共重合可能な他の単量体としては。When using a styrene resin, other monomers that can be copolymerized with the vinyl aromatic hydrocarbon compound include:
アクリル酸エステル、メタクリル酸エステル、Ｎ−置換
マレイミドが好ましく、特にメチルメタクリレート、メ
チルアクリレート、メタクリル酸ノルボルニル、メタク
リル酸トリシクロ［５，ＺＬＯ“〕〕デカー８−イが好
ましい。また、この場合、ビニル芳香族化合物と、それ
と共重合可能な他の単量体との比率は、前者／後者の重
量比で５０〜１００１５０〜０（重量比）であることが
好ましく、特て好ましぐａ７０〜１００／３０〜０（重
量比）である。Acrylic esters, methacrylic esters, and N-substituted maleimides are preferred, and methyl methacrylate, methyl acrylate, norbornyl methacrylate, and tricyclo[5,ZLO"]]decar-8-i methacrylate are particularly preferred. In this case, vinyl aromatic The ratio of the group compound to other monomers copolymerizable with it is preferably 50 to 100 to 150 to 0 (weight ratio), particularly preferably a70 to 100/ 30 to 0 (weight ratio).
ビニル系樹脂を製造する方法としては、ラジカル重合法
、イオン重合法、配位重合法等の公知の方法が適用でき
る。粒子状の重合体を得る方法としては、懸濁重合法に
よって直接球状の粒子を得る方法や塊状重合、乳化重合
、溶液重合等の公知の方法によって得られた重合体を押
出し機によってペレット状の粒子にする方法などが用い
られる。As a method for producing the vinyl resin, known methods such as radical polymerization, ionic polymerization, and coordination polymerization can be applied. Particulate polymers can be obtained by directly obtaining spherical particles by suspension polymerization, by polymerization by known methods such as bulk polymerization, emulsion polymerization, and solution polymerization, and by extruding into pellets using an extruder. A method such as making it into particles is used.
熱可塑性樹脂粒子に発泡性を付与する発泡剤としては、
常温常圧下に液体または気体であシ、かつ、上記重合体
を溶解しない易揮発性有機化合物が使用できる。このよ
うなものとしては２例えばプロパン、ブタン、ペンタン
、ヘキサ７、 石ｍエーテル等の脂肪族炭化水素、シク
ロヘキサン等の環状炭化水素、塩化メチレン、トリクロ
ロトリフルオロエタン、ジクロロジフルオロエタン等の
ハロゲン化脂肪族炭化水素が挙げられる。これら発泡剤
の使用量は、熱可塑性樹脂粒子１００重量部に対して１
〜２０重量部の範囲で用いるのが好ましく１％に２〜１
２重量部使用されるのが好ましい。As a blowing agent that imparts foamability to thermoplastic resin particles,
Easily volatile organic compounds that are liquid or gaseous at room temperature and pressure and do not dissolve the above polymer can be used. Examples of such substances include aliphatic hydrocarbons such as propane, butane, pentane, hexaether, and ether, cyclic hydrocarbons such as cyclohexane, and halogenated aliphatics such as methylene chloride, trichlorotrifluoroethane, and dichlorodifluoroethane. Examples include hydrocarbons. The amount of these blowing agents used is 1 part by weight per 100 parts by weight of thermoplastic resin particles.
It is preferably used in the range of 20 parts by weight to 1% by weight.
Preferably, 2 parts by weight are used.
熱可塑性樹脂粒子への発泡剤の含浸時に必要に応じて可
塑剤を存在させることができる。可塑剤としては、熱可
塑性樹脂粒子を溶解または膨潤させることができる有機
溶剤が使用でき、その沸点が、熱可塑性樹脂の軟化点よ
り約１０℃低い温度以上で１５０℃以下のものが好まし
い。可塑剤としてハウエチルベンゼン、トルエン、スチ
レン。A plasticizer can be present as necessary when impregnating thermoplastic resin particles with a blowing agent. As the plasticizer, an organic solvent that can dissolve or swell the thermoplastic resin particles can be used, and those having a boiling point of at least about 10° C. lower than the softening point of the thermoplastic resin and at most 150° C. are preferable. Howethylbenzene, toluene, styrene as plasticizers.
ベンゼン、キシレン等の芳香族炭化水素、Ｌ２−ジクロ
ロプロパン、トリクロロエチレン、パークロロエチレン
等のハロゲン化炭化水素などがある。Examples include aromatic hydrocarbons such as benzene and xylene, and halogenated hydrocarbons such as L2-dichloropropane, trichlorethylene, and perchloroethylene.
可塑剤は熱可塑性樹脂粒子に対し０〜５重量Ｘ使用され
るのが好ましく、使用する場合、熱可塑性樹脂粒子に対
しα５重ｔｘ以上が好ましい。The plasticizer is preferably used in an amount of 0 to 5 weight x relative to the thermoplastic resin particles, and when used, it is preferably α5 weight tx or more relative to the thermoplastic resin particles.
また９発泡剤としては、熱分解によシＮ３ガス。9. As a blowing agent, N3 gas is used by thermal decomposition.
ＣＯ！ガス等のガスを発生する熱分解型化学発泡剤を使
用してもよい。このようなものとしては、アゾジカルボ
ンアミド、アゾビスイソブチロニトリル、ジアゾアミノ
ベンゼン、Ｎ〆−ジニトロペンタメチレンテトラミン、
ベンゼンスルホニルヒドラジド、トリヒドロラジノトリ
アジン等がある。CO! Pyrolytic chemical blowing agents that generate gases such as gas may also be used. These include azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, N-dinitropentamethylenetetramine,
Examples include benzenesulfonyl hydrazide and trihydrazinotriazine.
このような発泡剤は熱可塑性樹脂粒子に対して０．５〜
５重量％含まれるのが好ましい。Such a blowing agent is used in an amount of 0.5 to
Preferably, it is contained in an amount of 5% by weight.
本発明において、易揮発性有機化合物を発泡剤として、
これを熱可塑性樹脂粒子に含浸させるＫは１本発明にお
ける熱可塑性樹脂粒子を水性媒体中に懸濁させ、これに
易揮発性有機化合物を添加する方法がある。懸濁下での
含浸は９０〜１３０℃で行うのが好ましい。ま九、別の
方法としては。In the present invention, an easily volatile organic compound is used as a blowing agent,
One method for impregnating thermoplastic resin particles with K is to suspend the thermoplastic resin particles in an aqueous medium and add a readily volatile organic compound thereto. Impregnation in suspension is preferably carried out at 90-130°C. Well, there's another way.
本発明における熱可塑性樹脂粒子と易揮発性有機化合物
を溶融混合してもよい。この場合主に、押出機が使用さ
れる。The thermoplastic resin particles and easily volatile organic compound in the present invention may be melt-mixed. In this case, extruders are mainly used.
熱分解型発泡剤を使用するときは９本発明における熱可
塑性樹脂と該発泡剤の分解温度以下で溶融混合される。When a thermally decomposable blowing agent is used, it is melt-mixed with the thermoplastic resin of the present invention at a temperature below the decomposition temperature of the blowing agent.
このときも、主に押出機が使用される。Also at this time, an extruder is mainly used.
なお９本発明に用いられる未被覆の発泡性熱可塑性樹脂
粒子は、顔料、難燃剤、酸化防止剤等の公知の添加剤を
含有させてもよい。Note that the uncoated expandable thermoplastic resin particles used in the present invention may contain known additives such as pigments, flame retardants, and antioxidants.
以上のようにして得られる本発明の発泡性熱可塑性樹脂
粒子は、常法に従い発泡成形し９発泡成形品とされる。The expandable thermoplastic resin particles of the present invention obtained as described above are foam-molded according to a conventional method to form a foamed molded article.
（実施例）
以下、実施例により本発明を更に詳細に説明する。なお
、特にことわらない限り９％は重量％を意味する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that 9% means % by weight unless otherwise specified.
実施例１
スチレン５００番にベンゾイルパーオキサイドα６Ｉを
溶解した後、その溶液をイオン交換水６００９、燐ＩＲ
三カルシウム１ｓｔ、ドデシルベンゼンスルホン酸ソー
ダ０．５％水溶液３廖おヨヒ硫酸ソーダ０．３蓼をそれ
ぞれ分散または溶解し加えであるオートクレーブ内に２
７ Ｏｒｐｍ の攪拌下で投入した。次いで、８５℃迄
昇温し、同温度で５時間重合し、引き続き１０５℃まで
反応温度を高め３時間重合した。この反応温度工程で、
シクロへキサンをＩＯ，５ｇ（対スチレンモノマー重合
率２１％）、液状のブタンガスを６５−圧入した。Example 1 After dissolving benzoyl peroxide α6I in styrene No. 500, the solution was mixed with ion exchange water 6009 and phosphorus IR.
Disperse or dissolve 1 liter of tricalcium, 3 liters of a 0.5% aqueous solution of sodium dodecylbenzenesulfonate, and 0.3 liters of sodium sulfate, respectively, and add 2 liters of sodium tricalcium to an autoclave.
The mixture was charged under stirring at 7 Orpm. Next, the temperature was raised to 85°C, polymerization was carried out at the same temperature for 5 hours, and then the reaction temperature was raised to 105°C and polymerization was carried out for 3 hours. In this reaction temperature step,
5 g of cyclohexane (polymerization rate of styrene monomer: 21%) and 65 g of liquid butane gas were introduced under pressure.
その後１１５℃まで反応温度を高め８重合率９９．５Ｘ
以上となるように１時間はどこの温度忙保持し続けた。After that, the reaction temperature was increased to 115℃ and the polymerization rate was 99.5X.
I continued to maintain the temperature at all levels for over an hour.
その後、０．５℃／分の速度で冷却し９反応液の温度が
４５℃に到達した段階で過剰のブタンガスを除いた。こ
の操作が終了した後、ポリスチレン粒子を取υ出し、塩
酸で粒子表面に付着している燐酸三カルシウムを溶解、
除去し、水洗を繰シ返し行い、その後、脱水、乾燥した
。Thereafter, the mixture was cooled at a rate of 0.5° C./min, and when the temperature of the reaction solution 9 reached 45° C., excess butane gas was removed. After this operation is completed, the polystyrene particles are taken out and the tricalcium phosphate attached to the particle surface is dissolved with hydrochloric acid.
It was removed, washed with water repeatedly, and then dehydrated and dried.
ゲルパーミェーションクロマトグラフィー４により測定
したポリスチレンの重量平均分子量は２３Ｘ１０４であ
った。このブタン含有ポリスチレンを２３℃の雰囲気下
に３日間放置した。この時の２００℃１０分間保持した
状態での加熱減量率は、ａ８％であつ九。この発泡性ポ
リスチレン粒子４００９に、ステアリン酸６３％、パル
ミチン１１３０％、ミリスチン酸４Ｘ、その他の脂肪１
１３Ｘよりなる飽和脂肪酸混合物とグリセリンのトリエ
ステル（日本油脂■製、牛脂極度硬化油）を０．９６ｇ
（対ポリスチレン０．２４％）、グリセロリン酸カルシ
ウム（和光紬薬工業■製’）０．４ａ（対ポリスチレン
０．１％）、ジメチルシリコーンオイル（信越化学工業
■製、商品名ＫＦＱ６゜２５℃における粘度１００Ｃ８
）０．１６９（対ポリスチレン０．０４％）をポリエチ
レン容器に加え。The weight average molecular weight of the polystyrene measured by gel permeation chromatography 4 was 23×104. This butane-containing polystyrene was left in an atmosphere at 23°C for 3 days. At this time, the heating loss rate when held at 200°C for 10 minutes was a8%. This expandable polystyrene particle 4009 contains 63% stearic acid, 1130% palmitic acid, 4x myristic acid, and 1x other fat.
0.96g of a saturated fatty acid mixture consisting of 13X and glycerin triester (manufactured by Nihon Yushi ■, extremely hardened beef tallow oil)
(0.24% based on polystyrene), calcium glycerophosphate (manufactured by Wako Tsumugi Kogyo ■) 0.4a (0.1% based on polystyrene), dimethyl silicone oil (manufactured by Shin-Etsu Chemical ■, trade name KFQ 6° Viscosity at 25°C 100C8
)0.169 (0.04% of polystyrene) was added to a polyethylene container.
これをローラーに設置し、３０分間攪拌、混合した。得
られた発泡性ポリスチレン粒子のグリセロリン酸カルシ
ウムの被覆量は、未被覆の粒子に対し０．０８重重量で
あった。なお、被覆量は、■高滓製作所製フレームレス
原子吸光装置（ＡＡ−６７０Ｇ）を用い、付着している
カルシウム量を定量し、グリセロリン酸カルシウムの量
を算出した（以下の各側も同様、但し、グリセロリン散
ナトリウムの場合はナトリウム量を定量した。）。This was placed on a roller and stirred and mixed for 30 minutes. The amount of calcium glycerophosphate coated on the resulting expandable polystyrene particles was 0.08 weight based on the uncoated particles. The amount of coating was determined by quantifying the amount of calcium adhered using a frameless atomic absorption spectrometer (AA-670G) manufactured by Takafusa Seisakusho, and calculating the amount of calcium glycerophosphate (same for each side below). (In the case of sodium glyceroline powder, the amount of sodium was determined.)
−この混合物をスチームによって１００℃に加熱された
バッチ式小型予備発泡機（日立化成工業■製）に投入し
予備発泡させ、見掛密度２０＠／ｌの予備発泡粒子を得
た。この中にブロッキング物はなかった。予備発泡粒子
をナイロン製網袋に入れ。- This mixture was charged into a small batch type pre-foaming machine (manufactured by Hitachi Chemical Co., Ltd.) heated to 100°C by steam and pre-foamed to obtain pre-foamed particles with an apparent density of 20@/l. There were no blocking objects in this. Place the pre-expanded particles into a nylon mesh bag.
２０時間熟成した。熟成された予備発泡粒子を成形機（
ダイセン工業■製、Ｖ８−３００型）に圧送し、スチー
ム圧力１１７Ｘ１０’Ｐａの条件で成形した。予備発泡
粒子を圧送してから成形品の発泡残圧が９．８Ｘ１０”
Ｐａと低下し、脱型するまでの成形時間は４５秒であっ
た。成形品の破断面の融着度は９５Ｘであった。Aged for 20 hours. The aged pre-expanded particles are molded into a molding machine (
The molded product was pressure-fed to a V8-300 model (manufactured by Daisen Kogyo Co., Ltd.) and molded under a steam pressure of 117×10'Pa. After the pre-expanded particles are pumped, the foaming residual pressure of the molded product is 9.8X10”
The molding time until the pressure decreased to Pa and the mold was removed was 45 seconds. The degree of fusion of the fractured surface of the molded article was 95X.
実施例２
単量体の組成をスチレン４７５％ｌ、 メタクリル酸
トリシクα（５，Ｚｌ、０”］］デカー８−イル２５の
２成分とする以外は、実施例１と同様な方法に従い１発
泡性スチレン系樹脂粒子を得た。この粒子４００Ｇ、１
２−ヒト０キシステアリン醗８３％、ステアリン酸１２
Ｘその他の脂肪酸５ｘよシなる脂肪酸混合物とグリセリ
ンのエステル（日本油脂■製のヒマシ硬化油）α６８ｓ
（対スチレン系樹脂ｏ、ｘ７Ｎ）、グリセロリン酸す）
ｉＪウム（和光純薬工業■製、５．５水和物）ｏ、ｓｚ
Ｑ。Example 2 One foaming was carried out in the same manner as in Example 1, except that the monomer composition was 475% styrene and 25 tricycloα(5,Zl,0'']]dec-8-yl methacrylate. Polystyrene resin particles were obtained.These particles were 400G, 1
2-human oxystearin 83%, stearic acid 12
X Other fatty acids 5x Ester of other fatty acids and glycerin (hardened castor oil manufactured by NOF ■) α68s
(For styrene resin o, x7N), glycerophosphoric acid)
iJum (manufactured by Wako Pure Chemical Industries, 5.5 hydrate) o, sz
Q.
ジメチルシリコーンオイルｏ、ｉｓ＠を加え、ローラー
で３０分間攪拌、混合した。得られた発泡性スチレン系
粒子のグリ七ロリン駿ナトリウムの被覆量は、未被覆の
粒子に対し０．０６２重量％であった。これを予備発泡
し、見掛密度１９．２ｓ／／の発泡粒子を得た。この中
にブロッキング物はなかった。これを実施例１と同様に
成形したところ。Dimethyl silicone oil o and is@ were added and stirred and mixed using a roller for 30 minutes. The amount of the resulting expandable styrene-based particles coated with sodium glyceptioline was 0.062% by weight based on the uncoated particles. This was pre-foamed to obtain foamed particles with an apparent density of 19.2 s//. There were no blocking objects in this. This was molded in the same manner as in Example 1.
成形時間は５１秒であり、融着度は８５％であった。The molding time was 51 seconds, and the degree of fusion was 85%.
実施例３
スチレン５００９にアジピン酸ジ（２−エチルヘキシル
）Ｚ５ ｇを溶解した他は、実施例１と同様な方法によ
って発泡性ポリスチレン粒子を得た。Example 3 Expandable polystyrene particles were obtained in the same manner as in Example 1, except that 5 g of di(2-ethylhexyl) adipate was dissolved in styrene 5009.
この発泡性ポリスチレン粒子４００聾に、ステアリン酸
モノグリセライド（和光紬薬工業■製）α９６ｓ、グリ
セロリン酸カルシウム０．２聾、ジメチルシリコーンオ
イル０．１６９．ステアリン酸亜鉛（和光純薬■製）０
．２９を加え、ローラーで３０分間攪拌、混合した。得
られた発泡性ポリスチレン粒子のグリセロリン酸カルシ
ウムの被覆量は、未被覆の粒子に対し０．０３８重量％
であった。To this expandable polystyrene particle 400%, stearic acid monoglyceride (manufactured by Wako Tsumugi Kogyo ■) α96s, calcium glycerophosphate 0.2%, dimethyl silicone oil 0.169%. Zinc stearate (manufactured by Wako Pure Chemical) 0
．． 29 was added and stirred and mixed using a roller for 30 minutes. The amount of calcium glycerophosphate coated on the obtained expandable polystyrene particles was 0.038% by weight based on the uncoated particles.
Met.
これを予備発泡し見掛密＆２０．４９／！の発泡粒子を
得た。この中にブロッキング物はなかった。This is pre-foamed and the apparent density is &20.49/! foamed particles were obtained. There were no blocking objects in this.
これを実施例１と同様に成形したところ、成形時間は６
０秒であり、融着度Ｆｉ９２Ｎであった。When this was molded in the same manner as in Example 1, the molding time was 6
The time was 0 seconds, and the degree of fusion was Fi92N.
実施例４
スチレン５００藝にエチレンビスステアリルアミド（日
本化成■製）ｏ、ｚｓｇを溶解し、他は実施例１と同様
な方法によって発泡性ポリスチレン粒子を得た。この発
泡性ポリスチレン粒子にパラフィンロウ（和光紬薬■製
、融点４６〜４８℃）ｏ、９６ｓ、 グリセロリン酸
カルシウム０．４Ｂ、ステアリン酸マグネシウム０．２
１を加え、ａ−ラーで３０分間攪拌、混合した。得られ
九発泡性ポリスチレン粒子のグリセロリン酸カルシウム
の被覆量は、未被覆の粒子に対し０．０７２重量重量あ
った。これを予備発泡し、見掛密ｆｔｉａｅｇ／ｚの発
泡粒子を得た。ブロッキング物はなかった。これを実施
例１と同様に成形したところ、成形時間は５４秒であシ
、融着度Ｆｉｓｓｓであった。Example 4 Expandable polystyrene particles were obtained in the same manner as in Example 1, except that ethylene bisstearylamide (manufactured by Nippon Kasei ■) and zsg were dissolved in styrene 500g. Paraffin wax (manufactured by Wako Tsumugi Pharmaceutical ■, melting point 46-48°C) o, 96s, calcium glycerophosphate 0.4B, magnesium stearate 0.2 were added to the expandable polystyrene particles.
1 was added, and the mixture was stirred and mixed using an a-lar for 30 minutes. The amount of calcium glycerophosphate coated on the resulting nine expandable polystyrene particles was 0.072 weight based on the uncoated particles. This was pre-foamed to obtain foamed particles with an apparent density of ftiaeg/z. There were no blocking objects. When this was molded in the same manner as in Example 1, the molding time was 54 seconds and the degree of fusion was Fisss.
比較例１
実施例１と同様な方法によって発泡性ポリスチレン５０
０９を得た。この粒子４ｏｏｇに牛脂極度硬化油（日本
油脂■製）０．９６ｇ、ステアリン駿亜鉛α４Ｇｅ ジ
メチルシリコーンオイル０．１６９を加えローラーで３
０分間攪拌、混合した。これを予備発泡し、見掛密度１
９．６９／／の発泡粒子を得た。ブロッキング物が５．
７ｇ発生し、成形機に発泡粒子を圧送する時、ホースが
詰まり、成形できなかった。Comparative Example 1 Expandable polystyrene 50 was prepared in the same manner as in Example 1.
I got 09. Add 0.96 g of extremely hardened beef tallow oil (manufactured by Nippon Oil & Fats) and 0.169 g of stearin zinc α4Ge dimethyl silicone oil to 400 g of these particles, and use a roller to
Stir and mix for 0 minutes. This is pre-foamed and the apparent density is 1
Expanded particles with a weight of 9.69// were obtained. Blocking object is 5.
7g was generated, and when the foamed particles were being fed under pressure to the molding machine, the hose was clogged and molding could not be performed.
比較例２
実施例１と同様な方法によって発泡性ポリスチレン５０
０ｇを得た。この粒子４００９に牛脂極度硬化油（日本
油脂■製）０．９６１．タルク＆２１、ジメチルシリコ
ーンオイル０．１６ｇを加え。Comparative Example 2 Expandable polystyrene 50 was prepared in the same manner as in Example 1.
Obtained 0g. This particle 4009 has an extremely hardened beef tallow oil (manufactured by NOF ■) of 0.961. Add talc & 21 and 0.16g of dimethyl silicone oil.
ローラーで３０分間攪拌、混合した。これを予備発泡し
、見掛密Ｗ１１９．２＠／ｌの発泡粒子を得た。The mixture was stirred and mixed using a roller for 30 minutes. This was pre-foamed to obtain foamed particles with an apparent density of W119.2@/l.
ブロッキング物量は２２９であった。成形時間は４４秒
であった。成形品の融着度は２５％と悪く。The blocking amount was 229. The molding time was 44 seconds. The degree of fusion of the molded product was poor at 25%.
成形品の強Ｉｔは小さかった。The strong It of the molded article was small.
なお、融着度は、得られた成形品を割った時に。The degree of fusion is measured when the molded product is broken.
粒子界面で剥離せず粒子自身が割れるものの割合をいう
。This refers to the percentage of particles that do not peel off at the particle interface but break themselves.
（発明の効果）
本発明に係る発泡性熱可塑性樹脂粒子は、予備発泡時に
、ブロッキングは発生しない。このため。(Effects of the Invention) The expandable thermoplastic resin particles according to the present invention do not cause blocking during pre-foaming. For this reason.
予備発泡粒子の熟成と風乾のための熟成槽への移送や成
形機への移送が簡便に行うことができ、生産性向上に本
役立つ。また、得られる発泡成形品は粒子間の融着が優
れる本のである。The pre-expanded particles can be easily transferred to an aging tank for aging and air drying, or to a molding machine, which is very useful for improving productivity. Furthermore, the resulting foamed molded product has excellent interparticle fusion.
征−−−入、Conquest---Enter,
Claims (1)
徴とする発泡性熱可塑性樹脂粒子。 ２、発泡性熱可塑性樹脂粒子の樹脂成分がビニル系樹脂
である請求項１記載の発泡性熱可塑性樹脂粒子。 ３、発泡性熱可塑性樹脂粒子の樹脂成分がスチレン系樹
脂である請求項１記載の発泡性熱可塑性樹脂粒子。 ４、グリセロリン酸の金属塩の被覆量が、未被覆の発泡
性熱可塑性樹脂粒子に対して０．０５〜０．５重量％で
ある請求項１、２又は３記載の発泡性熱可塑性樹脂粒子
。 ５、請求項１、２、３または４記載の発泡性熱可塑性樹
脂粒子を発泡成形して得られる発泡成形品。[Scope of Claims] 1. Expandable thermoplastic resin particles characterized by being coated with a metal salt of glycerophosphoric acid. 2. The expandable thermoplastic resin particles according to claim 1, wherein the resin component of the expandable thermoplastic resin particles is a vinyl resin. 3. The expandable thermoplastic resin particles according to claim 1, wherein the resin component of the expandable thermoplastic resin particles is a styrene resin. 4. The expandable thermoplastic resin particles according to claim 1, 2 or 3, wherein the coating amount of the metal salt of glycerophosphoric acid is 0.05 to 0.5% by weight based on the uncoated expandable thermoplastic resin particles. . 5. A foam molded article obtained by foam molding the expandable thermoplastic resin particles according to claim 1, 2, 3, or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31003990A JPH04180941A (en) | 1990-11-15 | 1990-11-15 | Foamable thermoplastic resin particle and molded foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31003990A JPH04180941A (en) | 1990-11-15 | 1990-11-15 | Foamable thermoplastic resin particle and molded foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04180941A true JPH04180941A (en) | 1992-06-29 |
Family
ID=18000428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31003990A Pending JPH04180941A (en) | 1990-11-15 | 1990-11-15 | Foamable thermoplastic resin particle and molded foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04180941A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219711A (en) * | 2010-03-26 | 2011-11-04 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, production method therefor, preliminary foamed particle, and foamed molded body |
| JP2021147597A (en) * | 2020-03-24 | 2021-09-27 | 積水化成品工業株式会社 | Foamable styrene resin particle, preliminary foamed styrene resin particle, and styrene resin foam molding |
-
1990
- 1990-11-15 JP JP31003990A patent/JPH04180941A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219711A (en) * | 2010-03-26 | 2011-11-04 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, production method therefor, preliminary foamed particle, and foamed molded body |
| JP2021147597A (en) * | 2020-03-24 | 2021-09-27 | 積水化成品工業株式会社 | Foamable styrene resin particle, preliminary foamed styrene resin particle, and styrene resin foam molding |
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