JP2021155517A - Expandable polystyrene-based resin particle, polystyrene-based foam particle, and bead cushioning material - Google Patents
Expandable polystyrene-based resin particle, polystyrene-based foam particle, and bead cushioning material Download PDFInfo
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- JP2021155517A JP2021155517A JP2020055446A JP2020055446A JP2021155517A JP 2021155517 A JP2021155517 A JP 2021155517A JP 2020055446 A JP2020055446 A JP 2020055446A JP 2020055446 A JP2020055446 A JP 2020055446A JP 2021155517 A JP2021155517 A JP 2021155517A
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- Prior art keywords
- polystyrene
- weight
- parts
- based resin
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- 239000002245 particle Substances 0.000 title claims abstract description 250
- 229920005989 resin Polymers 0.000 title claims abstract description 113
- 239000011347 resin Substances 0.000 title claims abstract description 113
- 239000011324 bead Substances 0.000 title claims abstract description 19
- 229920006248 expandable polystyrene Polymers 0.000 title claims abstract description 13
- 239000004793 Polystyrene Substances 0.000 title claims description 136
- 229920002223 polystyrene Polymers 0.000 title claims description 136
- 239000000463 material Substances 0.000 title claims description 7
- 239000006260 foam Substances 0.000 title description 6
- 238000005187 foaming Methods 0.000 claims abstract description 34
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims abstract description 28
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019359 magnesium stearate Nutrition 0.000 claims abstract description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920006327 polystyrene foam Polymers 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 abstract description 27
- 239000002216 antistatic agent Substances 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 4
- 229920005990 polystyrene resin Polymers 0.000 description 35
- 238000011156 evaluation Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 21
- -1 2-hydroxytetradecyl Chemical group 0.000 description 19
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- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
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- 229940088594 vitamin Drugs 0.000 description 10
- 229930003231 vitamin Natural products 0.000 description 10
- 239000004342 Benzoyl peroxide Substances 0.000 description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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 3
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- 239000004711 α-olefin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
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- 239000004744 fabric Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 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
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子、及びビーズクッション材に関するものである。 The present invention relates to effervescent polystyrene-based resin particles, polystyrene-based effervescent particles, and bead cushioning material.
発泡性ポリスチレン系粒子は安価で発泡、成形が容易であり、緩衝性能、断熱性能に優れることから、広く使用されている。 Effervescent polystyrene particles are widely used because they are inexpensive, easy to foam and mold, and have excellent cushioning and heat insulating properties.
発泡性ポリスチレン系粒子の緩衝性能を利用した用途の一つとして、布製の袋などの袋体の内部にポリスチレン系発泡粒子（以下、単に発泡粒子と記載することがある）を封入したビーズクッションがあり、クッション、ソファー、枕（以下、まとめてクッションと記載することがある）などとして提供されている。ビーズクッションは、袋体内で発泡粒子が自由に動くことにより、着座時などにその衝撃を吸収し、体形に合った座面に容易に変形する。また、着座時における体圧分布の多方向への分散性が良好であることなどから座り心地に優れている。また、ビーズクッションを敷き布団として使用した場合には、褥そう防止などにも効果がみられる。 As one of the applications utilizing the cushioning performance of polystyrene-based foamable particles, a bead cushion in which polystyrene-based foamed particles (hereinafter, may be simply referred to as foamed particles) are enclosed inside a bag such as a cloth bag. Yes, it is provided as cushions, sofas, pillows (hereinafter, may be collectively referred to as cushions), etc. The bead cushion absorbs the impact when the foamed particles move freely in the bag, such as when sitting, and easily deforms into a seating surface suitable for the body shape. In addition, it is excellent in sitting comfort because the body pressure distribution at the time of sitting is well dispersed in multiple directions. In addition, when the bead cushion is used as a mattress, it is also effective in preventing swelling.
このビーズクッションを製造する際、袋体の内部に発泡粒子を充填する工程で発生する静電気が充填不良や埃の付着を引き起こすため、通常、特許文献１から３に記載されているように、帯電防止剤が使用されることが知られている。例えば、特許文献１では分子中に一つのアミノ基及び二つのヒドロキシル基を有するヒドロキシアルキルアミンをビーズクッション用の帯電防止剤として使用している。特許文献２では、帯電防止剤として主にポリエチレングリコールを使用し、帯電量の絶対値が５ｋV以下のクッション用発泡性ポリスチレンを提供している。特許文献３では、帯電防止剤としてカチオン系界面活性剤とノニオン系界面活性剤をポリスチレン系発泡性樹脂粒子の発泡剤含浸工程で導入することで優れた帯電防止性能を有する発泡成形体を得ている。 When manufacturing this bead cushion, static electricity generated in the process of filling the foam particles inside the bag causes improper filling and adhesion of dust. Therefore, as described in Patent Documents 1 to 3, it is usually charged. It is known that inhibitors are used. For example, Patent Document 1 uses a hydroxyalkylamine having one amino group and two hydroxyl groups in the molecule as an antistatic agent for a bead cushion. Patent Document 2 mainly uses polyethylene glycol as an antistatic agent, and provides foamable polystyrene for cushions having an absolute value of 5 kV or less. In Patent Document 3, a cationic surfactant and a nonionic surfactant are introduced as antistatic agents in the foaming agent impregnation step of polystyrene-based foamable resin particles to obtain a foamed molded product having excellent antistatic performance. There is.
しかしながら、特許文献１に開示されているヒドロキシアルキルアミンは、帯電防止性能に優れるものの、帯電防止剤が高湿度下で発泡性樹脂粒子の流動性を悪化させやすいことから、湿度が高い環境ではクッション充填性を悪化させる可能性がある。また、特許文献２では、帯電防止剤が使用されているものの、その使用量が不足しているため、クッション充填性が安定化する帯電防止性能としては十分でない。さらに、特許文献３では、多量の帯電防止剤を使用しているため、吸湿による流動性悪化が生じやすく、発泡時のブロッキングも発生しやすい懸念がある。本発明は上記課題に鑑みてなされたものであり、発泡時のブロッキングの発生が少なく、ポリスチレン系発泡粒子とした際の帯電防止性能に優れ、かつ吸湿による流動性悪化も起こりにくい、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子、及びクッションビーズ材を提供することである。 However, although the hydroxyalkylamine disclosed in Patent Document 1 has excellent antistatic performance, the antistatic agent tends to deteriorate the fluidity of the foamable resin particles under high humidity, so that the hydroxyalkylamine is cushioned in a high humidity environment. It may worsen the filling property. Further, in Patent Document 2, although an antistatic agent is used, the amount used is insufficient, so that the antistatic performance for stabilizing the cushion filling property is not sufficient. Further, in Patent Document 3, since a large amount of antistatic agent is used, there is a concern that fluidity is likely to deteriorate due to moisture absorption and blocking during foaming is likely to occur. The present invention has been made in view of the above problems, and foamable polystyrene is less likely to cause blocking during foaming, has excellent antistatic performance when polystyrene-based foamed particles are used, and is less likely to cause deterioration of fluidity due to moisture absorption. It is an object of the present invention to provide based resin particles, polystyrene foamed particles, and cushion bead material.
本発明者らは、鋭意検討の結果、平均粒子径が０．２５ｍｍ以上０．５ｍｍ以下である発泡性ポリスチレン系樹脂粒子であって、発泡性ポリスチレン系樹脂粒子本体の表面に、帯電防止剤として脂肪酸モノグリセライドを特定量含有し、ブロッキング防止剤としてステアリン酸マグネシウムを特定量含有することで、発泡時のブロッキングの発生が少なく、ポリスチレン系発泡粒子とした際の帯電防止性能に優れ、かつ吸湿による流動性悪化も起こりにくい発泡性ポリスチレン系樹脂粒子を得られることを見出し、本発明に至った。すなわち、本発明は、以下のとおりである。
[１] 基材樹脂及び発泡剤を含有する発泡性ポリスチレン系樹脂粒子本体を備え、
前記基材樹脂１００重量部に対して、ステアリン酸マグネシウムが０．４重量部以上１．５重量部以下、脂肪酸モノグリセリドが０．２重量部以上０．４重量部未満、ヒドロキシアルキルアミンが０．１重量部未満、を前記発泡性ポリスチレン系樹脂粒子本体の表面に含有し、平均粒子径が０．２５ｍｍ以上０．５０ｍｍ以下である、発泡性ポリスチレン系樹脂粒子。
[２]
平均粒子径±１５％の変動幅に入る割合が９０％以上である、[１]記載の発泡性ポリスチレン系樹脂粒子。
[３]
脂肪酸モノグリセライドがステアリン酸モノグリセライドである、[１]又は[２]のいずれかに記載の発泡性ポリスチレン系樹脂粒子。
[４]
前記発泡性ポリスチレン系樹脂粒子本体の表面に、基材樹脂１００重量部に対して０．０４重量部以上０．１５重量部以下のヒマシ硬化油を含有する、[１]〜[３]のいずれかに記載の発泡性ポリスチレン系樹脂粒子。
[５]
発泡性ポリスチレン系樹脂粒子中のスチレン単量体の残存量が１００ｐｐｍ未満である、[１]〜[４]のいずれかに記載の発泡性ポリスチレン系樹脂粒子。
[６]
重量平均分子量が２２万以上３０万未満である、[１]〜[５]のいずれかに記載の発泡性ポリスチレン系樹脂粒子。
[７]
前記発泡剤は、ペンタン及び／またはシクロヘキサンを含み、前記ペンタン及びシクロヘキサンの合計添加量は、前記基材樹脂１００重量％に対して、１．５重量％以上５．０重量％以下である、[１]〜[６]のいずれかに記載の発泡性ポリスチレン系樹脂粒子。
[８]
[１]〜[７]のいずれかに記載の発泡性ポリスチレン系樹脂粒子を発泡させてなる、ポリスチレン系発泡粒子。
[９]
嵩密度が０．０１８ｇ／ｃｍ３以上０．０２９ｇ／ｃｍ３以下である、請求項８に記載のポリスチレン系発泡粒子。
[１０] [８]または[９]に記載のポリスチレン系発泡粒子からなるビーズクッション材。
As a result of diligent studies, the present inventors have made foamable polystyrene-based resin particles having an average particle diameter of 0.25 mm or more and 0.5 mm or less, and as an antistatic agent on the surface of the foamable polystyrene-based resin particle main body. By containing a specific amount of fatty acid monoglyceride and a specific amount of magnesium stearate as a blocking inhibitor, blocking occurs less during foaming, excellent antistatic performance when polystyrene-based foamed particles are used, and flow due to moisture absorption. We have found that foamable polystyrene-based resin particles that are less likely to cause deterioration of sex can be obtained, and have arrived at the present invention. That is, the present invention is as follows.
[1] A foamable polystyrene-based resin particle body containing a base resin and a foaming agent is provided.
With respect to 100 parts by weight of the base resin, magnesium stearate was 0.4 parts by weight or more and 1.5 parts by weight or less, fatty acid monoglyceride was 0.2 parts by weight or more and less than 0.4 parts by weight, and hydroxyalkylamine was 0. An effervescent polystyrene-based resin particle containing less than 1 part by weight on the surface of the effervescent polystyrene-based resin particle main body and having an average particle diameter of 0.25 mm or more and 0.50 mm or less.
[2]
The effervescent polystyrene-based resin particles according to [1], wherein the ratio within the fluctuation range of the average particle size ± 15% is 90% or more.
[3]
The effervescent polystyrene-based resin particles according to any one of [1] and [2], wherein the fatty acid monoglyceride is stearic acid monoglyceride.
[4]
Any of [1] to [3], wherein the surface of the foamable polystyrene-based resin particle body contains 0.04 part by weight or more and 0.15 part by weight or less of the castor-hardened oil with respect to 100 parts by weight of the base resin. Effervescent polystyrene-based resin particles described in Crab.
[5]
The foamable polystyrene-based resin particles according to any one of [1] to [4], wherein the residual amount of the styrene monomer in the foamable polystyrene-based resin particles is less than 100 ppm.
[6]
The foamable polystyrene-based resin particles according to any one of [1] to [5], wherein the weight average molecular weight is 220,000 or more and less than 300,000.
[7]
The foaming agent contains pentane and / or cyclohexane, and the total amount of pentane and cyclohexane added is 1.5% by weight or more and 5.0% by weight or less with respect to 100% by weight of the base resin. 1] The foamable polystyrene-based resin particle according to any one of [6].
[8]
Polystyrene-based foamed particles obtained by foaming the foamable polystyrene-based resin particles according to any one of [1] to [7].
[9]
Bulk density of 0.018 g / cm 3 or more 0.029 g / cm 3 or less, polystyrene foam particles according to claim 8.
[10] The bead cushion material made of the polystyrene-based foamed particles according to [8] or [9].
本発明により、発泡時のブロッキングの発生が少なく、ポリスチレン系発泡粒子とした際の帯電防止性能に優れ、かつ吸湿による流動性悪化も起こりにくい、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子、及びクッションビーズ材が得られる。 According to the present invention, foamable polystyrene-based resin particles, polystyrene-based foamed particles, and polystyrene-based foamed particles, which are less likely to cause blocking during foaming, have excellent antistatic performance when made into polystyrene-based foamed particles, and are less likely to cause deterioration of fluidity due to moisture absorption. Cushion bead material can be obtained.
以下、本発明の一実施形態について説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能である。また、異なる実施形態及び／又は実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態及び／又は実施例についても本発明の技術的範囲に含まれる。また、本明細書中に記載された学術文献及び特許文献の全てが、本明細書中において参考文献として援用される。また、本明細書において特記しない限り、数値範囲を示す「Ａ〜Ｂ」は、「Ａ以上（Ａを含みかつＡより大きい）Ｂ以下（Ｂを含みかつＢより小さい）」を意図する。 Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments and / or examples obtained by appropriately combining the technical means disclosed in different embodiments and / or examples. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" indicating a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".
本発明の発泡性ポリスチレン系樹脂粒子は平均粒子径が０．２５ｍｍ以上０．５０ｍｍ以下でである。平均粒子径が０．２５ｍｍ未満となると、発泡力が不足してブロッキングが発生しやすい上、発泡機の目皿につまって汚染しやすい。平均粒子径が０．５０ｍｍ以上であった場合、そのポリスチレン系発泡粒子をクッションビーズにした際の感触が悪化する。また、本発明の発泡性ポリスチレン系樹脂粒子は平均粒子径±１５％の変動幅に入る割合が９０％以上であることが好ましい。平均粒子径±１５％の変動幅に入る割合が９０％以上であることで、発泡時の発泡倍率のばらつきが抑えられるため均一なポリスチレン系発泡粒子を得やすく、製品品質が安定しやすい。 The foamable polystyrene-based resin particles of the present invention have an average particle size of 0.25 mm or more and 0.50 mm or less. If the average particle size is less than 0.25 mm, the foaming power is insufficient and blocking is likely to occur, and the particle size is likely to be clogged with the foaming machine and contaminated. When the average particle size is 0.50 mm or more, the feel when the polystyrene-based foamed particles are used as cushion beads is deteriorated. Further, it is preferable that the effervescent polystyrene-based resin particles of the present invention have a ratio of 90% or more within the fluctuation range of the average particle size ± 15%. When the ratio within the fluctuation range of the average particle size ± 15% is 90% or more, the variation in the foaming ratio at the time of foaming is suppressed, so that uniform polystyrene-based foamed particles can be easily obtained, and the product quality is easily stabilized.
また、本発明のポリスチレン系樹脂粒子に対しては、発泡時の発泡性ポリスチレン系樹脂粒子同士の結合(ブロッキング)を防止するため、ブロッキング防止剤としてステアリン酸マグネシウムが用いられ、ステアリン酸マグネシウムの含有量は発泡性ポリスチレン系樹脂粒子１００重量部に対して、０．４重量部以上１．５重量部以下である。０．４重量部未満より少ないと発泡時にブロッキングが起こりやすい。また、１．５重量部を超えると、発泡粒子の空気輸送中に剥離しやすく、配管の閉塞の原因となる。ブロッキング抑制効果と剥離のバランスから０．５重量部以上１．０重量部以下が好ましく、より好ましくは０．６重量部以上０．８重量部以下である。 Further, with respect to the polystyrene-based resin particles of the present invention, magnesium stearate is used as a blocking inhibitor in order to prevent binding (blocking) between the foamable polystyrene-based resin particles during foaming, and the polystyrene-based resin particles contain magnesium stearate. The amount is 0.4 parts by weight or more and 1.5 parts by weight or less with respect to 100 parts by weight of the foamable polystyrene resin particles. If it is less than 0.4 parts by weight, blocking is likely to occur during foaming. On the other hand, if it exceeds 1.5 parts by weight, the foamed particles are easily peeled off during air transportation, which causes clogging of the pipe. From the balance between the blocking suppressing effect and peeling, it is preferably 0.5 parts by weight or more and 1.0 part by weight or less, and more preferably 0.6 parts by weight or more and 0.8 parts by weight or less.
通常、発泡性ポリスチレン系樹脂粒子に使用されるブロッキング防止剤としては、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ラウリン酸亜鉛、ラウリン酸カルシウムなどの脂肪酸金属塩が挙げられるが、本発明の平均粒子径においては通常よりもブロッキングが発生しやすため、少量で優れたブロッキング防止性能を有するステアリン酸マグネシウムを使用する必要がある。 Examples of the blocking inhibitor usually used for effervescent polystyrene resin particles include fatty acid metal salts such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc laurate, and calcium laurate. Since blocking is more likely to occur at the average particle size of the present invention, it is necessary to use magnesium stearate having excellent blocking prevention performance in a small amount.
本発明のポリスチレン系樹脂粒子に対しては、帯電防止剤として脂肪酸モノグリセライドが使用され、脂肪酸モノグリセライドの含有量は発泡性ポリスチレン系樹脂粒子１００重量部に対して０．２重量部以上０．４重量部以下である。０．２重量部以下であると十分な帯電防止性能が得られず、０．４重量部以上であると高湿度の環境下で流動性が悪化しやすい。脂肪酸モノグリセライドの含有量はより好ましくは０．２５重量部以上０．３５重量部以下である。脂肪酸モノグリセライドとしては、ステアリン酸モノグリセライド、パルチミン酸モノグリセライド、ラウリン酸モノグリセライド、ベヘン酸モノグリセライド、ヒドロキシステアリン酸モノグリセライド、カプリン酸モノグリセライド等が挙げられ、おれらは単独で用いても良いし、２種類以上併用しても良いが、ハンドリング性からステアリン酸モノグリセライド、ベヘン酸モノグリセライド、ヒドロキシステアリン酸モノグリセライドが好ましく、粉体形状としやすく特にハンドリングしやすいことからステアリン酸モノグリセライドが特に好ましい。 For the polystyrene-based resin particles of the present invention, fatty acid monoglyceride is used as an antistatic agent, and the content of the fatty acid monoglyceride is 0.2 parts by weight or more and 0.4 weight by weight with respect to 100 parts by weight of the effervescent polystyrene-based resin particles. It is less than a part. If it is 0.2 parts by weight or less, sufficient antistatic performance cannot be obtained, and if it is 0.4 parts by weight or more, the fluidity tends to deteriorate in a high humidity environment. The content of fatty acid monoglyceride is more preferably 0.25 parts by weight or more and 0.35 parts by weight or less. Examples of the fatty acid monoglyceride include stearic acid monoglyceride, partimate monoglyceride, laurate monoglyceride, behenic acid monoglyceride, hydroxystearic acid monoglyceride, capric acid monoglyceride, etc., and we may use them alone or in combination of two or more. However, stearic acid monoglyceride, behenic acid monoglyceride, and hydroxystearic acid monoglyceride are preferable from the viewpoint of handleability, and stearic acid monoglyceride is particularly preferable because it is easy to form a powder and is particularly easy to handle.
更に、本発明のポリスチレン系樹脂粒子のヒドロキシアルキルアミンの含有量は発泡性ポリスチレン系樹脂粒子１００重量部に対して０．１重量部未満である必要がある。０．１重量部を超えるとヒドロキシアルキルアミンの吸湿により、高湿度環境下では発泡粒子の流動性が悪化しやすく、好ましくは０．０５重量部未満、より好ましくは使用しないことである。ヒドロキシアルキルアミンとしては、Ｎ−ヒドロキシエチル−Ｎ−（２−ヒドロキシアルキル）アミン、Ｎ，Ｎ−ビス（ヒドロキシエチル）ドデシルアミン、Ｎ，Ｎ−ビス（ヒドロキシエチル）テトラデシルアミン、Ｎ，Ｎ−ビス（ヒドロキシエチル）ヘキサデシルアミン、Ｎ，Ｎ−ビス（ヒドロキシエチル）オクタデシルアミン、Ｎ−ヒドロキシエチル−Ｎ−（２−ヒドロキシテトラデシル）アミン、Ｎ−ヒドロキシエチル−Ｎ−（２−ヒドロキシヘキサデシル）アミン、Ｎ−ヒドロキシエチル−Ｎ−（２−ヒドロキシオクタデシル）アミン、Ｎ−ヒドロキシプロピル−Ｎ−（２−ヒドロキシテトラデシル）アミン、Ｎ−ヒドロキシブチル−Ｎ−（２−ヒドロキシテトラデシル）アミン、Ｎ−ヒドロキシペンチル−Ｎ−（２−ヒドロキシテトラデシル）アミン、Ｎ−ヒドロキシペンチル−Ｎ−（２−ヒドロキシヘキサデシル）アミン、Ｎ−ヒドロキシペンチル−Ｎ−（２−ヒドロキシオクタデシル）アミンが挙げられる。なお、上記脂肪酸モノグリセライドと併用しても良いが、併用する場合には少量で帯電防止効果が得られやすいことから、アルキル炭素数が１４のものを主成分とするＮ−ヒドロキシエチル−Ｎ−（２−ヒドロキシアルキル）アミンを使用することが好ましい。
これらのブロッキング防止剤、帯電防止剤等の添付剤は発泡性ポリスチレン系樹脂粒子もしくは発泡粒子の表面に存在して効果を発揮することから、重合・乾燥工程を経た発泡性ポリスチレン系発泡性樹脂粒子表面に塗布することが好ましい。塗布する方法としては、攪拌機中で添付剤とともに発泡性ポリスチレン系樹脂粒子を攪拌するのが好ましく、攪拌機としてはナウターミキサー、スーパーミキサー、ユニバーサルミキサー、タンブラーミキサー、レディゲミキサーなどが用いられる。
Further, the content of hydroxyalkylamine in the polystyrene-based resin particles of the present invention needs to be less than 0.1 parts by weight with respect to 100 parts by weight of the effervescent polystyrene-based resin particles. If it exceeds 0.1 parts by weight, the fluidity of the foamed particles tends to deteriorate in a high humidity environment due to the moisture absorption of the hydroxyalkylamine, preferably less than 0.05 parts by weight, and more preferably not used. Examples of the hydroxyalkylamine include N-hydroxyethyl-N- (2-hydroxyalkyl) amine, N, N-bis (hydroxyethyl) dodecylamine, N, N-bis (hydroxyethyl) tetradecylamine, N, N-. Bis (hydroxyethyl) hexadecylamine, N, N-bis (hydroxyethyl) octadecylamine, N-hydroxyethyl-N- (2-hydroxytetradecyl) amine, N-hydroxyethyl-N- (2-hydroxyhexadecyl) ) Amines, N-hydroxyethyl-N- (2-hydroxyoctadecyl) amines, N-hydroxypropyl-N- (2-hydroxytetradecyl) amines, N-hydroxybutyl-N- (2-hydroxytetradecyl) amines, Examples thereof include N-hydroxypentyl-N- (2-hydroxytetradecyl) amine, N-hydroxypentyl-N- (2-hydroxyhexadecyl) amine, and N-hydroxypentyl-N- (2-hydroxyoctadecyl) amine. It may be used in combination with the above fatty acid monoglyceride, but when used in combination, an antistatic effect can be easily obtained with a small amount. It is preferable to use 2-hydroxyalkyl) amine.
Since these attachments such as antiblocking agents and antistatic agents are present on the surface of the foamable polystyrene-based resin particles or the foamed particles and exert their effects, the foamable polystyrene-based foamable resin particles that have undergone the polymerization / drying step are effective. It is preferably applied to the surface. As a method of coating, it is preferable to stir the effervescent polystyrene resin particles together with the attachment in a stirrer, and as the stirrer, a Nauter mixer, a super mixer, a universal mixer, a tumbler mixer, a Ladyge mixer and the like are used.
これらのブロッキング防止剤、帯電防止剤等の添付剤が発泡性ポリスチレン系樹脂粒子から剥がれにくくするため、塗布する際に添着剤を併用することが好ましい。添着剤としては、ヒマシ硬化油、オリーブ油、菜種油、ポリエチレングリコール、ポリプロピレングリコール、ジメチルポリシロキサン、メチルフェニルポリシロキサンなどが挙げられ、少量で剥離抑制効果に優れることからヒマシ硬化油が好ましい。発泡性ポリスチレン系樹脂粒子の表面のヒマシ硬化油の含有量としては０．０４重量部以上０．１５重量部以下が好ましく、より好ましくは０．０５重量部以上０．０８重量部以下である。０．０４重量部以下だと添付剤の剥離抑制効果が得られづらく、０．１５重量部を超えると発泡性ポリスチレン系樹脂粒子の流動性が悪化しやすくブロッキングも増加しやすい。 In order to prevent the attachments such as antiblocking agent and antistatic agent from peeling off from the foamable polystyrene resin particles, it is preferable to use an adhering agent together at the time of application. Examples of the adhering agent include hydrogenated castor oil, olive oil, rapeseed oil, polyethylene glycol, polypropylene glycol, dimethylpolysiloxane, and methylphenylpolysiloxane, and hydrogenated castor oil is preferable because it is excellent in peeling inhibitory effect even in a small amount. The content of castor oil on the surface of the foamable polystyrene resin particles is preferably 0.04 parts by weight or more and 0.15 parts by weight or less, and more preferably 0.05 parts by weight or more and 0.08 parts by weight or less. If it is 0.04 parts by weight or less, it is difficult to obtain the effect of suppressing the peeling of the attachment, and if it exceeds 0.15 parts by weight, the fluidity of the foamable polystyrene resin particles tends to deteriorate and blocking tends to increase.
本発明に用いる発泡性ポリスチレン系樹脂粒子は、基材樹脂及び発泡剤を含有している。より詳しくは、基材樹脂にに発泡剤が含浸したものである。基材樹脂には、一般的に知られているポリスチレン系樹脂粒子を用いることができる。ポリスチレン系樹脂粒子を製造する際に用いられる単量体としては、スチレン、及び、α−メチルスチレン、パラメチルスチレン、ｔ−ブチルスチレン、クロルスチレンなどのスチレン系誘導体が挙げられ、さらにスチレンと共重合が可能な成分、例えばメチルアクリレート、ブチルアクリレート、メチルメタクリレート、エチルメタクリレート、セチルメタクリレートなどのアクリル酸及びメタクリル酸のエステル、あるいはアクリロニトリル、ジメチルフマレート、エチルフマレートなどの各種単量体、ジビニルベンゼン、アルキレングリコールジメタクリレートなどの２官能性単量体が挙げられる。すなわち、基材樹脂としては、上述のスチレンと共重合が可能な成分を含まない重合体、若しくは、スチレンと共重合が可能な成分を１種又は２種以上使用した共重合体であってもよい。尚、スチレン中に含まれるフェニルアセチレン量は０〜１５０ｐｐｍが好ましい。フェニルアセチレン量が１５０ｐｐｍを超える場合には残存スチレン量が増える傾向にあるため好ましくない。 The effervescent polystyrene-based resin particles used in the present invention contain a base resin and a foaming agent. More specifically, the base resin is impregnated with a foaming agent. Generally known polystyrene-based resin particles can be used as the base resin. Examples of the monomer used in producing the polystyrene-based resin particles include styrene and styrene-based derivatives such as α-methylstyrene, paramethylstyrene, t-butylstyrene, and chlorostyrene, and the same as styrene. Polymerizable components such as acrylic acid and styrenic esters such as methyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, cetyl methacrylate, various monomers such as acrylonitrile, dimethyl fumarate, ethyl fumarate, divinyl benzene , Bifunctional monomers such as alkylene glycol dimethacrylate. That is, the base resin may be a polymer that does not contain the above-mentioned component that can be copolymerized with styrene, or a copolymer that uses one or more components that can be copolymerized with styrene. good. The amount of phenylacetylene contained in styrene is preferably 0 to 150 ppm. When the amount of phenylacetylene exceeds 150 ppm, the amount of residual styrene tends to increase, which is not preferable.
本発明における発泡性ポリスチレン系樹脂粒子は、水性懸濁液中に分散したポリスチレン系樹脂種粒子にスチレン系単量体を添加して該種粒子に含浸させながら重合せしめる、いわゆる懸濁シード重合法によって製造されることが好ましい。 The effervescent polystyrene-based resin particles in the present invention are a so-called suspension seed polymerization method in which a styrene-based monomer is added to polystyrene-based resin seed particles dispersed in an aqueous suspension and the seed particles are impregnated and polymerized. It is preferably manufactured by.
懸濁シード重合法に用いる樹脂種粒子は、（１）通常の懸濁重合法、（２）重合性単量体を規則的な振動下にノズルを通すことにより液滴群として水性媒体中に分散させ、合着および付加的な分散を生じせしめることなく重合させる方法、などによって得ることができる。本発明においては、樹脂種粒子の製造方法は粒度分布を狭くできる点で(２)の方が好ましい。 The resin seed particles used in the suspension seed polymerization method are (1) a normal suspension polymerization method, and (2) a polymerizable monomer is passed through a nozzle under regular vibration to form a group of droplets in an aqueous medium. It can be obtained by a method of dispersing and polymerizing without causing coalescence and additional dispersion, and the like. In the present invention, the method for producing resin seed particles is preferably (2) in that the particle size distribution can be narrowed.
ポリスチレン系樹脂種粒子の量は、目的とするポリスチレン系樹脂粒子の量に対して５〜６０重量％であることが好ましい。５重量％未満になる場合、水性懸濁液に添加する重合性単量体が該樹脂種粒子内で重合せずに、単独で重合する割合が増える傾向にあり、６０重量％を超える場合は、一回の重合工程でより多くのモノマーを重合させることが出来ずに、不経済である。 The amount of polystyrene-based resin seed particles is preferably 5 to 60% by weight with respect to the amount of the target polystyrene-based resin particles. If it is less than 5% by weight, the proportion of the polymerizable monomer added to the aqueous suspension that does not polymerize in the resin seed particles but polymerizes alone tends to increase, and if it exceeds 60% by weight, it tends to increase. , It is uneconomical because more monomers cannot be polymerized in one polymerization step.
ポリスチレン系樹脂種粒子の平均粒径は０．１３〜０．３０ｍｍとすることが好ましい。より好ましくは０．１６〜０．２６ｍｍ、更に好ましくは０．２０〜０．２５ｍｍである。平均粒径が０．１３〜０．３０ｍｍのポリスチレン系樹脂種粒子を用いて上記方法で発泡性ポリスチレン系樹脂粒子を製造することで、発泡性ポリスチレン系樹脂粒子の平均粒子径を０．２５ｍｍ以上０．５０ｍｍ以下に制御しやすくなる。
また、平均粒子径±１５％の変動幅に入る割合が９０％以上の発泡性ポリスチレン系樹脂粒子を生産するために、ポリスチレン系樹脂種粒子の平均粒子径±１５％の変動幅に入る割合は９０％以上であることが好ましく、９５％以上がより好ましい。
The average particle size of the polystyrene resin seed particles is preferably 0.13 to 0.30 mm. It is more preferably 0.16 to 0.26 mm, still more preferably 0.25 to 0.25 mm. By producing foamable polystyrene-based resin particles by the above method using polystyrene-based resin seed particles having an average particle size of 0.13 to 0.30 mm, the average particle size of the foamable polystyrene-based resin particles is 0.25 mm or more. It becomes easy to control to 0.50 mm or less.
Further, in order to produce foamable polystyrene-based resin particles having a fluctuation range of 90% or more in the fluctuation range of the average particle size ± 15%, the ratio of the polystyrene-based resin seed particles in the fluctuation range of ± 15% is included. It is preferably 90% or more, and more preferably 95% or more.
本発明の発泡性ポリスチレン系樹脂粒子の重量平均分子量は２２万以上３０万未満であることが好ましい。より好ましくは２３万以上２８万未満である。重量平均分子量が２２万より低い場合、ポリスチレン系樹脂粒子自体の機械強度が低下する上ブロッキングも発生しやすく、３０万を超える場合には、発泡性が悪化しやすく、無理に発泡させたにセル膜が破れ発泡粒子のセル構造に欠陥ができやすい。 The weight average molecular weight of the effervescent polystyrene-based resin particles of the present invention is preferably 220,000 or more and less than 300,000. More preferably, it is 230,000 or more and less than 280,000. When the weight average molecular weight is lower than 220,000, the mechanical strength of the polystyrene resin particles themselves is lowered and blocking is likely to occur. The film is torn and the cell structure of the foamed particles is liable to be defective.
更に、本発明の発泡性ポリスチレン系樹脂粒子中のスチレン単量体の残存量は１５０ｐｐｍ未満であることが好ましい。より好ましくは１００ｐｐｍ未満である。発泡性ポリスチレン系樹脂粒子中のスチレン単量体の残存量が１５０ｐｐｍ未満であることで、特に、クッションビーズ材として使用した際に問題となる臭気を抑制することができる。 Further, the residual amount of the styrene monomer in the foamable polystyrene-based resin particles of the present invention is preferably less than 150 ppm. More preferably, it is less than 100 ppm. When the residual amount of the styrene monomer in the foamable polystyrene-based resin particles is less than 150 ppm, it is possible to suppress an odor which is a problem especially when used as a cushion bead material.
本発明の発泡性ポリスチレン系樹脂粒子の製造方法で使用する分散剤としては、一般的に用いられている分散剤、例えば、燐酸カルシウム、ハイドロキシアパタイト、ピロリン酸マグネシウムなどの難水溶性無機塩が挙げられる。これら、難水溶性無機塩を用いる場合には、α−オレフィンスルフォン酸ソーダ、ドデシルベンゼンスルフォン酸ソーダなどのアニオン性界面活性剤を併用すると、分散安定性が増すので効果的である。また、難溶性無機塩は得られる発泡性ポリスチレン系樹脂粒子の粒子径を調節するために、重合中に１回以上追加することもある。
上記製造方法で用いられる重合開始剤は、ベンゾイルパーオキサイド、ラウリルパーオキサイド、ｔ−ブチルパーオキシベンゾエート、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、ｔ−アミルパーオキシ−２−エチルヘキシルモノカーボネート、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシイソプロピルモノカーボネート等があげられる。これらは、単独で用いてもよいし、２種類以上併用しても良い。
中でもベンゾイルパーオキサイドとｔ−ブチルパーオキシー２−エチルヘキシルモノカーボネートを併用することが重量平均分子量とスチレン単量体残存量のバランスと取りやすいため好ましい。本発明における重量平均分子量はベンゾイルパーオキサイドの総添加量と単位時間当たりの添加量を変更することで調整が可能であり、総添加量としては０．１４重量以上０．２２８重量部以下で、ベンゾイルパーオキサイドの単位時間当たりの添加量を減少させていくか、又は一定であるのが望ましい。
Examples of the dispersant used in the method for producing foamable polystyrene-based resin particles of the present invention include commonly used dispersants, for example, poorly water-soluble inorganic salts such as calcium phosphate, hydroxyapatite, and magnesium pyrophosphate. Be done. When these poorly water-soluble inorganic salts are used, it is effective to use an anionic surfactant such as α-olefin sulphonate soda or dodecylbenzene sulphonate soda in combination because the dispersion stability is increased. Further, the poorly soluble inorganic salt may be added once or more during the polymerization in order to adjust the particle size of the obtained foamable polystyrene-based resin particles.
The polymerization initiators used in the above production method are benzoyl peroxide, lauryl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexyl monocarbonate, t-amylperoxy-2-ethylhexyl monocarbonate, and the like. Examples thereof include t-hexyl peroxyisopropyl monocarbonate and t-butylperoxyisopropyl monocarbonate. These may be used alone or in combination of two or more.
Of these, it is preferable to use benzoyl peroxide and t-butylperoxy-2-ethylhexyl monocarbonate in combination because it is easy to balance the weight average molecular weight and the residual amount of styrene monomer. The weight average molecular weight in the present invention can be adjusted by changing the total amount of benzoyl peroxide added and the amount added per unit time, and the total amount added is 0.14 weight or more and 0.228 parts by weight or less. It is desirable to reduce or keep the amount of benzoyl peroxide added per unit time.
本発明において使用する発泡剤としては、プロパン、イソブタン、ノルマルブタン、イソペンタン、ノルマルペンタン、ネオペンタンなど炭素数３以上５以下の炭化水素等の脂肪族炭化水素類、およびジフルオロエタン、テトラフルオロエタンなどのオゾン破壊係数がゼロであるフッ化炭化水素類などの揮発性発泡剤が挙げられる。尚、本発明においてはブタンとペンタンを併用する、もしくはブタンとシクロヘキサンを併用するのが長期的に発泡性を維持しやすく好ましい。
ブタンの添加量としてはポリスチレン系樹脂粒子１００重量部に対して、好ましくは５重量部以上８重量部未満である。５重量部より少ないと所定倍率(５０倍)まで発泡することができず、また発泡操作中にブタンが散逸しやすく、発泡粒子内に残るブタンが少なくなるため、発泡粒子の内圧が低下し、座屈しやすくなる。その結果、短期的にクッション性が悪化する。８重量部以上の場合は、発泡の際に倍率ばらつきが発生しやすくなるため、クッション性が悪化する。
添加するブタン組成としては、イソブタン濃度が５０％以上が好ましい。イソブタン濃度が５０％未満になると、発泡操作中に主にノルマルブタンが散逸しやすく、発泡粒子内に残るブタン総量が少なくなるため、発泡粒子の内圧が低下し、座屈しやすくなる。その結果、短期的にクッション性が悪化する。
ペンタン又はシクロヘキサンの添加量としてはポリスチレン系樹脂粒子１００重量部に対して、好ましくは２重量部以上５重量部以下が好ましい。１．５重量未満になると長期にわたって発泡性が維持しづらくなるため品質が安定しづらい。５重量部を超える場合は、発泡速度がはやくなりすぎるため、発泡の際に倍率ばらつきが大きくなり、発泡粒子の粒度分布が悪くなる。その結果、感触、クッション性が悪化する。また、発泡操作時のブロッキングが増える傾向にある。
ペンタンを添加する際の組成としては、発泡速度を得られやすい点から、イソペンタン濃度が３０％以上が好ましい。より好ましいイソペンタン濃度は５０％以上である。
The effervescent agent used in the present invention includes aliphatic hydrocarbons such as hydrocarbons having 3 to 5 carbon atoms such as propane, isobutane, normal butane, isopentane, normal pentane and neopentane, and ozone such as difluoroethane and tetrafluoroethane. Examples thereof include volatile foaming agents such as fluorinated hydrocarbons having a destruction coefficient of zero. In the present invention, it is preferable to use butane and pentane in combination, or butane and cyclohexane in combination because it is easy to maintain foamability for a long period of time.
The amount of butane added is preferably 5 parts by weight or more and less than 8 parts by weight with respect to 100 parts by weight of the polystyrene-based resin particles. If it is less than 5 parts by weight, it cannot be foamed up to a predetermined magnification (50 times), butane is easily dissipated during the foaming operation, and the amount of butane remaining in the foamed particles is reduced, so that the internal pressure of the foamed particles is lowered. It becomes easy to buckle. As a result, the cushioning property deteriorates in the short term. If the amount is 8 parts by weight or more, the magnification tends to vary during foaming, so that the cushioning property deteriorates.
The butane composition to be added is preferably an isobutane concentration of 50% or more. When the isobutane concentration is less than 50%, normal butane is likely to dissipate mainly during the foaming operation, and the total amount of butane remaining in the foamed particles is reduced, so that the internal pressure of the foamed particles is lowered and buckling is likely to occur. As a result, the cushioning property deteriorates in the short term.
The amount of pentane or cyclohexane added is preferably 2 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polystyrene resin particles. If the weight is less than 1.5, it is difficult to maintain foamability for a long period of time, and it is difficult to stabilize the quality. If it exceeds 5 parts by weight, the foaming rate becomes too fast, so that the magnification variation becomes large during foaming and the particle size distribution of the foamed particles becomes poor. As a result, the feel and cushioning property deteriorate. In addition, blocking during the foaming operation tends to increase.
As the composition when the pentane is added, the isopentane concentration is preferably 30% or more from the viewpoint that the foaming rate can be easily obtained. A more preferable isopentane concentration is 50% or more.
尚、発泡性ポリスチレン系樹脂粒子には、物性を損なわない範囲内において、可塑剤、気泡調整剤、難燃剤、難燃助剤等が使用できる。可塑剤としては、例えば、ステアリン酸トリグリセライド、パルミチン酸トリグリセライド、ラウリン酸トリグリセライド、ステアリン酸ジグリセライド、ステアリン酸モノグリセライド等の脂肪酸グリセライド、ヤシ油、パーム油、パーム核油等の植物油、ジオクチルアジペート、ジブチルセバケート等の脂肪族エステル、流動パラフィン、シクロヘキサン等の有機炭化水素等があげられ、これらは併用しても何ら差し支えない。気泡調整剤としては、例えば、ポリメタクリル酸メチル、メチレンビスステアリン酸アマイド、エチレンビスステアリン酸アマイド等の脂肪族ビスアマイド、ポリエチレンワックス等が挙げられる。難燃剤としては、臭素化スチレン、臭素化ブタジエン・ビニル芳香族共重合体、臭素化ノボラック樹脂アリルエーテル、臭素化ポリ（１，３−シクロアルカジエン）及び臭素化ポリ（４−ビニルフェノールアリルエーテル）などの臭素化ポリマーやポリグリセリンジブロモプロピルエーテル、テトラブロモビスフェノールＡ、テトラブロモビスフェノール−Ａ−ビス（２，３−ジブロモ−２−メチルプロピルエーテル）等々の低分子化合物が上げられる。難燃助剤としては、例えば、クメンパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、２，３−ジメチルー２，３−ジフェニルブタン等の高温分解型の有機物があげられる。 As the foamable polystyrene-based resin particles, a plasticizer, a bubble adjusting agent, a flame retardant, a flame retardant aid, or the like can be used as long as the physical properties are not impaired. Examples of the plasticizer include fatty acid glycerides such as triglyceride stearate, triglyceride palmitic acid, triglyceride laurate, diglyceride stearate and monoglyceride stearate, vegetable oils such as coconut oil, palm oil and palm kernel oil, dioctyl adipate and dibutyl sebacate. Examples thereof include aliphatic esters such as, liquid paraffin, and organic hydrocarbons such as cyclohexane, and these may be used in combination. Examples of the bubble regulator include aliphatic bisamides such as polymethyl methacrylate, methylene bisstearic acid amide, ethylene bisstearic acid amide, and polyethylene wax. Flame retardants include brominated styrene, brominated butadiene-vinyl aromatic copolymer, brominated novolak resin allyl ether, brominated poly (1,3-cycloalkaziene) and brominated poly (4-vinylphenol allyl ether). ), And low molecular weight compounds such as polyglycerin dibromopropyl ether, tetrabromobisphenol A, and tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether). Examples of the flame retardant aid include high temperature decomposition type organic substances such as cumene peroxide, dicumyl peroxide, t-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane.
本発明の発泡性ポリスチレン系樹脂粒子は公知の方法で発泡させることが出来る。例えば、発泡性ポリスチレン系樹脂粒子を回転攪拌式予備発泡装置で、水蒸気を用いて８０〜１０５℃程度で加熱することにより、発泡粒子を作製することできる。８０℃未満になると、発泡時間がながいため生産性が悪化する。１０５℃を超えると、セル膜が破れ発泡粒子のセル構造に欠陥ができやすい。 The effervescent polystyrene-based resin particles of the present invention can be foamed by a known method. For example, foamed polystyrene-based resin particles can be produced by heating them with a rotary stirring type pre-foaming device at about 80 to 105 ° C. using steam. If the temperature is lower than 80 ° C., the foaming time is long and the productivity is deteriorated. If the temperature exceeds 105 ° C., the cell film is torn and the cell structure of the foamed particles is likely to be defective.
前記発泡性ポリスチレン系樹脂粒子をクッションビーズとして使用する際の好ましい嵩密度は０．０１８ｇ／ｃｍ３以上０．０２９ｇ／ｃｍ３以下である。０．０１８ｇ／ｃｍ３未満の場合、発泡粒子が座屈しやすくなるため、短期間でクッション性が悪化しやすく、０．０２９ｇ／ｃｍ３を超えると発泡粒子が硬くなりクッション性が悪化する。 The preferred bulk density for using expandable polystyrene resin particles as a cushioning beads is 0.018 g / cm 3 or more 0.029 g / cm 3 or less. If it is less than 0.018 g / cm 3 , the foamed particles tend to buckle, so that the cushioning property tends to deteriorate in a short period of time. If it exceeds 0.029 g / cm 3 , the foamed particles become hard and the cushioning property deteriorates.
得られるポリスチレン系発泡粒子の平均気泡径は１０〜１００μmが好ましい。この範囲であれば、発泡倍率のバラツキが小さい発泡粒子ができ、更にこの発泡粒子は座屈しにくく、長期的にクッション性を維持できる。 The average cell diameter of the obtained polystyrene-based foamed particles is preferably 10 to 100 μm. Within this range, foamed particles having a small variation in foaming ratio can be produced, and the foamed particles are less likely to buckle and can maintain cushioning properties for a long period of time.
得られるポリスチレン系発泡体はクッションビーズ、軽量骨材用途等に使用できるが、帯電防止性能と流動性に優れることから特にクッション用途に好ましい。 The obtained polystyrene-based foam can be used for cushion beads, lightweight aggregates, etc., but is particularly preferable for cushion applications because of its excellent antistatic performance and fluidity.
以下に実施例、及び比較例を挙げるが、本発明はこれによって限定されるものではない。
実施例、及び比較例中の発泡性ポリスチレン系樹脂粒子及びポリスチレン系樹脂粒子の重量平均分子量測定、ポリスチレン系発泡粒子の帯電量、感触評価、へたり評価(発泡粒子の座屈度)、発泡操作時のブロッキング量については以下の方法で測定した。また、「部」「％」は特に断りのない限り重量基準である。
Examples and comparative examples are given below, but the present invention is not limited thereto.
Weight average molecular weight measurement of foamable polystyrene-based resin particles and polystyrene-based resin particles in Examples and Comparative Examples, charge amount of polystyrene-based foamed particles, feel evaluation, settling evaluation (bending degree of foamed particles), foaming operation The amount of blocking at the time was measured by the following method. In addition, "part" and "%" are based on weight unless otherwise specified.
＜発泡性ポリスチレン系樹脂粒子の平均粒子径の測定及び粒度分布の評価＞
発泡性ポリスチレン系樹脂粒子画像処理方式ミリトラックＪＰＡ粒度分析計にて粒度分布と平均粒子径を測定した。
測定した粒度分布と平均粒子径に基づき、発泡性ポリスチレン系樹脂粒子の平均粒子径±１５％の変動幅に入る割合を算出した。
<Measurement of average particle size and evaluation of particle size distribution of foamable polystyrene resin particles>
Foamable polystyrene resin particle image processing method The particle size distribution and average particle size were measured with a Millitrack JPA particle size analyzer.
Based on the measured particle size distribution and average particle size, the ratio within the fluctuation range of the average particle size ± 15% of the foamable polystyrene resin particles was calculated.
＜発泡性ポリスチレン系樹脂粒子の重量平均分子量の測定法＞
発泡性ポリスチレン系樹脂粒子をテトラヒドロフランに溶解し、ＧＰＣ（東ソー（株）製ＨＬＣ−８０２０、カラム：ＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＺＭ−Ｈ、カラム温度：４０℃、流速：０．３５ｍｌ／１ｍｉｎ．）にて測定した。
<Measurement method of weight average molecular weight of foamable polystyrene resin particles>
Expandable polystyrene resin particles were dissolved in tetrahydrofuran and measured by GPC (HLC-8020 manufactured by Tosoh Corporation, column: TSKgel Super HZM-H, column temperature: 40 ° C., flow velocity: 0.35 ml / 1 min.). ..
＜発泡性ポリスチレン系樹脂粒子のスチレン単量体残存量の測定法＞
発泡性ポリスチレン系樹脂粒子を塩化メチレン（内部標準シクロペンタノール）に溶解し、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：ＰＥＧ−２０Ｍ ２５％、カラム温度：１１０℃、キャリアガス：ヘリウム）を用いて、発泡性ポリスチレン系樹脂粒子中に含まれる残存スチレン単量体量を定量した。
<Measurement method of residual amount of styrene monomer in foamable polystyrene resin particles>
Effervescent polystyrene resin particles are dissolved in methylene chloride (internal standard cyclopentanol) and gas chromatography (GC-14B manufactured by Shimadzu Corporation, column: 3 m, filler: PEG-20M 25%, column temperature: 110 ° C., Carrier gas: helium) was used to quantify the amount of residual styrene monomer contained in the effervescent polystyrene-based resin particles.
＜発泡性ポリスチレン系樹脂粒子の発泡性の評価方法＞
発泡性ポリスチレン系樹脂粒子を１００℃の蒸し器に入れ、５分間加熱することにより、ポリスチレン系発泡粒子を得た。得られたポリスチレン系発泡粒子１０ｇを、１０００ｃｍ３のメスシリンダーに入れ、ポリスチレン系発泡粒子の体積（ｃｍ３）を測定した。以下の式で、嵩密度（ｇ／ｃｍ３）を計算した：
嵩密度（ｇ／ｃｍ３）＝１０ｇ／ポリスチレン系発泡粒子の体積（ｃｍ３）
<Evaluation method of foamability of foamable polystyrene resin particles>
Expandable polystyrene-based resin particles were placed in a steamer at 100 ° C. and heated for 5 minutes to obtain polystyrene-based expanded polystyrene particles. 10 g of the obtained polystyrene-based foamed particles were placed in a 1000 cm 3 measuring cylinder, and the volume (cm 3 ) of the polystyrene-based foamed particles was measured. The bulk density (g / cm 3 ) was calculated by the following formula:
Bulk density (g / cm 3 ) = 10 g / volume of polystyrene-based foamed particles (cm 3 )
得られた嵩密度を用いて、下記指標に基づき、発泡性ポリスチレン系樹脂粒子の発泡性を評価した。
〇：嵩密度が０．０２５０ｇ／ｃｍ３未満である場合
△：嵩密度が０．０２５０ｇ／以上０．０３００ｇ／以下である場合
×：嵩密度が０．０３００ｇ／ｃｍ３を超える場合
Using the obtained bulk density, the foamability of the expandable polystyrene-based resin particles was evaluated based on the following indexes.
〇: When the bulk density is less than 0.0250 g / cm 3 Δ: When the bulk density is 0.0250 g / or more and 0.0300 g / or less ×: When the bulk density exceeds 0.0300 g / cm 3.
＜発泡操作時のブロッキングの評価＞
ブロッキングとは、発泡性ポリスチレン系樹脂粒子を発泡させてポリスチレン系発泡粒子を製造した時（発泡操作時）に、ポリスチレン系発泡粒子同士が結合した塊である。ブロッキングがクッション内に入ると感触の悪化など起こるため、ブロッキング量が多い場合においては発泡操作後に取り除く必要がある。尚、ブロッキング量の測定は以下の通りに実施した。
<Evaluation of blocking during foaming operation>
Blocking is a mass in which polystyrene-based foamed particles are bonded to each other when polystyrene-based foamed particles are produced by foaming foamable polystyrene-based resin particles (during foaming operation). If the blocking amount enters the cushion, the feel may deteriorate. Therefore, if the blocking amount is large, it is necessary to remove it after the foaming operation. The blocking amount was measured as follows.
発泡操作により得られたポリスチレン系発泡粒子全量を、編み目間隔が1cmの金網に通した。金網に残った塊の重量を測定し、以下の式でブロッキング量を計算し、下記指標に基づきて評価した。 The entire amount of polystyrene-based foamed particles obtained by the foaming operation was passed through a wire mesh having a stitch spacing of 1 cm. The weight of the mass remaining on the wire net was measured, the blocking amount was calculated by the following formula, and the evaluation was made based on the following index.
ブロッキング量(重量％)＝塊の重さ/ポリスチレン系発泡粒子全量の重さ×１００
〇：ブロッキング量が０．５重量％未満、
△：ブロッキング量が０．５重量％以上１重量％以下、
×：１重量％以上。
Blocking amount (% by weight) = Weight of mass / Weight of total polystyrene-based foamed particles x 100
〇: Blocking amount is less than 0.5% by weight,
Δ: Blocking amount is 0.5% by weight or more and 1% by weight or less,
X: 1% by weight or more.
＜発泡性ポリスチレン系樹脂粒子の添付剤の剥離量の評価＞
装置 ：電動篩 ＤＹ−５０
網 ：ＳＵＳ網（目開き：３５５μｍ、４２メッシュ、φ７５０ｍｍ）
発泡性ポリスチレン系樹脂粒子１ｋｇを秤量し、電動篩の網上に広げて２分間、篩い分けを行った。その後、網を通過した粉体を回収し（但し、樹脂が混じっている場合は当該樹脂を除去し）、その重量を計量して添付剤の剥離量とした。そして、下記算出式
剥離率［重量％］＝剥離量［ｇ］／発泡性ポリスチレン系樹脂粒子に添加した添付剤の全量［ｇ］×１００
に基づいて添付剤の剥離率を算出し、下記指標に基づき評価した。
〇：剥離率が２．０重量％以下である場合、
△：剥離率が２．０重量％以上５．０重量％以下である場合、
×：剥離率が５．０重量％を超えある場合。
<Evaluation of the amount of adhesive peeled off from foamable polystyrene resin particles>
Equipment: Electric sieve DY-50
Net: SUS net (opening: 355 μm, 42 mesh, φ750 mm)
1 kg of foamable polystyrene resin particles were weighed, spread on a net of an electric sieve, and sieved for 2 minutes. Then, the powder that passed through the net was collected (however, if the resin was mixed, the resin was removed), and the weight thereof was measured to obtain the peeling amount of the attachment. Then, the following calculation formula peeling rate [% by weight] = peeling amount [g] / total amount of the attachment added to the foamable polystyrene resin particles [g] × 100
The peeling rate of the attachment was calculated based on the above, and evaluated based on the following indexes.
〇: When the peeling rate is 2.0% by weight or less
Δ: When the peeling rate is 2.0% by weight or more and 5.0% by weight or less
X: When the peeling rate exceeds 5.0% by weight.
＜ポリスチレン系発泡粒子の帯電量の測定法＞
発泡倍率４０倍（嵩密度０．０２５ｇ／ｃｍ３）に発泡させたポリスチレン系発泡粒子１Ｌを、ポリエチレン製の袋(ＯＫ袋Ｎｏ．１５、大倉工業株式会社製)に入れ、口を開けた状態で、２３℃、湿度５０％の恒温室で一晩保管する。その後、ポリエチレン製の袋の口を縛り、口を縛った状態で１００回振った。その後、ポリエチレン袋の口を開け、スチレン系発泡粒子表面の帯電量を静電気測定器「シシド静電気製スタチロンＤＸ」によって３回以上測定し、その平均値を発泡粒子の帯電量とした（測定距離３０ｍｍ、電荷量測定は２３℃、相対湿度５０％の雰囲気下で行った）。その後、直ちにポリエチレン袋から発泡粒子を取り出し、ポリエチレン袋に静電気により残った発泡粒子の重量を測定した。そして、以下の指標に基づき評価した。
〇：帯電量の絶対値が０．３ｋＶ以下、かつ、ポリエチレン袋の発泡粒子の残量が３％以下の場合、
△：帯電量の絶対値が０．３ｋＶ以下だが、ポリエチレン袋の発泡粒子の残量が３％を超える場合、
×：帯電量の絶対値が０．３ｋＶを超える場合。
<Measurement method of charge amount of polystyrene-based foamed particles>
1 L of polystyrene-based foamed particles foamed at a foaming ratio of 40 times (bulk density 0.025 g / cm 3 ) is placed in a polyethylene bag (OK bag No. 15, manufactured by Okura Industrial Co., Ltd.) with the mouth open. Then, store it in a constant temperature room at 23 ° C. and 50% humidity overnight. Then, the mouth of the polyethylene bag was tied, and the bag was shaken 100 times with the mouth tied. After that, the mouth of the polyethylene bag was opened, and the amount of charge on the surface of the styrene-based foamed particles was measured three times or more with the electrostatic measuring device "Sisid Electrostatic Statylon DX", and the average value was taken as the amount of charge of the foamed particles (measurement distance 30 mm). The charge amount was measured in an atmosphere of 23 ° C. and a relative humidity of 50%). Immediately after that, the foamed particles were taken out from the polyethylene bag, and the weight of the foamed particles remaining in the polyethylene bag due to static electricity was measured. Then, it was evaluated based on the following indicators.
〇: When the absolute value of the amount of charge is 0.3 kV or less and the remaining amount of foamed particles in the polyethylene bag is 3% or less.
Δ: When the absolute value of the charge amount is 0.3 kV or less, but the remaining amount of foamed particles in the polyethylene bag exceeds 3%,
X: When the absolute value of the charge amount exceeds 0.3 kV.
＜ポリスチレン系発泡粒子の流動性の評価＞
ポリスチレン系発泡粒子１Ｌを網袋に入れ、湿度９０％に加湿した部屋に４時間静置した。その後、湿度９０％に加湿した部屋で発泡粒子１Ｌを口径１ｃｍ２のステンレス製漏斗（足部：上部径３０ｍｍφ、下部径１５ｍｍφ、足長４５ｍｍ、口内径２３５ｍｍ）を通し、漏斗に残った発泡粒子の重量比率により判定した。そして、以下の指標に基づき評価した。
〇：漏斗に残った発泡粒子が１０重量未満％の場合、
△：１０重量％以上５０重量％以下の場合、
×：５０重量％を超える場合。
<Evaluation of fluidity of polystyrene-based foamed particles>
1 L of polystyrene-based foamed particles was placed in a net bag and allowed to stand in a room humidified at 90% humidity for 4 hours. Then, in a room humidified to 90% humidity, 1 L of foamed particles was passed through a 1 cm2 diameter stainless steel funnel (foot: upper diameter 30 mmφ, lower diameter 15 mmφ, foot length 45 mm, mouth inner diameter 235 mm), and the foamed particles remaining in the funnel. It was judged by the weight ratio. Then, it was evaluated based on the following indicators.
〇: When the foamed particles remaining in the funnel are less than 10% by weight,
Δ: When 10% by weight or more and 50% by weight or less
X: When it exceeds 50% by weight.
＜クッションの触感＞
ポリスチレン系発泡粒子を３．５Ｌ測定し、内容積４Ｌの布製袋に封入し、ビーズクッションを作製した。６人で評価を行いビーズクッションの感触を評価した。
〇：４人以上が好感触の場合、
△：２〜３人が好感触の場合、
×：好感触が０〜１人となる場合。
<Cushion feel>
3.5 L of polystyrene-based foamed particles were measured and sealed in a cloth bag having an internal volume of 4 L to prepare a bead cushion. Six people evaluated the feel of the bead cushion.
〇: If 4 or more people feel good,
Δ: When 2 to 3 people feel good
X: When the favorable feeling is 0 to 1 person.
（実施例１）
＜発泡性ポリスチレン系樹脂粒子の製造＞
（１）発泡性ポリスチレン系樹脂粒子本体の製造工程
撹拌機付属の６Ｌのオートクレーブに、純水重量８５重量部、第３リン酸カルシウム０．５７重量部、α―オレフィンスルフォン酸ソーダ０．００４７６重量部、塩化ナトリウム０．１重量部、平均粒子径が０．２５ｍｍのスチレン系樹脂種粒子(平均粒径±１５％の変動幅に入る割合：９８％)３２重量部を仕込んだ後、攪拌を開始した。その後、開始剤として、ｔ−ブチルパーオキシー２−エチルヘキシルモノカーボネート０．０８重量部を仕込んだ。続いて、９２℃まで昇温させた後、ベンゾイルパーオキサイド３０％溶液０．２２８重量部を４時間５０分（０〜１時間目の追加量を０．０６８重量部、１〜２時間目の追加量を０．０５７重量部、２〜３時間目の追加量を０．０４６重量部、３〜４時間目の追加量を０．０３４重量部、４時間〜４時間５０分目の追加量を０．０２３重量部）、スチレン単量体６８重量部を５時間３０分（０〜１時間目の追加量を８重量部、１〜２時間目の追加量を１０重量部、２〜３時間目の追加量を１２重量部、３〜４時間目の追加量を１５重量部、４〜５時間目の追加量を１５重量部、５時間〜５時間３０分目の追加量を８重量部）かけて反応器中に仕込みながら重合した。その後、３０分間９２℃を保持した後、直ちに１２０℃に昇温して１時間保持した。９５℃に冷却後、反応器内に、発泡剤として、ブタン６．０重量部（ノルマルブタン：イソブタン＝７０：３０）及びペンタン４．０重量部（ノルマルペンタン：イソペンタン＝５０：５０）を仕込み更に１時間１２０℃で保持した後、冷却した。室温まで冷却して、オートクレーブから重合スラリーを取り出した。取り出した重合スラリーを洗浄、脱水・乾燥することにより、発泡性ポリスチレン系樹脂粒子本体を得た。
（２）添加剤の塗布工程
上記で得た発泡性ポリスチレン系樹脂粒子本体１００重量部に対して、ステアリン酸マグネシウムとしてマグネシウムステアレート［日油（株）製］を０．８重量部、ひまし硬化油［日油（株）製］を０．７２重量部、及び帯電防止剤としてステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．３０重量部を、スーパーミキサー［（株）川田製、ＳＭＶ−２０］に投入し、１０００ｒｐｍで１２０秒間ブレンドした。その後払い出し、添付剤で被覆された発泡性ポリスチレン系樹脂粒子を作製した。
(Example 1)
<Manufacturing of foamable polystyrene resin particles>
(1) Manufacturing process of foamable polystyrene resin particle body In a 6 L autoclave attached to a stirrer, 85 parts by weight of pure water, 0.57 parts by weight of tertiary calcium phosphate, 0.00476 parts by weight of sodium α-olefin sulphonate, Stirring was started after charging 32 parts by weight of styrene resin seed particles having 0.1 part by weight of sodium chloride and an average particle size of 0.25 mm (ratio within a fluctuation range of ± 15% of average particle size: 98%). .. Then, 0.08 parts by weight of t-butylperoxy-2-ethylhexyl monocarbonate was charged as an initiator. Subsequently, after raising the temperature to 92 ° C., 0.228 parts by weight of a benzoyl peroxide 30% solution was added for 4 hours and 50 minutes (additional amount for 0 to 1 hour was 0.068 parts by weight, and 1 to 2 hours). The additional amount is 0.057 parts by weight, the additional amount at 2 to 3 hours is 0.046 parts by weight, the additional amount at 3 to 4 hours is 0.034 parts by weight, and the additional amount at 4 hours to 4 hours and 50 minutes. 0.023 parts by weight), 68 parts by weight of styrene monomer for 5 hours and 30 minutes (additional amount for 0 to 1 hour is 8 parts by weight, additional amount for 1 to 2 hours is 10 parts by weight, 2-3 The additional amount at the hour is 12 parts by weight, the additional amount at the 3rd to 4th hours is 15 parts by weight, the additional amount at the 4th to 5th hours is 15 parts by weight, and the additional amount at the 5th to 5 hours and 30 minutes is 8 parts by weight. Part) and polymerized while being charged in the reactor. Then, after holding at 92 ° C. for 30 minutes, the temperature was immediately raised to 120 ° C. and held for 1 hour. After cooling to 95 ° C., 6.0 parts by weight of butane (normal butane: isobutane = 70:30) and 4.0 parts by weight of pentane (normal pentane: isopentane = 50:50) were charged into the reactor as a foaming agent. After holding at 120 ° C. for 1 hour, the mixture was cooled. After cooling to room temperature, the polymerized slurry was removed from the autoclave. The removed polymer slurry was washed, dehydrated and dried to obtain an effervescent polystyrene resin particle body.
(2) Additive application step 0.8 parts by weight of magnesium stearate [manufactured by Nichiyu Co., Ltd.] as magnesium stearate was added to 100 parts by weight of the foamable polystyrene resin particle body obtained above. 0.72 parts by weight of hydrogenated oil [manufactured by Nichiyu Co., Ltd.], and 0.30 parts by weight of stearic acid monoglyceride [Rikemar S-100, manufactured by Riken Vitamin Co., Ltd.] as an antistatic agent, super mixer [( It was put into SMV-20] manufactured by Kawada Co., Ltd. and blended at 1000 rpm for 120 seconds. After that, it was dispensed to prepare foamable polystyrene resin particles coated with an attachment.
＜ポリスチレン系発泡粒子の製造（予備発泡工程）＞
添付剤で被覆された発泡性ポリスチレン系樹脂粒子を回転攪拌式予備発泡装置に投入して、約１００℃の水蒸気中で嵩密度が０．０２５０ｇ／ｃｍ３になるまで約４分間発泡してポリスチレン系発泡粒子を得た。得られたポリスチレン系発泡粒子を用いて評価を行い、その結果を表１に示す。
<Manufacture of polystyrene-based foamed particles (preliminary foaming process)>
Effervescent polystyrene-based resin particles coated with an attachment are put into a rotary stirring pre-foaming device and foamed in steam at about 100 ° C. for about 4 minutes until the bulk density reaches 0.0250 g / cm 3. System foam particles were obtained. Evaluation was performed using the obtained polystyrene-based foamed particles, and the results are shown in Table 1.
（実施例２）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．２０重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 2)
In the process of applying the additive, the foamable polystyrene resin particles were operated in the same manner as in Example 1 except that the stearic acid monoglyceride [Rikemar S-100, manufactured by Riken Vitamin Co., Ltd.] was changed to 0.20 parts by weight. , Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（実施例３）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．３５重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 3)
In the process of applying the additive, the foamable polystyrene resin particles were operated in the same manner as in Example 1 except that the stearic acid monoglyceride [Rikemar S-100, manufactured by Riken Vitamin Co., Ltd.] was changed to 0.35 parts by weight. , Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
(実施例４)
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．２０重量部に変更し、更にＮ−ヒドロキシエチル−Ｎ−２−ヒドロキシアルキルアミン［アルキル基の炭素数Ｃ＝１４：（株）タナカ化学研究所製、アンチスタ８０ＦＳ］を０．０５重量部を使用した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 4)
In the process of applying the additive, polystyrene monoglyceride [Rikemar S-100, manufactured by RIKEN Vitamin Co., Ltd.] was changed to 0.20 parts by weight, and N-hydroxyethyl-N-2-hydroxyalkylamine [alkyl group] was added. Carbon number C = 14: Polystyrene-based resin particles and polystyrene-based expanded particles by the same operation as in Example 1 except that 0.05 parts by weight of Antista 80FS manufactured by Tanaka Chemical Laboratory Co., Ltd. was used. Got The evaluation results are shown in Table 1.
（実施例５）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、ベンゾイルパーオキサイド３０％溶液（０．２２８重量部、４時間５０分）の添加パターンを、０〜１時間目の追加量を０．００２５重量部、１〜２時間目の追加量を０．００３５重量部、２〜３時間目の追加量を０．００５０重量部、３〜４時間目の追加量を０．００５２重量部、４時間〜４時間５０分目の追加量を０．００６６重量部へと変更し、ペンタン（ノルマルペンタン：イソペンタン＝５０：５０）を０重量部として代わりにシクロヘキサン２．３重量部、ブタン（ノルマルブタン：イソブタン＝７０：３０）を７．８重量部とした以外は実施例１と同様に実施し、ポリスチレン系発泡粒子を得た。
(Example 5)
In the manufacturing process of the foamable polystyrene resin particle body, an addition pattern of a 30% benzoyl peroxide solution (0.228 parts by weight, 4 hours and 50 minutes) was added, and an additional amount of 0 to 1 hour was added to 0.0025 parts by weight. The additional amount for the 1st to 2nd hours is 0.0035 parts by weight, the additional amount for the 2nd to 3rd hours is 0.0050 parts by weight, and the additional amount for the 3rd to 4th hours is 0.0052 parts by weight for 4 hours to 4 hours. The additional amount at the 50th minute was changed to 0.0066 parts by weight, and the pentane (normal pentane: isopentane = 50: 50) was replaced with 0 parts by weight, and instead, 2.3 parts by weight of cyclohexane and butane (normal butane: isobutane = 70) were used. The same procedure as in Example 1 was carried out except that: 30) was set to 7.8 parts by weight to obtain polystyrene-based foamed particles.
（実施例６）
添加剤の塗布工程において、マグネシウムステアレート［日油（株）製］を０．５重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 6)
Expandable polystyrene-based resin particles and polystyrene-based expanded particles were operated in the same manner as in Example 1 except that magnesium stearate [manufactured by NOF CORPORATION] was changed to 0.5 parts by weight in the additive coating step. Got The evaluation results are shown in Table 1.
（実施例７）
添加剤の塗布工程において、マグネシウムステアレート［日油（株）製］を１．３重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 7)
In the process of applying the additive, the polystyrene-based resin particles and polystyrene-based expanded particles were operated in the same manner as in Example 1 except that magnesium stearate [manufactured by NOF CORPORATION] was changed to 1.3 parts by weight. Got The evaluation results are shown in Table 1.
（実施例８）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、ペンタン（ノルマルペンタン：イソペンタン＝５０：５０）を６重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 8)
In the manufacturing process of the foamable polystyrene-based resin particle main body, the foamable polystyrene-based resin particles and polystyrene were carried out by the same operation as in Example 1 except that the pentane (normal pentane: isopentane = 50: 50) was changed to 6 parts by weight. System foam particles were obtained. The evaluation results are shown in Table 1.
（実施例９）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、ペンタン（ノルマルペンタン：イソペンタン＝５０：５０）を１．５重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 9)
In the manufacturing process of the foamable polystyrene resin particles main body, the foamable polystyrene resin particles were operated in the same manner as in Example 1 except that the pentane (normal pentane: isopentane = 50: 50) was changed to 1.5 parts by weight. , Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（実施例１０）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、ベンゾイルパーオキサイド３０％溶液０．１４０重量部を４時間５０分（０〜１時間目の追加量０．０１５重量部、１〜２時間目の追加量を０．０２２重量部、２〜３時間目の追加量を０．０３１重量部、３〜４時間前の追加量を０．０３２重量部、４時間〜４時間５０分目の追加量を０．０４０重量部）かけて追加と変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 10)
In the manufacturing process of the foamable polystyrene resin particle body, 0.140 parts by weight of a benzoyl peroxide 30% solution was added for 4 hours and 50 minutes (additional amount of 0.015 parts by weight in 0 to 1 hour, addition in 1 to 2 hours). The amount is 0.022 parts by weight, the additional amount at 2 to 3 hours is 0.031 parts by weight, the additional amount before 3 to 4 hours is 0.032 parts by weight, and the additional amount at 4 hours to 4 hours and 50 minutes is Expandable polystyrene-based resin particles and polystyrene-based expanded particles were obtained by the same operation as in Example 1 except that they were added or changed over 0.040 parts by weight). The evaluation results are shown in Table 1.
（実施例１１）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、ベンゾイルパーオキサイド３０％溶液０．２２８重量部を３時間（０〜１時間目の追加量を０．１４０重量部、１〜２時間目の追加量を０．１２９重量部、２〜３時間目の追加量を０．０１９重量部、３時間目以降は追加無し）かけて追加と変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 11)
In the manufacturing process of the foamable polystyrene resin particle body, 0.228 parts by weight of a benzoyl peroxide 30% solution was added for 3 hours (additional amount for 0 to 1 hour was 0.140 parts by weight, additional amount for 1 to 2 hours). The foamability was changed by the same operation as in Example 1 except that the addition amount was changed to 0.129 parts by weight and the addition amount in the 2nd to 3rd hours was changed to 0.019 parts by weight (no addition after the 3rd hour). Polystyrene-based resin particles and polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（実施例１２）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、スチレン系樹脂種粒子２０重量部、スチレン単量体８０重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Example 12)
In the manufacturing process of the foamable polystyrene-based resin particle main body, the foamable polystyrene-based resin particles were subjected to the same operation as in Example 1 except that the styrene-based resin seed particles were changed to 20 parts by weight and the styrene monomer was changed to 80 parts by weight. Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（実施例１３）
特開２０１１−７４２３９の実施例１に記載の方法で発泡性ポリスチレン系樹脂粒子本体を得た。但し、発泡性ポリスチレン系樹脂粒子本体を製造する際の発泡剤の種類、追加量は本明細書の実施例１と同様とした。その後の添付剤の塗布、予備発泡についても実施例１と同様に行った。評価結果を表１に示す。
(Example 13)
A foamable polystyrene resin particle body was obtained by the method described in Example 1 of JP-A-2011-74239. However, the type and additional amount of the foaming agent in producing the foamable polystyrene-based resin particle body were the same as in Example 1 of the present specification. Subsequent application of the attachment and pre-foaming were also carried out in the same manner as in Example 1. The evaluation results are shown in Table 1.
（比較例１）
添加剤の塗布工程において、マグネシウムステアレート［日油（株）製］を０．３重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 1)
Expandable polystyrene-based resin particles and polystyrene-based expanded particles were operated in the same manner as in Example 1 except that magnesium stearate [manufactured by NOF CORPORATION] was changed to 0.3 parts by weight in the additive coating step. Got The evaluation results are shown in Table 1.
（比較例２）
添加剤の塗布工程において、マグネシウムステアレート［日油（株）製］を１．５重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 2)
In the process of applying the additive, the polystyrene-based resin particles and polystyrene-based expanded particles were operated in the same manner as in Example 1 except that magnesium stearate [manufactured by NOF CORPORATION] was changed to 1.5 parts by weight. Got The evaluation results are shown in Table 1.
（比較例３）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．１０重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 3)
In the process of applying the additive, the foamable polystyrene resin particles were operated in the same manner as in Example 1 except that the stearic acid monoglyceride [Rikemar S-100, manufactured by Riken Vitamin Co., Ltd.] was changed to 0.10 parts by weight. , Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（比較例４）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０．５０重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 4)
In the process of applying the additive, the foamable polystyrene resin particles were operated in the same manner as in Example 1 except that the stearic acid monoglyceride [Rikemar S-100, manufactured by Riken Vitamin Co., Ltd.] was changed to 0.50 parts by weight. , Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
（比較例５）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０部に変更し、Ｎ−ヒドロキシエチル−Ｎ−２−ヒドロキシアルキルアミン［アルキル基の炭素数Ｃ＝１４：（株）タナカ化学研究所製、アンチスタ８０ＦＳ］を０．１０重量部を使用した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 5)
In the process of applying the additive, polystyrene monoglyceride [Rikemar S-100, manufactured by RIKEN Vitamin Co., Ltd.] was changed to 0 parts, and N-hydroxyethyl-N-2-hydroxyalkylamine [alkyl group carbon number C = 14: Polystyrene-based resin particles and polystyrene-based expanded particles were obtained by the same operation as in Example 1 except that 0.10 part by weight of Antista 80FS manufactured by Tanaka Chemical Laboratory Co., Ltd. was used. The evaluation results are shown in Table 1.
（比較例６）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０部に変更し、Ｎ−ヒドロキシエチル−Ｎ−２−ヒドロキシアルキルアミン［アルキル基の炭素数Ｃ＝１４：（株）タナカ化学研究所製、アンチスタ８０ＦＳ］を０．２０重量部を使用した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 6)
In the process of applying the additive, polystyrene monoglyceride [Rikemar S-100, manufactured by RIKEN Vitamin Co., Ltd.] was changed to 0 parts, and N-hydroxyethyl-N-2-hydroxyalkylamine [alkyl group carbon number C = 14: Polystyrene-based resin particles and polystyrene-based expanded particles were obtained by the same operation as in Example 1 except that 0.20 part by weight of Antista 80FS manufactured by Tanaka Chemical Laboratory Co., Ltd. was used. The evaluation results are shown in Table 1.
（比較例７）
添加剤の塗布工程において、ステアリン酸モノグリセリド［理研ビタミン（株）製、リケマールＳ−１００］を０部に変更し、ポリエチレングリコール：理研ビタミン（株）製、ＰＥＧ２００］を０．３０重量部を使用した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 7)
In the additive application process, stearic acid monoglyceride [Riken Vitamin Co., Ltd., Rikemar S-100] was changed to 0 parts, and polyethylene glycol: Riken Vitamin Co., Ltd., PEG200] was used in 0.30 parts by weight. Expandable polystyrene-based resin particles and polystyrene-based expanded particles were obtained by the same operation as in Example 1. The evaluation results are shown in Table 1.
（比較例８）
撹拌機付属の６Ｌのオートクレーブに、純水重量８５重量部、第３リン酸カルシウム０．５７重量部、α―オレフィンスルフォン酸ソーダ０．００４７６重量部、塩化ナトリウム０．１重量部、平均粒子径が０．２５ｍｍのスチレン系樹脂種粒子１００重量部を仕込んだ後、攪拌を開始した。９５℃に昇温した後、系内にブタン６．０重量部（ノルマルブタン：イソブタン＝７０：３０）、ペンタン４．０重量部（ノルマルペンタン：イソペンタン＝５０：５０）を仕込み更に１時間１２０℃で保持した後、冷却した。室温まで冷却して、オートクレーブから重合スラリーを取り出した。取り出した重合スラリーを洗浄、脱水・乾燥することにより、発泡性ポリスチレン系樹脂粒子本体を得た。その後の添加剤の塗布工程、及び予備発泡工程については実施例１と同様に行った。評価結果を表１に示す。
(Comparative Example 8)
In a 6L autoclave attached to the stirrer, the weight of pure water is 85 parts by weight, the weight of tricalcium phosphate is 0.57 parts by weight, the amount of sodium α-olefin sulphonate is 0.00476 parts by weight, the weight of sodium chloride is 0.1 parts by weight, and the average particle size is 0. After charging 100 parts by weight of .25 mm styrene resin seed particles, stirring was started. After the temperature was raised to 95 ° C., 6.0 parts by weight of butane (normal butane: isobutane = 70:30) and 4.0 parts by weight of pentane (normal pentane: isopentane = 50:50) were charged in the system for another 1 hour and 120 parts. After holding at ° C, it was cooled. After cooling to room temperature, the polymerized slurry was removed from the autoclave. The removed polymer slurry was washed, dehydrated and dried to obtain an effervescent polystyrene resin particle body. Subsequent application step of additive and pre-foaming step were carried out in the same manner as in Example 1. The evaluation results are shown in Table 1.
（比較例９）
発泡性ポリスチレン系樹脂粒子本体の製造工程において、スチレン系樹脂種粒子１０重量部、スチレン単量体９０重量部に変更した以外は、実施例１と同様の操作により、発泡性ポリスチレン系樹脂粒子、ポリスチレン系発泡粒子を得た。評価結果を表１に示す。
(Comparative Example 9)
In the manufacturing process of the foamable polystyrene-based resin particle main body, the foamable polystyrene-based resin particles were subjected to the same operation as in Example 1 except that the styrene-based resin seed particles were changed to 10 parts by weight and the styrene monomer was changed to 90 parts by weight. Polystyrene-based foamed particles were obtained. The evaluation results are shown in Table 1.
Claims (10)
前記基材樹脂１００重量部に対して、
ステアリン酸マグネシウムが０．４重量部以上１．５重量部以下、
脂肪酸モノグリセリドが０．２重量部以上０．４重量部未満、
ヒドロキシアルキルアミンが０．１重量部未満、
を前記発泡性ポリスチレン系樹脂粒子本体の表面に含有し、
平均粒子径が０．２５ｍｍ以上０．５０ｍｍ以下である、発泡性ポリスチレン系樹脂粒子。 Equipped with a foamable polystyrene-based resin particle body containing a base resin and a foaming agent,
With respect to 100 parts by weight of the base resin
Magnesium stearate is 0.4 parts by weight or more and 1.5 parts by weight or less,
Fatty acid monoglyceride is 0.2 parts by weight or more and less than 0.4 parts by weight,
Hydroxyalkylamine less than 0.1 parts by weight,
Is contained on the surface of the foamable polystyrene-based resin particle body,
Expandable polystyrene-based resin particles having an average particle size of 0.25 mm or more and 0.50 mm or less.
前記ペンタン及びシクロヘキサンの合計添加量は、前記基材樹脂１００重量％に対して、１．５重量％以上５．０重量％以下である、
請求項１〜６のいずれかに記載の発泡性ポリスチレン系樹脂粒子。 The foaming agent comprises pentane and / or cyclohexane.
The total amount of pentane and cyclohexane added is 1.5% by weight or more and 5.0% by weight or less with respect to 100% by weight of the base resin.
The effervescent polystyrene-based resin particles according to any one of claims 1 to 6.
A bead cushion material made of polystyrene-based foamed particles according to claim 8 or 9.
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