JP4771457B2 - Method for producing styrene resin particles - Google Patents
Method for producing styrene resin particles Download PDFInfo
- Publication number
- JP4771457B2 JP4771457B2 JP2005226761A JP2005226761A JP4771457B2 JP 4771457 B2 JP4771457 B2 JP 4771457B2 JP 2005226761 A JP2005226761 A JP 2005226761A JP 2005226761 A JP2005226761 A JP 2005226761A JP 4771457 B2 JP4771457 B2 JP 4771457B2
- Authority
- JP
- Japan
- Prior art keywords
- surfactant
- resin particles
- polymerization
- sodium
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000002245 particle Substances 0.000 title claims description 232
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 127
- 229920005989 resin Polymers 0.000 title claims description 120
- 239000011347 resin Substances 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 111
- 238000006116 polymerization reaction Methods 0.000 claims description 47
- 229920001890 Novodur Polymers 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 239000000375 suspending agent Substances 0.000 claims description 8
- RUTSRVMUIGMTHJ-UHFFFAOYSA-M sodium;tetradec-1-ene-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCC=CS([O-])(=O)=O RUTSRVMUIGMTHJ-UHFFFAOYSA-M 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001174 sulfone group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 description 28
- -1 alkylbenzene sulfonate Chemical class 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 238000000465 moulding Methods 0.000 description 23
- 238000009826 distribution Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000010557 suspension polymerization reaction Methods 0.000 description 18
- 238000009833 condensation Methods 0.000 description 15
- 230000005494 condensation Effects 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 10
- 239000001273 butane Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004904 shortening Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 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 5
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920006248 expandable polystyrene Polymers 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 235000015278 beef Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
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- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
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- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
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- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
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- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明はスチレン系樹脂粒子の製造方法に関し、詳しくは難水溶性無機塩と界面活性剤を用いた懸濁重合によるスチレン系樹脂粒子および発泡剤を含有する発泡性スチレン系樹脂粒子の製造方法に関する。 The present invention relates to a method for producing styrene resin particles, and more particularly to a method for producing expandable styrene resin particles containing a styrene resin particle and a foaming agent by suspension polymerization using a hardly water-soluble inorganic salt and a surfactant. .
懸濁重合によって製造されるスチレン系樹脂粒子のうち、発泡剤を含有する発泡性スチレン系樹脂粒子を発泡し、次いで成形することにより得られる成形体は成形が容易であると共に安価であり、高い断熱性、緩衝特性を持つため、魚箱、緩衝材、断熱材等の発泡成形品の製造に広く用いられている。また発泡剤を含有しないスチレン系樹脂粒子においてもディスプレーの光拡散材や重合法トナーバインダーなどとして用いられている。 Of the styrene resin particles produced by suspension polymerization, a molded product obtained by foaming and then molding foamable styrene resin particles containing a foaming agent is easy to mold and inexpensive. Since it has heat insulating properties and cushioning properties, it is widely used in the production of foam molded products such as fish boxes, cushioning materials, and heat insulating materials. In addition, styrene resin particles not containing a foaming agent are also used as a light diffusing material for display, a toner binder for polymerization, and the like.
前記スチレン系樹脂粒子の製造は、一般にスチレンおよびスチレンと共重合可能な単量体を水性媒体中に懸濁剤と共に攪拌することにより分散させて重合を行う懸濁重合により行われる。該懸濁重合により得られる樹脂は粒子状なので、懸濁重合はトナーバインダーや光拡散剤など粒子をそのままの形状で用いる分野には有用な方法である。またこの樹脂粒子の重合途中もしくは終了後に発泡剤を含浸させれば、発泡性スチレン系樹脂粒子を得ることができ、該発泡性スチレン系樹脂粒子を蒸気で発泡・成形することにより容易に発泡体成形品を製造することができる。 The styrene resin particles are generally produced by suspension polymerization in which styrene and a monomer copolymerizable with styrene are dispersed in an aqueous medium by stirring together with a suspending agent. Since the resin obtained by the suspension polymerization is in the form of particles, suspension polymerization is a useful method in the field where particles such as a toner binder and a light diffusing agent are used as they are. Further, if the foaming agent is impregnated during or after the polymerization of the resin particles, expandable styrene resin particles can be obtained, and the foam can be easily formed by foaming and molding the expandable styrene resin particles with steam. Molded articles can be manufactured.
前記スチレン系樹脂粒子の懸濁重合では、従来より、（１）懸濁剤として難水溶性無機塩とアニオン性界面活性剤の組み合わせを用いる方法、もしくは（２）ポリビニルアルコール、ポリビニルピロリドン等の水溶性高分子を用いる方法が主に行われている。このうち（２）水溶性高分子を用いる方法は、水溶性高分子が得られる樹脂粒子表面に残留しやすいため、樹脂粒子の品質に悪影響を及ぼす場合がある。例えば発泡用途に使用した場合に、得られる発泡成形品の強度低下や水漏れが発生しやすくなるといった問題がある。また、重合終了後粒子を分離した後の排水の水質が悪化するため、排水処理の負荷が大きくなるといった問題もある。 In suspension polymerization of the styrene-based resin particles, conventionally, (1) a method using a combination of a poorly water-soluble inorganic salt and an anionic surfactant as a suspending agent, or (2) a water-soluble solution such as polyvinyl alcohol or polyvinylpyrrolidone. A method using a conductive polymer is mainly performed. Among these, (2) the method using a water-soluble polymer tends to remain on the surface of the resin particles from which the water-soluble polymer is obtained, and thus may adversely affect the quality of the resin particles. For example, when used for foaming applications, there is a problem that the resulting foamed molded product is liable to have a reduced strength and water leakage. Moreover, since the water quality of the waste water after separating the particles after the polymerization is deteriorated, there is a problem that the load of the waste water treatment is increased.
従って、（１）懸濁剤として難水溶性無機塩とアニオン性界面活性剤とを組み合わせて用いる方法が行われることが多い。この方法で使用される難水溶性無機塩としては第３リン酸カルシウム、ピロリン酸マグネシウムなどが一般的であり、アニオン性界面活性剤としてはドデシルベンゼンスルホン酸ナトリウムのようなアルキルベンゼンスルホン酸塩、ラウリル硫酸ナトリウムといったアルキル硫酸塩などが一般的である。 Therefore, (1) a method using a combination of a poorly water-soluble inorganic salt and an anionic surfactant as a suspending agent is often performed. As the poorly water-soluble inorganic salt used in this method, tribasic calcium phosphate, magnesium pyrophosphate and the like are common. As the anionic surfactant, alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate. Such alkyl sulfates are generally used.
一方、この様な懸濁重合により得られるスチレン系樹脂粒子においては、その粒径分布が性能・品質面および経済的な面から狭いものが好ましい。例えば、光拡散剤などに使用される架橋スチレン系樹脂粒子は粒径がその光学的性能に影響を与えるため、粒径が均一であることが要求される場合が多い）。また発泡性スチレン系樹脂粒子においては、その発泡成形品が用いられる用途、形状に応じて、それに適した粒子径の粒子を使い分ける事が一般的に行われている。従って、用途に対応して異なる粒子径のスチレン系樹脂粒子を製造する必要がある。ところが、得られた樹脂粒子の粒径分布が広すぎると不必要な粒径の粒子が多く含まれるので、その目的を達し難くなる。
このような状況下、難水溶性無機塩とアニオン性界面活性剤を併用する懸濁重合（１）には、アニオン性界面活性剤として従来からよく用いられているアルキルベンゼンスルホン酸ナトリウム、アルキル硫酸ナトリウムなどを単独で用いた場合、得られる粒子の粒径分布が比較的広くなるという問題がある。
On the other hand, styrene resin particles obtained by such suspension polymerization preferably have a narrow particle size distribution from the viewpoints of performance, quality and economy. For example, cross-linked styrene resin particles used for light diffusing agents and the like are often required to have a uniform particle size because the particle size affects the optical performance. In the case of expandable styrenic resin particles, it is a common practice to use particles having a particle size suitable for the use and shape of the expanded molded product. Therefore, it is necessary to produce styrene resin particles having different particle sizes according to the application. However, if the particle size distribution of the obtained resin particles is too wide, many particles having unnecessary particle sizes are included, and thus it is difficult to achieve the purpose.
Under such circumstances, sodium alkylbenzene sulfonate and sodium alkyl sulfate, which have been conventionally used as anionic surfactants, are used in suspension polymerization (1) in which a poorly water-soluble inorganic salt and an anionic surfactant are used in combination. When these are used alone, there is a problem that the particle size distribution of the obtained particles becomes relatively wide.
また、スチレン系樹脂粒子の懸濁重合においては、８０℃〜１００℃で重合の第１段階を行い、モノマーの消費を促進すると共に重合時間を短縮するために、重合温度を１００〜１３０℃に上げて第２段階の重合を行い、それぞれの温度に適した２種類の重合開始剤を用いる懸濁重合法が一般的に行われている。この際の懸濁剤として、前記難水溶性無機塩とアニオン性界面活性剤を併用する場合、アニオン性界面活性剤として前記の様なアルキルベンゼンスルホン酸ナトリウム、アルキル硫酸ナトリウムなどを単独で用いた場合、第２段階の高温に昇温したときに、一度形成されて水性媒体中に分散していた樹脂粒子が互いに固着し塊状となる樹脂粒子の凝結といった現象が起こりやすくなるという問題もある。
この様な樹脂粒子の凝結が多く発生すると、反応器からの内容物の排出ができなくなったり、製品から凝結した樹脂粒子を取り除く作業が必要になったりするなどの不都合が発生する。この問題を解決するために様々な試みが行われてきた。
In the suspension polymerization of styrene resin particles, the polymerization temperature is increased to 100 to 130 ° C. in order to accelerate the monomer consumption and shorten the polymerization time by performing the first stage of polymerization at 80 to 100 ° C. In general, a suspension polymerization method using two kinds of polymerization initiators suitable for respective temperatures is performed by performing the second stage polymerization. When using the sparingly water-soluble inorganic salt and an anionic surfactant together as a suspending agent in this case, when using an alkyl surfactant sulfonate sodium, sodium alkyl sulfate or the like alone as an anionic surfactant There is also a problem that when the temperature is raised to a high temperature in the second stage, the resin particles once formed and dispersed in the aqueous medium are likely to adhere to each other and agglomerate of the resin particles that become agglomerated.
If such agglomeration of the resin particles occurs frequently, there will be inconveniences such as it becomes impossible to discharge the contents from the reactor and it becomes necessary to remove the agglomerated resin particles from the product. Various attempts have been made to solve this problem.
特許文献１には、粒径２μ以下の塩基性リン酸カルシウム、α−オレフィンスルホン酸ソーダ、および水系で中性を示す水溶性金属塩を用いることにより、粒径分布の狭いスチレン系樹脂粒子を得る懸濁重合法が開示されている。しかし、この方法では、粒径分布は狭くなるものの、樹脂粒子の凝結の発生を低減することはできない。 In Patent Document 1, basic calcium phosphate having a particle size of 2 μm or less, α-olefin sulfonic acid soda, and a water-soluble metal salt that is neutral in an aqueous system are used to obtain styrene resin particles having a narrow particle size distribution. A turbid polymerization method is disclosed. However, with this method, although the particle size distribution becomes narrow, the occurrence of condensation of the resin particles cannot be reduced.
このような樹脂粒子同士の凝結を防ぎつつ短い重合時間でスチレン系樹脂粒子を得る懸濁重合方法としては、特許文献２に開示されているものがある。特許文献２には、１分子中にスルホン基もしくは硫酸エステル基のいずれか１つを持つ第１界面活性剤と、１分子中にスルホン基を少なくとも２つ以上持つ第２界面活性剤を併用する方法が記載されている。この方法によれば、重合中の粒子凝結の発生量は少なくなる。しかし、第１界面活性剤が特許文献２で好ましいとされているアルキルベンゼンスルホン酸ナトリウムまたはアルキルスルホン酸ナトリウムである場合、得られる樹脂粒子の粒径分布は満足できる狭さではない。従って、得られる樹脂粒子の粒径分布が狭く、かつ重合後半に重合温度を上げて重合を行う場合においても樹脂粒子の凝結が少ないスチレン系樹脂粒子の懸濁重合方法が求められている。 As a suspension polymerization method for obtaining styrene-based resin particles in a short polymerization time while preventing such aggregation between resin particles, there is one disclosed in Patent Document 2. In Patent Document 2, a first surfactant having any one of a sulfone group or a sulfate ester group in one molecule and a second surfactant having at least two sulfone groups in one molecule are used in combination. A method is described. According to this method, the amount of particle condensation during polymerization is reduced. However, when the first surfactant is sodium alkylbenzenesulfonate or sodium alkylsulfonate, which is preferred in Patent Document 2, the particle size distribution of the resin particles obtained is not narrow enough. Accordingly, there is a need for a suspension polymerization method of styrene resin particles in which the particle size distribution of the obtained resin particles is narrow, and even when the polymerization is carried out by raising the polymerization temperature in the latter half of the polymerization, the resin particles are less condensed.
一方、懸濁重合時に発泡剤を含浸することにより、発泡性スチレン系樹脂粒子を得ることができる。更に、得られる発泡性スチレン系樹脂粒子を予備発工程で発泡させ、それに続く成形工程で型内成形することにより発泡樹脂成形体を製造することができる。即ち、まず予備発泡工程において発泡性スチレン系樹脂粒子を発泡機中でスチームにて加熱し所望の嵩密度まで発泡させれば、予備発泡粒子が得られる。次いで成形工程において、所定の熟成期間を置いた予備発泡粒子を成形機金型に充填し、金型内にスチームを導入し加圧・加熱し予備発泡粒子を融着させて成形した後、型内を水冷、さらに減圧しながら放冷することにより成形品温度を下げ、金型内が大気圧付近まで減圧された後に金型から離型すれば、成形品が得られる。 On the other hand, expandable styrene resin particles can be obtained by impregnating a foaming agent during suspension polymerization. Furthermore, a foamed resin molded article can be produced by foaming the obtained expandable styrene resin particles in a preliminary process and molding in the mold in a subsequent molding process. That is, first, in the pre-foaming step, the expandable styrene resin particles are heated with steam in a foaming machine and foamed to a desired bulk density to obtain pre-foamed particles. Next, in the molding process, the pre-expanded particles after a predetermined aging period are filled into the molding machine mold, steam is introduced into the mold, pressurized and heated, and the pre-expanded particles are fused and molded. The molded product is obtained by lowering the temperature of the molded product by cooling the interior with water and allowing it to cool while reducing the pressure, reducing the pressure inside the mold to near atmospheric pressure, and then releasing it from the mold.
この成形工程において、加熱後に放冷する際、充分に金型内部を冷却・減圧しないと離型後の成形品が膨張変形しやすくなるため、変形のない美麗な成形品を得るためには充分な放冷時間を取ることが必要となる。しかも、この放冷に要する時間が成形工程の大半を占めるため、放冷時間の長短が成形品の生産性に大きな影響を与える。
この放冷時間を短くするために、発泡性スチレン系樹脂粒子を改質することが行われてきた。そのための一般的な手段として、樹脂粒子表面を当該樹脂に対して可塑性を持った物質で被覆することにより粒子表面を侵し、予備発泡する際に表面セル膜に穴を開けて、成形時に予備発泡粒から発泡剤を逸散させやすくし、成形放冷工程における減圧速度を速め放冷時間を短縮する方法が行われている。
In this molding process, when it is allowed to cool after heating, if the inside of the mold is not sufficiently cooled and depressurized, the molded product after mold release tends to expand and deform, so it is sufficient to obtain a beautiful molded product without deformation. It is necessary to take a long cooling time. In addition, since the time required for this cooling is the majority of the molding process, the length of the cooling time greatly affects the productivity of the molded product.
In order to shorten the cooling time, the foamable styrene resin particles have been modified. As a general means for that purpose, the resin particle surface is coated with a material having plasticity with respect to the resin to attack the particle surface. There is a method of facilitating the dissipation of the foaming agent from the grains and increasing the pressure reduction rate in the molding and cooling step to shorten the cooling time.
この可塑性を持った物質で被覆する方法の中で最も多く用いられている方法は、高級脂肪酸の脂肪族アルコールエステル、特に常温で固体の牛脂硬化油、ヒマシ硬化油といった高級脂肪酸のトリグリセリンエステルを成分に含む粒状・粉状のコーティング剤を当該樹脂粒子の表面にブレンダー、ミキサーなどで被覆する方法である（特許文献３〜６）。この方法は簡便であり、またコーティング剤の組成および量によって樹脂粒子の特性を効果的に変えることができるため一般的に行われている。ところが、この方法には次のような欠点がある。 The most commonly used method of coating with this plastic material is a fatty acid ester of a higher fatty acid, particularly a triglycerin ester of a higher fatty acid such as a beef tallow oil or a castor oil hardened at room temperature. This is a method of coating the surface of the resin particles with a granular / powder coating agent contained in the components using a blender, a mixer or the like (Patent Documents 3 to 6). This method is generally performed because it is simple and the properties of the resin particles can be effectively changed depending on the composition and amount of the coating agent. However, this method has the following drawbacks.
上記コーティング剤は、所望される効果を得るために、数百〜数千ｐｐｍを樹脂粒子表面に付着させなければならない。しかし、粒子一つ一つに均一に付着させることは難しく、製造上のバラツキが避けられない。その結果、得られる製品の物性のバラツキも発生しやすい。また、樹脂粒子の送粒などの際に剥がれやすいため、剥離したコーティング剤の送粒ライン・発泡機への付着や送粒ブロワーのフィルターの目詰まり、成形金型のスケール生成といった問題が発生し、清掃が必要となるため生産性が落ちてしまう。更に、コーティング剤の剥がれ落ちによる樹脂粒子自体の性能の劣化、バラツキの発生といった問題もある。すなわち成形時間を短縮するためにはこのような物質を多くコーティングしなければならないが、その分これら物質の剥離による問題、その他の物性に与える悪影響が増加することとなる問題がある。 In order to obtain the desired effect, the coating agent must adhere several hundred to several thousand ppm on the surface of the resin particles. However, it is difficult to uniformly adhere to each particle, and manufacturing variations are unavoidable. As a result, variations in the physical properties of the obtained product are likely to occur. In addition, since it is easy to peel off when resin particles are sent, problems such as adhesion of the peeled coating agent to the feed line / foaming machine, clogging of the filter of the feed blower, and scale formation of the mold occur. , Productivity will be reduced because cleaning is required. Furthermore, there are problems such as deterioration in performance of the resin particles themselves due to peeling off of the coating agent and occurrence of variations. That is, in order to shorten the molding time, a large amount of such substances must be coated. However, there is a problem that the adverse effect on the physical properties increases due to the peeling of these substances.
また、樹脂粒子に流動パラフィン等の液状の有機化合物を塗布する方法もある（特許文献７、８）。しかし、この方法にも、樹脂粒子に均一に塗布することが難しい、塗布した有機化合物により樹脂粒子がべとつき送粒しづらくなる、樹脂粒子を発泡する際にブロッキングが生じやすい、といった問題がある。 There is also a method of applying a liquid organic compound such as liquid paraffin to resin particles (Patent Documents 7 and 8). However, this method also has problems that it is difficult to uniformly apply to the resin particles, that the resin particles are sticky and difficult to feed due to the applied organic compound, and that blocking tends to occur when the resin particles are foamed.
加えて、固体状・液状を問わず、これらの可塑性のある物質が被覆された樹脂粒子は表面が可塑化されるため、成形加熱時に溶融しやすく成形品表面の外観が悪くなりやすい、発泡倍率が上がらなくなり低密度の成形品が得られることが難しくなる、成形品強度が低下するといった欠点も有する。またこの様に可塑性を持った物質で樹脂粒子を被覆する方法では、予備発泡および成形時にスチームや金型冷却水のドレンとともにこれら物質が一部流れ落ち、水質を悪化させる問題もある。従って、コーティング剤の使用量はできる限り少量であることが望まれるが、量が少なすぎると、本来の目的である成形時の放冷時間を短縮することを達成することが困難になるという問題もある。従って、コーティング剤の使用量を少なくしても、放冷時間の短縮が可能なスチレン系樹脂粒子の製造方法の開発が期待されている。 In addition, regardless of whether it is solid or liquid, the surface of resin particles coated with these plastic substances is plasticized, so it is easy to melt during molding and heat, and the appearance of the molded product surface tends to deteriorate. However, it is difficult to obtain a low-density molded product and the strength of the molded product is reduced. Further, in the method of coating the resin particles with a plastic material in this way, there is a problem that these materials partially flow down together with steam and mold cooling water drain during preliminary foaming and molding, thereby deteriorating the water quality. Therefore, it is desired that the amount of the coating agent used is as small as possible, but if the amount is too small, it is difficult to achieve a reduction in the cooling time during molding, which is the original purpose. There is also. Accordingly, development of a method for producing styrene resin particles that can shorten the cooling time even when the amount of the coating agent used is reduced is expected.
本発明は、重合反応時の温度が高くても粒子同士の凝結がなく、なおかつ得られる粒子の粒径分布が狭く均一で安定した粒子を短い重合時間で得ることができるスチレン系樹脂粒子の製造方法を提供することを課題とする。さらに、本発明は、発泡剤を含浸し発泡性スチレン系樹脂粒子とした場合、成形時の放冷時間が短く生産性に優れ、放冷時間短縮のために樹脂粒子表面に被覆するコーティング剤の量を少なくすることができる発泡性スチレン系樹脂粒子の製造方法を提供することを課題とする。 The present invention is a process for producing styrene-based resin particles that can be obtained in a short polymerization time with no condensation between particles even when the temperature during the polymerization reaction is high, and with which the obtained particle size distribution is narrow and uniform and stable. It is an object to provide a method. Furthermore, when the present invention impregnates a foaming agent to form expandable styrene resin particles, the cooling time during molding is short and the productivity is excellent, and the coating agent for coating the resin particle surface for shortening the cooling time. It aims at providing the manufacturing method of the expandable styrene-type resin particle which can reduce the quantity.
本発明によれば、以下に示すスチレン系樹脂粒子の製造方法が提供される。
〔１〕 スチレン系単量体を、懸濁剤として難水溶性無機塩と界面活性剤とを用いて水系媒体に分散させ、該スチレン系単量体を加熱下において重合反応させるスチレン系樹脂粒子の懸濁重合による製造方法において、前記界面活性剤は、テトラデセンスルホン酸ナトリウムからなる第１界面活性剤と、１分子中にスルホン基を少なくとも２つ以上持つ第２界面活性剤を併用してなり、該第１界面活性剤と第２界面活性剤との重量比が１０：９０から９０：１０の範囲にあり、該第１界面活性剤と第２界面活性剤との合計添加量は、仕込み単量体の全重量１００重量部に対し０．０００１〜０．０５重量部であることを特徴とするスチレン系樹脂粒子の製造方法。
〔２〕 第２界面活性剤がアルキルジフェニルエーテルジスルホン酸ナトリウムであることを特徴とする前記〔１〕に記載のスチレン系樹脂粒子の製造方法。
〔３〕 重合反応途中もしくは重合反応後に、反応器内に発泡剤を添加することを特徴とする前記〔１〕または〔２〕に記載のスチレン系樹脂粒子の製造方法。
According to this invention, the manufacturing method of the styrene resin particle shown below is provided.
[1] Styrenic resin particles in which a styrene monomer is dispersed in an aqueous medium using a hardly water-soluble inorganic salt and a surfactant as a suspending agent, and the styrene monomer is polymerized under heating. In the production method by suspension polymerization, the surfactant is a combination of a first surfactant comprising sodium tetradecenesulfonate and a second surfactant having at least two sulfone groups in one molecule. The weight ratio of the first surfactant to the second surfactant is in the range of 10:90 to 90:10, and the total addition amount of the first surfactant and the second surfactant is: A method for producing styrenic resin particles, which is 0.0001 to 0.05 parts by weight based on 100 parts by weight of the total weight of charged monomers.
[ 2 ] The method for producing styrene resin particles according to [1 ], wherein the second surfactant is sodium alkyldiphenyl ether disulfonate.
[ 3 ] The method for producing styrene resin particles according to [1] or [2] , wherein a foaming agent is added in the reactor during or after the polymerization reaction.
本発明請求項１に係わる発明のスチレン系樹脂粒子の製造方法によれば、特定の第１界面活性剤と特定の第２界面活性剤とを特定量用いて、スチレン系単量体を懸濁することにより、樹脂粒子同士を凝結させることなく、かつ扁平状や長球状の粒子を発生させることなく、真球状のスチレン系樹脂粒子を得ることができ、第１界面活性剤としてテトラデセンスルホン酸ナトリウムを用いることにより、その効果がより顕著なものとなる。
本発明請求項２に係わる発明のスチレン系樹脂粒子の製造方法によれば、特定の第２界面活性剤を用いることにより、請求項１の効果がより顕著なものとなる。
本発明請求項３に係わる発明のスチレン系樹脂粒子の製造方法によれば、特定の第１界面活性剤（テトラデセンスルホン酸ナトリウム）と第２界面活性剤とを特定量用いて、スチレン系単量体を懸濁重合することにより、発泡性スチレン系樹脂粒子を製造するので、成形放冷時間を短縮するためのコーティング剤（ハイサイクルコーティング剤）の添加量が少なくても、従来の界面活性剤を用いた場合と同様の成形放冷時間で成形可能な発泡性スチレン系樹脂粒子を得ることができる。
According to the method for producing styrene resin particles of the invention according to claim 1 of the present invention, the styrene monomer is suspended using a specific amount of the specific first surfactant and the specific second surfactant. By doing this, it is possible to obtain true spherical styrene resin particles without condensing the resin particles and without generating flat or oblong particles, and tetradecenesulfonic acid as the first surfactant. By using sodium, the effect becomes more remarkable .
According to the method for producing styrene-based resin particles of the invention according to claim 2 of the present invention, the effect of claim 1 becomes more remarkable by using the specific second surfactant.
According to the method for producing styrenic resin particles of the invention according to claim 3 of the present invention, a specific amount of the specific first surfactant (sodium tetradecene sulfonate) and the second surfactant are used in a specific amount. Since foamable styrene resin particles are produced by suspension polymerization of the polymer, the conventional surface activity can be achieved even with a small amount of coating agent (high cycle coating agent) added to shorten the molding cooling time. Expandable styrenic resin particles that can be molded in the same molding and cooling time as when an agent is used can be obtained.
以下、本発明のスチレン系樹脂粒子（以下、単に樹脂粒子ともいう。）の製造方法について詳細に説明する。
本発明の製造方法においては、スチレン系単量体を、懸濁剤として難水溶性無機塩と界面活性剤とを用いて水系媒体に分散させ、該スチレン系単量体を加熱下において重合反応（懸濁重合）させることにより、スチレン系樹脂粒子が製造される。かかる懸濁重合によるスチレン系樹脂粒子の製造方法は従来公知であるが、本発明は、前記界面活性剤として、アルケンモノスルホン酸塩からなる第１界面活性剤と、１分子中にスルホン基を少なくとも２つ以上持つ第２界面活性剤を併用することを特徴とするものである。即ち、本発明においては、スチレン系樹脂粒子の分子量を要求されるものとし、且つモノマーの消費を促進すると共に重合時間を短縮するために、比較的低温度で重合の第１段階を行い、次いで比較的高い温度で第２段階の重合を行なうことが好ましい。この場合、前記２種類の界面活性剤を用いると、第２段階の重合温度として比較的高い温度に昇温したとしても、生成する樹脂粒子同士の凝結を防ぎ、かつ扁平状や長球状の粒子が存在しないスチレン系樹脂粒子を得ることができる。また第２段階の重合温度を高い温度とすることができるため重合時間を短くすることができる。さらに、第１界面活性剤としてアルケンモノスルホン酸塩を用いることにより、得られる樹脂粒子の粒径分布が狭くなり、発泡性スチレン系樹脂粒子とした場合には、後述するように、発泡樹脂成形品の成形時の放冷時間が短縮される。
但し、本発明は重合温度を２段階に分けることに限定するものではない。例えば、重合温度を３段階に分けてもよければ、最初から最後まで同一の温度、例えば、１００℃で重合してもよい。これらの場合においても、特定の第１界面活性剤と特定の第２界面活性剤を併用して特定量用いることにより、所望される分子量を有し、粒径分布が狭い樹脂粒子を、樹脂粒子同士の凝結を防ぐと共に、扁平状や長球状の粒子を発生させないで懸濁重合により得ることができる。
Hereinafter, a method for producing the styrene resin particles (hereinafter also simply referred to as resin particles) of the present invention will be described in detail.
In the production method of the present invention, a styrene monomer is dispersed in an aqueous medium using a hardly water-soluble inorganic salt and a surfactant as a suspending agent, and the styrene monomer is subjected to a polymerization reaction under heating. By (suspension polymerization), styrene resin particles are produced. A method for producing styrene resin particles by such suspension polymerization is conventionally known. In the present invention, as the surfactant, a first surfactant composed of an alkene monosulfonate and a sulfone group in one molecule are used. A second surfactant having at least two or more is used in combination. That is, in the present invention, the molecular weight of the styrenic resin particles is required, and in order to promote monomer consumption and shorten the polymerization time, the first stage of polymerization is performed at a relatively low temperature, and then It is preferred to carry out the second stage polymerization at a relatively high temperature. In this case, when the two kinds of surfactants are used, even if the temperature is raised to a relatively high temperature as the polymerization temperature in the second stage, the resulting resin particles are prevented from condensing with each other, and flat or oval spherical particles are used. Styrenic resin particles that do not exist can be obtained. In addition, since the polymerization temperature in the second stage can be increased, the polymerization time can be shortened. Further, when the alkene monosulfonate is used as the first surfactant, the particle size distribution of the obtained resin particles becomes narrow, and when the foamable styrene resin particles are used, as described later, the foamed resin molding is performed. The cooling time when molding the product is shortened.
However, the present invention is not limited to dividing the polymerization temperature into two stages. For example, if the polymerization temperature may be divided into three stages, the polymerization may be carried out at the same temperature, for example, 100 ° C. from the beginning to the end. In these cases, resin particles having a desired molecular weight and a narrow particle size distribution can be obtained by using a specific amount in combination with a specific first surfactant and a specific second surfactant. It can be obtained by suspension polymerization while preventing condensation between each other and without generating flat or oblong particles.
本発明においては、第１界面活性剤としてアルケンモノスルホン酸塩が用いられる。該アルケンモノスルホン酸塩（α−オレフィンスルホン酸塩）としてはテトラデセンスルホン酸ナトリウム（α−オレフィンスルホン酸ナトリウム）が選択される。市販されているアルケンモノスルホン酸ナトリウムはその製法上ヒドロキシアルカンスルホン酸ナトリウムが含まれている事が多いが、本発明ではテトラデセンスルホン酸ナトリウム中にヒドロキシアルカンスルホン酸ナトリウムが含まれていても良い。 In the present invention, alkene monosulfonate is used as the first surfactant. As the alkene monosulfonate (α-olefin sulfonate), sodium tetradecene sulfonate (sodium α-olefin sulfonate) is selected. Commercially available sodium alkene monosulfonates often contain sodium hydroxyalkane sulfonate due to its production method, but in the present invention, sodium tetradecene sulfonate may contain sodium hydroxyalkane sulfonate. .
また、第２界面活性剤として、１分子中にスルホン基を少なくとも２つ以上持つ界面活性剤が用いられる。該第２界面活性剤としては、アルキルジフェニルエーテルジスルホン酸ナトリウム、β−ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩、ポリスチレンスルホン酸ナトリウムなどが挙げられる。中でもアルキルジフェニルエーテルスルホン酸ナトリウムが望ましい。 Further, as the second surfactant, a surfactant having at least two sulfone groups in one molecule is used. Examples of the second surfactant include sodium alkyldiphenyl ether disulfonate, sodium salt of β-naphthalene sulfonic acid formalin condensate, sodium polystyrene sulfonate, and the like. Of these, sodium alkyldiphenyl ether sulfonate is preferable.
本発明において、第１界面活性剤と第２界面活性剤との比率は、重量比で１０：９０から９０：１０の範囲内であり、５０：５０から９０：１０の範囲内が好ましい。第１界面活性剤の比率が上記範囲より小さくなると、樹脂粒子が真球状になりづらくなり、扁平状や長球状の樹脂粒子が多くなる。また粒径分布を狭くしにくくなる傾向があり、発泡性樹脂粒子とした場合には放冷時間を短くする効果が得られなくなる。また、第２界面活性剤の比率が上記範囲より小さくなると、反応時間を短くするために重合温度を１１０℃以上の高い温度に上げると、樹脂粒子が凝結しやすくなる。 In the present invention, the ratio of the first surfactant to the second surfactant is in the range of 10:90 to 90:10, and preferably in the range of 50:50 to 90:10, by weight. When the ratio of the first surfactant is smaller than the above range, the resin particles are less likely to be spherical, and the number of flat or oval resin particles increases. In addition, it tends to be difficult to narrow the particle size distribution, and when foamed resin particles are used, the effect of shortening the cooling time cannot be obtained. On the other hand, if the ratio of the second surfactant is smaller than the above range, the resin particles tend to condense when the polymerization temperature is raised to a high temperature of 110 ° C. or higher in order to shorten the reaction time.
前記第１界面活性剤と第２界面活性剤との合計添加量は、仕込み単量体の全重量１００重量部に対し０．０００１〜０．０５重量部であり、０．０００５〜０．０１００重量部であることが望ましい。合計添加量が、上記範囲よりも少ない場合には懸濁状態を安定化させるには界面活性剤量が不十分になり、反応系が全て固化してしまい、粒子形状として得られなくなったり、本発明で解決できる課題の改善度合いが小さくなるといった問題が発生したりする。上記範囲よりも界面活性剤使用量が多い場合においても懸濁状態が不安定となり反応系が固化するといった問題が発生する。 The total addition amount of the first surfactant and the second surfactant is 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the total weight of the charged monomers, and 0.0005 to 0.0100. A part by weight is desirable. When the total amount added is less than the above range, the amount of the surfactant becomes insufficient to stabilize the suspended state, the reaction system is completely solidified, and it may not be obtained as a particle shape. The problem that the improvement degree of the problem which can be solved by the invention becomes small occurs. Even when the amount of the surfactant used is larger than the above range, the suspension state becomes unstable and the reaction system solidifies.
前記界面活性剤の添加時期は、重合開始前および重合途中でも良く、２回以上に分けて添加しても良く、また第１界面活性剤と第２界面活性剤を別々に添加しても良い。ただし少なくとも第１界面活性剤の一部は重合開始前もしくは重合初期に水系媒体中に添加することが望ましい。第１界面活性剤の添加が遅れると懸濁状態を安定に保ちにくくなり、反応中に固化して、樹脂粒子が得られなくなる。また樹脂粒子が得られたとしても、粒度分布を狭くしにくくなる。また凝結発生防止の効果を得るためには少なくとも第２界面活性剤は、第２段階の重合温度への昇温前に添加することが望ましい。 The addition timing of the surfactant may be before the start of polymerization or during polymerization, may be added in two or more times, and the first surfactant and the second surfactant may be added separately. . However, it is desirable that at least a part of the first surfactant is added to the aqueous medium before or at the beginning of the polymerization. If the addition of the first surfactant is delayed, it becomes difficult to keep the suspension in a stable state, solidifying during the reaction, and resin particles cannot be obtained. Even if resin particles are obtained, it is difficult to narrow the particle size distribution. In order to obtain the effect of preventing the occurrence of condensation, it is desirable to add at least the second surfactant before raising the temperature to the polymerization temperature in the second stage.
本発明で用いられる難水溶性無機塩としては、例えば第３リン酸カルシウム、ハイドロキシアパタイト、ピロリン酸マグネシウム、リン酸マグネシウム、水酸化アルミニウム、水酸化第２鉄、水酸化チタン、水酸化マグネシウム、リン酸バリウム、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸カルシウム、硫酸バリウム、タルク、カオリン、ベントナイト等の微粒子状の難水溶性無機塩が挙げられる。なお上記難水溶性無機塩の添加量は、仕込み単量体の全重量１００重量部に対して０．０５〜３．０重量部であることが望ましい。上記範囲よりも少ない場合には得られる樹脂粒子の粒径が大きくなりすぎる、もしくは粒子形状を保てなくなり反応器内全体が固化しやすくなるといった問題が発生する。また上記範囲よりも多い場合においても得られる樹脂粒子の粒径が小さくなりすぎる虞がある。 Examples of the poorly water-soluble inorganic salt used in the present invention include tricalcium phosphate, hydroxyapatite, magnesium pyrophosphate, magnesium phosphate, aluminum hydroxide, ferric hydroxide, titanium hydroxide, magnesium hydroxide, and barium phosphate. , Calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, talc, kaolin, bentonite and the like in a particulate water-insoluble inorganic salt. The amount of the hardly water-soluble inorganic salt added is desirably 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the total weight of the charged monomers. When the amount is less than the above range, there is a problem that the particle diameter of the obtained resin particles becomes too large, or the particle shape cannot be maintained and the entire reactor is easily solidified. Further, even when the amount is larger than the above range, the particle size of the obtained resin particles may be too small.
また特開平８−２５３５１０号公報に示されているように、分散安定剤を添加した水系媒体中で難水溶性無機塩をグラインディング処理した、微小化した難水溶性無機塩を含む懸濁剤含有スラリーを用いても良い。 Further, as disclosed in JP-A-8-253510, a suspending agent containing a micronized slightly water-soluble inorganic salt obtained by grinding a water-insoluble inorganic salt in an aqueous medium to which a dispersion stabilizer is added. A contained slurry may be used.
また、必要に応じ懸濁重合の開始時点または懸濁重合中に電解質、例えば塩化リチウム、塩化カリウム、塩化ナトリウム、塩化マグネシウム、塩化カルシウム、硫酸ナトリウム、硝酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、塩化アルミニウム、硫酸マグネシウム、硫酸カリウム、硫酸アルミニウム、硫酸アンモニウム、硝酸マグネシウム、硝酸カリウム、硝酸カルシウム、炭酸カリウム、炭酸アンモニウム、水酸化ナトリウム、水酸化カリウム、リン酸水素２ナトリウム、リン酸２水素ナトリウム等の無機塩類、酢酸ナトリウム、コハク酸ナトリウム、安息香酸ナトリウム、シュウ酸ナトリウム、ギ酸ナトリウム、プロピオン酸ナトリウム、酪酸ナトリウム、吉草酸ナトリウム、マロン酸ナトリウム、アジピン酸ナトリウム、エチレンジアミン四酢酸二ナトリウム、エチレンジアミン四酢酸四ナトリウム、１，２，３−プロパントリカルボン酸ナトリウム、クエン酸ナトリウムや上記のカリウム塩、マグネシウム塩等の有機酸塩等を加えることができる。また過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素といった水溶性ラジカル発生剤を加えても良い。 If necessary, an electrolyte such as lithium chloride, potassium chloride, sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, sodium nitrate, sodium carbonate, sodium bicarbonate, aluminum chloride can be used at the start of suspension polymerization or during suspension polymerization. Inorganic salts such as magnesium sulfate, potassium sulfate, aluminum sulfate, ammonium sulfate, magnesium nitrate, potassium nitrate, calcium nitrate, potassium carbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, Sodium acetate, sodium succinate, sodium benzoate, sodium oxalate, sodium formate, sodium propionate, sodium butyrate, sodium valerate, sodium malonate, sodium adipate, sodium Diamine tetraacetic acid disodium, ethylenediaminetetraacetic acid tetrasodium, 1,2,3-propane tricarboxylic acid, sodium and said potassium salt of citric acid, may be added an organic acid salt such as magnesium salt. A water-soluble radical generator such as potassium persulfate, sodium persulfate, ammonium persulfate, or hydrogen peroxide may be added.
本発明に使用できるスチレン系単量体としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ビニルトルエン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、２，４−ジクロロスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−オクチルスチレン、スチレンスルホン酸、スチレンスルホン酸ナトリウム等が挙げられる。 Examples of the styrenic monomer that can be used in the present invention include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-ethylstyrene, 2,4-dimethylstyrene, p-methoxystyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, pn-butylstyrene, pt-butylstyrene, pn- Examples include hexyl styrene, p-octyl styrene, styrene sulfonic acid, sodium styrene sulfonate and the like.
また本発明においては、スチレンと共重合可能なビニル系単量体を併用しても良く、この例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸−２−エチルヘキシル等のアクリル酸の炭素数が１〜１０のアルキルエステルや、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸−２−エチルヘキシル等のメタクリル酸の炭素数が１〜１０のアルキルエステル、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート等の水酸基を有する不飽和化合物、アクリロニトリル、メタクリロニトリル等のニトリル基含有不飽和化合物、酢酸ビニル、プロピオン酸ビニル等の有機酸ビニル化合物、エチレン、プロピレン、１−ブテン、２−ブテン、イソブテン等の不飽和モノオレフィン類、ブタジエン、イソプレン、クロロプレン等のジエン化合物、塩化ビニル、塩化ビニリデン、臭化ビニル、フッ化ビニル等のハロゲン化ビニル、ビニルメチルケトン、ビニルエチルケトン、ビニルヘキシルケトン等のビニルケトン類、ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテル等のビニルエーテル類、Ｎ−ビニルピロリドン、Ｎ−ビニルインドール、Ｎ−ビニルカルバゾール、Ｎ−ビニルピロール等のＮ−ビニル化合物、アクリルアミン、メタクリルアミン、Ｎ−メチロールアクリルアミン、Ｎ−メチロールメタクリルアミン等のアミン基を有する不飽和化合物、アクリル酸、メタクリル酸、イタコン酸等の不飽和カルボン酸、Ｎ−フェニルマレイミド、Ｎ−（メチル）フェニルマレイミド、Ｎ−（ヒドロキシ）フェニルマレイミド、Ｎ−（メトキシ）フェニルマレイミド、Ｎ−安息香酸マレイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−ｎ−プロピルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ｎ−ブチルマレイミド、Ｎ−イソブチルマレイミド、Ｎ−ｔ−ブチルマレイミド等のマレイミド系化合物、ジビニルベンゼン、エチレングリコールジメタクリレート等の架橋性多官能ビニル化合物、グリシジルアクリレート、グリシジルメタクリレート等のエポキシ基を有する不飽和化合物などの各種のビニル系化合物が挙げられる。 In the present invention, a vinyl monomer copolymerizable with styrene may be used in combination. Examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and acrylic acid-2- C 1-10 alkyl esters of acrylic acid such as ethylhexyl, and 1-10 carbon atoms of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Alkyl ester, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl unsaturated unsaturated compounds, acrylonitrile, methacrylo Nitrile group-containing unsaturated compounds such as tolyl, organic acid vinyl compounds such as vinyl acetate and vinyl propionate, unsaturated monoolefins such as ethylene, propylene, 1-butene, 2-butene and isobutene, butadiene, isoprene, chloroprene, etc. Diene compounds, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl indole, N-vinyl carbazole, N-vinyl pyrrole, acrylic amine, methacrylamine, N-methylol acrylic amine, N-methylol meta Unsaturated compounds having an amine group such as rilamine, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid, N-phenylmaleimide, N- (methyl) phenylmaleimide, N- (hydroxy) phenylmaleimide, N- ( Methoxy) phenylmaleimide, N-benzoic acid maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, Nt-butyl Examples thereof include various vinyl compounds such as maleimide compounds such as maleimide, crosslinkable polyfunctional vinyl compounds such as divinylbenzene and ethylene glycol dimethacrylate, and unsaturated compounds having an epoxy group such as glycidyl acrylate and glycidyl methacrylate.
また、本発明に使用できる重合開始剤としては、たとえばアゾビスイソブチロニトリル等のアゾ系化合物、クメンヒドロパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシベンゾエート、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシ２−エチルヘキシルモノカーボネート、１，１−ジメチルプロピルパーオキシ−２−エチルヘキシルモノカーボネート、１，１−ジメチルブチルパーオキシ−２−エチルヘキシルモノカーボネート、ペンチルパーオキシ２−エチルヘキシルモノカーボネート、ヘキシルパーオキシ２−エチルヘキシルモノカーボネート、ラウロイルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ジ−ｔ−ブチルパーオキシ−２−メチルシクロヘキサン等のスチレン系単量体に可溶な開始剤が挙げられる。 Examples of the polymerization initiator that can be used in the present invention include azo compounds such as azobisisobutyronitrile, cumene hydroperoxide, dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t -Butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, 1,1-dimethylpropyl peroxy-2-ethylhexyl monocarbonate, 1,1-dimethylbutyl Peroxy-2-ethylhexyl monocarbonate, pentylperoxy 2-ethylhexyl monocarbonate, hexyl peroxy 2-ethylhexyl monocarbonate, lauroyl peroxide, 1,1-bis (t-butyl peroxide) ) -3,3,5-trimethylcyclohexane, soluble initiators styrenic monomers such as 1,1-di -t- butyl-peroxy-2-methyl cyclohexane.
本発明では、スチレン系樹脂粒子の重合の際に、短時間でスチレン系樹脂粒子に要求される分子量を得るために、８０℃〜１００℃で重合の第１段階を行い、モノマーの消費を促進し重合時間を短縮する目的で重合後半の重合温度を１００〜１３０℃に上げて第２段階の重合を行うことが好ましく、それぞれの温度に適した２種類の重合開始剤を用いることが好ましい。第１段階の重合温度用の重合開始剤としては１０時間半減期温度の低いベンゾイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエートなどが用いられ、第２段階の高温での重合開始剤としては、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシ２−エチルヘキシルモノカーボネートなどが用いられる。
上記の重合開始剤は、１種類を単独で、または２種以上を混合して使用することができる。
In the present invention, during the polymerization of styrene resin particles, in order to obtain the molecular weight required for styrene resin particles in a short time, the first stage of polymerization is performed at 80 ° C. to 100 ° C. to promote monomer consumption. For the purpose of shortening the polymerization time, it is preferable to carry out the second stage polymerization by raising the polymerization temperature in the latter half of the polymerization to 100 to 130 ° C., and it is preferable to use two kinds of polymerization initiators suitable for each temperature. As the polymerization initiator for the first stage polymerization temperature, benzoyl peroxide having a low 10-hour half-life temperature, t-butylperoxy-2-ethylhexanoate, or the like is used, and the second stage polymerization starts at a high temperature. As the agent, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, or the like is used.
Said polymerization initiator can be used individually by 1 type or in mixture of 2 or more types.
また、必要に応じて、分子量を調整するためにα−メチルスチレンダイマー、ドデシルメルカプタンなどの連鎖移動剤も添加することができる。 Moreover, in order to adjust molecular weight, chain transfer agents, such as (alpha) -methylstyrene dimer and dodecyl mercaptan, can also be added as needed.
更にスチレン系樹脂粒子、発泡性スチレン系樹脂粒子に対して、通常使用されている添加剤、すなわち難燃剤、可塑剤、セル核剤、帯電防止剤、導電化剤なども適宜添加することができる。 Furthermore, additives that are usually used, that is, flame retardants, plasticizers, cell nucleating agents, antistatic agents, conductive agents, and the like can be added as appropriate to styrene resin particles and expandable styrene resin particles. .
本発明においては、重合反応途中もしくは重合反応後に反応器内に発泡剤を添加することにより、成形時の放冷時間が短い発泡性スチレン系樹脂粒子を得ることができる。
上記発泡剤としては、例えばプロパン、ブタン、ペンタンなどの脂肪族炭化水素、塩化メチル、塩化メチレン等のハロゲン化炭化水素、１，１，１，２−テトラフルオロエタン、１，１，１−トリフルオロエタン等のフッ素化炭化水素等、窒素、酸素、二酸化炭素、水等の無機ガス等が挙げられる。中でも脂肪族炭化水素、特にブタンを発泡剤とすることが、得られる発泡性ポリスチレン系樹脂粒子の物性面、経済的な面、環境・安全面から優れるため望ましい。
In the present invention, expandable styrene resin particles having a short cooling time during molding can be obtained by adding a foaming agent in the reactor during or after the polymerization reaction.
Examples of the blowing agent include aliphatic hydrocarbons such as propane, butane and pentane, halogenated hydrocarbons such as methyl chloride and methylene chloride, 1,1,1,2-tetrafluoroethane, 1,1,1-trimethyl. Examples thereof include fluorinated hydrocarbons such as fluoroethane, and inorganic gases such as nitrogen, oxygen, carbon dioxide, and water. Among them, it is preferable to use an aliphatic hydrocarbon, particularly butane, as a foaming agent because it is excellent in physical properties, economical aspects, and environmental and safety aspects of the resulting expandable polystyrene resin particles.
前記ブタンはイソブタン、ノルマルブタン、シクロブタンいずれも使用することができる。ブタンの添加量はその発泡成形品の用途に応じた密度を得るのに適した量を添加できる。また、他の発泡剤たとえばノルマルペンタン、イソペンタン、ネオペンタン、ヘキサン等のブタンよりも沸点の高い脂肪族炭化水素等も併用することができるが、これらの発泡剤の占める割合が多くなるとブタン単独で使用したときよりも樹脂粒子の発泡力は落ちるため低密度のものを得ることが難しく、また発泡成形品が収縮しやすくなる、強度・表面が弱くなるといった問題が出やすくなる。またプロパンのような沸点の低いガスも併用できるが成形時の放冷時間が長くなる欠点を持つ。よって、少なくともブタンを全発泡剤量の半分以上にするのが望ましい。 As the butane, any of isobutane, normal butane, and cyclobutane can be used. The amount of butane added can be an amount suitable for obtaining a density corresponding to the use of the foamed molded product. In addition, other blowing agents such as normal hydrocarbons such as normal pentane, isopentane, neopentane, and hexane can be used in combination with aliphatic hydrocarbons having a boiling point higher than butane. However, when the proportion of these blowing agents increases, butane is used alone. As a result, the foaming power of the resin particles is lower than that of the resin particles, so that it is difficult to obtain a low-density one, and the foamed molded product tends to shrink, and the strength and the surface become weak. Further, a gas having a low boiling point such as propane can be used in combination, but it has a disadvantage that the cooling time during molding becomes long. Therefore, it is desirable to make at least butane half or more of the total amount of blowing agent.
また、本発明の発泡性ポリスチレン樹脂粒子の製造には、一般に成形放冷時間を短縮するためのコーティング剤（ハイサイクルコーティング剤）、例えば高級脂肪酸の脂肪族アルコールエステル、特に常温で固体の牛脂硬化油、ヒマシ硬化油といったトリグリセリンエステル、流動パラフィン等を必要に応じ併用することもできる。その際、第１界面活性剤としてアルケンスルホン酸塩を使うと、他の界面活性剤を用いたときよりも成形時の放冷時間が短縮されるため、これらコーティング剤量は他の界面活性剤を使用するときよりも少ない添加量で目的の成形放冷時間とすることができる。 In addition, in the production of the expandable polystyrene resin particles of the present invention, generally a coating agent (high cycle coating agent) for shortening the mold cooling time, for example, a fatty alcohol ester of a higher fatty acid, particularly a beef tallow cured at room temperature. Triglycerin esters such as oil and castor oil, liquid paraffin, etc. can be used in combination as required. At that time, when the alkene sulfonate is used as the first surfactant, the cooling time at the time of molding is shortened compared with the case of using another surfactant. The desired cooling time can be achieved with a smaller amount of addition than when using.
また一般的に発泡性ポリスチレン系樹脂粒子に用いられるその他の樹脂粒子コーティング剤も用いることができる。具体的には脂肪酸金属塩、エチレンビス脂肪酸アミド、シリカ、タルクといったブロッキング防止剤、グリセリンモノステアレート、ポリエチレングリコール、アルキルジエタノールアミン、グリセリンといった帯電防止剤、シリコーンオイルなどが挙げられる。 In addition, other resin particle coating agents generally used for expandable polystyrene resin particles can also be used. Specific examples include anti-blocking agents such as fatty acid metal salts, ethylene bis-fatty acid amide, silica and talc, antistatic agents such as glycerin monostearate, polyethylene glycol, alkyldiethanolamine and glycerin, and silicone oil.
以下、実施例により本発明を更に詳細に説明する。但し、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
実施例１
５０Ｌの反応器に純水１６０００ｇ、難水溶性無機塩として第３リン酸カルシウムを４５．０ｇ、第１界面活性剤としてライオン株式会社製、商品名「リポランＬＢ４４０」（テトラデセンスルホン酸ナトリウム成分を３６重量％含有）を１．７７１ｇ、第２界面活性剤として花王株式会社製、商品名「ペレックスＳＳＨ」（ドデシルジフェニルエーテルジスルホン酸ナトリウム成分を５０重量％含有）を０．４２５ｇ、および酢酸ナトリウム２４．０ｇを投入し攪拌した。次いで、スチレン１７０００ｇに、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート４７．０ｇ、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート１７．０ｇを添加したスチレン溶液を反応器に投入し、反応器を密閉した。
尚、仕込み単量体１００重量部当たりの、第１界面活性剤の添加量（重量部）、第２界面活性剤の添加量（重量部）、第１界面活性剤と第２界面活性剤の重量比、第１界面活性剤と第２界面活性剤の合計添加量（重量部）を表１に示す（実施例２〜５についても同様）。
Example 1
In a 50 L reactor, 16000 g of pure water, 45.0 g of tricalcium phosphate as a poorly water-soluble inorganic salt, Lion Corporation, trade name “Lipolane LB440” (36% by weight of sodium tetradecene sulfonate component) as the first surfactant 1.72 g) as a second surfactant, 0.425 g of a trade name “Perex SSH” (containing 50% by weight of sodium dodecyl diphenyl ether disulfonate component) as a second surfactant, and 24.0 g of sodium acetate. Charged and stirred. Next, a styrene solution obtained by adding 47.0 g of t-butylperoxy-2-ethylhexanoate and 17.0 g of t-butylperoxy-2-ethylhexyl monocarbonate as a polymerization initiator to 17000 g of styrene was charged into the reactor. And the reactor was sealed.
In addition, the addition amount (parts by weight) of the first surfactant, the addition amount (parts by weight) of the second surfactant per 100 parts by weight of the charged monomer, the first surfactant and the second surfactant The weight ratio and the total addition amount (parts by weight) of the first surfactant and the second surfactant are shown in Table 1 (the same applies to Examples 2 to 5).
その後昇温を開始し１時間かけて９０℃まで昇温した。昇温途中６０℃で過硫酸カリウムを０．０８ｇ添加した。
９０℃到達後、１００℃まで５時間かけて昇温し、さらに１１２℃まで１時間３０分で昇温しそのまま１１２℃で１００分保持した。その後室温まで冷却し樹脂粒子を得た。
次いで反応器から粒子スラリーを抜き出し、水系媒体と粒子を分離した後、流動乾燥装置で乾燥しスチレン系樹脂粒子を得た。
重合中における樹脂粒子の凝結の有無、扁平状や長球状の粒子の発生についての評価を表１に示す（実施例２〜５についても同様）。
Thereafter, the temperature was raised and the temperature was raised to 90 ° C. over 1 hour. During the temperature increase, 0.08 g of potassium persulfate was added at 60 ° C.
After reaching 90 ° C., the temperature was raised to 100 ° C. over 5 hours, further raised to 112 ° C. over 1 hour 30 minutes, and kept at 112 ° C. for 100 minutes. Thereafter, the mixture was cooled to room temperature to obtain resin particles.
Next, the particle slurry was extracted from the reactor, the aqueous medium and the particles were separated, and then dried with a fluidized drying apparatus to obtain styrene resin particles.
Table 1 shows the evaluation of the presence or absence of condensation of the resin particles during the polymerization and the generation of flat or oblong particles (the same applies to Examples 2 to 5).
実施例２
「リポランＬＢ４４０」を２．１２５ｇ、「ペレックスＳＳＨ」を０．１７０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 2
Styrenic resin particles were obtained in the same manner as in Example 1 except that 2.125 g of “Lipolane LB440” and 0.170 g of “Perex SSH” were used.
実施例３
「リポランＬＢ４４０」を０．２３６ｇ、「ペレックスＳＳＨ」を１．５３０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 3
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.236 g of “Lipolane LB440” and 1.530 g of “Perex SSH” were used.
実施例４
「リポランＬＢ４４０」を１．１８１ｇ、「ペレックスＳＳＨ」を０．８５０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 4
Styrenic resin particles were obtained in the same manner as in Example 1 except that 1.181 g of “Lipolane LB440” and 0.850 g of “Perex SSH” were used.
実施例５
「リポランＬＢ４４０」を０．０３５ｇ、「ペレックスＳＳＨ」を０．００８５ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 5
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.035 g of “Lipolane LB440” and 0.0085 g of “Perex SSH” were used.
実施例６
「リポランＬＢ４４０」を１７．７０８ｇ、「ペレックスＳＳＨ」を４．２５０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
尚、第１界面活性剤の添加量（重量部）、第２界面活性剤の添加量（重量部）、第１界面活性剤と第２界面活性剤の重量比、第１界面活性剤と第２界面活性剤の合計添加量（重量部）、重合中における樹脂粒子の凝結の有無、扁平状や長球状の粒子の発生についての評価を表２に示す（実施例７〜９についても同様）。
Example 6
Styrenic resin particles were obtained in the same manner as in Example 1 except that 17.708 g of “Lipolane LB440” and 4.250 g of “Perex SSH” were used.
Incidentally, the addition amount (parts by weight) of the first surfactant, the addition amount (parts by weight) of the second surfactant, the weight ratio of the first surfactant to the second surfactant, the first surfactant and the second surfactant. Table 2 shows the total addition amount (parts by weight) of 2 surfactants, presence / absence of condensation of resin particles during polymerization, and generation of flat or oblong particles (the same applies to Examples 7 to 9). .
実施例７
「リポランＬＢ４４０」を０．３５４ｇ、「ペレックスＳＳＨ」を０．０８５ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 7
Styrenic resin particles were obtained in the same manner as in Example 1 except that “Lipolane LB440” was 0.354 g and “Perex SSH” was 0.085 g.
実施例８
「リポランＬＢ４４０」を３．５４２ｇ、「ペレックスＳＳＨ」を０．８５０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 8
Styrene resin particles were obtained in the same manner as in Example 1 except that 3.542 g of “Lipolane LB440” and 0.850 g of “Perex SSH” were used.
実施例９
第２界面活性剤として、「ペレックスＳＳＨ」の替わりに花王株式会社製、商品名「デモールＮＬ」（β−ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩を４１重量％含有）を０．５１９ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Example 9
As the second surfactant, instead of “Perex SSH”, the product name “Demol NL” (containing 41% by weight of sodium salt of β-naphthalenesulfonic acid formalin condensate) manufactured by Kao Corporation was changed to 0.519 g. Obtained styrene resin particles in the same manner as in Example 1.
比較例１
「リポランＬＢ４４０」を２．２４３ｇ、「ペレックスＳＳＨ」を０．０８５０ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
尚、第１界面活性剤の添加量（重量部）、第２界面活性剤の添加量（重量部）、第１界面活性剤と第２界面活性剤の重量比、第１界面活性剤と第２界面活性剤の合計添加量（重量部）、重合中における樹脂粒子の凝結の有無、扁平状や長球状の粒子の発生についての評価を表３に示す（比較例２〜５についても同様）。
Comparative Example 1
Styrenic resin particles were obtained in the same manner as in Example 1 except that 2.243 g of “Lipolane LB440” and 0.0850 g of “Perex SSH” were used.
Incidentally, the addition amount (parts by weight) of the first surfactant, the addition amount (parts by weight) of the second surfactant, the weight ratio of the first surfactant to the second surfactant, the first surfactant and the second surfactant. Table 3 shows the total addition amount (parts by weight) of 2 surfactants, presence / absence of condensation of resin particles during polymerization, and generation of flat or oval particles (the same applies to Comparative Examples 2 to 5). .
比較例２
「リポランＬＢ４４０」を０．１１８ｇ、「ペレックスＳＳＨ」を１．６１５ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 2
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.118 g of “Lipolane LB440” and 1.615 g of “Perex SSH” were used.
比較例３
「リポランＬＢ４４０」を０．０１８ｇ、「ペレックスＳＳＨ」を０．００４ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 3
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.018 g of “Lipolane LB440” and 0.004 g of “Perex SSH” were used.
比較例４
「リポランＬＢ４４０」を２１．２５０ｇ、「ペレックスＳＳＨ」を５．１００ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 4
Styrenic resin particles were obtained in the same manner as in Example 1 except that 21.250 g of “Lipolane LB440” and 5.100 g of “Perex SSH” were used.
比較例５
「リポランＬＢ４４０」の代わりにドデシルベンゼンスルホン酸ナトリウム（東京化成工業株式会社製）を０．６３８ｇ、とした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 5
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.638 g of sodium dodecylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of “Lipolane LB440”.
比較例６
「ペレックスＳＳＨ」の代わりにドデシルベンゼンスルホン酸ナトリウム（東京化成工業株式会社製）を０．２１３ｇとした以外は実施例１と同様にスチレン系樹脂粒子を得た。
尚、仕込み単量体１００重量部当たりの、第１界面活性剤の添加量（重量部）、第２界面活性剤の添加量（重量部）、第１界面活性剤と第２界面活性剤の重量比、第１界面活性剤と第２界面活性剤の合計添加量（重量部）、重合中における樹脂粒子の凝結の有無、扁平状や長球状の粒子の発生についての評価を表４に示す（比較例７、８についても同様）。
Comparative Example 6
Styrenic resin particles were obtained in the same manner as in Example 1 except that 0.213 g of sodium dodecylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of “Perex SSH”.
In addition, the addition amount (parts by weight) of the first surfactant, the addition amount (parts by weight) of the second surfactant per 100 parts by weight of the charged monomer, the first surfactant and the second surfactant Table 4 shows the evaluation of the weight ratio, the total addition amount (parts by weight) of the first surfactant and the second surfactant, the presence or absence of condensation of the resin particles during the polymerization, and the generation of flat or oval particles. (The same applies to Comparative Examples 7 and 8.)
比較例７
「リポランＬＢ４４０」を２．３６１ｇ、「ペレックスＳＳＨ」を未添加とした以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 7
Styrenic resin particles were obtained in the same manner as in Example 1 except that 2.361 g of “Lipolane LB440” and “Perex SSH” were not added.
比較例８
「リポランＬＢ４４０」を未添加とし、「ペレックスＳＳＨ」を１．７００ｇ添加する以外は実施例１と同様にスチレン系樹脂粒子を得た。
Comparative Example 8
Styrenic resin particles were obtained in the same manner as in Example 1 except that “Lipolane LB440” was not added and 1.700 g of “Perex SSH” was added.
実施例１０
５０Ｌの反応器に純水１６０００ｇ、難水溶性無機塩として第３リン酸カルシウム４５．０ｇ、第１界面活性剤としてライオン株式会社製、商品名「リポランＬＢ４４０」（テトラデセンスルホン酸ナトリウム成分を３６重量％含有）を１．７７１ｇ、第２界面活性剤として花王株式会社製、商品名「ペレックスＳＳＨ」（ドデシルジフェニルエーテルジスルホン酸ナトリウム成分を５０重量％含有）を０．４２５ｇ、および酢酸ナトリウム２４．０ｇを投入し攪拌した。次いで、スチレン１７０００ｇに、重合開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート４７．０ｇ、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート１７．０ｇ、可塑剤としてシクロヘキサン２６０ｇ、牛脂硬化油（グリセリントリステアレート）１２０ｇ、さらにセル核剤としてポリエチレンワックス８．５ｇを添加したスチレン溶液を反応器に投入し、反応器を密閉した。
Example 10
In a 50 L reactor, 16000 g of pure water, 45.0 g of tricalcium phosphate as a poorly water-soluble inorganic salt, Lion Corporation, trade name “Lipolane LB440” (36% by weight of sodium tetradecene sulfonate component) (Contained) as a second surfactant, 0.425 g of trade name “Perex SSH” (containing 50% by weight of sodium dodecyl diphenyl ether disulfonate component), and 24.0 g of sodium acetate as a second surfactant. And stirred. Subsequently, 17,000 g of styrene, 47.0 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, 17.0 g of t-butylperoxy-2-ethylhexyl monocarbonate, 260 g of cyclohexane as a plasticizer, hydrogenated beef tallow oil 120 g of (glycerin tristearate) and a styrene solution added with 8.5 g of polyethylene wax as a cell nucleating agent were charged into the reactor, and the reactor was sealed.
その後昇温を開始し１時間かけて９０℃まで昇温した。昇温途中６０℃で過硫酸カリウムを０．０８ｇ添加した。
９０℃到達後、１００℃まで５時間かけて昇温し、さらに１１２℃まで１時間３０分で昇温しそのまま１１２℃で１００分保持した。途中９０度到達から４時間３０分目に発泡剤としてブタン（イソブタン ３５％、ノルマルブタン ６５％の混合物）を１４００ｇ反応機内に圧入した。その後室温まで冷却し樹脂粒子を得た。
次いで反応器から粒子スラリーを抜き出し、水系媒体と粒子を分離した後、流動乾燥装置で乾燥し発泡性スチレン系樹脂粒子を得た。
尚、仕込み単量体１００重量部当たりの、第１界面活性剤の添加量（重量部）、第２界面活性剤の添加量（重量部）、第１界面活性剤と第２界面活性剤の重量比、第１界面活性剤と第２界面活性剤の合計添加量（重量部）、重合中における樹脂粒子の凝結の有無、扁平状や長球状の粒子の発生についての評価を表５に示す（実施例１１、比較例９、１０についても同様）。
Thereafter, the temperature was raised and the temperature was raised to 90 ° C. over 1 hour. During the temperature increase, 0.08 g of potassium persulfate was added at 60 ° C.
After reaching 90 ° C., the temperature was raised to 100 ° C. over 5 hours, further raised to 112 ° C. over 1 hour 30 minutes, and kept at 112 ° C. for 100 minutes. 4 hours and 30 minutes after reaching 90 degrees midway, butane (a mixture of isobutane 35% and normal butane 65%) was injected into a 1400 g reactor as a blowing agent. Thereafter, the mixture was cooled to room temperature to obtain resin particles.
Next, the particle slurry was extracted from the reactor, the aqueous medium and the particles were separated, and then dried by a fluidized drying device to obtain expandable styrene resin particles.
In addition, the addition amount (parts by weight) of the first surfactant, the addition amount (parts by weight) of the second surfactant per 100 parts by weight of the charged monomer, the first surfactant and the second surfactant Table 5 shows the evaluation of the weight ratio, the total addition amount (parts by weight) of the first surfactant and the second surfactant, the presence or absence of condensation of the resin particles during the polymerization, and the generation of flat or oblong particles. (The same applies to Example 11 and Comparative Examples 9 and 10).
次いでこの粒子を０．７〜１．４ｍｍに篩い分けをした後、ヘンシェルミキサーに投入し放冷時間短縮のためのハイサイクルコーティング剤としてグリセリントリステアレートを０．１４重量％添加し、さらにグリセリンモノステアレート０．１０重量％、ステアリン酸亜鉛０．１５重量％を添加してコーティングした。
次いで、樹脂粒子１００ｋｇを直径３５ｃｍの円筒形容器に入れ流量５５ｍ３／ｈｒ、４０℃の温風を容器下部より導入し、そのまま９０分処理して発泡性ポリスチレン系樹脂粒子を得た。
得られた発泡性スチレン系樹脂粒子を加圧バッチ予備発泡機で蒸気発泡し嵩密度２０．０ｋｇ／ｍ２の予備発泡粒子を得た。得られた予備発泡粒子を室温で１日熟成後、型物成形機で直径３００ｍｍ×厚さ５０ｍｍの円筒形成形品の成形を行った。成形の条件は０．０７ＭＰａ（ゲージ圧）のスチーム圧力で２０秒間加熱した後、水冷５秒行いさらに−０．０８ＭＰａ（ゲージ圧）の減圧度で真空放冷を行い金型内圧力が０．０１ＭＰａ（ゲージ圧）に到達したときに金型を開き成形品を離型した。真空放冷開始から離型までの時間を放冷時間として記録した。
尚、放冷時間、得られた発泡成形品の表面状態の評価を表５に示す（実施例１１、比較例９、１０についても同様）。
Next, after sieving the particles to 0.7 to 1.4 mm, they are put into a Henschel mixer and 0.14% by weight of glycerin tristearate is added as a high cycle coating agent for shortening the cooling time. Coating was performed by adding 0.10% by weight of monostearate and 0.15% by weight of zinc stearate.
Subsequently, 100 kg of resin particles were put into a cylindrical container having a diameter of 35 cm, hot air at a flow rate of 55 m 3 / hr and 40 ° C. was introduced from the lower part of the container, and treated as it was for 90 minutes to obtain expandable polystyrene resin particles.
The obtained expandable styrenic resin particles were vapor-foamed with a pressure batch pre-foaming machine to obtain pre-expanded particles having a bulk density of 20.0 kg / m 2 . The obtained pre-expanded particles were aged at room temperature for 1 day, and then a cylinder-shaped product having a diameter of 300 mm and a thickness of 50 mm was molded by a mold molding machine. The molding condition was that after heating for 20 seconds at a steam pressure of 0.07 MPa (gauge pressure), water cooling was performed for 5 seconds, followed by vacuum cooling at a reduced pressure of -0.08 MPa (gauge pressure), and the pressure in the mold was 0. When the pressure reached 01 MPa (gauge pressure), the mold was opened to release the molded product. The time from the start of vacuum cooling to release was recorded as the cooling time.
The evaluation of the cooling time and the surface state of the obtained foamed molded product are shown in Table 5 (the same applies to Example 11 and Comparative Examples 9 and 10).
実施例１１
ヘンシェルミキサーに投入するグリセリントリステアレートの量を０．１８重量％に変更した以外は実施例１０と同様にスチレン系樹脂粒子を得た。
Example 11
Styrenic resin particles were obtained in the same manner as in Example 10 except that the amount of glycerin tristearate charged into the Henschel mixer was changed to 0.18% by weight.
比較例９
「リポランＬＢ４４０」の代わりにドデシルベンゼンスルホン酸ナトリウム（東京化成工業株式会社製）を０．６３８ｇとした以外は実施例１０と同様にスチレン系樹脂粒子を得た。
Comparative Example 9
Styrenic resin particles were obtained in the same manner as in Example 10 except that 0.638 g of sodium dodecylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of “Lipolane LB440”.
比較例１０
「リポランＬＢ４４０」の代わりにドデシルベンゼンスルホン酸ナトリウム（東京化成工業株式会社製）を０．６３８ｇとした以外は実施例１１と同様にスチレン系樹脂粒子を得た。
Comparative Example 10
Styrenic resin particles were obtained in the same manner as in Example 11 except that 0.638 g of sodium dodecylbenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of “Lipolane LB440”.
実施例、比較例で得られた樹脂粒子１００ｇを直径３００ｍｍのＪＩＳ篩を用いて篩い分けを行い、各々の篩上にスチレン系樹脂粒子の重量を測定し、平均粒径（Ｄ５０：重量累積％で５０％の時の粒子径）を算出した。結果を表１〜５に示す。 100 g of the resin particles obtained in Examples and Comparative Examples were sieved using a JIS sieve having a diameter of 300 mm, and the weight of styrene resin particles was measured on each sieve, and the average particle diameter (D50: weight cumulative%) The particle diameter at 50% was calculated. The results are shown in Tables 1-5.
上記平均粒径（Ｄ５０）は、画像解析粒度分布測定装置（日機装株式会社製ミリトラックＪＰＡ）で粒度分布を測定し、全粒子の体積に対する累積体積が５０％になる時の粒子径を５０％粒子径（Ｄ５０）として求めた値である。尚、測定に際しての測定装置の粒子の形状ファクターは１（球形）とした。また、後述の粒径分布におけるＤ１０及びＤ９０は、全粒子の体積に対する累積体積が１０％及び９０％になる時の粒子径をそれぞれ１０％粒子径（Ｄ１０）及び９０％粒子径（Ｄ９０）と定義される。 The average particle size (D50) is determined by measuring the particle size distribution with an image analysis particle size distribution measuring apparatus (Millitrack JPA manufactured by Nikkiso Co., Ltd.), and the particle size when the cumulative volume with respect to the volume of all particles is 50% is 50%. This is the value obtained as the particle diameter (D50). In addition, the shape factor of the particle | grains of the measuring device in the case of measurement was set to 1 (spherical shape). In addition, D10 and D90 in the particle size distribution described later are the particle sizes when the cumulative volume with respect to the volume of all particles is 10% and 90%, respectively, as 10% particle size (D10) and 90% particle size (D90). Defined.
粒径分布は次の数値で表した。結果を表１〜５に示す。
Ｃｖ（％）＝（Ｄ９０−Ｄ１０）／Ｄ５０×１００
The particle size distribution was represented by the following numerical values. The results are shown in Tables 1-5.
Cv (%) = (D90−D10) / D50 × 100
樹脂粒子の凝結については、得られた樹脂粒子を小皿に取り、目視で確認して次の３段階評価を行った。結果を表１〜５に示す。
○：粒子凝結無し
△：一部凝結あり
×：反応器内で粒子が殆ど凝結
Regarding the condensation of the resin particles, the obtained resin particles were placed in a small dish and visually confirmed to perform the following three-stage evaluation. The results are shown in Tables 1-5.
○: No particle condensation Δ: Partial condensation ×: Particles are almost condensed in the reactor
扁平状や長球状の粒子の発生については、得られた樹脂粒子を小皿に取り、目視で確認して次の３段階評価を行った。結果を表１〜５に示す。
○：扁平状や長球状の粒子無し
△：一部扁平状や長球状の粒子あり
×：殆どが扁平状や長球状の粒子
About generation | occurrence | production of a flat shape and an oblong particle, the obtained resin particle was picked up to the small dish, and it confirmed visually and performed the following three-stage evaluation. The results are shown in Tables 1-5.
○: No flat or oblong particles Δ: Some flat or oblong particles ×: Most flat or oblong particles
発泡成形品の表面については、表面に並ぶ発泡粒子間の間隙有無、間隙の大小、および発泡粒子の熱による表面溶融の有無について目視で観察し、次の基準で評価を行った。
◎：粒子間隙がほとんどなく平滑で美麗な表面
○：間隙もしくは表面溶融がややあるが目立たない程度
△：間隙、表面溶融があり凸凹が目立つ
×：発泡粒子が殆ど伸びておらず粒子形状がそのまま残っている状態
結果を表５に示す。
With respect to the surface of the foam molded article, the presence or absence of gaps between the foam particles aligned on the surface, the size of the gap, and the presence or absence of surface melting due to the heat of the foam particles were visually observed and evaluated according to the following criteria.
A: Smooth and beautiful surface with almost no interstices between particles ○: Slight gap or surface melting but inconspicuous Δ: Interspersed with gaps and surface melting and conspicuous unevenness ×: Expanded particles hardly stretched and particle shape remains as it is Table 5 shows the remaining state results.
表１〜４から、特定の第１界面活性剤と特定の第２界面活性剤を併用し、第１界面活性剤と第２界面活性剤との重量比を特定範囲内とし、第１界面活性剤と第２界面活性剤との合計添加量を特定範囲内にすることにより、粒子凝結や扁平粒子等を発生させることなく、懸濁重合によりスチレン系樹脂粒子を得ることができることが判る。しかも、得られるスチレン系樹脂粒子の平均粒径が比較的小さく（具体的には、１．４１ｍｍ以下）、粒度分布Ｃｖが比較的狭く（具体的には、３８％以下）なることも判る。
これに対し、第２界面活性剤に対する第１界面活性剤の重量比が大きくなりすぎると、部分的に樹脂粒子の凝結が起きることが判る（比較例１）。また、第１界面活性剤に対する第２界面活性剤の重量比が大きくなりすぎると、部分的に扁平状や長球状の粒子が発生し、粒度分布Ｃｖが広く（具体的には、４０％）なることが判る。
また、第１界面活性剤と第２界面活性剤との合計添加量が少なすぎても、多すぎても、スチレン系樹脂が凝固してしまうことが判る（比較例３、４）。
また、第１界面活性剤としてドデシルベンゼンスルホン酸ナトリウムを用いると、粒子凝結や扁平粒子の発生は防止されるが、得られる樹脂粒子の粒度分布Ｃｖが広く（具体的には、４０％）なってしまうことが判る（比較例５）。
また、第２界面活性剤として、ドデシルベンゼンスルホン酸ナトリウムを用いると、凝結や扁平粒子等の発生を防止することができなくなることが判る（比較例６）。
また、第２界面活性剤を添加しないと、凝結や扁平粒子の発生を防止することができなくなり（比較例７）、第１界面活性剤を添加しないと、得られる樹脂粒子の殆どが扁平状や長球状の粒子になることが判る（比較例８）。
From Tables 1-4, the specific 1st surfactant and the specific 2nd surfactant are used together, the weight ratio of the 1st surfactant and the 2nd surfactant is in the specific range, the 1st surfactant It can be seen that, by setting the total addition amount of the agent and the second surfactant within a specific range, styrene resin particles can be obtained by suspension polymerization without generating particle condensation, flat particles, or the like. Moreover, it can be seen that the average particle size of the resulting styrene resin particles is relatively small (specifically, 1.41 mm or less) and the particle size distribution Cv is relatively narrow (specifically, 38% or less).
On the other hand, when the weight ratio of the first surfactant to the second surfactant becomes too large, it is found that the resin particles partially condense (Comparative Example 1). Further, if the weight ratio of the second surfactant to the first surfactant becomes too large, partially flat or oval particles are generated, and the particle size distribution Cv is wide (specifically, 40%). It turns out that it becomes.
It can also be seen that the styrenic resin coagulates if the total addition amount of the first surfactant and the second surfactant is too small or too large (Comparative Examples 3 and 4).
Further, when sodium dodecylbenzenesulfonate is used as the first surfactant, particle aggregation and generation of flat particles are prevented, but the particle size distribution Cv of the obtained resin particles is wide (specifically, 40%). (Comparative Example 5).
Moreover, it turns out that generation | occurrence | production of a condensation, a flat particle, etc. cannot be prevented when sodium dodecylbenzenesulfonate is used as a 2nd surfactant (comparative example 6).
Moreover, if the second surfactant is not added, it is impossible to prevent the formation of coagulation and flat particles (Comparative Example 7). If the first surfactant is not added, most of the resin particles obtained are flat. It turns out that it becomes a long spherical particle (comparative example 8).
表５から、発泡性スチレン系樹脂粒子ついても、実施例の樹脂粒子の粒度分布Ｃｖは、比較例の樹脂粒子の粒度分布Ｃｖより狭いことが判る。
また、実施例の発泡粒子は、比較例の発泡粒子より放冷時間が短縮され、ハイサイクルコーティング剤の添加量が少なくても、放冷時間が同程度になることが判る。
From Table 5, it can be seen that for the expandable styrene resin particles, the particle size distribution Cv of the resin particles of the example is narrower than the particle size distribution Cv of the resin particles of the comparative example.
In addition, it can be seen that the foamed particles of the examples have a shorter cooling time than the foamed particles of the comparative example, and the cooling time is comparable even if the amount of the high cycle coating agent added is small.
Claims (3)
The method for producing styrene resin particles according to claim 1 or 2 , wherein a foaming agent is added into the reactor during or after the polymerization reaction.
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