JP5008442B2 - Method for producing expandable polystyrene resin particles - Google Patents
Method for producing expandable polystyrene resin particles Download PDFInfo
- Publication number
- JP5008442B2 JP5008442B2 JP2007102655A JP2007102655A JP5008442B2 JP 5008442 B2 JP5008442 B2 JP 5008442B2 JP 2007102655 A JP2007102655 A JP 2007102655A JP 2007102655 A JP2007102655 A JP 2007102655A JP 5008442 B2 JP5008442 B2 JP 5008442B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- resin particles
- polymerizable monomer
- weight
- styrene
- 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.)
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- 239000002245 particle Substances 0.000 title claims description 54
- 229920005989 resin Polymers 0.000 title claims description 49
- 239000011347 resin Substances 0.000 title claims description 49
- 229920006248 expandable polystyrene Polymers 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims description 101
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 84
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 229920005990 polystyrene resin Polymers 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 14
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 238000010097 foam moulding Methods 0.000 claims description 2
- 239000006260 foam Substances 0.000 description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 7
- 239000001273 butane Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229920001890 Novodur Polymers 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 210000003141 lower extremity Anatomy 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 210000002303 tibia Anatomy 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PYOLJOJPIPCRDP-UHFFFAOYSA-N 1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1 PYOLJOJPIPCRDP-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical compound CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- UIZDKHDPZRCOBN-UHFFFAOYSA-N 3-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCC1=CC(=O)NC1=O UIZDKHDPZRCOBN-UHFFFAOYSA-N 0.000 description 1
- MXVZVCCKUVRGQC-UHFFFAOYSA-N 3-hexylpyrrole-2,5-dione Chemical compound CCCCCCC1=CC(=O)NC1=O MXVZVCCKUVRGQC-UHFFFAOYSA-N 0.000 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- BLHDYAXSQWGYSM-UHFFFAOYSA-N 3-octadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(=O)NC1=O BLHDYAXSQWGYSM-UHFFFAOYSA-N 0.000 description 1
- VOYQCFMGTRPFKT-UHFFFAOYSA-N 3-octylpyrrole-2,5-dione Chemical compound CCCCCCCCC1=CC(=O)NC1=O VOYQCFMGTRPFKT-UHFFFAOYSA-N 0.000 description 1
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- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は発泡性ポリスチレン系樹脂粒子の製造方法、および該製造方法より得られる発泡性ポリスチレン系樹脂粒子から得られるポリスチレン系樹脂発泡成形体に関する。 The present invention relates to a method for producing expandable polystyrene resin particles, and a polystyrene resin foam molded article obtained from expandable polystyrene resin particles obtained by the production method.
自動車に使用される部材には、燃費性向上及びコスト削減の観点から軽量化が求められており、多くの部品に各種の発泡プラスチックが使用されている。発泡プラスチックとしては、発泡ウレタンや発泡粒子を型内成形したビーズ発泡成形体がよく使用されており、ビーズ発泡成形体としては、ポリプロピレン系樹脂発泡体、ポリスチレン系樹脂発泡体、アクリロニトリル/スチレン系共重合樹脂発泡体などがある。 The parts used in automobiles are required to be light in weight from the viewpoint of improving fuel efficiency and reducing costs, and various foamed plastics are used for many parts. As the foamed plastic, a bead foam molded body in which molded urethane or foamed particles are molded is often used. As the bead foam molded body, a polypropylene resin foam, a polystyrene resin foam, an acrylonitrile / styrene copolymer are used. There is a polymer resin foam.
自動車に使用される部材のうち、発泡成形体が適用される部材としては、自動車が衝突したときに運転席及び乗員の足を保護するために足元とエンジンルームの間に装着されるティビアパッドと呼ばれる下肢部保護材、自動車のピラーやドアの内部に装着される頭部保護材及び側突パッド、自動車の床下にあるフロアスペーサーと呼ばれる床下嵩上げ材、トランクルーム下の収納ボックスであるラゲージボックス、バンパーに内部に装着されるバンパー芯材などがある。 Among members used in automobiles, members to which foamed molded products are applied are called tibia pads that are installed between the feet and the engine compartment to protect the driver's seat and passenger's feet when the automobile collides. For lower limb protection materials, head protection materials and side impact pads mounted inside automobile pillars and doors, underfloor raising materials called floor spacers under the car floor, luggage boxes that are storage boxes under the trunk room, bumpers There are bumper cores installed inside.
この様に、自動車に多く用いられる発泡成形体ではあるが、とりわけ自動車内装用部材として用いられるものについては、スチレン系モノマー等の残存単量体の人体に与える影響が懸念されるため残存単量体量が極力低減させることが求められ、具体的にはガスクロマトグラフィーにおいて検出されないレベルまで低減させることが求められる場合もある。 In this way, although it is a foamed molded article that is often used in automobiles, especially for those used as automobile interior parts, there is concern about the effects of residual monomers such as styrene monomers on the human body, so the residual unit It is required to reduce the body weight as much as possible, specifically, it may be required to reduce it to a level that is not detected by gas chromatography.
スチレン系モノマーの重合途中にこれらのスチレン系モノマーと共重合可能なモノマーを追加することは知られている(例えば、特許文献1、2)。しかし、これらの文献におけるモノマー追加の目的は分子量分布を広くし、また射出成形を行う際に成形性のよいスチレン系樹脂を得ることであり、本発明の目的である残存単量体量の低減とは異なる。実際、特許文献1、2に記載の重合転化率は最大でも99.96%であり、残存単量体量は自動車内装用部材に用いる程度には十分に低減されていないことが想定される。
本発明の目的は、発泡性ポリスチレン系樹脂粒子中に含まれるスチレン系単量体等の残存単量体量が低減された発泡性ポリスチレン系樹脂粒子を提供することにある。 An object of the present invention is to provide expandable polystyrene resin particles in which the amount of residual monomers such as styrene monomers contained in the expandable polystyrene resin particles is reduced.
本発明者らは前記課題を解決すべく鋭意検討を行った結果、重合時間または重合温度等の反応条件を特殊な条件にせずとも、スチレン系単量体を含んでなる重合性単量体(A)の重合転化率が85%以上のときに重合性単量体(A)と共重合可能な重合性単量体(B)を添加することで発泡性樹脂粒子に含まれるスチレン系単量体等の残存単量体量を低減させられることを見出し、本発明の完成に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymerizable monomer comprising a styrene-based monomer (reactive conditions such as polymerization time or polymerization temperature) are not required. A styrene monomer contained in the expandable resin particles by adding a polymerizable monomer (B) copolymerizable with the polymerizable monomer (A) when the polymerization conversion of A) is 85% or more The present inventors have found that the amount of residual monomer such as a body can be reduced and have completed the present invention.
すなわち、本発明の第1は、
スチレン系単量体を含んでなる重合性単量体(A)を水性媒体中で懸濁重合中、または懸濁重合後、発泡剤を含浸させる発泡性ポリスチレン系樹脂粒子の製造方法において、
重合性単量体(A)の重合転化率が85重量%以上の時に、ニトリル系単量体を重合性単量体(A)仕込量100重量部に対して0.7重量部以上1.3重量部以下>添加することを特徴とする、発泡性ポリスチレン系樹脂粒子の製造方法に関する。
That is, the first present invention,
In the method for producing expandable polystyrene resin particles in which a polymerizable monomer (A) comprising a styrene monomer is impregnated with a foaming agent during suspension polymerization in an aqueous medium or after suspension polymerization,
When the polymerization conversion rate of the polymerizable monomer (A) is 85% by weight or more, the nitrile monomer is added in an amount of 0.7 parts by weight or more with respect to 100 parts by weight of the polymerizable monomer (A) charged . 3 parts by weight or less> is characterized by adding to a process for the preparation of expandable polystyrene resin particles.
本発明の第2は、前記記載の製造方法によって得られる発泡性ポリスチレン系樹脂粒子を予備発泡させて、ポリスチレン系樹脂発泡粒子とし、該ポリスチレン系樹脂発泡粒子を型内成形してなるポリスチレン系樹脂発泡成形体に関する。 A second aspect of the present invention is a polystyrene resin obtained by pre-expanding expandable polystyrene resin particles obtained by the production method described above to form polystyrene resin expanded particles, and molding the polystyrene resin expanded particles in a mold. The present invention relates to a foam molded article.
本発明によれば、残存単量体量の少ない発泡性スチレン系樹脂粒子を提供することができる。本発明の製造方法によって得られた発泡性スチレン系樹脂粒子を用いて得られるポリスチレン系樹脂発泡成形体は、残存単量体量が低減されているため、とりわけ、下肢部保護材、頭部保護材、側突パット、床下嵩上げ材、ラゲージボックス等の自動車用内装部材として好適に使用することが出来る。 According to the present invention, expandable styrene resin particles with a small amount of residual monomer can be provided. The polystyrene-based resin foam molded article obtained by using the expandable styrene-based resin particles obtained by the production method of the present invention has a reduced residual monomer amount. It can be suitably used as an automobile interior member such as a material, side collision pad, underfloor raising material, and luggage box.
本発明における重合性単量体(A)は、スチレン単量体を含んでなり、好ましくはスチレン系単量体を50重量%以上、更に好ましくは60重量%以上、より好ましくは75重量%含んでなる。ここでいうスチレン系単量体とは、スチレンやα―メチルスチレン、ビニルトルエン、パラメチルスチレン、t−ブチルスチレン、クロロスチレン、スチレンスルホン酸及びその塩等などのスチレン系誘導体が挙げられる。 The polymerizable monomer (A) in the present invention contains a styrene monomer, preferably 50% by weight or more, more preferably 60% by weight or more, and more preferably 75% by weight. It becomes. Examples of the styrene monomer here include styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, paramethylstyrene, t-butylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
また重合性単量体(A)は、スチレン系単量体を含んでいれば、他の単量体を含んでいてもかまわない。重合性単量体(A)のスチレン系単量体以外の単量体としては、スチレンと共重合可能なものであれば特に限定はなく、例えば、アクリロニトリル、メタクリロニトリル等のニトリル系単量体;一般式HC=CH−(C=O)−OR1で表されるアクリル酸系単量体(なお、式中R1は水素または炭素数1以上20以下の有機基であればとくに限定はない。);一般式HC=C(CH3)−(C=O)−OR2で表されるメタクリル酸系単量体(なお、式中R2水素または炭素数1以上20以下の有機基であれば特に限定はない。);パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニル単量体;ビニルトリメトキシシラン、ビニルトリエトキシシラン等のケイ素含有ビニル系単量体;無水マレイン酸、マレイン酸、マレイン酸のモノアルキルエステル及びジアルキルエステル;フマル酸、フマル酸のモノアルキルエステル及びジアルキルエステル;マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系単量体;アクリルアミド、メタクリルアミド等のアミド基含有ビニル系単量体;酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル類;エチレン、プロピレン等のアルケン類;ブタジエン、イソプレン等の共役ジエン類;塩化アリル、アリルアルコール等が挙げられる。これらの中でも、ニトリル系単量体、アクリル酸系単量体、メタクリル酸系単量体であることが好ましい。 The polymerizable monomer (A) may contain other monomers as long as it contains a styrene monomer. The monomer other than the styrene monomer of the polymerizable monomer (A) is not particularly limited as long as it is copolymerizable with styrene. For example, nitrile monomers such as acrylonitrile and methacrylonitrile Body; acrylic acid-based monomer represented by the general formula HC═CH— (C═O) —OR 1 (in the formula, R 1 is particularly limited if it is hydrogen or an organic group having 1 to 20 carbon atoms) A methacrylic acid monomer represented by the general formula HC═C (CH 3 ) — (C═O) —OR 2 (in the formula, R 2 hydrogen or an organic compound having 1 to 20 carbon atoms) If it is a group, there is no particular limitation.); Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Anhydrous male Maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, Maleimide monomers such as stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc. Vinyl esters of the above; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; allyl chloride and allyl alcohol. Among these, nitrile monomers, acrylic monomers, and methacrylic monomers are preferable.
重合性単量体(A)は、一般的な懸濁重合法によって重合される。懸濁重合法は、従来公知の方法でよく、例えば、特開2004−307729号公報記載の方法のようにして行うことが出来る。 The polymerizable monomer (A) is polymerized by a general suspension polymerization method. The suspension polymerization method may be a conventionally known method, and can be performed, for example, as described in JP-A No. 2004-307729.
また懸濁重合を行うに際して、重合性単量体(A)をそのまま懸濁重合に供しても良いが、一部の単量体をマクロモノマーとし、その他の単量体とマクロモノマーを懸濁重合に供しても良い。マクロモノマーについては後述する。 When performing suspension polymerization, the polymerizable monomer (A) may be subjected to suspension polymerization as it is, but some monomers are macromonomers and other monomers and macromonomers are suspended. You may use for superposition | polymerization. The macromonomer will be described later.
懸濁重合する際には、懸濁安定剤を使用することが好ましく、懸濁安定剤としては、例えば、ポリビニルアルコール、メチルセルロース、ポリビニルピロリドン、ポリアクリルアミド等の水溶性高分子、ピロリン酸マグネシウム、燐酸カルシウム、ハイドロキシアパタイト等の難溶性無機塩等を用いることができ、また界面活性剤を併用してもよい。なお、難溶性無機塩を用いる場合は、アルキルスルホン酸ソーダ、ドデシルベンゼンスルホン酸ソーダ等のアニオン性界面活性剤を併用するのが好ましい。 In suspension polymerization, a suspension stabilizer is preferably used. Examples of the suspension stabilizer include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyvinyl pyrrolidone, and polyacrylamide, magnesium pyrophosphate, and phosphoric acid. Insoluble inorganic salts such as calcium and hydroxyapatite can be used, and a surfactant may be used in combination. In addition, when using a hardly soluble inorganic salt, it is preferable to use together anionic surfactants, such as sodium alkyl sulfonate and sodium dodecylbenzene sulfonate.
本発明において重合性単量体(A)を重合する場合に使用する重合開始剤としては、一般の熱可塑性重合体の製造に用いられるラジカル発生型重合開始剤を用いることができ、代表的なものとしては、例えば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、t−ブチルパーベンゾエート、t−ブチルパーピバレート、t−ブチルパーオキシイソプロピルカーボネート、t−ブチルパーオキシアセテート、2,2−ジ−t−ブチルパーオキシブタン、ジ−t−ブチルパーオキシヘキサハイドロテレフタレート、1,1−ジ(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)シクロヘキサン、1,1−ジ(t−アミルパーオキシ)3,3,5−トリメチルシクロヘキサン、1,1−ジ(t−アミルパーオキシ)シクロヘキサンなどの有機過酸化物や、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリルなどのアゾ化合物が挙げられる。これらの重合開始剤は単独もしくは2種以上を混合して用いることができる。 As a polymerization initiator used when polymerizing the polymerizable monomer (A) in the present invention, a radical generating polymerization initiator used for production of a general thermoplastic polymer can be used. For example, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, t-butyl perpivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-di-t- Butyl peroxybutane, di-t-butylperoxyhexahydroterephthalate, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane 1,1-di (t-amylperoxy) 3,3,5-trimethylcyclohexane, 1,1 And organic peroxides such as di (t-amyl peroxy) cyclohexane, azobisisobutyronitrile, an azo compound such as azo-bis-dimethyl valeronitrile. These polymerization initiators can be used alone or in admixture of two or more.
マクロモノマーとは、高分子量の単量体であり、かつ、分子末端に少なくとも1つ以上の重合性反応基を有するものである。本発明においては、重合性単量体(A)の一部を予めマクロモノマーとし、その後、懸濁重合を行うことが出来る。 The macromonomer is a high molecular weight monomer and has at least one polymerizable reactive group at the molecular end. In the present invention, a part of the polymerizable monomer (A) is previously made a macromonomer, and then suspension polymerization can be performed.
マクロモノマーの分子末端に存在する重合性の反応基は、特に限定されず、例えば、アリル基、ビニルシリル基、ビニルエーテル基、ジシクロペンタジエニル基等があげられるが、他の単量体との共重合反応性から、少なくとも一つが炭素−炭素二重結合であることが好ましく、更には下記一般式
−OC(O)C(R3)=CH2
で表される基が好ましい。
The polymerizable reactive group present at the molecular end of the macromonomer is not particularly limited, and examples thereof include an allyl group, a vinylsilyl group, a vinyl ether group, a dicyclopentadienyl group, and the like. In view of copolymerization reactivity, at least one of them is preferably a carbon-carbon double bond, and further, the following general formula —OC (O) C (R 3 ) ═CH 2
The group represented by these is preferable.
なお、式中、R3は水素または炭素数1以上20以下の有機基であればとくに限定はなく、中でも、−H、−CH3、−CH2CH3、−(CH2)nCH3(nは2以上19以下の整数を表す)、−C6H5、−CH2OH、−CNの中から選ばれる基が好ましく、更に好ましくは−H、−CH3である。 In the formula, R 3 is not particularly limited as long as it is hydrogen or an organic group having 1 to 20 carbon atoms, and among them, —H, —CH 3 , —CH 2 CH 3 , — (CH 2 ) n CH 3 (N represents an integer of 2 or more and 19 or less), a group selected from —C 6 H 5 , —CH 2 OH, and —CN is preferable, and —H and —CH 3 are more preferable.
本発明においてマクロモノマーを使用する場合、本発明のポリスチレン系樹脂発泡成形体のゲル分率が1重量%以上40重量%以下となるようなマクロモノマーであることが好ましく、具体的には、マクロモノマーの少なくとも2つの分子末端に重合性の反応基を各々1個以上有することが好ましい。ゲル分率が1重量%以上40重量%以下となるのであれば、重合性の反応基を有する分子末端を1個有するマクロモノマーが混在していても良い。例えば、重合性の反応基を2つの分子末端にそれぞれ1個有するマクロモノマーの製造過程で重合性の反応基を有する分子末端を1個有するマクロモノマーが混在する場合があるが、混在したまま使用しても良い。 When a macromonomer is used in the present invention, the macromonomer is preferably such that the gel fraction of the polystyrene-based resin foam molded article of the present invention is 1% by weight or more and 40% by weight or less. It is preferable to have at least one polymerizable reactive group at each of at least two molecular ends of the monomer. If the gel fraction is 1% by weight or more and 40% by weight or less, a macromonomer having one molecular terminal having a polymerizable reactive group may be mixed. For example, in the process of producing a macromonomer having one polymerizable reactive group at each of two molecular ends, a macromonomer having one molecular terminal having a polymerizable reactive group may be mixed, but it is still used You may do it.
本発明のポリスチレン系樹脂発泡成形体のゲル分の測定は、発泡成形体から所定の大きさの試験片を20枚切り出し、発泡成形体1gにつき80gのキシレンを使用し、沸騰キシレンによる抽出を行う。沸騰開始から2時間経過後、200メッシュの金網で濾過を行い、濾液を取り除き、濾物を再び沸騰キシレンによる抽出を沸騰開始から2時間行い、再び200メッシュの金網で濾過を行い、濾液を取り除き、残る濾物を再び沸騰キシレンによる抽出を沸騰開始から1時間行い、200メッシュの金網で濾過を行い、濾物を沸騰キシレンに抽出されないゲル分とし、得られたゲル分を150℃の乾燥機で1時間乾燥させ、もとの発泡成形体重量に対する割合をゲル分率とする。 In the measurement of the gel content of the polystyrene resin foam molded article of the present invention, 20 test pieces of a predetermined size are cut out from the foam molded article, and 80 g of xylene is used per 1 g of the foam molded article, and extraction with boiling xylene is performed. . After 2 hours from the start of boiling, filter through a 200 mesh wire mesh, remove the filtrate, extract the filtrate again with boiling xylene for 2 hours from the start of boiling, filter again through a 200 mesh wire mesh, and remove the filtrate. The remaining filtrate is again extracted with boiling xylene for 1 hour from the start of boiling, filtered through a 200 mesh wire net, the filtrate is made into a gel that cannot be extracted into boiling xylene, and the resulting gel is dried at 150 ° C. And dried for 1 hour, and the ratio relative to the weight of the original foamed molded product is defined as the gel fraction.
マクロモノマーの重合体主鎖を構成するモノマーとしては、重合性単量体(A)に用いることが出来る単量体を使用することが出来、なかでも、生成物の物性等から、スチレン系単量体、アクリル酸系単量体、メタクリル酸系単量体が好ましい。より好ましくは、アクリル酸エステル単量体、メタクリル酸エステル単量体であり、更に好ましくは、アクリル酸エステルモノマーであり、特に好ましくはアクリル酸エチル、アクリル酸ブチルであり、最も好ましくはアクリル酸ブチルである。 As the monomer constituting the polymer main chain of the macromonomer, a monomer that can be used for the polymerizable monomer (A) can be used. Preference is given to monomers, acrylic acid monomers and methacrylic monomers. More preferred are acrylate monomers and methacrylate monomers, more preferred are acrylate monomers, particularly preferred are ethyl acrylate and butyl acrylate, and most preferred is butyl acrylate. It is.
マクロモノマーのガラス転移温度は、−20℃以下であることが好ましい。ガラス転移温度が−20℃より高いと、得られた発泡性ポリスチレン系樹脂粒子の柔軟性が低下するため発泡に時間がかかり、また成形時、発泡粒子を融着させるための蒸気圧が高くなる傾向がある。 The glass transition temperature of the macromonomer is preferably −20 ° C. or lower. When the glass transition temperature is higher than −20 ° C., the flexibility of the obtained expandable polystyrene resin particles is reduced, so that it takes time to foam, and the vapor pressure for fusing the expanded particles during molding increases. Tend.
本発明において用いるマクロモノマーは、分子量分布、すなわち、ゲルパーミエーションクロマトグラフィー(以下、GPCと称す場合がある)で測定した重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が、好ましくは1.8未満であることが好ましく、さらに好ましくは1.6以下であり、特に好ましくは1.4以下である。本発明におけるGPC測定の際には、通常は、クロロホルム又はテトラヒドロフラン等を移動相として、ポリスチレンゲルカラム等を使用し、分子量の値はポリスチレン換算値等で求めている。分子量分布が広いマクロモノマーは、共重合反応の進行が不均一になるおそれがあり、未反応のマクロモノマーが残存する可能性がある。 The macromonomer used in the present invention has a molecular weight distribution, that is, a ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter sometimes referred to as GPC). ) Is preferably less than 1.8, more preferably 1.6 or less, and particularly preferably 1.4 or less. In the GPC measurement in the present invention, usually, a polystyrene gel column or the like is used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene. A macromonomer having a broad molecular weight distribution may cause the copolymerization reaction to become non-uniform, and unreacted macromonomer may remain.
本発明においては、重合性単量体(A)を懸濁重合し、重合転化率が85%以上のとき、好ましくは90%以上、より好ましくは、95%以上のときに、重合性単量体(A)と共重合可能な重合性単量体(B)を添加する。 In the present invention, the polymerizable monomer (A) is subjected to suspension polymerization, and when the polymerization conversion rate is 85% or more, preferably 90% or more, more preferably 95% or more, the polymerizable monomer A polymerizable monomer (B) copolymerizable with the body (A) is added.
本発明における重合転化率とは重合性単量体(A)100%に対する重合体の割合である。重合転化率が85%よりも低いときに重合性単量体(B)を添加する場合、発泡性スチレン系樹脂粒子内の残存スチレン量が減少しない。また、重合転化率が85%よりも低いときに重合性単量体(B)を添加する場合は、重合性単量体(B)の添加量を増やす必要が生じる。重合性単量体(B)を増量しすぎることは、本発明により得られるポリスチレン系樹脂発泡成形体の物性に影響を与える。 The polymerization conversion rate in the present invention is a ratio of the polymer to 100% of the polymerizable monomer (A). When the polymerizable monomer (B) is added when the polymerization conversion rate is lower than 85%, the amount of residual styrene in the expandable styrene resin particles does not decrease. Further, when the polymerizable monomer (B) is added when the polymerization conversion rate is lower than 85%, it is necessary to increase the addition amount of the polymerizable monomer (B). Excessive increase of the polymerizable monomer (B) affects the physical properties of the polystyrene resin foam molded article obtained by the present invention.
なお、重合転化率は、
重合転化率(%)=100−a(%)
に表される式で算出する。式中a%は重合途中における重合性単量体(A)の重量%である。重合途中における重合性単量体(A)の重量%は、途中の重合体をサンプリングし、重合体乾燥後、ガスクロマトグラフィーにて測定した。ガスクロマトグラフィーの測定条件については後述する。
The polymerization conversion rate is
Polymerization conversion rate (%) = 100-a (%)
It is calculated by the formula represented by In the formula, a% is the weight% of the polymerizable monomer (A) during the polymerization. The weight% of the polymerizable monomer (A) in the middle of the polymerization was measured by gas chromatography after sampling the polymer in the middle and drying the polymer. The measurement conditions for gas chromatography will be described later.
重合性単量体(B)は、重合性単量体(A)仕込量100重量部に対して、0.5重量部以上3重量部以下、好ましくは0.6重量部以上2重量部以下、更に好ましくは、0.7重量部以上1.3重量部以下添加する。 The polymerizable monomer (B) is 0.5 parts by weight or more and 3 parts by weight or less, preferably 0.6 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the polymerizable monomer (A). More preferably, 0.7 parts by weight or more and 1.3 parts by weight or less are added.
重合性単量体(B)の添加量が、0.5重量部より少ないと、発泡性スチレン系樹脂粒子に含まれるスチレン系単量体量(以降、残存スチレンと称する場合がある)が十分に減少しない。重合性単量体(B)の添加量が3重量部を超えては、発泡性スチレン系樹脂粒子にニトリル系単量体が残存する可能性がある。また本発明により得られるポリスチレン系樹脂発泡成形体の物性に影響を与えるため好ましくない。 When the addition amount of the polymerizable monomer (B) is less than 0.5 parts by weight, the amount of styrene monomer contained in the expandable styrene resin particles (hereinafter sometimes referred to as residual styrene) is sufficient. Does not decrease. When the addition amount of the polymerizable monomer (B) exceeds 3 parts by weight, the nitrile monomer may remain in the expandable styrene resin particles. Moreover, since it affects the physical property of the polystyrene-type resin foam molding obtained by this invention, it is not preferable.
重合性単量体(B)としては、前記重合性単量体(A)で例示した単量体のうち、スチレン系単量体以外の、スチレン系単量体と共重合性可能なものであればよい。 The polymerizable monomer (B) can be copolymerized with a styrene monomer other than the styrene monomer among the monomers exemplified for the polymerizable monomer (A). I just need it.
重合性単量体(B)としては、アクリロニトリル、メタクリロニトリル等のニトリル系単量体であることが好ましい。中でも、アクリロニトリルが特に好ましい。 The polymerizable monomer (B) is preferably a nitrile monomer such as acrylonitrile or methacrylonitrile. Of these, acrylonitrile is particularly preferable.
以上のようにして、重合性単量体(A)を懸濁重合し、重合性単量体(B)を添加して得られた樹脂粒子に発泡剤を追加および含浸させ本発明の発泡性スチレン系樹脂粒子が得られる。 The foaming property of the present invention is obtained by adding and impregnating a foaming agent to the resin particles obtained by suspension polymerization of the polymerizable monomer (A) and adding the polymerizable monomer (B) as described above. Styrenic resin particles are obtained.
本発明で使用する発泡剤としては、公知の発泡剤を使用することが出来、例えば、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ヘキサン等の脂肪族炭化水素類およびシクロヘキサン、シクロペンタン、シクロブタン等の脂環族炭化水素さらにはトリフロロモノクロロエタン、ジフロロジクロロメタン等のハロゲン化炭化水素等の沸点が80℃以下の揮発性発泡剤が使用できる。また、これらは、単独もしくは2種以上を併せて用いることができる。成形時の収縮・変形を少なくするには、発泡剤としてブタンおよび/またはペンタンを用いることが好ましく、ブタンが特に好ましい。 As the blowing agent used in the present invention, known blowing agents can be used. For example, aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, hexane, and cyclohexane, cyclopentane, cyclobutane. A volatile blowing agent having a boiling point of 80 ° C. or less, such as alicyclic hydrocarbons such as halogenated hydrocarbons such as trifluoromonochloroethane and difluorodichloromethane, can be used. Moreover, these can be used individually or in combination of 2 or more types. In order to reduce shrinkage and deformation during molding, it is preferable to use butane and / or pentane as a foaming agent, and butane is particularly preferable.
本発明においては、粒子状の熱可塑性樹脂粒子に発泡剤を含浸させて発泡性熱可塑性樹脂粒子とすることが好ましい。その方法としては、懸濁重合中に添加してもよいし、懸濁重合後に添加してもよい。 In the present invention, it is preferable to make foamed thermoplastic resin particles by impregnating particulate thermoplastic resin particles with a foaming agent. As the method, it may be added during suspension polymerization or after suspension polymerization.
以上のようにして得られた本発明の発泡性スチレン系樹脂粒子は、残存単量体量が低減されているという特徴を有し、具体的には、残存単量体量が、400ppm未満であることが好ましく、300ppm以下がさらに好ましい。 The expandable styrenic resin particles of the present invention obtained as described above have a feature that the amount of residual monomer is reduced. Specifically, the amount of residual monomer is less than 400 ppm. It is preferable that it is 300 ppm or less.
ここで言う残存単量体とは、実際に、懸濁重合に供した重合性単量体(A)の成分および添加した重合性単量体(B)の成分を言う。例えば、重合性単量体(A)としてスチレンを使用し、重合性単量体(B)としてアクリロニトリルを使用して得られた発泡性スチレン系樹脂粒子の場合、スチレン、アクリロニトリルをいう。 The residual monomer mentioned here actually means the component of the polymerizable monomer (A) subjected to suspension polymerization and the component of the added polymerizable monomer (B). For example, in the case of expandable styrene resin particles obtained by using styrene as the polymerizable monomer (A) and acrylonitrile as the polymerizable monomer (B), it means styrene or acrylonitrile.
本発明の残存単量体量の測定は、発泡性スチレン系樹脂粒子0.2gを入れたサンプル瓶に塩化メチレン20mlを投入し、8時間攪拌した後に、上澄みの塩化メチレン溶液を採取してガスクロマトグラフィー(島津製作所製 GC−14B、カラム3m、充填剤 GLサイエンス製PEG20M、カラム温度110℃、インジェエクション温度170℃、ディテクション温度170℃、キャリアーガス ヘリウム50ml/min、内部標準液 シクロペンタノール(0.1%))にて測定し、本発明の残存単量体量は、リテンションタイム4.2〜17.0分の間の成分の合計である。 In the measurement of the amount of residual monomer of the present invention, 20 ml of methylene chloride was put into a sample bottle containing 0.2 g of expandable styrene resin particles and stirred for 8 hours. Chromatography (Shimadzu GC-14B, column 3m, packing material GL Science PEG20M, column temperature 110 ° C, injection temperature 170 ° C, detection temperature 170 ° C, carrier gas helium 50ml / min, internal standard solution cyclopen The amount of residual monomer of the present invention is the total of components during the retention time of 4.2 to 17.0 minutes.
本発明の発泡性スチレン系樹脂粒子は、更に水蒸気等で加熱して、ポリスチレン系樹脂発泡粒子とし、該ポリスチレン系樹脂発泡粒子を型内発泡成形してポリスチレン系樹脂発泡成形体とすることが出来る。 The expandable styrene resin particles of the present invention can be further heated with steam or the like to form polystyrene resin foam particles, and the polystyrene resin foam particles can be foamed in-mold to obtain a polystyrene resin foam molded article. .
本発明のポリスチレン系樹脂発泡成形体は、発泡性スチレン系樹脂粒子の残存単量体量が低減されていることから、揮発性有機成分の放散が少ない傾向にある。本発明のポリスチレン系樹脂発泡成形体の残存単量体量は、好ましくは400ppm未満であり、より好ましくは300ppm以下である。ポリスチレン系樹脂発泡成形体中の残存単量体量は、発泡性ポリスチレン系樹脂粒子中の残存単量体量の測定と同様に行うことが出来る。 Since the residual monomer amount of the expandable styrene resin particles is reduced, the polystyrene resin foam molded article of the present invention tends to emit less volatile organic components. The residual monomer amount of the polystyrene-based resin foam molded article of the present invention is preferably less than 400 ppm, more preferably 300 ppm or less. The amount of residual monomer in the polystyrene resin foam molded product can be measured in the same manner as the measurement of the amount of residual monomer in the expandable polystyrene resin particles.
本発明の、発泡性ポリスチレン系樹脂粒子、ポリスチレン系樹脂発泡成形体は、例えば、以下のようにして作ることが出来る。 The expandable polystyrene resin particles and polystyrene resin foam molded article of the present invention can be produced, for example, as follows.
水中に懸濁安定剤の共存下、重合開始剤を溶解させた重合性単量体(A)を分散させ、重合温度まで昇温する。所定の時間重合し、重合性単量体(B)を添加する。発泡剤を追加し、さらに昇温して発泡剤を含浸させて発泡性ポリスチレン性樹脂粒子が得られる。このようにしてえられた発泡性ポリスチレン性樹脂粒子をさらに水蒸気等で加熱してポリスチレン系発泡粒子とし、該ポリスチレン系発泡樹脂粒子を型内成形してポリスチレン系樹脂発泡成形体が得られる。 In the presence of a suspension stabilizer in water, the polymerizable monomer (A) in which the polymerization initiator is dissolved is dispersed, and the temperature is raised to the polymerization temperature. Polymerize for a predetermined time and add the polymerizable monomer (B). A foaming agent is added, the temperature is further raised, and the foaming agent is impregnated to obtain expandable polystyrene resin particles. The expandable polystyrene resin particles thus obtained are further heated with water vapor or the like to form polystyrene-based expanded particles, and the polystyrene-based expanded resin particles are molded in-mold to obtain a polystyrene-based resin expanded molded body.
以上のようにして得られた本発明のポリスチレン系樹脂発泡成形体は、残存単量体量が低減されていることから、とりわけ、自動車が衝突したときに運転席及び乗員の足を保護するために足元とエンジンルームの間に装着されるティビアパッドと呼ばれる下肢部保護材、自動車のピラーやドアの内部に装着される頭部保護材及び側突パット、自動車の床下にあるフロアスペーサーと呼ばれる床下嵩上げ材、トランクルーム下の収納ボックスであるラゲージボックス等の自動車用内装部材として好適に使用することが出来る。 Since the polystyrene-based resin foam molded article of the present invention obtained as described above has a reduced amount of residual monomer, in particular, to protect the driver's seat and passenger's feet when the automobile collides. Lower leg protection material called tibia pad that is installed between the foot and the engine room, head protection material and side pad that is installed inside the pillar and door of an automobile, and under floor raising called a floor spacer under the automobile floor It can be suitably used as an interior member for automobiles such as a luggage box which is a storage box under a material or a trunk room.
以下に実施例および比較例を挙げるが、これによって本発明は限定されるものではない。特に断りのない限り、「部」「%」は重量基準である。 Examples and Comparative Examples are given below, but the present invention is not limited thereby. Unless otherwise specified, “parts” and “%” are based on weight.
<マクロモノマーの製造>
下記マクロモノマーの製造例中、数平均分子量および分子量分布(重量平均分子量と数平均分子量の比)は、ゲルパーミネーションクロマトグラフィー(GPC)を用いた標準ポリスチレン換算法により算出した。なお、GPCカラムとしてポリスチレン架橋ゲルを充填したもの(shodex GPC K−804;昭和電工(株)製)、GPC溶媒としてクロロホルムを用いた。
<Manufacture of macromonomer>
In the following macromonomer production examples, the number average molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). A GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
また、下記マクロモノマー製造例中、マクロモノマーのガラス転移温度はDSCで測定した。 In the following macromonomer production examples, the glass transition temperature of the macromonomer was measured by DSC.
(製造例1)アクリロイル基量末端ポリアクリル酸n‐ブチルの合成
特開2004−203932号公報の製造例2及び実施例2記載の方法に基づき実施した。精製後のマクロモノマーの数平均分子量は25600、分子量分布は1.25、ガラス転移温度−54℃であった。
(Production Example 1) Synthesis of acryloyl group content terminal poly-n-butyl acrylate This was carried out based on the method described in Production Example 2 and Example 2 of JP-A-2004-203932. The number average molecular weight of the purified macromonomer was 25600, the molecular weight distribution was 1.25, and the glass transition temperature was −54 ° C.
(実施例1)
6Lの回転撹拌機付きオートクレーブ内に、蒸留水2403.4g、第三リン酸カルシウム31.6g、α―オレフィンスルホン酸ソーダ13.6g、食塩6.8gを仕込んだ。次いで、スチレン1769.7g、アクリロニトリル339.0g、製造例1で作製した両末端にアクリロイル基を有するマクロモノマー124.3gの混合溶液にベンゾイルパーオキサイド8.02g、1,1−ジ(t−ブチルパーオキシ)3,3,5−トリメチルシクロヘキサン4.77g、ヘキサブロモシクロドデカン16.95g、2,3−ジメチル−2,3−ジフェニルブタン4.77g、2,4−ジフェニル−4−メチル−1−ペンテン4.5g、ヤシ油22.6gを溶解させ、オートクレーブに仕込んだ。次に、該オートクレーブを85℃の温度まで昇温して同温度で6時間重合させ、重合性単量体(B)として、アクリロニトリル28.25gを追加圧入した。混合ブタン(重量比:ノルマル/イソ=75/25)135.6gを圧入し、その後、オートクレーブを114℃の温度まで昇温させて、生成したスチレン系樹脂粒子中に混合ブタンを5時間かけて含浸させた。この後、反応系を40℃の温度にまで徐冷し、重合を終了させ発泡性スチレン系樹脂粒子を得た。
Example 1
In a 6 L autoclave equipped with a rotary stirrer, 2403.4 g of distilled water, 31.6 g of tricalcium phosphate, 13.6 g of sodium α-olefin sulfonate, and 6.8 g of sodium chloride were charged. Subsequently, 8.02 g of benzoyl peroxide, 1,1-di (t-butyl) were added to a mixed solution of 1769.7 g of styrene, 339.0 g of acrylonitrile, and 124.3 g of a macromonomer having acryloyl groups at both ends prepared in Production Example 1. Peroxy) 3,3,5-trimethylcyclohexane 4.77 g, hexabromocyclododecane 16.95 g, 2,3-dimethyl-2,3-diphenylbutane 4.77 g, 2,4-diphenyl-4-methyl-1 -4.5 g of pentene and 22.6 g of coconut oil were dissolved and charged into an autoclave. Next, the autoclave was heated to 85 ° C. and polymerized at the same temperature for 6 hours, and 28.25 g of acrylonitrile was additionally injected as the polymerizable monomer (B). 135.6 g of mixed butane (weight ratio: normal / iso = 75/25) was injected, and then the autoclave was heated to a temperature of 114 ° C., and the mixed butane was added to the produced styrene resin particles over 5 hours. Impregnated. Thereafter, the reaction system was gradually cooled to a temperature of 40 ° C. to complete the polymerization, and expandable styrene resin particles were obtained.
(実施例2)
重合性単量体(B)のアクリロニトリル量を22.6gとした以外は実施例1と同様に行い、発泡性スチレン系樹脂粒子を得た。
(Example 2)
Except that the amount of acrylonitrile of the polymerizable monomer (B) was 22.6 g, the same procedure as in Example 1 was performed to obtain expandable styrene resin particles.
(実施例3)
重合性単量体(B)のアクリロニトリル量を16.95gとした以外は実施例1と同様に行い、発泡性スチレン系樹脂粒子を得た。
(Example 3)
Except that the amount of acrylonitrile of the polymerizable monomer (B) was 16.95 g, the same procedure as in Example 1 was performed to obtain expandable styrene resin particles.
(比較例1)
重合性単量体(B)であるアクリロニトリルを添加しなかったこと以外は実施例1と同様に行い、発泡性スチレン系樹脂粒子を得た。
(Comparative Example 1)
Except that the acrylonitrile which is the polymerizable monomer (B) was not added, the same procedure as in Example 1 was carried out to obtain expandable styrene resin particles.
(比較例2)
重合性単量体(B)であるアクリロニトリルを添加せず、混合ブタン含浸時間を10時間に延長したこと以外は実施例1と同様に行い、発泡性スチレン系樹脂粒子を得た。
(Comparative Example 2)
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that acrylonitrile as the polymerizable monomer (B) was not added and the mixed butane impregnation time was extended to 10 hours.
(比較例3)
重合性単量体(B)であるアクリロニトリルを添加せず、混合ブタン含浸温度を120℃10時間としたこと以外は実施例1と同様に行い、発泡性スチレン系樹脂粒子を得た。
(Comparative Example 3)
Expandable styrene resin particles were obtained in the same manner as in Example 1 except that the polymerizable monomer (B) acrylonitrile was not added and the mixed butane impregnation temperature was 120 ° C. for 10 hours.
〈発泡性スチレン系樹脂粒子の分析〉
(分子量の測定)
本発明の発泡性熱可塑性樹脂粒子の重量平均分子量測定は、ゲルパーミエーションクロマトグラフィー(GPC)を用いた標準ポリスチレン換算法により算出した。(GPC 東ソー(株)製HLC−8020、カラム:TSKgel GMHXL30cm×2、カラム温度:35℃、流速:1ml/min)GPC溶媒としてテトラヒドロフランを用いた
発泡性熱可塑性樹脂粒子0.2gを入れたサンプル瓶にテトラヒドロフラン20mlを投入し、8時間攪拌した後に、上澄みのテトラヒドロフラン溶液を採取し、0.2μmのフィルター(東ソー製 マイショリディスクH−13−2)で濾過した溶液で重量平均分子量の測定を実施した。
<Analysis of expandable styrene resin particles>
(Measurement of molecular weight)
The weight average molecular weight measurement of the foamable thermoplastic resin particles of the present invention was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). (GPC Tosoh Corporation HLC-8020, column: TSKgel GMHXL 30 cm × 2, column temperature: 35 ° C., flow rate: 1 ml / min) Sample containing 0.2 g of expandable thermoplastic resin particles using tetrahydrofuran as a GPC solvent After adding 20 ml of tetrahydrofuran to the bottle and stirring for 8 hours, the supernatant tetrahydrofuran solution was collected, and the weight average molecular weight was measured with a solution filtered through a 0.2 μm filter (Mishori Disc H-13-2 manufactured by Tosoh Corporation). Carried out.
(残存単量体量の測定)
発泡性スチレン系樹脂粒子0.2gを入れたサンプル瓶に塩化メチレン20mlを投入し、8時間攪拌した後に、上澄みの塩化メチレン溶液を採取してガスクロマトグラフィー(島津製作所製 GC−14B、カラム3m、充填剤 GLサイエンス製PEG20M、カラム温度110℃、インジェエクション温度170℃、ディテクション温度170℃、キャリアーガス ヘリウム50ml/min、内部標準液 シクロペンタノール(0.1%))にて測定した。検出限界は100ppmであった。
(Measurement of residual monomer amount)
20 ml of methylene chloride was put into a sample bottle containing 0.2 g of expandable styrene resin particles and stirred for 8 hours, and then the supernatant methylene chloride solution was collected and gas chromatographed (GC-14B, Shimadzu Corporation, column 3 m). , PEG 20M manufactured by GL Sciences, column temperature 110 ° C., injection temperature 170 ° C., detection temperature 170 ° C., carrier gas helium 50 ml / min, internal standard solution cyclopentanol (0.1%)) . The detection limit was 100 ppm.
アクリロニトリルを添加しない比較例1では残存スチレンが1086ppmであったのに対し、実施例1〜3では残存スチレンが300ppm以下まで減少した。残存スチレン量の低減方法としては重合時間の延長または重合温度を上げることが考えられるが、比較例2、3の結果からこれらの方法では十分な効果が得られなかったことがわかる。 In Comparative Example 1 where acrylonitrile was not added, the residual styrene was 1086 ppm, whereas in Examples 1 to 3, the residual styrene was reduced to 300 ppm or less. Although it is conceivable to extend the polymerization time or raise the polymerization temperature as a method for reducing the amount of residual styrene, the results of Comparative Examples 2 and 3 indicate that these methods did not provide a sufficient effect.
本発明により、スチレン系単量体を重合する際重合転化率85%以上のときにスチレン系単量体と共重合可能な単量体を添加することで重合温度または重合時間を変更することなしに樹脂中の残存スチレンが減少させることができる。 According to the present invention, when polymerizing a styrene monomer, the polymerization temperature or polymerization time is not changed by adding a monomer copolymerizable with the styrene monomer when the polymerization conversion rate is 85% or more. In addition, the residual styrene in the resin can be reduced.
本発明の発泡性スチレン系樹脂粒子およびポリスチレン系樹脂発泡成形体は自動車内装用部材として、下肢部保護材、保護材及び側突パット、自動車の床下にあるフロアスペーサーと呼ばれる床下嵩上げ材、ラゲージボックス、下肢部保護材等に好適に使用できる。 The expandable styrenic resin particles and the polystyrene resin foam molded article of the present invention are used as automobile interior members, lower limb protection materials, protective materials and side impact pads, underfloor raising materials called floor spacers under the floor of automobiles, luggage boxes It can be suitably used for lower limb protection materials and the like.
Claims (2)
重合性単量体(A)の重合転化率が85重量%以上の時に、ニトリル系単量体を重合性単量体(A)仕込量100重量部に対して0.7重量部以上1.3重量部以下添加することを特徴とする、発泡性ポリスチレン系樹脂粒子の製造方法。 In the method for producing expandable polystyrene resin particles in which a polymerizable monomer (A) comprising a styrene monomer is impregnated with a foaming agent during suspension polymerization in an aqueous medium or after suspension polymerization,
When the polymerization conversion rate of the polymerizable monomer (A) is 85% by weight or more, the nitrile monomer is added in an amount of 0.7 parts by weight or more with respect to 100 parts by weight of the polymerizable monomer (A) charged . It is characterized by adding 3 parts by weight or less, the production method of the expandable polystyrene resin particles.
The expandable polystyrene resin particles obtained by the production method according to claim 1, by pre-expansion, a polystyrene type resin foamed particles, and characterized by being obtained by in-mold molding the polystyrene type resin foamed particles, Polystyrene resin foam molding.
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