JP2023063388A - Styrenic resin composition, and method for producing foamable styrenic resin particle - Google Patents
Styrenic resin composition, and method for producing foamable styrenic resin particle Download PDFInfo
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- JP2023063388A JP2023063388A JP2023036939A JP2023036939A JP2023063388A JP 2023063388 A JP2023063388 A JP 2023063388A JP 2023036939 A JP2023036939 A JP 2023036939A JP 2023036939 A JP2023036939 A JP 2023036939A JP 2023063388 A JP2023063388 A JP 2023063388A
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- styrene
- carbon
- resin particles
- styrene resin
- resin composition
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- 239000002245 particle Substances 0.000 title claims abstract description 184
- 239000011342 resin composition Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 95
- 229920001890 Novodur Polymers 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 176
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 89
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 657
- 229920005989 resin Polymers 0.000 claims description 288
- 239000011347 resin Substances 0.000 claims description 288
- 239000006260 foam Substances 0.000 claims description 67
- 229910002804 graphite Inorganic materials 0.000 claims description 50
- 239000010439 graphite Substances 0.000 claims description 50
- 238000004898 kneading Methods 0.000 claims description 39
- 239000004088 foaming agent Substances 0.000 claims description 36
- 238000005520 cutting process Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000004604 Blowing Agent Substances 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 abstract description 20
- 238000000465 moulding Methods 0.000 abstract description 18
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 238000005259 measurement Methods 0.000 description 31
- 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 26
- 238000011156 evaluation Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 25
- 239000000523 sample Substances 0.000 description 22
- 238000005187 foaming Methods 0.000 description 21
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 238000010097 foam moulding Methods 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 16
- 239000003063 flame retardant Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 238000013461 design Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 230000003796 beauty Effects 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- -1 diene compounds Chemical class 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 238000000790 scattering method Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance 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
- IYOVSGHZOIZSDC-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromo-2-methylpropoxy)phenyl]propan-2-yl]-2-(2,3-dibromo-2-methylpropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)(CBr)C)=C(Br)C=C1C(C)(C)C1=CC(Br)=C(OCC(C)(Br)CBr)C(Br)=C1 IYOVSGHZOIZSDC-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 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
- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 1
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 1
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 description 1
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- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
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- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
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- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
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- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
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- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
本発明は、スチレン系樹脂組成物、および発泡性スチレン系樹脂粒子の製造方法に関する。 TECHNICAL FIELD The present invention relates to a styrenic resin composition and a method for producing expandable styrenic resin particles.
発泡性スチレン系樹脂粒子を用いて得られるスチレン系樹脂発泡成形体は、軽量性、断熱性、及び緩衝性等を有するバランスに優れた発泡体であり、従来から食品容器箱、保冷箱、緩衝材、及び住宅等の断熱材として広く利用されている。中でも、近年、地球温暖化等の諸問題に関連し、住宅等建築物の断熱性向上による省エネルギー化が志向されつつあり、スチレン系樹脂発泡成形体の需要拡大が期待されている。 Styrene-based resin foam molded products obtained using expandable styrene-based resin particles are foams with an excellent balance of lightness, heat insulation, shock-absorbing properties, etc., and have been used in food container boxes, cooler boxes, and shock-absorbing products. It is widely used as a heat insulating material for houses, etc. In particular, in recent years, in relation to various problems such as global warming, there is a growing desire to save energy by improving the heat insulating properties of buildings such as houses, and an increase in demand for styrene-based resin foam moldings is expected.
ただし、スチレン系樹脂発泡成形体は、断熱材としてはグラスウール等他素材との競合市場にあるゆえ、スチレン系樹脂発泡成形体の製造にあたっては、徹底したコストダウンが求められている。スチレン系樹脂発泡成形体は、発泡倍率が大きくなるほど熱伝導率が大きくなり断熱性が悪化するため、スチレン系樹脂発泡成形体の熱伝導率をより低くすることが望まれる。熱伝導率がより低いスチレン系樹脂発泡成形体であれば、発泡倍率をより高くした場合にも、発泡倍率の低い従来のスチレン系樹脂発泡成形体と同等の断熱性が得られるため、原料である発泡性スチレン系樹脂粒子の使用量を減らすことができる。従って、スチレン系樹脂発泡成形体を備える断熱材を安価に製造することができる。 However, since styrene resin foam moldings are in a competitive market with other materials such as glass wool as heat insulating materials, thorough cost reduction is required in the production of styrene resin foam moldings. The thermal conductivity of the styrene-based resin foam-molded product increases as the expansion ratio increases, and the heat insulating property deteriorates. With a styrene resin foam molded product with a lower thermal conductivity, even if the expansion ratio is increased, it is possible to obtain the same heat insulation as a conventional styrene resin foam molded product with a low expansion ratio. The amount of certain expandable styrenic resin particles used can be reduced. Therefore, it is possible to inexpensively manufacture a heat insulating material comprising a styrene-based resin foam molded article.
また、スチレン系樹脂発泡成形体に含有されるブタン又はペンタン等の発泡剤は、熱伝導率の低減効果があるが、このような発泡剤は、時間の経過と共にスチレン系樹脂発泡成形体から逸散して大気(空気)と置換されるため、スチレン系樹脂発泡成形体の熱伝導率は時間経過と共に大きくなり、従って、時間経過と共に断熱性は悪化することが知られている。 In addition, a foaming agent such as butane or pentane contained in a styrene resin foam molded product has the effect of reducing thermal conductivity, but such a foaming agent escapes from the styrene resin foam molded product over time. It is known that the thermal conductivity of a styrene-based resin foam molded product increases with the lapse of time because the styrenic resin foam is dispersed and replaced with the atmosphere (air), and therefore the heat insulating property deteriorates with the lapse of time.
そのため、スチレン系樹脂発泡成形体に含有されるブタン又はペンタン等の発泡剤が空気に置換された後も、スチレン系樹脂発泡成形体の熱伝導率を低く維持することが求められている。 Therefore, it is required to keep the thermal conductivity of the styrene resin foam molding low even after the blowing agent such as butane or pentane contained in the styrene resin foam molding is replaced with air.
上記事情から、スチレン系樹脂発泡成形体の熱伝導率をより低くするべく、種々検討がなされており、スチレン系樹脂発泡成形体にグラファイト等の輻射伝熱抑制剤を使用する方法が知られている。輻射伝熱抑制剤は、発泡成形体中を伝わる伝熱機構のうち輻射伝熱を抑制することができる物質であって、樹脂、発泡剤、セル構造、及び密度が同一である無添加系の発泡成形体と比較して、熱伝導率を低くすることができる効果を有する。 In view of the above circumstances, various studies have been made to lower the thermal conductivity of styrene resin foam moldings, and a method of using a radiation heat transfer inhibitor such as graphite in styrene resin foam moldings is known. there is A radiation heat transfer suppressor is a substance that can suppress radiation heat transfer among the heat transfer mechanisms that propagate in a foamed molded product. It has the effect of being able to lower the thermal conductivity as compared with foam molded articles.
例えば、特許文献1には、35g/L以下の密度を有する発泡体をもたらすことができ、かつ均斉に分布されたグラファイト粉末を含有する発泡性スチレン系樹脂粒子が提案されている。 For example, Patent Document 1 proposes expandable styrenic resin particles containing evenly distributed graphite powder, capable of yielding foams with densities of 35 g/L or less.
特許文献2には、密度が10~100kg/m3、独立気泡率が60%以上、平均気泡径が20~1000μmであり、グラファイト粉を0.05~9重量%含有し、このグラファイト粉は、アスペクト比が5以上、体積平均粒子径(50%粒子径)が0.1~100μm、比表面積が0.7m2/cm3以上、90%粒子径を10%粒子径で除した値1~20である、スチレン系樹脂発泡成形体が記載されている。 Patent Document 2 discloses that the graphite powder has a density of 10 to 100 kg/m3, a closed cell ratio of 60% or more, an average cell diameter of 20 to 1000 μm, and contains 0.05 to 9% by weight of graphite powder. The aspect ratio is 5 or more, the volume average particle diameter (50% particle diameter) is 0.1 to 100 μm, the specific surface area is 0.7 m2/cm3 or more, and the value obtained by dividing the 90% particle diameter by the 10% particle diameter is 1 to 20. A certain styrenic resin foam molded article is described.
特許文献3には、グラファイト粒子を含有したスチレン系樹脂マイクロペレットに、炭素数6~10の芳香族炭化水素の存在下で、スチレン系単量体をシード重合すると同時に発泡剤を投入する発泡性スチレン系樹脂粒子の製造方法が提案されている。 In Patent Document 3, in the presence of an aromatic hydrocarbon having 6 to 10 carbon atoms, a styrene-based monomer is seed-polymerized in a styrene-based resin micropellet containing graphite particles, and at the same time, a foaming agent is added. A method for producing styrenic resin particles has been proposed.
特許文献4には、ポリスチレン系樹脂、難燃剤、グラファイト、及び揮発性発泡剤を含む樹脂組成物を押出機内で溶融混練し、得られた溶融混練物をダイから加圧された水中に押出し、押出された溶融混練物を切断することにより発泡性スチレン系樹脂粒子を製造する方法が提案されている。 In Patent Document 4, a resin composition containing a polystyrene resin, a flame retardant, graphite, and a volatile foaming agent is melt-kneaded in an extruder, and the resulting melt-kneaded product is extruded from a die into pressurized water, A method of producing expandable styrenic resin particles by cutting an extruded melt-kneaded product has been proposed.
特許文献5には、平均粒径が50μmを超えるグラファイトを0.1~25質量%含有する発泡性スチレン系樹脂粒子が提案されている。 Patent Document 5 proposes expandable styrene-based resin particles containing 0.1 to 25% by mass of graphite having an average particle size of more than 50 μm.
特許文献6には、スチレン及び必要に応じてスチレンに共重合可能なモノマー化合物をグラファイト粒子の存在下に懸濁水性液中で重合させ、重合前、重合中又は重合後に発泡剤を添加する、発泡性スチレン系樹脂粒子の製造方法が提案されている。 In Patent Document 6, styrene and optionally a monomer compound copolymerizable with styrene are polymerized in an aqueous suspension in the presence of graphite particles, and a foaming agent is added before, during, or after polymerization. A method for producing expandable styrene resin particles has been proposed.
特許文献7には、グラファイト及びノニオン性界面活性剤の存在下に懸濁水性液中で重合され、DIN52612に準じて10℃で測定した熱伝導率が32mW/m・K未満、及び密度が25g/L未満である、発泡性スチレン系樹脂粒子の製造方法が提案されている。 In Patent Document 7, it is polymerized in an aqueous suspension in the presence of graphite and a nonionic surfactant, and has a thermal conductivity of less than 32 mW / m K measured at 10 ° C. according to DIN 52612 and a density of 25 g A method for producing expandable styrenic resin particles having a density of less than /L has been proposed.
特許文献1~7の様に、スチレン系樹脂発泡成形体にグラファイト等の輻射伝熱抑制剤を使用する方法によって、低い熱伝導率、即ち高い断熱性能を有するスチレン形樹脂発泡体を得ることができる。 As in Patent Documents 1 to 7, it is possible to obtain a styrene resin foam having a low thermal conductivity, that is, a high heat insulating performance, by using a radiation heat transfer inhibitor such as graphite in a styrene resin foam molded product. can.
グラファイト等の輻射伝熱抑制剤をスチレン系樹脂に含有させる方法としては、大別して、スチレン単量体の重合工程においてグラファイトを含有させる方法と、押出機等の混練設備を用いて予め重合されたスチレン系樹脂とグラファイトを溶融混練する方法がある。これらの製造方法のうち、押出混練設備を用いた溶融混練法は、初期投資額及び製造の簡便性の観点から優れるものの、発泡性及び断熱性などの性能面については、さらなる改善の余地がある。また、スチレン系樹脂発泡体の他素材に対する競争力をより高めるために、製造コストの更なる低減が望まれる。 Methods for incorporating a radiation heat transfer inhibitor such as graphite into a styrene resin are broadly classified into a method in which graphite is incorporated in the polymerization process of a styrene monomer, and a method in which graphite is incorporated in advance using a kneading facility such as an extruder. There is a method of melt-kneading styrene-based resin and graphite. Among these manufacturing methods, the melt-kneading method using extrusion kneading equipment is superior in terms of initial investment and manufacturing simplicity, but there is room for further improvement in terms of performance such as foamability and heat insulation. . In addition, in order to increase the competitiveness of styrene-based resin foams against other materials, further reductions in manufacturing costs are desired.
従って、本発明の目的は、高い発泡倍率、及び、低い熱伝導率、即ち、高い断熱性能を有するスチレン系樹脂発泡成形体を与えうるスチレン系樹脂組成物、および、発泡性スチレン系樹脂粒子の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a styrene resin composition and expandable styrene resin particles that can provide a styrene resin foam molded article having a high expansion ratio and low thermal conductivity, i.e., high heat insulation performance. It is to provide a manufacturing method.
本願の発明者らは、前述した課題を解決すべく鋭意検討を重ねた結果、炭素およびスチレン系樹脂との混練を特定の溶融混練条件に制御することによって、得られる溶融混練物の断熱性を向上させられることを見出した。中でも、スチレン系樹脂発泡成形体に使用した場合に、グラファイトを含有しているにもかかわらず、表面美麗性を損なうことなく、高発泡倍率及び高独立気泡率であり、低熱伝導率であり、熱伝導率の経時的な上昇が顕著に抑制され、かつ、断熱性が長期的に高いスチレン系樹脂発泡成形体を得ることに成功し、本発明を完成するに至った。 The inventors of the present application conducted intensive studies to solve the above-mentioned problems, and found that the heat insulating property of the obtained melt-kneaded product was improved by controlling the kneading with carbon and styrene resin to specific melt-kneading conditions. I found that it could be improved. Among them, when used in a styrene-based resin foam molded product, it has a high expansion ratio, a high closed cell content, and a low thermal conductivity, without impairing the surface beauty despite containing graphite. The inventors have succeeded in obtaining a styrene-based resin foam molded article in which an increase in thermal conductivity over time is remarkably suppressed and which has high heat insulating properties over a long period of time, thereby completing the present invention.
即ち、本発明は、スチレン系樹脂及び炭素を二軸押出機に供給し溶融混練する、スチレン系樹脂組成物の製造方法であって、前記二軸押出機において、比エネルギーが0.13kWh/kg以上である、スチレン系樹脂組成物の製造方法に関する(以下、「本発明におけるスチレン系樹脂組成物の製法」と称することがある。)。 That is, the present invention is a method for producing a styrenic resin composition, in which a styrenic resin and carbon are supplied to a twin-screw extruder and melt-kneaded, wherein the twin-screw extruder has a specific energy of 0.13 kWh/kg. The above-described method for producing a styrene-based resin composition (hereinafter sometimes referred to as "method for producing a styrene-based resin composition according to the present invention").
本発明におけるスチレン系樹脂組成物の製法において、上記炭素の含有量が、スチレン系樹脂組成物100重量%に対して2~90重量%であることが好ましい。 In the method for producing the styrene resin composition of the present invention, the carbon content is preferably 2 to 90% by weight with respect to 100% by weight of the styrene resin composition.
本発明のスチレン系樹脂組成物の製法において、上記炭素が、グラファイト、グラフェン、カーボンブラック、カーボンナノチューブ、活性炭グラファイト、および、膨張黒鉛からなる群から選ばれる少なくとも1種であることが好ましい。 In the method for producing the styrenic resin composition of the present invention, the carbon is preferably at least one selected from the group consisting of graphite, graphene, carbon black, carbon nanotube, activated carbon graphite, and expanded graphite.
本発明におけるスチレン系樹脂組成物の製法において、上記炭素が、平均粒径2.5~9.0μmであることが好ましい。 In the method for producing the styrenic resin composition of the present invention, the carbon preferably has an average particle size of 2.5 to 9.0 μm.
本発明におけるスチレン系樹脂組成物の製法において、上記スチレン系樹脂組成物中の炭素単位溶液濃度あたりのレーザー散乱強度が4.0{%/(mg/ml)}/重量%以上であることが好ましい。 In the method for producing the styrene resin composition of the present invention, the laser scattering intensity per carbon unit solution concentration in the styrene resin composition is 4.0 {%/(mg/ml)}/wt% or more. preferable.
本発明においては、上記スチレン系樹脂組成物の製法において、上記スチレン系樹脂組成物にさらに発泡剤を添加させることで発泡性スチレン系樹脂組成物を製造することができる。 In the present invention, an expandable styrene resin composition can be produced by further adding a foaming agent to the styrene resin composition in the method for producing the styrene resin composition.
また、本発明における第一の発泡性スチレン系樹脂粒子の製造方法は、スチレン系樹脂、および、炭素を二軸押出機に供給、溶融混練する工程、前記二軸押出機以降に取り付けた小孔を多数有するダイスを通じて、循環水で満たされたカッターチャンバー内に発泡剤を含有するスチレン系樹脂組成物の溶融物を押し出し、押し出し直後から、ダイスと接する回転カッターにより切断する工程を含む、発泡性スチレン系樹脂粒子の製造方法であって、前記二軸押出機の比エネルギーが0.13kwh/kg以上0.41kwh/kg未満である。 In addition, the first method for producing expandable styrene resin particles in the present invention comprises a step of supplying a styrene resin and carbon to a twin-screw extruder and melt-kneading them, a small hole attached after the twin-screw extruder Extruding a melt of a styrenic resin composition containing a foaming agent into a cutter chamber filled with circulating water through a die having a large number of In the method for producing styrenic resin particles, the twin-screw extruder has a specific energy of 0.13 kwh/kg or more and less than 0.41 kwh/kg.
本発明における第二の発泡性スチレン系樹脂粒子の製造方法は、スチレン系樹脂、および、炭素を二軸押出機に供給し溶融混練する工程、上記二軸押出機以降に取り付けた小孔を多数有するダイスを通じてスチレン系樹脂組成物の溶融物を押し出し、カッターにより切断してスチレン系樹脂粒子を得る工程、上記スチレン系樹脂粒子を水中に懸濁させて発泡剤を含浸させる工程を含む、発泡性スチレン系樹脂粒子の製造方法であって、上記二軸押出機の比エネルギーが0.13kwh/kg以上である(以下、第一の発泡性スチレン系樹脂粒子の製造方法および第二の発泡性スチレン系樹脂粒子の製造方法を単に「本発明における発泡性スチレン系樹脂粒子の製法」と称することがある。)。 The second method for producing expandable styrene-based resin particles in the present invention includes a step of supplying a styrene-based resin and carbon to a twin-screw extruder and melt-kneading them, and forming a large number of small holes attached after the twin-screw extruder. a step of extruding a melt of a styrene resin composition through a die having a styrene resin composition and cutting it with a cutter to obtain styrene resin particles; A method for producing styrene-based resin particles, wherein the twin-screw extruder has a specific energy of 0.13 kwh/kg or more (hereinafter referred to as the first method for producing expandable styrene-based resin particles and the second expandable styrene-based resin particles). The method for producing the styrene-based resin particles may be simply referred to as "the method for producing expandable styrene-based resin particles in the present invention").
本発明における発泡性スチレン系樹脂粒子の製法において、上記比エネルギーが0.16kwh/kg以上0.41kwh/kg未満であることが好ましい。 In the method for producing expandable styrene-based resin particles in the present invention, the specific energy is preferably 0.16 kwh/kg or more and less than 0.41 kwh/kg.
本発明のける発泡性スチレン系樹脂粒子の製法において、上記二軸押出機の先端における樹脂温度が160℃以上210℃未満であることが好ましい。 In the method for producing expandable styrene resin particles according to the present invention, it is preferable that the resin temperature at the tip of the twin-screw extruder is 160°C or higher and lower than 210°C.
本発明における発泡性スチレン系樹脂粒子において、上記炭素が、グラファイト、グラフェン、カーボンブラック、カーボンナノチューブ、活性炭グラファイト、および、膨張黒鉛からなる群から選ばれる少なくとも1種であることが好ましい。 In the expandable styrene-based resin particles of the present invention, the carbon is preferably at least one selected from the group consisting of graphite, graphene, carbon black, carbon nanotube, activated carbon graphite, and expanded graphite.
本発明における発泡性スチレン系樹脂粒子の製法において、上記炭素が、平均粒径2.5~9.0μmであることが好ましい。 In the method for producing expandable styrene-based resin particles according to the present invention, the carbon preferably has an average particle size of 2.5 to 9.0 μm.
本発明における発泡性スチレン系樹脂粒子の製法において、上記炭素が上記スチレン系樹脂組成物100重量%に対して2~8重量%含有されることが好ましい。 In the method for producing the expandable styrene-based resin particles of the present invention, it is preferable that the carbon content is 2 to 8% by weight with respect to 100% by weight of the styrene-based resin composition.
本発明における泡性スチレン系樹脂粒子の製法において、上記発泡性スチレン系樹脂粒子の単位溶液濃度あたりのレーザー散乱強度が15.0%/(mg/ml)以上であることが好ましい。 In the method for producing the expandable styrene resin particles of the present invention, the laser scattering intensity per unit solution concentration of the expandable styrene resin particles is preferably 15.0%/(mg/ml) or more.
本発明における発泡性スチレン系樹脂粒子の製法において、上記発泡性スチレン系樹脂粒子中の炭素単位溶液濃度あたりのレーザー散乱強度が4.0{%/(mg/ml)}/重量%以上であることが好ましい。 In the method for producing the expandable styrene resin particles of the present invention, the laser scattering intensity per carbon unit solution concentration in the expandable styrene resin particles is 4.0 {%/(mg/ml)}/% by weight or more. is preferred.
本発明における発泡性スチレン系樹脂粒子の製法において、上記発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0330(W/mK)以下であることが好ましく、0.0320(W/mK)以下がより好ましい。 In the method for producing the expandable styrene resin particles of the present invention, when the expandable styrene resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the expanded molded article having an expansion ratio of 80 times is allowed to stand at a temperature of 50° C. for 30 days. Further, after standing at a temperature of 23° C. for 24 hours, the thermal conductivity at 23° C. measured according to JIS A9511:2006R is preferably 0.0330 (W / mK) or less, and 0.0330 (W / mK) or less. 0320 (W/mK) or less is more preferable.
本発明によれば、炭素の分散性が良好で、断熱性に優れるスチレン系樹脂組成物および発泡性スチレン系樹脂組成物を製造することができる。当該スチレン系樹脂組成物および発泡性スチレン系樹脂組成物を用いることにより、高い発泡倍率、及び、低い熱伝導率、即ち断熱性の高いスチレン系樹脂発泡成形体、および、当該発泡成形体を与える発泡性スチレン系樹脂粒子を得ることができる。 INDUSTRIAL APPLICABILITY According to the present invention, a styrene-based resin composition and an expandable styrene-based resin composition having good carbon dispersibility and excellent heat insulating properties can be produced. By using the styrene-based resin composition and the expandable styrene-based resin composition, a styrene-based resin foam-molded article having a high expansion ratio and a low thermal conductivity, i.e., a high heat insulating property, and the foam-molded article can be obtained. Expandable styrene resin particles can be obtained.
本発明によれば、高い発泡倍率、及び、低い熱伝導率、即ち断熱性の高いスチレン系樹脂発泡成形体を与えうる発泡性スチレン系樹脂粒子を製造することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce expandable styrene-based resin particles capable of providing a styrene-based resin foam molded product having a high expansion ratio and a low thermal conductivity, that is, having a high heat insulating property.
(スチレン系樹脂) 本発明で用いられるスチレン系樹脂は、スチレン単独重合体(スチレンホモポリマー)のみならず、本発明に係る効果を損なわない範囲で、スチレンと、スチレンと共重合可能な他の単量体又はその誘導体とが共重合されているものであっても良い。ただし、後述する臭素化スチレン・ブタジエン共重合体は除く。 (Styrene-Based Resin) The styrene-based resin used in the present invention is not limited to styrene homopolymers (styrene homopolymers). It may be copolymerized with a monomer or a derivative thereof. However, the brominated styrene/butadiene copolymer described later is excluded.
スチレンと共重合可能な他の単量体又はその誘導体としては、例えば、メチルスチレン、ジメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブロモスチレン、ジブロモスチレン、トリブロモスチレン、クロロスチレン、ジクロロスチレン、及びトリクロロスチレン等のスチレン誘導体;ジビニルベンゼン等の多官能性ビニル化合物;アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、及びメタクリル酸ブチル等の(メタ)アクリル酸エステル化合物;(メタ)アクリロニトリル等のシアン化ビニル化合物;ブタジエン等のジエン系化合物又はその誘導体;無水マレイン酸、及び無水イタコン酸等の不飽和カルボン酸無水物;N-メチルマレイミド、N-ブチルマレイミド、N-シクロヘキシルマレイミド、N-フェニルマレイミド、N-(2)-クロロフェニルマレイミド、N-(4)-ブロモフェニルマレイミド、及びN-(1)-ナフチルマレイミド等のN-アルキル置換マレイミド化合物等があげられる。これらは単独で使用してもよく、2種以上を組み合わせて使用しても良い。 Other monomers copolymerizable with styrene or derivatives thereof include, for example, methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, and styrene derivatives such as trichlorostyrene; polyfunctional vinyl compounds such as divinylbenzene; (meth)acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate compounds; vinyl cyanide compounds such as (meth)acrylonitrile; diene compounds such as butadiene or derivatives thereof; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; N-methylmaleimide, N-butylmaleimide, and N-alkyl-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, N-(2)-chlorophenylmaleimide, N-(4)-bromophenylmaleimide, and N-(1)-naphthylmaleimide. . These may be used alone or in combination of two or more.
本発明で用いられるスチレン系樹脂は、前述のスチレン単独重合体、及び/又は、スチレンと、スチレンと共重合可能な他の単量体又はその誘導体との共重合体に限らず、本発明に係る効果を損なわない範囲で、前述の他の単量体又は誘導体の単独重合体、又はそれらの共重合体とのブレンド物であっても良い。 The styrenic resin used in the present invention is not limited to the aforementioned styrene homopolymer and/or copolymers of styrene and other monomers copolymerizable with styrene or derivatives thereof. A homopolymer of the above-mentioned other monomers or derivatives, or a blend with a copolymer thereof may be used as long as the effect is not impaired.
本発明で用いられるスチレン系樹脂には、例えば、ジエン系ゴム強化ポリスチレン、アクリル系ゴム強化ポリスチレン、及び/又は、ポリフェニレンエーテル系樹脂等をブレンドすることもできる。 The styrene resin used in the present invention may be blended with, for example, diene rubber-reinforced polystyrene, acrylic rubber-reinforced polystyrene, and/or polyphenylene ether resin.
本発明で用いられるスチレン系樹脂の中では、比較的安価で、特殊な方法を用いずに低圧の水蒸気等で発泡成形ができ、断熱性、難燃性、緩衝性のバランスに優れることから、スチレンホモポリマー、スチレン-アクリロニトリル共重合体、又はスチレン-アクリル酸ブチル共重合体が望ましい。 Among the styrene resins used in the present invention, it is relatively inexpensive, can be foam-molded with low-pressure steam or the like without using a special method, and has an excellent balance of heat insulation, flame retardancy, and cushioning properties. Styrene homopolymers, styrene-acrylonitrile copolymers, or styrene-butyl acrylate copolymers are preferred.
本発明におけるスチレン系樹脂のメルトフローレート(以下、「MFR」と称する。)は、1~15g/10分のものを用いることが好ましい。MFRがこの範囲にあると、後述する二軸押出機での炭素とスチレン系樹脂との溶融混練時に、炭素の分散に必要な比エネルギーが得られやすくなり、結果として、優れた断熱性能を発揮するスチレン系樹脂発泡成形体を与えうるスチレン系樹脂組成物を得やすい傾向にある。また、発泡性(高倍率、高独気率)、表面美麗性に優れた発泡性スチレン系樹脂粒子、スチレン系樹脂予備発泡粒子及びスチレン系樹脂発泡成形体を得やすい傾向にある。そして、得られるスチレン系樹脂発泡成形体は、圧縮強度、曲げ強度または曲げたわみ量といった機械的強度や、靱性などの特性のバランスがとれたものとなる。より好ましい範囲は、2~10g/10分である。なお、本発明におけるMFRは、JIS K7210により測定される値である。 The melt flow rate (hereinafter referred to as "MFR") of the styrene resin in the present invention is preferably 1 to 15 g/10 minutes. When the MFR is in this range, it becomes easier to obtain the specific energy necessary for dispersing carbon during melt-kneading of carbon and styrene resin in a twin-screw extruder, which will be described later, and as a result, excellent heat insulation performance is exhibited. It tends to be easy to obtain a styrenic resin composition that can give a styrenic resin foam molded article that has a high viscosity. In addition, there is a tendency to easily obtain expandable styrene resin particles, styrene resin pre-expanded particles, and styrene resin expansion moldings that are excellent in expandability (high expansion ratio, high air content) and surface beauty. The styrene-based resin foam molded article obtained has well-balanced properties such as mechanical strength such as compressive strength, bending strength or amount of bending deflection, and toughness. A more preferred range is 2 to 10 g/10 minutes. The MFR in the present invention is a value measured according to JIS K7210.
(炭素) 本発明においては、輻射伝熱抑制剤として、炭素をスチレン系樹脂に添加することにより、高い断熱性を有するスチレン系樹脂発泡成形体が得られる。ここでいう輻射伝熱抑制剤とは、近赤外又は赤外領域の光を反射、散乱又は吸収する特性を有する物質をいう。 (Carbon) In the present invention, by adding carbon as a radiation heat transfer suppressor to the styrene resin, a styrene resin foam molded article having high heat insulating properties can be obtained. The term "radiation heat transfer inhibitor" as used herein refers to a substance having properties of reflecting, scattering or absorbing light in the near-infrared or infrared region.
本発明で用いられる炭素としては、グラファイト、グラフェン、カーボンブラック、カーボンナノチューブ、活性炭、膨張黒鉛などが挙げられる。これらの炭素は1種を単独で又は2種以上を組み合わせて使用できる。これらの中でも、コストに対する輻射伝熱抑制効果の高さから、グラファイトが好ましい。グラファイトとしては、例えば、鱗片状黒鉛、土状黒鉛、球状黒鉛、又は人造黒鉛等が挙げられ、これらのうち、鱗片状黒鉛が高い輻射抑制効果を発揮することから好ましい。なお、本明細書において、「鱗片状」という用語は、鱗状、薄片状又は板状のものをも包含する。 Carbon used in the present invention includes graphite, graphene, carbon black, carbon nanotubes, activated carbon, expanded graphite, and the like. These carbons can be used individually by 1 type or in combination of 2 or more types. Among these, graphite is preferable because of its high effect of suppressing radiation heat transfer with respect to cost. Examples of graphite include flake graphite, earthy graphite, spherical graphite, and artificial graphite. Among these, flake graphite is preferable because it exhibits a high radiation suppressing effect. In the present specification, the term "scale-like" includes scale-like, flaky or plate-like ones.
本発明のグラファイトは平均粒径が2.5~9.0μmであることが好ましく、3.0~6.0μmがより好ましく、4.0~6.0μmが最も好ましい。本明細書において、グラファイトの平均粒径は、ISO13320:2009,JIS Z8825-1に準拠したMie理論に基づくレーザー回折散乱法により粒度分布を測定・解析し、全粒子の体積に対する累積体積が50%になる時の粒径(レーザー回折散乱法による体積平均粒径)を平均粒径とする。 The graphite of the present invention preferably has an average particle size of 2.5 to 9.0 μm, more preferably 3.0 to 6.0 μm, most preferably 4.0 to 6.0 μm. In this specification, the average particle size of graphite is measured and analyzed by a laser diffraction scattering method based on Mie theory in accordance with ISO13320:2009 and JIS Z8825-1, and the cumulative volume of all particles is 50%. The particle size (volume average particle size by laser diffraction scattering method) when it becomes is taken as the average particle size.
グラファイトは平均粒径が大きいほど製造コストが低くなる。特に平均粒径が2.5μm以上であるグラファイトは、粉砕のコストを含む製造コストが低いため、非常に安価であり、コストを下げることができる。さらに、グラファイトの平均粒径が2.5μm以上であると、断熱性の良好なスチレン系樹脂発泡成形体を製造することが可能となる。平均粒径が9.0μm以下であると、発泡性スチレン系樹脂粒子から予備発泡粒子及びスチレン系樹脂発泡成形体を製造する際に、セル膜が破れにくくなるため、高発泡化が容易であったり、成形容易性が増加したり、スチレン系樹脂発泡成形体の圧縮強度が増加したりする傾向がある。 The larger the average particle size of graphite, the lower the manufacturing cost. In particular, graphite having an average particle size of 2.5 μm or more is very inexpensive and can be reduced in cost because the production cost including the cost of pulverization is low. Furthermore, when the average particle size of graphite is 2.5 μm or more, it is possible to produce a styrene-based resin foam molded article having good heat insulation properties. When the average particle diameter is 9.0 μm or less, the cell membrane is less likely to break when producing pre-expanded particles and a styrene resin foam molded article from the expandable styrene resin particles, and high expansion is facilitated. Also, there is a tendency that the easiness of molding is increased, and the compression strength of the styrene-based resin foam molded product is increased.
グラファイトの平均粒径が3.0μm以上であれば、より低い熱伝導率、従ってより高い断熱性を得ることができる。また、グラファイトの平均粒径が6.0μm以下であれば、成形体の表面美麗性に優れ、より低い熱伝導率、従ってより高い断熱性を得ることができる。 If the graphite has an average particle size of 3.0 μm or more, a lower thermal conductivity and therefore a higher heat insulating property can be obtained. Further, when the average particle size of graphite is 6.0 μm or less, the surface of the molded article is excellent, and lower thermal conductivity and thus higher heat insulation can be obtained.
本発明において、炭素の含有量は特に限定されないが、スチレン系樹脂組成物100重量%において0.1~90重量%であることが好ましく、2~90重量%がより好ましい。 In the present invention, the content of carbon is not particularly limited, but it is preferably 0.1 to 90% by weight, more preferably 2 to 90% by weight based on 100% by weight of the styrene resin composition.
本発明の好ましい一実施形態としてグラファイトを使用する場合、その含有量は熱伝導率低減効果とスチレン系樹脂組成物中のグラファイトの分散性等のバランスの点から、スチレン系樹脂組成物100重量%において2重量%以上90重量%以下であることが好ましい。グラファイト含有量が2重量%以上では、熱伝導率低減効果が十分となる傾向があり、一方、90重量%以下では、スチレン系樹脂組成物中の炭素の分散性に優れる傾向にある。炭素の分散性が優れることにより、断熱性能が優れる傾向にある。 When graphite is used as a preferred embodiment of the present invention, its content is 100% by weight of the styrene resin composition from the viewpoint of the balance between the effect of reducing thermal conductivity and the dispersibility of graphite in the styrene resin composition. is preferably 2% by weight or more and 90% by weight or less. When the graphite content is 2% by weight or more, the thermal conductivity reducing effect tends to be sufficient, while when it is 90% by weight or less, the carbon dispersibility in the styrene resin composition tends to be excellent. Excellent carbon dispersibility tends to result in excellent heat insulation performance.
尚、本発明におけるグラファイト含有量は、発泡性スチレン系樹脂粒子や、その予備発泡粒子やその発泡成形体として成形される場合は、本発明で得られる発泡性スチレン系樹脂粒子中、並びに、スチレン系樹脂組成物、発泡性スチレン系樹脂組成物及び発泡性スチレン系樹脂粒子より与えうるスチレン系樹脂発泡粒子及びスチレン系樹脂発泡成形体中のグラファイト含有量が、スチレン系樹脂組成物100重量%において2重量%以上8重量%以下であることが好ましい。グラファイト含有量が2重量%以上では、熱伝導率低減効果が十分となる傾向があり、8重量%以下では、炭素とスチレン系樹脂から、予備発泡粒子及びスチレン系樹脂発泡成形体を製造する際に、セル膜が破れにくくなるため、高発泡化が容易であり、発泡倍率の制御が容易になる傾向がある。 Incidentally, the graphite content in the present invention is determined in the expandable styrene resin particles obtained in the present invention, and in the case of molding as expandable styrene resin particles, pre-expanded particles thereof, or expansion molded articles thereof, as well as in styrene. The graphite content in the expanded styrene resin particles and the expanded styrene resin product that can be provided from the styrene resin composition, the expandable styrene resin composition, and the expandable styrene resin particles is 100% by weight of the styrene resin composition. It is preferably 2% by weight or more and 8% by weight or less. When the graphite content is 2% by weight or more, the effect of reducing thermal conductivity tends to be sufficient. In addition, since the cell membrane is less likely to break, high foaming can be easily achieved, and the foaming ratio tends to be easily controlled.
さらに、グラファイト含有量は、3重量%以上7重量%以下であることがより好ましい。グラファイトの含有量が3重量%以上であることにより、熱伝導率が低くなり従ってより高い断熱性を得ることができる。また、グラファイトの含有量が7重量%以下であることにより、発泡性、成形体の表面美麗性が良好となる。 Furthermore, the graphite content is more preferably 3% by weight or more and 7% by weight or less. When the graphite content is 3% by weight or more, the thermal conductivity is lowered, so that higher heat insulation can be obtained. Further, when the content of graphite is 7% by weight or less, the foamability and the surface beauty of the molded article are improved.
(発泡剤) 本発明においては、スチレン系樹脂組成物にさらに発泡剤を含ませて発泡性スチレン系樹脂組成物にしてもよい。発泡性スチレン系樹脂組成物は、後述の発泡性スチレン系樹脂粒子や発泡成形体に成形したり、押出発泡体に成形することができる。本発明で用いられる発泡剤は、特に限定されないが、発泡性と製品ライフのバランスが良く、実際に使用する際に高倍率化しやすい観点から、炭素数3~6の炭化水素が望ましく、更に望ましくは炭素数4~5の炭化水素である。発泡剤の炭素数が3以上であると揮発性が低くなり、発泡性スチレン系樹脂粒子にした場合に発泡剤が逸散しにくくなるため、実際に使用する際に発泡工程で発泡剤が十分に残り、十分な発泡力を得ることが可能となり、高倍率化が容易となるため好ましい。また、炭素数が6以下であると、発泡剤の沸点が高すぎないため、予備発泡時の加熱で十分な発泡力を得やすく、高発泡化が易しい傾向となる。炭素数3~6の炭化水素としては、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、ネオペンタン、シクロペンタン、ノルマルヘキサン、又はシクロヘキサン等の炭化水素が挙げられる。これらは1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。 (Foaming Agent) In the present invention, the styrene resin composition may further contain a foaming agent to form an expandable styrene resin composition. The expandable styrene-based resin composition can be molded into expandable styrene-based resin particles or foam-molded articles, which will be described later, or extruded foams. The foaming agent used in the present invention is not particularly limited, but hydrocarbons having 3 to 6 carbon atoms are desirable, and more desirable, from the viewpoint of good balance between foamability and product life, and easy to achieve high magnification when actually used. is a hydrocarbon having 4 to 5 carbon atoms. If the number of carbon atoms in the foaming agent is 3 or more, the volatility of the foaming agent becomes low, and when the foaming agent is made into expandable styrene-based resin particles, it becomes difficult for the foaming agent to dissipate. It is preferable because it remains at a low level, it becomes possible to obtain sufficient foaming power, and it becomes easy to increase the magnification. Further, when the number of carbon atoms is 6 or less, the boiling point of the foaming agent is not too high, so that sufficient foaming power can be easily obtained by heating during preliminary foaming, and high foaming tends to be easily achieved. Examples of hydrocarbons having 3 to 6 carbon atoms include hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, neopentane, cyclopentane, normal hexane, and cyclohexane. These may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明における発泡剤の添加量は、スチレン系樹脂組成物100重量部に対して、4~10重量部であることが好ましい。発泡性スチレン系樹脂粒子にした場合に発泡速度と発泡力のバランスがより良く、より安定して高倍率化しやすい、という効果を奏する。発泡剤の添加量が4重量部以上では、発泡に必要な発泡力が十分であるから、高発泡化が容易となり、50倍以上の高発泡倍率のスチレン系樹脂発泡成形体を製造し易くなる傾向がある。また、発泡剤の量が10重量部以下であると、難燃性能が良好となると共に、スチレン系樹脂発泡成形体を製造する際の製造時間(成形サイクル)が短くなるため、製造コストが低くなる傾向となる。なお、発泡剤の添加量は、スチレン系樹脂組成物100重量部に対して、4.5~9重量部であることがより好ましく、5~8.5重量部であることがさらに好ましい。 The amount of foaming agent added in the present invention is preferably 4 to 10 parts by weight with respect to 100 parts by weight of the styrene-based resin composition. When the expandable styrene resin particles are used, the expansion rate and expansion force are well balanced, and the expansion ratio can be stably increased. When the amount of the foaming agent added is 4 parts by weight or more, the foaming power required for foaming is sufficient, so high foaming is facilitated, and it is easy to produce a styrene-based resin foam molded article having a high expansion ratio of 50 times or more. Tend. In addition, when the amount of the foaming agent is 10 parts by weight or less, the flame retardancy is improved, and the production time (molding cycle) for producing the styrene-based resin foam molded article is shortened, resulting in a low production cost. tend to become The amount of foaming agent to be added is more preferably 4.5 to 9 parts by weight, more preferably 5 to 8.5 parts by weight, with respect to 100 parts by weight of the styrene-based resin composition.
(難燃剤) 本発明のスチレン系樹脂組成物には難燃剤を含有してもよい。本発明で用いられる難燃剤としては、特に限定されず、従来からスチレン系樹脂発泡成形体に用いられる難燃剤をいずれも使用できるが、その中でも、難燃性付与効果が高い臭素系難燃剤が望ましい。本発明で用いられる臭素系難燃剤としては、例えば、2,2-ビス[4-(2,3-ジブロモ-2-メチルプロポキシ)-3,5-ジブロモフェニル]プロパン(別名: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))、又は2,2-ビス[4-(2,3-ジブロモプロポキシ)-3,5-ジブロモフェニル]プロパン(別名:テトラブロモビスフェノールA-ビス(2,3-ジブロモプロピルエーテル))等の臭素化ビスフェノール系化合物、テトラブロモシクロオクタン、トリス(2,3-ジブロモプロピル)イソシアヌレート、臭素化スチレン・ブタジエンブロック共重合体、臭素化ランダムスチレン・ブタジエン共重合体、又は臭素化スチレン・ブタジエングラフト共重合体等の臭素化ブタジエン・ビニル芳香族炭化水素共重合体(例えば、特表2009-516019号公報に開示されている)等が挙げられる。これら臭素系難燃剤は1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。 (Flame Retardant) The styrenic resin composition of the present invention may contain a flame retardant. The flame retardant used in the present invention is not particularly limited, and any flame retardant conventionally used in foamed styrene resin articles can be used. desirable. Brominated flame retardants used in the present invention include, for example, 2,2-bis[4-(2,3-dibromo-2-methylpropoxy)-3,5-dibromophenyl]propane (also known as tetrabromobisphenol A -bis (2,3-dibromo-2-methylpropyl ether)), or 2,2-bis [4- (2,3-dibromopropoxy) -3,5-dibromophenyl] propane (also known as tetrabromobisphenol A - Brominated bisphenol compounds such as bis(2,3-dibromopropyl ether)), tetrabromocyclooctane, tris(2,3-dibromopropyl) isocyanurate, brominated styrene/butadiene block copolymer, brominated random Brominated butadiene/vinyl aromatic hydrocarbon copolymers such as styrene/butadiene copolymers or brominated styrene/butadiene graft copolymers (for example, disclosed in JP-T-2009-516019), and the like. be done. These brominated flame retardants may be used alone or in combination of two or more.
臭素系難燃剤は、目的とする発泡倍率に制御しやすいと共に、輻射伝熱抑制剤添加時の難燃性等のバランスの点から、スチレン系樹脂組成物100重量%において臭素含有量は好ましくは0.8重量%以上であることが好ましく、5.0重量%以下であることがより好ましい。臭素含有量が0.8重量%以上であると、難燃性付与効果が大きくなる傾向にあり、5.0重量%以下であると、得られるスチレン系樹脂発泡成形体の強度が増加しやすい。臭素含有量は、より好ましくは1.0~3.5重量%になるように、スチレン系樹脂組成物、発泡性スチレン系樹脂粒子配合される。 The brominated flame retardant is easy to control to the desired expansion ratio, and from the viewpoint of the balance of flame retardancy and the like when the radiation heat transfer inhibitor is added, the bromine content in 100% by weight of the styrene resin composition is preferably It is preferably 0.8% by weight or more, and more preferably 5.0% by weight or less. When the bromine content is 0.8% by weight or more, the effect of imparting flame retardancy tends to increase. . The styrenic resin composition and the expandable styrenic resin particles are blended such that the bromine content is more preferably 1.0 to 3.5% by weight.
(熱安定剤) 本発明においては、さらに、熱安定剤を併用することによって、製造工程における臭素系難燃剤の分解による難燃性の悪化及びスチレン系樹脂の劣化を抑制することができる。本発明における熱安定剤は、用いられるスチレン系樹脂の種類、発泡剤の種類及び含有量、炭素の種類及び含有量、難燃剤の種類及び含有量等に応じて、適宜組み合わせて用いることができる。 (Thermal Stabilizer) In the present invention, by using a thermal stabilizer in combination, it is possible to suppress deterioration of flame retardancy and deterioration of the styrene resin due to decomposition of the brominated flame retardant in the manufacturing process. The heat stabilizers in the present invention can be used in appropriate combination according to the type of styrene resin used, the type and content of the foaming agent, the type and content of carbon, the type and content of the flame retardant, and the like. .
本発明で用いられる熱安定剤としては、臭素系難燃剤含有混合物の熱重量分析における重量減少温度を任意に制御できる点から、ヒンダードアミン化合物、リン系化合物、フェノール系安定剤、又はエポキシ化合物が望ましい。熱安定剤は1種を単独で又は2種以上を組み合わせて使用できる。なお、これらの熱安定剤は、後述するように耐光性安定剤としても使用できる。(ラジカル発生剤) 本発明においては、ラジカル発生剤をさらに含有することにより、臭素系難燃剤と併用することによって、高い難燃性能を発現することができる。 As the heat stabilizer used in the present invention, a hindered amine compound, a phosphorus compound, a phenolic stabilizer, or an epoxy compound is desirable because the weight loss temperature in the thermogravimetric analysis of the brominated flame retardant-containing mixture can be arbitrarily controlled. . A heat stabilizer can be used individually by 1 type or in combination of 2 or more types. These heat stabilizers can also be used as light stabilizers as described later. (Radical Generating Agent) In the present invention, by further containing a radical generating agent, it is possible to express high flame retardancy by using it in combination with a brominated flame retardant.
本発明におけるラジカル発生剤は、用いるスチレン系樹脂の種類、発泡剤の種類及び含有量、輻射伝熱抑止剤の種類及び含有量、臭素系難燃剤の種類及び含有量に応じて適宜組み合わせて用いることができる。 The radical generator used in the present invention is used in appropriate combination according to the type and content of the styrene resin used, the type and content of the foaming agent, the type and content of the radiation heat transfer inhibitor, and the type and content of the brominated flame retardant. be able to.
本発明で用いられるラジカル発生剤としては、例えば、クメンハイドロパーオキサイド、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-2,3-ジフェニルブタン、又はポリ-1,4-イソプロピルベンゼン等が挙げられる。ラジカル発生剤は1種を単独で又は2種以上を組み合わせて使用できる。 Examples of the radical generator used in the present invention include cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, and poly-1,4- isopropylbenzene and the like. A radical generating agent can be used individually by 1 type or in combination of 2 or more types.
(その他の添加剤) 本発明に係るスチレン系樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、加工助剤、耐光性安定剤、造核剤、発泡助剤、帯電防止剤、及び顔料等の着色剤よりなる群から選ばれる1種以上のその他添加剤を含有していてもよい。 (Other Additives) The styrenic resin composition according to the present invention may optionally contain a processing aid, a light stabilizer, a nucleating agent, a foaming aid, and an electrifying agent within a range that does not impair the effects of the present invention. It may contain one or more other additives selected from the group consisting of inhibitors and colorants such as pigments.
加工助剤としては、ステアリン酸ナトリウム、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸バリウム、又は流動パラフィン等が挙げられる。 Processing aids include sodium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, liquid paraffin, and the like.
耐光性安定剤としては、前述したヒンダードアミン類、リン系安定剤、エポキシ化合物の他、フェノール系抗酸化剤、窒素系安定剤、イオウ系安定剤、又はベンゾトリアゾール類等が挙げられる。 Examples of light-resistant stabilizers include the aforementioned hindered amines, phosphorus stabilizers, epoxy compounds, phenolic antioxidants, nitrogen stabilizers, sulfur stabilizers, benzotriazoles, and the like.
造核剤としては、シリカ、ケイ酸カルシウム、ワラストナイト、カオリン、クレイ、マイカ、酸化亜鉛、炭酸カルシウム、炭酸水素ナトリウム、もしくはタルク等の無機化合物、メタクリル酸メチル系共重合体、もしくはエチレン-酢酸ビニル共重合体樹脂等の高分子化合物、ポリエチレンワックス等のオレフィン系ワックス、又はメチレンビスステアリルアマイド、エチレンビスステアリルアマイド、ヘキサメチレンビスパルミチン酸アマイド、もしくはエチレンビスオレイン酸アマイド等の脂肪酸ビスアマイド等が挙げられる。 Nucleating agents include inorganic compounds such as silica, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, calcium carbonate, sodium hydrogen carbonate, or talc, methyl methacrylate copolymers, or ethylene- Polymer compounds such as vinyl acetate copolymer resins, olefin waxes such as polyethylene wax, or fatty acid bisamides such as methylenebisstearylamide, ethylenebisstearylamide, hexamethylenebispalmitamide, or ethylenebisoleic acid amide. mentioned.
発泡助剤としては、大気圧下での沸点が200℃以下である溶剤を望ましく使用でき、例えば、スチレン、トルエン、エチルベンゼン、もしくはキシレン等の芳香族炭化水素、シクロヘキサン、もしくはメチルシクロヘキサン等の脂環式炭化水素、又は酢酸エチル、もしくは酢酸ブチル等の酢酸エステル等が挙げられる。 As the foaming aid, a solvent having a boiling point of 200° C. or less under atmospheric pressure can be desirably used. hydrocarbons, or acetates such as ethyl acetate or butyl acetate.
なお、帯電防止剤及び着色剤としては、各種樹脂組成物に用いられるものを特に限定なく使用できる。 As the antistatic agent and colorant, those used in various resin compositions can be used without particular limitation.
これらの他の添加剤は、1種を単独で又は2種以上を組み合わせて使用できる。(スチレン系樹脂組成物の製造方法) 本発明のスチレン系樹脂組成物および発泡性スチレン系樹脂組成物の製造方法(以下、単に「本発明のスチレン系樹脂組成物の製法」と称することがある。)は、スチレン系樹脂及び炭素を二軸押出機に供給し、溶融混練する溶融混練工程において、二軸押出機における比エネルギーを0.13kWh/kg以上に制御する。 These other additives can be used individually by 1 type or in combination of 2 or more types. (Method for Producing Styrene-Based Resin Composition) Method for producing the styrene-based resin composition and the expandable styrene-based resin composition of the present invention (hereinafter sometimes simply referred to as "method for producing the styrene-based resin composition of the present invention") ) controls the specific energy in the twin-screw extruder to 0.13 kWh/kg or more in the melt-kneading step in which the styrene-based resin and carbon are supplied to the twin-screw extruder and melt-kneaded.
本発明における、スチレン系樹脂および炭素を二軸押出機に供給する形態は、特に限定されないが、本発明の実効性が高い点から、粉状の炭素をスチレン系樹脂と二軸押出機に供給して溶融混練することが好ましい。即ち、本発明は、炭素とスチレン系樹脂とを予め混練して作製されたマスターバッチを使用するような、事前の炭素とスチレン系樹脂との混練工程を要することなく、炭素とスチレン系樹脂を直接、二軸押出機に供給し溶融混練しスチレン系樹脂組成物を得ることにより、製造コストに優れ、かつ断熱性能に優れたスチレン系樹脂発泡成形体を与えうるスチレン系樹脂組成物の製造方法を提供することができる。前記二軸押出機における比エネルギー値を特定範囲に確保することにより、スチレン系樹脂中の炭素の分散状態が良好となり、引いては高い断熱性能を有するスチレン系樹脂発泡成形体を低コストで得ることができることを見出した。 In the present invention, the form of supplying the styrene resin and carbon to the twin-screw extruder is not particularly limited, but from the viewpoint of the high effectiveness of the present invention, powdery carbon is supplied to the styrene resin and the twin-screw extruder. It is preferable to melt and knead the mixture. That is, the present invention does not require a prior kneading step of carbon and styrene resin, such as using a masterbatch prepared by kneading carbon and styrene resin in advance, and mixes carbon and styrene resin. A method for producing a styrenic resin composition that can provide a styrenic resin foam molded article that is excellent in production cost and excellent in heat insulation performance by directly supplying it to a twin-screw extruder and melt-kneading it to obtain a styrenic resin composition. can be provided. By ensuring the specific energy value in the twin-screw extruder within a specific range, the state of carbon dispersion in the styrene resin is improved, and a styrene resin foam molded product having high heat insulation performance is obtained at low cost. I found that it can be done.
なお、本発明は、炭素とスチレン系樹脂とを予め混練して作製されたマスターバッチを使用することを除外するものではない。 The present invention does not exclude the use of a masterbatch prepared by kneading carbon and a styrenic resin in advance.
本発明で使用される二軸押出機は、公知の二軸押出機を使用できるが、好ましくは同方向噛み合い二軸押出機である。連続的にスチレン系樹脂組成物を得ることができる混練設備のうちの単軸押出機は、二軸押出機と比較すると、炭素の分散性が劣る傾向にある。また、バッチ式のミキサー、ニーダー等の混練機は連続式である押出機と比較すると、炭素の分散性には優れる傾向にあるものの、生産性に乏しい傾向にある。以上のことから、性能・コストを両立するスチレン系樹脂組成物の製造方法としては、連続式の二軸押出機が優れる。 The twin-screw extruder used in the present invention may be a known twin-screw extruder, preferably a co-meshing twin-screw extruder. Single-screw extruders among kneading equipment capable of continuously obtaining a styrenic resin composition tend to have poorer carbon dispersibility than twin-screw extruders. In addition, batch-type kneaders such as mixers and kneaders tend to have better carbon dispersibility than continuous-type extruders, but tend to have poor productivity. As described above, a continuous twin-screw extruder is excellent as a method for producing a styrene-based resin composition that satisfies both performance and cost.
(溶融混練工程における各条件) 前記スチレン系樹脂組成物の製造工程におけるポリスチレン系樹脂と炭素との二軸押出機における溶融混練工程の各条件について説明する。 (Each condition in the melt-kneading process) Each condition of the melt-kneading process in the twin-screw extruder for the polystyrene-based resin and carbon in the manufacturing process of the styrene-based resin composition will be described.
(比エネルギー) 二軸押出機における比エネルギーは発泡剤の有無に関わらず0.13kWh/kg以上であり、好ましくは0.16kWh/kg以上である。比エネルギーが高いほど炭素の分散状態が優れる傾向にあり、結果として高い断熱性能を有するスチレン系樹脂発泡成形体を与えうるポリスチレン系樹脂組成物を得ることができる。0.13kWh/kg未満であると、炭素のポリスチレン系樹脂中における分散が不十分となり、断熱性能が悪化する傾向にある。一方スチレン系樹脂の分解防止の観点から0.50kWh/kg以下であることが好ましい。 (Specific Energy) The specific energy in the twin-screw extruder is 0.13 kWh/kg or more, preferably 0.16 kWh/kg or more, regardless of the presence or absence of a foaming agent. The higher the specific energy, the better the carbon dispersion state, and as a result, it is possible to obtain a polystyrene-based resin composition capable of providing a styrene-based resin foam molded article having high heat insulating performance. If it is less than 0.13 kWh/kg, the carbon will be insufficiently dispersed in the polystyrene resin, and the heat insulating performance will tend to deteriorate. On the other hand, it is preferably 0.50 kWh/kg or less from the viewpoint of preventing decomposition of the styrene resin.
なお上記比エネルギーとは、二軸押出機に供給する全原料に対して、二軸押出機で行った仕事を単位押出質量当たりで表した値をいい、モーター効率を加味した二軸押出機電動機消費電力量を押出質量、すなわち、単位時間に押し出される全原料の質量で除して求めることができる。 The above specific energy refers to the value of the work performed by the twin-screw extruder per unit extrusion mass for all raw materials supplied to the twin-screw extruder, and the motor efficiency of the twin-screw extruder motor It can be obtained by dividing the power consumption by the extrusion mass, that is, the mass of all raw materials extruded per unit time.
前記比エネルギーを制御する方法としては、二軸押出機のシリンダ設定温度を調整する方法、押出機のシリンダ内径(D)に対するスクリュ長(L)、即ちL/Dを調整する方法、スクリュ構成を調整する方法、スクリュの回転数(N)に対する押出量(Q)、即ちQ/Nを調整する方法、使用するスチレン系樹脂のMFRを調整する方法等が挙げられる。 Methods for controlling the specific energy include a method of adjusting the cylinder set temperature of the twin-screw extruder, a method of adjusting the screw length (L) with respect to the cylinder inner diameter (D) of the extruder, that is, L/D, and a screw configuration. A method of adjusting the extrusion rate (Q) with respect to the number of revolutions (N) of the screw, that is, a method of adjusting Q/N, a method of adjusting the MFR of the styrenic resin to be used, and the like.
二軸押出機のシリンダ設定温度については、原料フィード部分を除いて、100℃~250℃の範囲であることが好ましく、より好ましくは100~200℃である。シリンダ設定温度が低い程、ポリスチレン系樹脂の粘度が高くなるため、比エネルギーが上昇する傾向にある。尚、押出機の溶融混練部での設定温度が250℃以下の場合、臭素系難燃剤の分解が起こりにくく、所望の難燃性を得ることが可能となり、所望の難燃性を付与するために難燃剤を過剰に添加する必要がないという効果を奏する。一方、押出機の溶融混練部の設定温度が100℃以上の場合には、押出機の負荷が小さくなって押出が安定となる。 The set temperature of the cylinder of the twin-screw extruder is preferably in the range of 100°C to 250°C, more preferably 100°C to 200°C, except for the raw material feeding portion. The lower the cylinder set temperature, the higher the viscosity of the polystyrene resin, so the specific energy tends to increase. In addition, when the set temperature in the melt kneading section of the extruder is 250 ° C. or less, the decomposition of the brominated flame retardant is unlikely to occur, it is possible to obtain the desired flame retardancy, and the desired flame retardancy is imparted. There is an effect that it is not necessary to add a flame retardant excessively. On the other hand, when the set temperature of the melt-kneading section of the extruder is 100° C. or higher, the load on the extruder is reduced and the extrusion becomes stable.
押出機のL/Dについては、24以上36以下の範囲が好ましく、より好ましくは26以上32以下、さらに好ましくは28以上32以下である。L/Dが小さいと、押出運転の安定性に劣る傾向にある。L/Dが長すぎると設備コストアップに繋がる傾向にある。 The L/D of the extruder is preferably 24 or more and 36 or less, more preferably 26 or more and 32 or less, and still more preferably 28 or more and 32 or less. When L/D is small, the stability of extrusion operation tends to be poor. If the L/D is too long, it tends to lead to an increase in facility costs.
スクリュ構成については、炭素をスチレン系樹脂中に分配・分散させるニーディングエレメントを使用することが好ましい。使用するニーディングエレメントの数、厚み、角度等の種類は、比エネルギーに応じて適宜調整できるが、炭素をスチレン系樹脂中に分配・分散させるため、発泡剤を樹脂に含有する前に少なくとも1個以上存在することが好ましい。ニーディングエレメントが存在しないと比エネルギーを前記範囲に調整することが困難となり、結果として炭素をスチレン系樹脂に高度に分散させることが困難となる恐れがある。 Regarding the screw configuration, it is preferable to use a kneading element that distributes and disperses the carbon in the styrenic resin. The number, thickness, angle and other types of kneading elements to be used can be appropriately adjusted according to the specific energy. It is preferable that there are more than one. Without the kneading element, it becomes difficult to adjust the specific energy within the above range, and as a result, it may become difficult to disperse the carbon in the styrenic resin to a high degree.
スクリュ回転数については、炭素、並びに他の添加剤、発泡剤の分散性の観点から100rpm以上が好ましく、押出安定性の観点から500rpm以下が好ましい。 The screw rotation speed is preferably 100 rpm or more from the viewpoint of dispersibility of carbon, other additives, and a foaming agent, and preferably 500 rpm or less from the viewpoint of extrusion stability.
Q/Nについては、スクリュ1回転当たりの吐出量であり、押出機の量的効率を表すものであり、この値が小さいほど、比エネルギーが大きくなる。 Q/N is the discharge amount per screw rotation and represents the quantitative efficiency of the extruder. The smaller this value, the larger the specific energy.
<発泡性スチレン系樹脂粒子の製造方法> 本発明の発泡性スチレン系樹脂粒子の製造方法としては、以下の2つの方法が挙げられる。 <Method for Producing Expandable Styrene-Based Resin Particles> As a method for producing the expandable styrene-based resin particles of the present invention, the following two methods are exemplified.
第1の発泡性スチレン系樹脂粒子の製造方法としては、スチレン系樹脂、炭素、必要に応じて難燃剤、ラジカル発生剤、安定剤等の添加剤を二軸押出機で溶融混練し、小孔を有するダイスを通じてスチレン系樹脂組成物の溶融物を押し出した後、カッターで切断することによりスチレン系樹脂粒子を得た後、該スチレン系樹脂粒子を水中に懸濁させると共に、発泡剤を供給して、発泡剤をスチレン系樹脂粒子に含有させることで、発泡性スチレン系樹脂粒子を得る製造方法である。カッターで切断することによる造粒化は、コールドカット法であっても、ホットカット法であってもどちらでもよい。 As a first method for producing expandable styrene resin particles, a styrene resin, carbon, and, if necessary, additives such as a flame retardant, a radical generator, and a stabilizer are melted and kneaded by a twin-screw extruder to form small holes. After extruding the melt of the styrene resin composition through a die having a In this manufacturing method, expandable styrene-based resin particles are obtained by incorporating a foaming agent into styrene-based resin particles. Granulation by cutting with a cutter may be either a cold cut method or a hot cut method.
第2の発泡性スチレン系樹脂粒子の製造方法としては、スチレン系樹脂、炭素、必要に応じて、難燃剤、ラジカル発生剤、安定剤等の添加剤を二軸押出機に供給、溶融混練し、発泡剤を前記二軸押出機もしくは、二軸押出機以降の分散設備によって樹脂に溶解、分散させ、押出機以降に取り付けた小孔を多数有するダイスを通じて、加圧循環水で満たされたカッターチャンバー内に発泡剤含有スチレン系樹脂組成物の溶融物を押し出し、押し出し直後から、ダイスと接する回転カッターにより溶融樹脂を切断すると共に加圧循環水により冷却固化する方法である。 As a second method for producing expandable styrene resin particles, a styrene resin, carbon, and, if necessary, additives such as a flame retardant, a radical generator, and a stabilizer are supplied to a twin-screw extruder and melt-kneaded. , The blowing agent is dissolved and dispersed in the resin by the twin-screw extruder or the dispersing equipment after the twin-screw extruder, and through a die having many small holes attached after the extruder, a cutter filled with pressurized circulating water In this method, a melt of a foaming agent-containing styrene resin composition is extruded into a chamber, and immediately after extrusion, the melted resin is cut by a rotating cutter in contact with a die and cooled and solidified by pressurized circulating water.
尚、設備の簡便性から、スチレン系樹脂、炭素、及びその他の難燃剤、ラジカル発生剤、安定剤等の添加剤を供給、溶融混練する二軸押出機に直接発泡剤を圧入し、発泡剤を樹脂に溶解・分散させ、押出機以降に取り付けた小孔を多数有するダイスを通じて、循環水で満たされたカッターチャンバー内に押し出し、押し出し直後から、ダイスと接する回転カッターにより溶融樹脂を切断する発泡性スチレン系樹脂粒子の製造方法が好ましい。 In addition, due to the simplicity of the equipment, additives such as styrene resin, carbon, other flame retardants, radical generators, stabilizers are supplied, and the blowing agent is directly injected into the twin-screw extruder that melts and kneads. is dissolved and dispersed in the resin and extruded through a die with many small holes attached after the extruder into a cutter chamber filled with circulating water. A method for producing polystyrene-based resin particles is preferred.
本発明の発泡性スチレン系樹脂粒子の製造方法においては、上記第1および第2発泡性スチレン系樹脂粒子の製造方法における溶融混練工程として、上述のスチレン系樹脂組成物の溶融混練工程を同様に適用できる。また、第1および第2発泡性スチレン系樹脂粒子の製造方法におけるスチレン系樹脂組成物(発泡性粒子用スチレン系樹脂組成物)には、上述のスチレン系樹脂組成物で使用される、スチレン系樹脂や、炭素や、その他成分(発泡剤、添加剤等)等を、特に言及がない限り、同様に使用できる。 In the method for producing expandable styrene-based resin particles of the present invention, the melt-kneading step for the above-described styrene-based resin composition is similarly performed as the melt-kneading step in the method for producing the first and second expandable styrene-based resin particles. Applicable. The styrene-based resin composition (styrene-based resin composition for expandable particles) in the method for producing the first and second expandable styrene-based resin particles includes the styrene-based resin composition used in the above-described styrene-based resin composition. Resins, carbons, other components (blowing agents, additives, etc.), etc. can be used in the same manner unless otherwise specified.
尚、上記第2の発泡性スチレン系樹脂粒子の製造方法、即ち、スチレン系樹脂、炭素、必要に応じて、難燃剤、ラジカル発生剤、安定剤等の添加剤を二軸押出機に供給、溶融混練し、発泡剤を前記二軸押出機もしくは、二軸押出機以降の分散設備によって樹脂に溶解、分散させ、押出機以降に取り付けた小孔を多数有するダイスを通じて、加圧循環水で満たされたカッターチャンバー内に押し出し、押し出し直後から、ダイスと接する回転カッターにより溶融樹脂を切断すると共に加圧循環水により冷却固化する方法の場合は、比エネルギーは0.41kWh/kg未満であることが好ましく、更に0.33kWh/kg以下であることが好ましい。比エネルギーが高くなることによって、二軸押出機先端の樹脂温度が高くなる傾向にある。0.33kWh/kgを超え、樹脂温度が高くなると発泡性スチレン系樹脂粒子の形状が歪となり、成形性が悪化する恐れがあり、さらに0.41kWh/kg以上であると、更に樹脂温度が上昇する恐れが生じ、結果としてカッティングが困難となり、炭素の分散性は優れるものの発泡性スチレン系樹脂粒子が得られない恐れがある。 In addition, the second method for producing expandable styrene resin particles, that is, supplying a styrene resin, carbon, and, if necessary, additives such as a flame retardant, a radical generator, and a stabilizer to a twin-screw extruder, After melt-kneading, the foaming agent is dissolved and dispersed in the resin by the twin-screw extruder or the dispersing equipment after the twin-screw extruder, and filled with pressurized circulating water through a die having many small holes attached after the extruder. In the case of a method in which the molten resin is extruded into a cutter chamber where it is extruded, and immediately after extrusion, the molten resin is cut by a rotating cutter in contact with the die and cooled and solidified by pressurized circulating water, the specific energy is less than 0.41 kWh / kg. It is preferably 0.33 kWh/kg or less. As the specific energy increases, the resin temperature at the tip of the twin-screw extruder tends to increase. When the resin temperature exceeds 0.33 kWh/kg and the resin temperature rises, the shape of the expandable styrene resin particles may become distorted and the moldability may deteriorate. As a result, cutting becomes difficult, and although the carbon dispersibility is excellent, expandable styrene resin particles may not be obtained.
(二軸押出機先端の樹脂温度) 本発明の発泡性スチレン系樹脂粒子の製造方法における、二軸押出機先端樹脂温度については、難燃剤の分解、及び発泡性スチレン系樹脂粒子の切断時に影響を及ぼすか可能性があることから、二軸押出機先端において160℃以上210℃未満であることが好ましく、更に好ましくは、160℃以上190℃未満である。二軸押出機先端における樹脂温度が210℃を超えると難燃剤の分解の恐れがあり、結果として炭素含数スチレン系樹脂組成物の劣化を誘発し、難燃性能の低下に繋がる恐れがある。 (Resin Temperature at Tip of Twin-screw Extruder) In the method for producing expandable styrene resin particles of the present invention, the resin temperature at the tip of the twin-screw extruder affects the decomposition of the flame retardant and the cutting of the expandable styrene resin particles. , the temperature at the tip of the twin-screw extruder is preferably 160°C or higher and lower than 210°C, more preferably 160°C or higher and lower than 190°C. If the resin temperature at the tip of the twin-screw extruder exceeds 210°C, the flame retardant may decompose, resulting in deterioration of the carbon-containing styrenic resin composition, which may lead to a decrease in flame retardancy.
更に、上記の第2の発泡性スチレン系樹脂粒子の製造方法の場合、二軸押出機とダイス間において樹脂の冷却設備を設けない場合は、二軸押出機先端樹脂温度は、樹脂切断時の溶融樹脂の温度に大きな影響を及ぼす可能性がある。この場合、二軸押出機先端樹脂温度が190℃を超えると、ダイスでの樹脂切断時の樹脂温度が高くなることによって、発泡性スチレン系樹脂粒子の形状が歪となる恐れがあり、さらに210℃を超えるとカッターでの切断時にカッターに樹脂が巻きつきやすくなるため、切断が非常に困難になる恐れがある。 Furthermore, in the case of the above-described second method for producing expandable styrene resin particles, if cooling equipment for the resin is not provided between the twin-screw extruder and the die, the resin temperature at the tip of the twin-screw extruder is It can have a large effect on the temperature of the molten resin. In this case, if the temperature of the resin at the tip of the twin-screw extruder exceeds 190°C, the temperature of the resin at the time of cutting the resin with a die increases, which may distort the shape of the expandable styrene resin particles. If the temperature exceeds °C, the resin tends to wrap around the cutter during cutting, which may make cutting very difficult.
(造粒工程の各条件) 第一及び第二の発泡性スチレン系樹脂粒子の製造方法におけるスチレン系樹脂粒子の造粒工程の条件について説明する。 (Each condition of the granulation step) The conditions of the styrenic resin particle granulation step in the first and second methods for producing expandable styrene resin particles will be described.
ダイスは特に限定されないが、例えば、直径0.3mm~2.0mm、望ましくは0.4mm~1.0mmの小孔を有するものが挙げられる。 Although the die is not particularly limited, for example, it may have small holes with a diameter of 0.3 mm to 2.0 mm, preferably 0.4 mm to 1.0 mm.
第二の発泡性スチレン系樹脂粒子の製造方法において、ダイスより押出される直前の溶融樹脂の温度は、発泡剤を含まない状態での樹脂のガラス転移温度をTgとすると、Tg+40℃以上であることが好ましく、Tg+40℃~Tg+110℃であることがより好ましく、Tg+60℃~Tg+90℃であることがさらに好ましい。尚、スチレンホモポリマーの場合、Tgは約100℃であるため、好ましい温度範囲は140~210℃であり、更に好ましい範囲は160℃~190℃である。 In the second method for producing expandable styrene-based resin particles, the temperature of the molten resin immediately before it is extruded from the die is Tg+40° C. or higher, where Tg is the glass transition temperature of the resin in a state not containing a foaming agent. is preferred, Tg+40°C to Tg+110°C is more preferred, and Tg+60°C to Tg+90°C is even more preferred. In the case of styrene homopolymer, the Tg is about 100°C, so the preferred temperature range is 140°C to 210°C, and the more preferred range is 160°C to 190°C.
第二の発泡性スチレン系樹脂粒子の製造方法において、ダイスより押出される直前の溶融樹脂の温度がTg+40℃以上であれば、押出された溶融樹脂の粘度が低くなり、小孔詰まりが発生しにくく、実質小孔開口率の低下が起きないため、得られる発泡性スチレン系樹脂粒子の形状が歪もしくは不揃いとなる事態を避けることができる。一方で、ダイスより押出される直前の溶融樹脂の温度がTg+110℃以下であれば、押出された溶融樹脂が固化し易くなり、回転カッターに巻き付き難くなり、安定的に切断できる。 In the second method for producing expandable styrene resin particles, if the temperature of the molten resin immediately before being extruded from the die is Tg + 40°C or higher, the viscosity of the extruded molten resin becomes low and clogging of the small pores occurs. Since it is difficult to remove and does not cause a substantial decrease in small pore opening ratio, it is possible to avoid a situation in which the shape of the expandable styrene resin particles to be obtained is distorted or irregular. On the other hand, if the temperature of the molten resin immediately before it is extruded from the die is Tg+110° C. or less, the extruded molten resin is easily solidified, is less likely to wrap around the rotary cutter, and can be stably cut.
第二の発泡性スチレン系樹脂粒子の製造方法における循環加圧冷却水に押出された溶融樹脂を切断する切断装置としては、特に限定されないが、例えば、ダイスに接触する回転カッターで切断されて小球化され、加圧循環冷却水中を発泡することなく、遠心脱水機まで移送されて脱水・集約される装置、等が挙げられる。 The cutting device for cutting the molten resin extruded into the circulating pressurized cooling water in the second method for producing expandable styrene resin particles is not particularly limited. A device that spheroidizes, transfers to a centrifugal dehydrator, dehydrates and aggregates without foaming in pressurized circulating cooling water, and the like.
加圧循環冷却水の条件については、使用するスチレン系樹脂、添加剤、発泡剤、炭素の種類、含有量によって調整すべきであるが、ダイスより押し出される溶融樹脂の発泡が抑制され、安定的にカッターで切断される条件が好ましい。具体的には、スチレンホモポリマーの場合、加圧循環冷却水の温度条件としては、好ましくは45℃~75℃、より好ましくは50~65℃である。圧力条件としては、得られる発泡性スチレン系樹脂粒子の真密度が好ましくは950kg/m3~1050kg/m3、より好ましくは1000~1050kg/m3となる様、圧力を調整する。使用する発泡剤の種類にも依存するが、ブタン、ペンタンを発泡剤として使用する場合、好ましくは0.6~2.0MPa、より好ましくは0.7~1.7MPa、更に好ましくは0.8~1.5MPaである。 The conditions of the pressurized circulating cooling water should be adjusted according to the type and content of the styrenic resin, additives, foaming agent, and carbon used. It is preferable to use a condition in which the blade is cut by a cutter immediately. Specifically, in the case of styrene homopolymer, the temperature condition of the pressurized circulating cooling water is preferably 45°C to 75°C, more preferably 50°C to 65°C. As for the pressure conditions, the pressure is adjusted so that the true density of the expandable styrene resin particles to be obtained is preferably 950 kg/m 3 to 1050 kg/m 3 , more preferably 1000 to 1050 kg/m 3 . Although it depends on the type of foaming agent used, when butane or pentane is used as the foaming agent, it is preferably 0.6 to 2.0 MPa, more preferably 0.7 to 1.7 MPa, and still more preferably 0.8 MPa. ~1.5 MPa.
本発明の発泡性スチレン系樹脂粒子の製造方法において、上記第1の製法での発泡剤の含浸条件等は、一般的に行なわれる条件と同様でよく、適宜設定すればよい。 In the method for producing expandable styrene-based resin particles of the present invention, conditions such as the impregnation conditions of the foaming agent in the first production method may be the same as those generally carried out, and may be appropriately set.
<スチレン系樹脂組成物、発泡性スチレン系樹脂粒子> 本発明においては、スチレン系樹脂組成物および発泡性スチレン系樹脂粒子中の炭素の分散状態が、二軸押出機で与えられる比エネルギー値によって制御可能であり、炭素の分散状態を良好とすることによって、高い断熱性能が発現できることを見出した。 <Styrene-based resin composition, expandable styrene-based resin particles> In the present invention, the dispersion state of carbon in the styrene-based resin composition and the expandable styrene-based resin particles is determined by the specific energy value given by the twin-screw extruder. It has been found that the controllable state of carbon can be controlled, and high heat insulation performance can be achieved by improving the state of carbon dispersion.
(レーザー散乱強度) 本発明においては、特に平均粒径2.5~9.0μmの炭素を使用した場合、炭素の分散状態をレーザー回折散乱法により測定した単位溶液濃度あたりのレーザー散乱強度によって評価可能であることを見出した。 (Laser Scattering Intensity) In the present invention, especially when carbon having an average particle size of 2.5 to 9.0 μm is used, the dispersed state of carbon is evaluated by the laser scattering intensity per unit solution concentration measured by a laser diffraction scattering method. I found that it is possible.
本発明のレーザー散乱強度は、以下のようにして求められる。まず、スチレン系樹脂組成物または発泡性スチレン系樹脂粒子を含有しないトルエン溶液に波長632.8nmのHe-Neレーザー光を照射した際の透過光の強度Lbと、本発明のスチレン系樹脂組成物または発泡性スチレン系樹脂粒子を所定重量含有するトルエン溶液に波長632.8nmのHe-Neレーザー光を照射した際の透過光の強度Lsとから、レーザー散乱強度Ob(%)を式Ob=(1-Ls/Lb)×100から求める。次に、求めたレーザー散乱強度Obから本発明のスチレン系樹脂組成物または発泡性スチレン系樹脂粒子の単位溶液濃度あたりのレーザー散乱強度を求める。そして、求めた単位溶液濃度あたりのレーザー散乱強度を所定重量のスチレン系樹脂組成物または発泡性スチレン系樹脂粒子の炭素の含有量(重量%)で割って算出されるレーザー散乱強度が、炭素単位溶液濃度あたりのレーザー散乱強度である。 The laser scattering intensity of the present invention is determined as follows. First, the intensity Lb of transmitted light when a He—Ne laser beam with a wavelength of 632.8 nm is irradiated to a toluene solution that does not contain a styrene resin composition or expandable styrene resin particles, and the styrene resin composition of the present invention. Alternatively, from the intensity Ls of the transmitted light when a He—Ne laser beam with a wavelength of 632.8 nm is irradiated to a toluene solution containing a predetermined weight of expandable styrene resin particles, the laser scattering intensity Ob (%) is calculated by the formula Ob=( 1−Ls/Lb)×100. Next, from the determined laser scattering intensity Ob, the laser scattering intensity per unit solution concentration of the styrene resin composition or expandable styrene resin particles of the present invention is determined. Then, the laser scattering intensity calculated by dividing the obtained laser scattering intensity per unit solution concentration by the carbon content (% by weight) of the styrene resin composition or expandable styrene resin particles of a predetermined weight is expressed in units of carbon. Laser scattering intensity per solution concentration.
本発明に係るスチレン系樹脂組成物または発泡性スチレン系樹脂粒子は、スチレン系樹脂組成物または発泡性スチレン系樹脂粒子単位溶液濃度あたりのレーザー散乱強度が15.0%/(mg/ml)以上であることが好ましい。このレーザー散乱強度が15.0%/(mg/ml)以上であると、高い熱伝導率低減効果を得ることが可能となる。具体的には、発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0330(W/mK)以下を示す傾向にある。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。さらに、このレーザー散乱強度が17.5%/(mg/ml)以上であると、さらに高い熱伝導率低減効果を得ることが可能となる。具体的には、発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0320(W/mK)以下を示す傾向にある。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。 The styrene resin composition or expandable styrene resin particles according to the present invention has a laser scattering intensity of 15.0%/(mg/ml) or more per unit solution concentration of the styrene resin composition or expandable styrene resin particles. is preferably When the laser scattering intensity is 15.0%/(mg/ml) or more, a high thermal conductivity reduction effect can be obtained. Specifically, when the expandable styrene-based resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the 80-fold expanded molded article is allowed to stand at a temperature of 50°C for 30 days, and then at a temperature of 23°C. After standing for 24 hours, the thermal conductivity at 23° C. measured according to JIS A9511:2006R tends to be 0.0330 (W/mK) or less. That is, it is possible to obtain a low thermal conductivity at a high expansion ratio, and thus a high heat insulating property. Furthermore, when the laser scattering intensity is 17.5%/(mg/ml) or more, it is possible to obtain a higher thermal conductivity reduction effect. Specifically, when the expandable styrene-based resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the 80-fold expanded molded article is allowed to stand at a temperature of 50°C for 30 days, and then at a temperature of 23°C. After standing still for 24 hours, the thermal conductivity at 23° C. measured according to JIS A9511:2006R tends to be 0.0320 (W/mK) or less. That is, it is possible to obtain a low thermal conductivity at a high expansion ratio, and thus a high heat insulating property.
本発明に係るスチレン系樹脂組成物または発泡性スチレン系樹脂粒子は、炭素単位溶液濃度あたりのレーザー散乱強度が4.0{%/(mg/ml)}/重量%以上であることが望ましい。このレーザー散乱強度が4.0%/(mg/ml)/重量%以上であると、高い熱伝導率低減効果を得ることが可能となる。具体的には、発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0330(W/mK)以下を示す傾向にある。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。さらに、このレーザー散乱強度が4.9{%/(mg/ml)}/重量%以上であると、さらに高い熱伝導率低減効果を得ることが可能となる。炭素の含有量に対して高い熱伝導率低減効果を得ることが可能となる。具体的には、発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0320(W/mK)以下を示す傾向にある。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。 The styrenic resin composition or expandable styrenic resin particles according to the present invention preferably has a laser scattering intensity of 4.0 {%/(mg/ml)}/wt% or more per carbon unit solution concentration. When the laser scattering intensity is 4.0%/(mg/ml)/% by weight or more, a high thermal conductivity reduction effect can be obtained. Specifically, when the expandable styrene-based resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the 80-fold expanded molded article is allowed to stand at a temperature of 50°C for 30 days, and then at a temperature of 23°C. After standing for 24 hours, the thermal conductivity at 23° C. measured according to JIS A9511:2006R tends to be 0.0330 (W/mK) or less. That is, it is possible to obtain a low thermal conductivity at a high expansion ratio, and thus a high heat insulating property. Furthermore, when the laser scattering intensity is 4.9 {%/(mg/ml)}/% by weight or more, a higher thermal conductivity reduction effect can be obtained. It is possible to obtain a high thermal conductivity reduction effect with respect to the carbon content. Specifically, when the expandable styrene-based resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the 80-fold expanded molded article is allowed to stand at a temperature of 50°C for 30 days, and then at a temperature of 23°C. After standing still for 24 hours, the thermal conductivity at 23° C. measured according to JIS A9511:2006R tends to be 0.0320 (W/mK) or less. That is, it is possible to obtain a low thermal conductivity at a high expansion ratio, and thus a high heat insulating property.
(予備発泡樹脂粒子及びその製造方法) 本発明の製法で得られるスチレン系樹脂組成物は、マスターバッチとして発泡性スチレン系樹脂粒子の原料として使用されてもよいし、発泡剤を含有する発泡性スチレン系樹脂組成物として、発泡性スチレン系樹脂粒子やスチレン系樹脂発泡成形体に成形されてもよい。また、本発明の製法で得られる発泡性スチレン系樹脂粒子は、予備発泡されたのち型内発泡成形体に使用されうる。 (Pre-expanded resin particles and method for producing the same) The styrene resin composition obtained by the production method of the present invention may be used as a masterbatch as a raw material for expandable styrene resin particles, or may be used as an expandable resin containing a blowing agent. The styrene-based resin composition may be formed into expandable styrene-based resin particles or a styrene-based resin foam molded article. Also, the expandable styrene resin particles obtained by the production method of the present invention can be used for an in-mold expansion-molded product after being pre-expanded.
本発明の製法で得られる発泡性スチレン系樹脂粒子は、従来公知の予備発泡工程、例えば、加熱水蒸気によって10~110倍に発泡させて予備発泡樹脂粒子とし、必要に応じて一定時間養生させた後、成形に使用すればよい。得られた予備発泡樹脂粒子は、従来公知の成形機を用い、水蒸気によって成形(例えば型内成形)されてスチレン系樹脂発泡成形体が作製される。使用される金型の形状により、複雑な形の型物成形体やブロック状の成形体を得ることができる。 The expandable styrene-based resin particles obtained by the production method of the present invention are subjected to a conventionally known pre-expansion process, for example, by expanding to 10 to 110 times with heated steam to form pre-expanded resin particles, and if necessary, curing for a certain period of time. After that, it can be used for molding. The obtained pre-expanded resin particles are molded with steam (for example, in-mold molding) using a conventionally known molding machine to produce a styrene-based resin foam molded article. Depending on the shape of the mold used, it is possible to obtain molded articles of complicated shapes and block-shaped molded articles.
本発明の製法で得られる発泡性スチレン系樹脂粒子は高発泡倍率のスチレン系樹脂発泡成形体に成形することができ、発泡成形体の発泡倍率は、40倍以上が好ましく、60倍以上がより好ましく、80倍以上が特に好ましい。本発明の製法で得られるスチレン系樹脂組成物および発泡性スチレン系樹脂粒子によれば80倍以上のスチレン系樹脂発泡成形体とした場合でも低い熱伝導率を達成できるため、製造コストが安く、より高発泡のスチレン系樹脂発泡成形体としても高性能な断熱性能を発現できる。尚、断熱材については、長期間使用されるため、長期間経過後の断熱性能の維持が重要な課題である。本発明における製造方法によって得られるスチレン系樹脂組成物および発泡性スチレン系樹脂粒子で成形されるスチレン系樹脂発泡成形体については、スチレン系樹脂発泡成形体から熱伝導率測定サンプルを切り出し、サンプルを50℃条件で30日間アニーリングし、さらに23℃条件下にて24時間静置した後においても、低い熱伝導率を達成できる。50℃で30日間アニーリングすることにより、スチレン系樹脂発泡成形体中に含有されるブタン、ペンタン等の炭化水素系発泡剤の含有量は0.5%以下となっており、熱伝導率に与える影響は軽微となり、スチレン系樹脂発泡成形体を常温で長期間使用した場合の熱伝導率を評価することができる。 The expandable styrene resin particles obtained by the production method of the present invention can be molded into a styrene resin foam molded product having a high expansion ratio. Preferably, 80 times or more is particularly preferable. According to the styrene resin composition and expandable styrene resin particles obtained by the manufacturing method of the present invention, low thermal conductivity can be achieved even when a styrene resin foam molded article having a size of 80 times or more is formed. High-performance heat insulating performance can be exhibited even as a highly foamed styrene-based resin foam molded article. Since the heat insulating material is used for a long period of time, maintaining the heat insulating performance after a long period of time is an important issue. For the styrene resin foam molded article molded from the styrene resin composition and the expandable styrene resin particles obtained by the production method of the present invention, a thermal conductivity measurement sample is cut out from the styrene resin foam molded article, and the sample is measured. Even after annealing at 50°C for 30 days and then standing at 23°C for 24 hours, low thermal conductivity can be achieved. By annealing at 50° C. for 30 days, the content of hydrocarbon foaming agents such as butane and pentane contained in the styrene resin foam molding is 0.5% or less, which affects the thermal conductivity. The influence becomes slight, and the thermal conductivity can be evaluated when the styrene-based resin foam molded article is used at room temperature for a long period of time.
前記発泡性スチレン系樹脂粒子を発泡倍率80倍の発泡成形体とした時に、前記80倍発泡成形体を50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、JIS A9511:2006R準拠で測定した23℃での熱伝導率が、0.0330(W/mK)以下であることが好ましい。即ち、0.0330(W/mK)以下であれば、長期にわたって非常に低い熱伝導率ひいては高い断熱性を維持することができると言える。より好ましくは0.0320(W/mK)以下である。 When the expandable styrene resin particles are formed into an expanded molded article having an expansion ratio of 80 times, the 80-fold expanded molded article is allowed to stand at 50° C. for 30 days, and then at 23° C. for 24 hours. After that, the thermal conductivity at 23° C. measured according to JIS A9511:2006R is preferably 0.0330 (W/mK) or less. That is, it can be said that, if it is 0.0330 (W/mK) or less, it is possible to maintain very low thermal conductivity and high heat insulating properties over a long period of time. More preferably, it is 0.0320 (W/mK) or less.
なお、本明細書において、発泡倍率を「倍」又は「cm3/g」という単位で示すがこれらは互いに同じ意味である。 In this specification, the foaming ratio is indicated by the unit of "times" or "cm3/g", but these have the same meaning.
本発明のスチレン系樹脂予備発泡粒子及びそのスチレン系樹脂発泡成形体は、平均セル径が、好ましくは70~300μm、より好ましくは90~250μm、さらに好ましくは100~200μmである。平均セル径が前述の範囲にあることによって、断熱性のより高いスチレン系樹脂発泡成形体となる。平均セル径が70μm以上であると、発泡倍率の高倍化が容易となる傾向にあり、また、300μm以下であると、熱伝導率が増加、即ち断熱性能が悪化するのを避けることができる。 The styrene resin pre-expanded particles and the styrene resin expansion molding of the present invention preferably have an average cell diameter of 70 to 300 μm, more preferably 90 to 250 μm, still more preferably 100 to 200 μm. When the average cell diameter is within the above range, a styrene-based resin foam molded article with higher heat insulation can be obtained. When the average cell diameter is 70 μm or more, the foaming ratio tends to be increased easily, and when it is 300 μm or less, the thermal conductivity increases, ie, the deterioration of the heat insulation performance can be avoided.
(発泡成形体の用途) 本発明の製法で得られるスチレン系樹脂組成物および発泡性スチレン系樹脂粒子を用いて成形される発泡成形体は、面美麗性に優れるとともに、高発泡倍率及び高独立気泡率であり、低熱伝導率であり、熱伝導率の経時的な上昇が顕著に抑制され、かつ、断熱性が長期的に高い。従って、例えば、建築用断熱材、食品容器箱、保冷箱、緩衝材、農水産箱、浴室用断熱材及び貯湯タンク断熱材のような各種用途に好適である。 (Use of foamed molded article) The foamed molded article molded using the styrene resin composition and the expandable styrene resin particles obtained by the production method of the present invention is excellent in surface beauty, and has a high expansion ratio and high independence. It has a low porosity, low thermal conductivity, remarkably suppresses an increase in thermal conductivity over time, and has high heat insulating properties over a long period of time. Therefore, it is suitable for various uses such as construction insulation, food container boxes, cold insulation boxes, cushioning materials, agricultural and fisheries boxes, bathroom insulation and hot water storage tank insulation.
本発明の一実施形態は前述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態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についても本発明の一実施形態の技術的範囲に含まれる。 One embodiment of the present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments are appropriately combined. The obtained embodiment is also included in the technical scope of one embodiment of the present invention.
以下、実施例及び比較例に基づいて本発明の一実施形態を具体的に説明するが、本発明はこれらに限定されるものではない。 An embodiment of the present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these.
なお、以下の実施例及び比較例における測定方法及び評価方法は、以下のとおりである。 The measurement methods and evaluation methods in the following examples and comparative examples are as follows.
(スチレン系樹脂発泡成形体の熱伝導率の測定) 一般的に熱伝導率の測定平均温度が大きい方が熱伝導率の値は大きくなることが知られており、断熱性を比較するためには測定平均温度を定める必要がある。本明細書では発泡プラスチック保温材の規格であるJIS A9511:2006Rで定められた23℃を基準に採用している。また、長期間後において発泡剤が空気に置き換わった場合の熱伝導率を評価するためにスチレン系樹脂発泡成形体から熱伝導率測定サンプルを切り出し、サンプルを50℃温度下で30日間静置し、さらに23℃の温度下にて24時間静置した後、熱伝導率を測定した。 (Measurement of thermal conductivity of styrene-based resin foam molding) It is generally known that the higher the average temperature measured for thermal conductivity, the higher the value of thermal conductivity. must define the measured average temperature. In this specification, 23° C. defined by JIS A9511:2006R, which is a standard for foamed plastic heat insulating materials, is adopted as a standard. In addition, in order to evaluate the thermal conductivity when the foaming agent is replaced with air after a long period of time, a thermal conductivity measurement sample was cut out from the styrene-based resin foam molded product, and the sample was allowed to stand at 50°C for 30 days. , and further left to stand at a temperature of 23°C for 24 hours, and then the thermal conductivity was measured.
50℃で30日間アニーリングすることにより、スチレン系樹脂発泡成形体中に含有されるブタン、ペンタン等の炭化水素系発泡剤の含有量は0.5%以下となっており、熱伝導率に与える影響は軽微となり、スチレン系樹脂発泡成形体を常温で長期間使用した場合の熱伝導率をほぼ正確に評価することができる。 By annealing at 50° C. for 30 days, the content of hydrocarbon foaming agents such as butane and pentane contained in the styrene resin foam molding is 0.5% or less, which affects the thermal conductivity. The effect is slight, and the thermal conductivity of the styrene-based resin foam molded article used at room temperature for a long period of time can be evaluated almost accurately.
より詳しくは、スチレン系樹脂発泡成形体から、長さ300mm×幅300mm×厚さ25mmのサンプルを切り出した。サンプルを50℃温度下にて30日間静置し、さらに、23℃温度下にて24時間静置した後、熱伝導率測定装置(英弘精機(株)製、HC-074)を用いて、JIS A1412-2:1999に準拠して熱流計法にて平均温度23℃、温度差20℃で熱伝導率を測定した。 More specifically, a sample having a length of 300 mm, a width of 300 mm, and a thickness of 25 mm was cut out from the foamed styrene-based resin. The sample was allowed to stand at 50°C for 30 days, and then at 23°C for 24 hours. Thermal conductivity was measured at an average temperature of 23°C and a temperature difference of 20°C by a heat flow meter method according to JIS A1412-2:1999.
(炭素含有量の測定) スチレン系樹脂組成物、発泡性スチレン系樹脂粒子又はスチレン系樹脂発泡成形体それぞれ約10mgをサンプルとした。このサンプルを、熱分析システム:EXSTAR6000を備えた熱重量測定装置(エスアイアイ・ナノテクノロジー(株)製、TG/DTA 220U)を用いて、下記I~IIIを連続で実施し、IIIにおける重量減少量を炭素重量とし、試験片重量に対するパーセントで表した。I. 200mL/分の窒素気流下で40℃から600℃まで20℃/分で昇温した後600℃で10分保持、II. 200mL/分の窒素気流下で600℃から400℃まで10℃/分で降温した後400℃で5分保持、III.200mL/分の空気気流下で400℃から800℃まで20℃/分で昇温した後800℃で15分保持。 (Measurement of carbon content) About 10 mg of each of the styrene resin composition, the expandable styrene resin particles, or the styrene resin foam molded product was used as a sample. This sample is subjected to the following I to III using a thermogravimetry device (TG/DTA 220U, manufactured by SII Nanotechnology Co., Ltd.) equipped with a thermal analysis system: EXSTAR6000, and weight loss in III The amount was taken as carbon weight and expressed as a percentage of the specimen weight. I. The temperature was raised from 40° C. to 600° C. at a rate of 20° C./min under a nitrogen stream of 200 mL/min, and then held at 600° C. for 10 minutes, II. The temperature was lowered from 600° C. to 400° C. at a rate of 10° C./min under a nitrogen stream of 200 mL/min, and then held at 400° C. for 5 minutes, III. The temperature was raised from 400° C. to 800° C. at a rate of 20° C./min under an air flow of 200 mL/min, and then held at 800° C. for 15 minutes.
(炭素の平均粒径D50(μm)及びレーザー散乱強度(%)の測定) (1)試料溶液調整条件 (a)測定対象が、スチレン系樹脂組成物、発泡性スチレン系樹脂粒子又はスチレン系樹脂発泡成形体の場合スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体それぞれ500mgを0.1%(w/w)スパン80トルエン溶液20mLに溶解・分散させた。 (Measurement of carbon average particle diameter D50 (μm) and laser scattering intensity (%)) (1) Sample solution preparation conditions (a) Measurement target is styrene resin composition, expandable styrene resin particles or styrene resin In the case of foam molding, 500 mg each of the styrene resin composition, expandable styrene resin particles, or styrene resin foam molding was dissolved and dispersed in 20 mL of a 0.1% (w/w) span 80 toluene solution.
(b)測定対象が、混練前の炭素、即ち原材料の炭素自体の場合 炭素20mg及びスチレン系樹脂(PSジャパン(株)製、680)480mgを0.1%(w/w)スパン80トルエン溶液20mLに溶解・分散させた。 (b) When the object to be measured is carbon before kneading, that is, the raw material carbon itself 20 mg of carbon and 480 mg of a styrene resin (manufactured by PS Japan Co., Ltd., 680) in a 0.1% (w/w) span 80 toluene solution It was dissolved and dispersed in 20 mL.
尚、上記の溶解・分散とは、樹脂が溶解して、炭素が分散している状態のことをいう。 The dissolution/dispersion described above refers to a state in which the resin is dissolved and the carbon is dispersed.
次いで、超音波洗浄器にて、前記の試料溶液に超音波を照射し、炭素の凝集を緩和させた。 Next, the sample solution was irradiated with ultrasonic waves in an ultrasonic cleaner to relax the aggregation of carbon.
(2)超音波照射条件 使用装置 :アズワン株式会社製 超音波洗浄器 型番USM 発振周波数:42kHz 照射時間 :10分 温度 :室温。 (2) Ultrasonic irradiation conditions Apparatus used: Ultrasonic cleaner model number USM manufactured by AS ONE Corporation Oscillation frequency: 42 kHz Irradiation time: 10 minutes Temperature: Room temperature.
(3)粒径測定条件 測定装置 :マルバーン社製 レーザー回折式粒度分布測定装置 マスターサイザー3000 光源 :632.8nm赤色He-Neレーザー及び470nm青色LED 分散ユニット:湿式分散ユニット Hydro MV 以下の設定で分析を実施し、ISO13320:2009,JIS Z8825-1に準拠したMie理論に基づくレーザー回折・散乱法による測定・解析により、体積分布を求め、サンプル中の炭素のD50粒径を算出した。 (3) Particle size measurement conditions Measurement device: Mastersizer 3000 laser diffraction particle size distribution measurement device manufactured by Malvern Light source: 632.8 nm red He-Ne laser and 470 nm blue LED Dispersion unit: Wet dispersion unit Hydro MV Analysis with the following settings was carried out, and the volume distribution was determined by measurement and analysis by a laser diffraction/scattering method based on Mie theory in accordance with ISO13320:2009 and JIS Z8825-1, and the D50 particle size of carbon in the sample was calculated.
粒子の種類 :非球形
炭素屈折率 :2.42
炭素吸収率 :1.0
分散媒体 :0.1%(w/w)スパン80トルエン溶液
分散媒体の屈折率 :1.49 分散ユニット中の攪拌数:2500rpm
解析モデル :汎用、単一モードを維持
測定温度 :室温。
Particle type: Aspheric Carbon refractive index: 2.42
Carbon absorption rate: 1.0
Dispersion medium: 0.1% (w/w) span 80 toluene solution Refractive index of dispersion medium: 1.49 Stirring speed in dispersion unit: 2500 rpm
Analysis model: General purpose, single mode maintained Measurement temperature: Room temperature.
(4)測定手順 0.1%(w/w)スパン80トルエン溶液120mLを分散ユニットに注入し、2500rpmで攪拌し、安定化させた。測定セルに試料溶液サンプルが存在せず、分散媒体のみの状態で632.8nm赤色He-Neレーザー光を照射した際の中央検出器で測定された光の強度を透過光の強度Lbとした。次いで、超音波処理した試料溶液を2mL採取し、分散ユニットに追加した。試料溶液を追加して1分後の632.8nm赤色He-Neレーザー光を照射した際の中央検出器で測定された光の強度を透過光の強度Lsとした。また、同時に粒径(D50)を測定した。得られたLs及びLbより、以下の式で試料溶液のレーザー散乱強度Obを算出した。 (4) Measurement Procedure 120 mL of 0.1% (w/w) Span 80 toluene solution was injected into the dispersing unit, stirred at 2500 rpm and stabilized. The intensity of light measured by the central detector when a 632.8 nm red He—Ne laser beam was irradiated in a state in which no sample solution sample was present in the measurement cell and only the dispersion medium was present was defined as the transmitted light intensity Lb. 2 mL of the sonicated sample solution was then taken and added to the dispersing unit. One minute after the addition of the sample solution, the light intensity measured by the central detector when a 632.8 nm red He—Ne laser beam was irradiated was defined as the transmitted light intensity Ls. At the same time, particle size (D50) was also measured. From the obtained Ls and Lb, the laser scattering intensity Ob of the sample solution was calculated by the following formula.
Ob=(1-Ls/Lb)×100(%)
中央検出器はレーザー光の出力に対して対向した正面に位置する検出部であり、ここで検出される光が散乱に使用されなかった透過光の尺度である。レーザー散乱強度とは、解析装置のレーザーに試料を散乱させた際に失われるレーザー光の量の尺度である。
Ob = (1-Ls/Lb) x 100 (%)
The central detector is a detector located directly opposite the output of the laser light, where the detected light is a measure of the transmitted light that was not used for scattering. Laser scattering intensity is a measure of the amount of laser light that is lost when scattering a sample by the analyzer's laser.
(5)スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体の単位溶液濃度あたりのレーザー散乱強度の算出 以下の式にて、スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体の単位溶液濃度あたりのレーザー散乱強度を算出した。 (5) Calculation of laser scattering intensity per unit solution concentration of styrene resin composition, expandable styrene resin particles, or styrene resin foam molded product The laser scattering intensity per unit solution concentration of the resin particles or the foamed styrene-based resin was calculated.
スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体の単位溶液濃度あたりのレーザー散乱強度(%/(mg/ml))=レーザー散乱強度(Ob)/{サンプル重量(500mg)/トルエン量(20mL)×試料注入量(2mL)/分散ユニット内の全トルエン量(120mL+2mL)}
単位溶液濃度あたりのレーザー散乱強度とは、測定したレーザー散乱強度をトルエン中のサンプル濃度で割った値である。この測定装置は溶液で測定する必要のある装置であるため、トルエン溶液中のサンプル濃度を一定とし、一定のサンプル量における測定値を得ている。
Laser scattering intensity per unit solution concentration of styrene resin composition, expandable styrene resin particles, or styrene resin foam molded product (%/(mg/ml)) = laser scattering intensity (Ob)/{sample weight ( 500 mg)/toluene amount (20 mL)×sample injection amount (2 mL)/total toluene amount in dispersion unit (120 mL+2 mL)}
The laser scattering intensity per unit solution concentration is the measured laser scattering intensity divided by the sample concentration in toluene. Since this measuring device is a device that must be measured with a solution, the sample concentration in the toluene solution is kept constant, and the measured value is obtained at a constant sample amount.
(6)スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体中の炭素単位溶液濃度あたりのレーザー散乱強度の算出
以下の式にて、スチレン系樹脂組成物、発泡性スチレン系樹脂粒子、又はスチレン系樹脂発泡成形体(以下、「測定対象」と略す。)中に含有される炭素単位溶液濃度あたりのレーザー散乱強度を算出した。
(6) Calculation of laser scattering intensity per carbon unit solution concentration in styrene resin composition, expandable styrene resin particles, or styrene resin foam molded product The laser scattering intensity per carbon unit solution concentration contained in the styrene resin particles or the styrene resin foam molded article (hereinafter abbreviated as "measurement object") was calculated.
測定対象中の炭素単位溶液濃度あたりのレーザー散乱強度{%/(mg/ml)}/重量%=測定対象の単位溶液濃度あたりのレーザー散乱強度(%/(mg/ml))/測定対象の炭素含有量(重量%)
同じ重量の炭素であっても含有される炭素の分散状態によって断熱性を向上できることが本発明の一実施形態の本質である。前記炭素単位溶液濃度あたりのレーザー散乱強度を用いることによって本発明の一実施形態を表現することができる。
Laser scattering intensity per carbon unit solution concentration in measurement target {%/(mg/ml)}/% by weight = Laser scattering intensity per unit solution concentration of measurement target (%/(mg/ml))/measurement target Carbon content (wt%)
The essence of one embodiment of the present invention is that even with the same weight of carbon, the heat insulating property can be improved by the state of dispersion of the contained carbon. An embodiment of the present invention can be expressed by using the laser scattering intensity per carbon unit solution concentration.
なお、発泡性スチレン系樹脂粒子におけるグラファイト分散状態は、スチレン系樹脂組成物におけるグラファイト分散状態で決まるため、発泡性スチレン系樹脂粒子の炭素単位溶液濃度あたりのレーザー散乱強度と、スチレン系樹脂組成物(発泡性スチレン系樹脂組成物)の炭素単位溶液濃度あたりのレーザー散乱強度とは実質的に同一である。 In addition, since the graphite dispersion state in the expandable styrene resin particles is determined by the graphite dispersion state in the styrene resin composition, the laser scattering intensity per carbon unit solution concentration of the expandable styrene resin particles and the styrene resin composition It is substantially the same as the laser scattering intensity per carbon unit solution concentration of (expandable styrene resin composition).
(7)混練前の炭素とスチレン系樹脂との混合物の単位溶液濃度あたりのレーザー散乱強度の算出
以下の式にて、混練前の炭素とスチレン系樹脂との混合物の単位溶液濃度あたりのレーザー散乱強度を算出した。
(7) Calculation of laser scattering intensity per unit solution concentration of a mixture of carbon and styrene resin before kneading Laser scattering per unit solution concentration of a mixture of carbon and styrene resin before kneading is calculated using the following formula. Intensity was calculated.
混練前の炭素とスチレン系樹脂との混合物の単位溶液濃度あたりのレーザー散乱強度{%/(mg/ml)}=レーザー散乱強度(Ob)/[{炭素重量(20mg)+スチレン系樹脂(480mg)}/トルエン量(20mL)×試料注入量(2mL)/分散ユニット内の全トルエン量(120mL+2mL)]。 Laser scattering intensity per unit solution concentration of a mixture of carbon and styrene resin before kneading {% / (mg / ml)} = laser scattering intensity (Ob) / [{weight of carbon (20 mg) + styrene resin (480 mg )}/volume of toluene (20 mL)×volume of sample injection (2 mL)/total volume of toluene in dispersion unit (120 mL+2 mL)].
(8)混練前の炭素単位溶液濃度あたりのレーザー散乱強度以下の式にて、混練前の炭素、即ち原材料炭素単位溶液濃度あたりのレーザー散乱強度を算出した。 (8) Laser scattering intensity per carbon unit solution concentration before kneading Carbon before kneading, that is, laser scattering intensity per raw material carbon unit solution concentration was calculated by the following formula.
混練前の炭素単位溶液濃度あたりのレーザー散乱強度{%/(mg/ml)}/重量%=混練前の炭素とスチレン系樹脂との混合物の単位溶液濃度あたりのレーザー散乱強度(%/(mg/ml))/混練前の炭素とスチレン系樹脂との混合物中の炭素含有量(20/500×100=4重量%)。 Laser scattering intensity per unit solution concentration of carbon before kneading {%/(mg/ml)}/% by weight = Laser scattering intensity per unit solution concentration of a mixture of carbon and styrene resin before kneading (%/(mg /ml))/carbon content in the mixture of carbon and styrenic resin before kneading (20/500×100=4% by weight).
(発泡倍率の測定及び発泡性能、成形性能の評価)
スチレン系樹脂発泡成形体から、熱伝導率の測定の場合と同様に、長さ300mm×幅300mm×厚さ25mmのサンプルを切り出した。サンプルの重量(g)を測定すると共に、ノギスを用いて、縦寸法、横寸法、厚さ寸法を測定した。測定された各寸法からサンプルの体積(cm3)を計算し、下記計算式に従って発泡倍率を算出した。
(Measurement of foaming ratio and evaluation of foaming performance and molding performance)
A sample having a length of 300 mm, a width of 300 mm, and a thickness of 25 mm was cut from a styrene-based resin foam molded body in the same manner as in the measurement of thermal conductivity. The weight (g) of the sample was measured, and the vertical dimension, horizontal dimension and thickness dimension were measured using vernier calipers. The volume (cm3) of the sample was calculated from each dimension measured, and the foaming ratio was calculated according to the following formula.
発泡倍率(cm3/g)=サンプル体積(cm3)/サンプル重量(g)
なお、前述したように、スチレン系樹脂発泡成形体の発泡倍率「倍」は慣習的に「cm3/g」でも表されている。
Foaming ratio (cm3/g) = sample volume (cm3)/sample weight (g)
Incidentally, as mentioned above, the expansion ratio "times" of a styrene-based resin foam molded article is customarily expressed in "cm3/g".
さらに、得られた成形体について80倍のものの表面を観察し、粒子間の空隙が少ないものを表面美麗性が良い、空隙が目立つものを表面美麗性が悪いと判定した。 Further, the surface of the obtained molded product was observed at 80 times magnification, and the surface appearance was judged to be good when there were few voids between particles, and to be judged to be poor when the voids were conspicuous.
測定した発泡倍率及び成形体表面の美麗性に基づいて、スチレン系樹脂発泡体の発泡・成形性能について評価した。発泡・成形性能の評価は以下の基準とした。
◎:80倍発泡可能で美麗な成形体が得られる。
○:80倍発泡可能であるが、美麗な成形体が得られにくい。
The expansion/molding performance of the styrene-based resin foam was evaluated based on the measured expansion ratio and the beauty of the surface of the molded article. Evaluation of foaming/molding performance was based on the following criteria.
⊚: 80-fold expansion is possible and a beautiful molded product is obtained.
○: 80-fold expansion is possible, but it is difficult to obtain a beautiful molded product.
(難燃性の評価)
作製された発泡成形体に対して、60℃温度下にて48時間静置し、さらに23℃温度下にて24時間静置した後、JIS K7201に準じて、酸素指数を測定した。
(Evaluation of flame retardancy)
The foam molded article thus produced was allowed to stand at 60° C. for 48 hours and then at 23° C. for 24 hours, and then the oxygen index was measured according to JIS K7201.
(スチレン系樹脂発泡成形体の平均セル径の測定方法)
発泡倍率80倍のスチレン系樹脂発泡成形体をカミソリで切削し、光学顕微鏡で断面を観察した。断面の1000μm×1000μm四方の範囲内に存在するセル数を計測し、下記式(面積平均径)で測定した値を平均セル径とした。各サンプル5個の平均セル径を測定し、その平均を水準の平均セル径とした。
(Method for measuring average cell diameter of styrene-based resin foam molded product)
A styrene-based resin foam molded product having an expansion ratio of 80 was cut with a razor, and the cross section was observed with an optical microscope. The number of cells existing within a 1000 μm×1000 μm square of the cross section was counted, and the value measured by the following formula (average area diameter) was taken as the average cell diameter. The average cell diameter of five samples was measured, and the average was taken as the average cell diameter of the standard.
平均セル径(μm)=2×[1000μm×1000μm/(セル数×π)]1/2 以下に、実施例及び比較例で用いた原材料を示す。 Average cell diameter (μm)=2×[1000 μm×1000 μm/(number of cells×π)] 1/2 Raw materials used in Examples and Comparative Examples are shown below.
(スチレン系樹脂)
(A)スチレンホモポリマー[PSジャパン(株)製、680]
(炭素)
(B)グラファイト[(株)丸豊鋳材製作所製、鱗片状黒鉛SGP-40B]
平均粒径D50=5.8μm
炭素(グラファイト)単位溶液濃度当りのレーザー散乱強度=3.7%。
(styrene resin)
(A) Styrene homopolymer [manufactured by PS Japan Co., Ltd., 680]
(carbon)
(B) Graphite [Square graphite SGP-40B manufactured by Marutoyo Casting Co., Ltd.]
Average particle size D50 = 5.8 µm
Laser scattering intensity per carbon (graphite) unit solution concentration = 3.7%.
(臭素系難燃剤)
(C1)2,2-ビス[4-(2,3-ジブロモ-2-メチルプロポキシ)-3,5-ジブロモフェニル]プロパン[第一工業製薬(株)製、SR-130、臭素含有量=66重量%]
(C2)臭素化(スチレン-ブタジエン共重合体)[ケムチュラ社製、EMERALD INNOVATION 3000、臭素含有量=65重量%]
(熱安定剤)
(D1)テトラキス(2,2,6,6-テトラメチルピペリジルオキシカルボニル)ブタン[(株)ADEKA製 LA-57]
(D2)ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト[(株)ADEKA製 PEP-36]
(D3)3,9-ビス(2,4-ジ-tert-ブチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ[5.5]ウンデカン[ADDIVANT社製 Ultranox626]
(D4)ペンタエリトリトールテトラキス[3-(3’,5’-ジ-tert-ブチル-4’-ヒドロキシフェニル)プロピオネート][ADDIVANT社製 ANOX20] (D5)クレゾールノボラック型エポキシ樹脂[ハンツマンジャパン(株)製、ECN-1280,エポキシ当量212~233g/eq.]。
(Brominated flame retardant)
(C1) 2,2-bis[4-(2,3-dibromo-2-methylpropoxy)-3,5-dibromophenyl]propane [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., SR-130, bromine content = 66% by weight]
(C2) Bromination (Styrene-butadiene copolymer) [EMERALD INNOVATION 3000 manufactured by Chemtura, bromine content = 65% by weight]
(Heat stabilizer)
(D1) Tetrakis(2,2,6,6-tetramethylpiperidyloxycarbonyl)butane [LA-57 manufactured by ADEKA Corporation]
(D2) Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite [PEP-36 manufactured by ADEKA Corporation]
(D3) 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane [Ultranox626 manufactured by ADDIVANT]
(D4) Pentaerythritol tetrakis [3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate] [ANOX20 manufactured by ADDIVANT] (D5) Cresol novolac type epoxy resin [Huntsman Japan Co., Ltd. manufactured by ECN-1280, epoxy equivalent 212-233 g/eq. ].
(臭素系難燃剤と安定剤の混合物)
(E1)臭素系難燃剤(C1)、安定剤(D1)及び(D2)を、ミキサーで混合し、臭素系難燃剤と安定剤の混合物(E1)を得た。但し、各材料の重量比率は、(C1):(D1):(D2)=100:2.1:3.2、(C1)+(D1)+(D2)=100重量%とした。
(mixture of brominated flame retardant and stabilizer)
(E1) Brominated flame retardant (C1), stabilizers (D1) and (D2) were mixed in a mixer to obtain a mixture (E1) of brominated flame retardant and stabilizer. However, the weight ratio of each material was (C1):(D1):(D2)=100:2.1:3.2 and (C1)+(D1)+(D2)=100% by weight.
(E2)臭素系難燃剤(C2)、安定剤(D3)、(D4)及び(D5)を、ミキサーで混合し、臭素系難燃剤と安定剤の混合物(E2)を得た。但し、各材料の重量比率は、(C2):(D3):(D4):(D5)=100:0.5:10:5、(C2)+(D3)+(D4)+(D5)=100重量%とした。 (E2) Brominated flame retardant (C2), stabilizers (D3), (D4) and (D5) were mixed in a mixer to obtain a mixture (E2) of brominated flame retardant and stabilizer. However, the weight ratio of each material is (C2): (D3): (D4): (D5) = 100: 0.5: 10: 5, (C2) + (D3) + (D4) + (D5) = 100% by weight.
(ラジカル発生剤)
(F)ポリ-1,4-ジイソプロピルベンゼン[UNITED INITIATORS製、CCPIB]
(発泡剤)
(G1)ノルマルペンタン[エスケイ産業(株)製]
(G2)イソペンタン[エスケイ産業(株)製]
(G3)イソブタン[三井化学(株)製] 以下に実施例比較例で用いた二軸押出機及び予備発泡機及び成形機を示す。
(radical generator)
(F) Poly-1,4-diisopropylbenzene [manufactured by UNITED INITIATORS, CCPIB]
(foaming agent)
(G1) normal pentane [manufactured by SK Sangyo Co., Ltd.]
(G2) Isopentane [manufactured by SK Sangyo Co., Ltd.]
(G3) Isobutane [manufactured by Mitsui Chemicals, Inc.] The twin-screw extruder, pre-foaming machine and molding machine used in Examples and Comparative Examples are shown below.
(1)二軸押出機:同方向噛み合い二軸押出機(テクノベル(株)製、シリンダ内径D=40mm、L/D=32、モーター容量55kW,モーター効率;0.95)
(2)スクリュデザイン;少なくとも発泡剤圧入前に順送りニーディングエレメントと逆送りニーディングエレメントをそれぞれ1つ以上セッティングした。また、比エネルギーを調整するため、発泡剤圧入前のニーディングディスクエレメントの数の少ない順にスクリュデザイン#3、スクリュデザイン#1、スクリュデザイン#2を設計し、の合計3つのスクリュデザインを評価した。
(1) Twin-screw extruder: co-meshing twin-screw extruder (manufactured by Technobel Co., Ltd., cylinder inner diameter D = 40 mm, L/D = 32, motor capacity 55 kW, motor efficiency: 0.95)
(2) Screw design: At least one forward kneading element and one or more reverse kneading element were set before the blowing agent was injected. In addition, in order to adjust the specific energy, screw design #3, screw design #1, and screw design #2 were designed in descending order of the number of kneading disc elements before injecting the blowing agent, and a total of three screw designs were evaluated. .
(3)予備発泡機;大開工業株式会社製、BHP-300
(4)成形機;ダイセン工業(株)製、KR-57
(5)成形金型;型内成形用金型(長さ450mm×幅310mm×厚み25mm)。
(3) Pre-foaming machine; BHP-300 manufactured by Daikai Kogyo Co., Ltd.
(4) Molding machine; KR-57 manufactured by Daisen Kogyo Co., Ltd.
(5) Molding mold: mold for in-mold molding (length 450 mm×width 310 mm×thickness 25 mm).
(実施例1)
[発泡性スチレン系樹脂粒子の作製]
スチレン系樹脂(A)、炭素(B)、臭素系難燃剤と安定剤の混合物(E1)をそれぞれフィーダーにて二軸押出機に供給し、二軸押出機の原料フィード部以降のシリンダ設定温度を160℃とし、スクリュデザイン#1の構成にて、スクリュ回転数129rpmで溶融混練した。尚、(A):(B):(E1)=93.5:4.0:2.5の重量比率でトータル供給量を50kg/hrとした。
(Example 1)
[Production of expandable styrene resin particles]
Styrene-based resin (A), carbon (B), a mixture of brominated flame retardant and stabilizer (E1) are each supplied to the twin-screw extruder with a feeder, and the cylinder set temperature after the raw material feed section of the twin-screw extruder was set to 160° C., and melt-kneading was performed at a screw rotation speed of 129 rpm in the configuration of screw design #1. The weight ratio of (A):(B):(E1)=93.5:4.0:2.5 was used, and the total supply amount was 50 kg/hr.
二軸押出機の途中から、前記樹脂組成物100重量部に対して、混合ペンタン[ノルマルペンタン(G1)80重量%とイソペンタン(G2)20重量%の混合物]を4.3重量部、イソブタン(G3)を2.2重量部の割合で圧入した。その後、二軸押出機先端に接続した170℃設定のギアポンプ、ダイバータバルブを経て、ダイバータバルブの下流に取り付けられた直径0.65mm、ランド長3.0mmの小孔を36個有する250℃に設定したダイスから、吐出量53.25kg/hrで、温度65℃及び1.3MPaの加圧循環水中に押出した。押出された溶融樹脂は、ダイスに接触する10枚の刃を有する回転カッターを用いて、1800rpmの条件にて切断・小粒化され、遠心脱水機に移送されて、発泡性スチレン系樹脂粒子を得た。押出機先端での樹脂温度は176℃であり、比エネルギーは0.140kWh/kgであった。 From the middle of the twin-screw extruder, 4.3 parts by weight of mixed pentane [mixture of 80% by weight of normal pentane (G1) and 20% by weight of isopentane (G2)] with respect to 100 parts by weight of the resin composition, isobutane ( G3) was press-fitted at a rate of 2.2 parts by weight. After that, through a gear pump set to 170°C and a diverter valve connected to the tip of the twin-screw extruder, the temperature was set to 250°C with 36 small holes with a diameter of 0.65 mm and a land length of 3.0 mm attached downstream of the diverter valve. It was extruded from the die with a discharge rate of 53.25 kg/hr into pressurized circulating water at a temperature of 65° C. and 1.3 MPa. The extruded molten resin is cut and pulverized at 1800 rpm using a rotary cutter having ten blades in contact with the die, and transferred to a centrifugal dehydrator to obtain expandable styrene resin particles. rice field. The resin temperature at the tip of the extruder was 176° C. and the specific energy was 0.140 kWh/kg.
得られた発泡性スチレン系樹脂粒子100重量部に対して、ステアリン酸亜鉛0.08重量部をドライブレンドした後、15℃で保管した。 0.08 parts by weight of zinc stearate was dry-blended with 100 parts by weight of the expandable styrene-based resin particles obtained, and then stored at 15°C.
[予備発泡粒子の作製] 発泡性スチレン系樹脂粒子を予備発泡機に投入し、0.1MPaの水蒸気を予備発泡機に導入して発泡させ、発泡倍率において発泡倍率80倍の予備発泡粒子を得た。 [Preparation of Pre-Expanded Particles] Expandable styrene resin particles were put into a pre-expanding machine, and 0.1 MPa of steam was introduced into the pre-expanding machine to expand them to obtain pre-expanded particles having an expansion ratio of 80 times. rice field.
[スチレン系樹脂発泡成形体の作製]
得られた発泡倍率80倍の予備発泡粒子を、発泡スチロール用成形機に取り付けた型内成形用金型内に充填して、0.06MPaの水蒸気を導入して型内発泡させた後、金型に水を3秒間噴霧して冷却した。スチレン系樹脂発泡成形体が金型を押す圧力が0.015MPa(ゲージ圧力)なるまでスチレン系樹脂発泡成形体を金型内に保持した後に、スチレン系樹脂発泡成形体取り出して、直方体状のスチレン系樹脂発泡成形体を得た。発泡倍率は80倍であった。
[Preparation of styrene-based resin foam molded product]
The obtained pre-expanded particles with an expansion ratio of 80 times are filled in a mold for in-mold molding attached to a styrene foam molding machine, and after introducing steam of 0.06 MPa to expand in the mold, was cooled by spraying with water for 3 seconds. After holding the styrene resin foam molding in the mold until the pressure of the styrene resin foam molding against the mold reaches 0.015 MPa (gauge pressure), the styrene resin foam molding is taken out, and a rectangular parallelepiped styrene A system resin foam molded product was obtained. The expansion ratio was 80 times.
実施例1で得られた発泡性スチレン系樹脂粒子、及び、スチレン系樹脂発泡成形体について、上述の各種測定方法に従って測定・評価した。その測定結果及び評価結果を表1に示す。 The expandable styrene resin particles obtained in Example 1 and the foamed styrene resin article were measured and evaluated according to the various measurement methods described above. Table 1 shows the measurement results and evaluation results.
(実施例2)
[発泡性スチレン系樹脂粒子の作製]において、スクリュ回転数を162rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 2)
A styrene-based resin foam molded article was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw rotation speed was changed to 162 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例3)
[発泡性スチレン系樹脂粒子の作製]において、スクリュ回転数を195rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 3)
A styrene-based resin foam molded article was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw rotation speed was changed to 195 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例4)
[発泡性スチレン系樹脂粒子の作製]において、スクリュ回転数を229rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 4)
A styrene-based resin foam molded article was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw rotation speed was changed to 229 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例5)
[発泡性スチレン系樹脂粒子の作製]において、スクリュ回転数を292rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 5)
A styrene-based resin expansion molding was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw rotation speed was changed to 292 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例6)
[発泡性スチレン系樹脂粒子の作製]において、スクリュデザインを#2に変更し、スクリュ回転数を292rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 6)
A styrenic resin foam molded product was produced in the same manner as in Example 1, except that in [Preparation of expandable styrene resin particles], the screw design was changed to #2 and the screw rotation speed was changed to 292 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例7)
[発泡性スチレン系樹脂粒子の作製]において、スクリュデザインを#2に変更し、スクリュ回転数を420rpmに変更した以外は実施例1と同様の条件で、発泡性スチレン系樹脂粒子を作製した。ただし、ダイスにおけるカッティング不良が頻発し、スチレン系樹脂発泡成形体を作製可能なサンプル量を採取できなかった。得られた発泡性スチレン系樹脂粒子の測定結果及び評価結果を表1に示す。
(Example 7)
Expandable styrene-based resin particles were prepared under the same conditions as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw design was changed to #2 and the screw rotation speed was changed to 420 rpm. However, due to frequent occurrence of cutting defects in the die, it was not possible to obtain an amount of samples that could produce a styrene-based resin foam molded article. Table 1 shows the measurement results and evaluation results of the obtained expandable styrene resin particles.
(実施例8)
[発泡性スチレン系樹脂粒子の作製]において、スクリュデザインを#3に変更し、スクリュ回転数を195rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 8)
A styrene-based resin foam molded product was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw design was changed to #3 and the screw rotation speed was changed to 195 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例9)
[発泡性スチレン系樹脂粒子の作製]において、スクリュデザインを#3に変更し、スクリュ回転数を292rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 9)
A styrene-based resin foam molded product was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw design was changed to #3 and the screw rotation speed was changed to 292 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(実施例10)
[発泡性スチレン系樹脂粒子の作製]において、スチレン系樹脂(A)、炭素(B)、臭素系難燃剤と安定剤の混合物(E2)、ラジカル発生剤(F)をそれぞれフィーダーにて二軸押出機に供給し、二軸押出機の原料フィード部以降のシリンダ設定温度を160℃とし、スクリュデザイン#1の構成にて、スクリュ回転数195rpmで溶融混練した。尚、(A):(B):(E2):(F)=93.05:4.0:2.75:0.2の重量比率でトータル供給量を50kg/hrとした。以降の操作は、実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。
(Example 10)
In [Production of expandable styrene resin particles], a styrene resin (A), carbon (B), a mixture of a brominated flame retardant and a stabilizer (E2), and a radical generator (F) are fed in a biaxial feeder. The mixture was supplied to an extruder, and melted and kneaded at a screw rotation speed of 195 rpm with a screw design #1 configuration and a set cylinder temperature of 160° C. after the raw material feed section of the twin-screw extruder. The weight ratio of (A):(B):(E2):(F)=93.05:4.0:2.75:0.2 and the total supply amount was 50 kg/hr. Subsequent operations were performed in the same manner as in Example 1 to produce a styrene-based resin foam molded article. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
(比較例1) [発泡性スチレン系樹脂粒子の作製]において、スクリュ回転数を97rpmに変更した以外は実施例1と同様の処理によりスチレン系樹脂発泡成形体を作製した。実施例1と同様に評価し、その測定結果及び評価結果を表1に示す。 (Comparative Example 1) A styrene-based resin foam molded article was prepared in the same manner as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw rotation speed was changed to 97 rpm. Evaluation was performed in the same manner as in Example 1, and the measurement results and evaluation results are shown in Table 1.
実施例の結果より、比エネルギーの制御によって、炭素の分散性を向上することができ、高い発泡倍率、及び、低い熱伝導率、即ち、高い断熱性能を有するスチレン系樹脂発泡成形体を与えうるスチレン系樹脂組成物、および、発泡性スチレン系樹脂粒子の製造方法が提供できることが判る。 From the results of Examples, it is possible to improve the dispersibility of carbon by controlling the specific energy, and it is possible to provide a styrene-based resin foam molded product having a high expansion ratio and a low thermal conductivity, that is, a high heat insulating performance. It can be seen that a styrenic resin composition and a method for producing expandable styrenic resin particles can be provided.
(参考例7)
[発泡性スチレン系樹脂粒子の作製]において、スクリュデザインを#2に変更し、スクリュ回転数を420rpmに変更した以外は実施例1と同様の条件で、発泡性スチレン系樹脂粒子を作製した。ただし、ダイスにおけるカッティング不良が頻発し、スチレン系樹脂発泡成形体を作製可能なサンプル量を採取できなかった。得られた発泡性スチレン系樹脂粒子の測定結果及び評価結果を表1に示す。
( Reference example 7)
Expandable styrene-based resin particles were prepared under the same conditions as in Example 1, except that in [Preparation of expandable styrene-based resin particles], the screw design was changed to #2 and the screw rotation speed was changed to 420 rpm. However, due to frequent occurrence of cutting defects in the die, it was not possible to obtain an amount of samples that could produce a styrene-based resin foam molded article. Table 1 shows the measurement results and evaluation results of the obtained expandable styrene resin particles.
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