CN115210340A - 发泡苯乙烯树脂用阻燃剂组合物、阻燃性发泡苯乙烯系树脂组合物及其挤出发泡成形体 - Google Patents
发泡苯乙烯树脂用阻燃剂组合物、阻燃性发泡苯乙烯系树脂组合物及其挤出发泡成形体 Download PDFInfo
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- CN115210340A CN115210340A CN202180018551.9A CN202180018551A CN115210340A CN 115210340 A CN115210340 A CN 115210340A CN 202180018551 A CN202180018551 A CN 202180018551A CN 115210340 A CN115210340 A CN 115210340A
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- styrene resin
- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 120
- 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 title claims abstract description 114
- 229920005989 resin Polymers 0.000 title claims abstract description 82
- 239000011347 resin Substances 0.000 title claims abstract description 82
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 239000006260 foam Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- -1 phosphate ester compound Chemical class 0.000 claims abstract description 61
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 20
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 13
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- 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 claims description 7
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- 239000004615 ingredient Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
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- 239000004604 Blowing Agent Substances 0.000 description 9
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- 239000002667 nucleating agent Substances 0.000 description 6
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- 239000011701 zinc Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
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- 239000002699 waste material Substances 0.000 description 4
- 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 3
- QTHRIIFWIHUMFH-UHFFFAOYSA-N 3-chloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCl QTHRIIFWIHUMFH-UHFFFAOYSA-N 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 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 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- FKFQIJICWPMWAX-UHFFFAOYSA-N phenyl bis(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC1=CC=CC=C1 FKFQIJICWPMWAX-UHFFFAOYSA-N 0.000 description 1
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- 229920001195 polyisoprene Polymers 0.000 description 1
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- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
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- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
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- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
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- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- IVJLIUKQYNWCEZ-UHFFFAOYSA-N tris(2-bromophenyl) phosphate Chemical compound BrC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)Br)OC1=CC=CC=C1Br IVJLIUKQYNWCEZ-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- IJOFZIRWMBOMHP-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphite Chemical compound CC(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C IJOFZIRWMBOMHP-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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Abstract
本发明提供一种能够制造具有优异的阻燃性及耐热性的挤出发泡成形体的发泡苯乙烯树脂用阻燃剂组合物、苯乙烯系树脂组合物及该苯乙烯系树脂组合物的挤出发泡成形体。本发明的发泡苯乙烯树脂用阻燃剂组合物至少包含(B1)四溴双酚A‑双(2,3‑二溴‑2‑甲基丙基醚)、(C)锌改性水滑石及(D)磷酸酯系化合物,相对于所述成分(B1)及所述成分(D)的总量,包含10质量%~98质量%的所述成分(B1)。
Description
技术领域
本发明涉及一种发泡苯乙烯树脂用阻燃剂组合物、阻燃性发泡苯乙烯系树脂组合物及其挤出发泡成形体。
背景技术
苯乙烯系树脂发泡体由于质量轻,因此例如除了家电制品及建材等的隔热用途、筑堤施工方法等土木用途以外,在多种领域中也被广泛应用。苯乙烯系树脂仅由碳和氢形成,因此具有一旦着火则会产生黑烟而剧烈燃烧的性质。因此,需要根据苯乙烯系树脂发泡体的用途而利用阻燃剂使树脂阻燃化。
以往,已知在基于挤出法的苯乙烯系树脂发泡体的阻燃化中,使用六溴环十二烷(HBCD)作为阻燃剂,以较少的使用量获得所期望的阻燃效果。另一方面,HBCD的热稳定性低,若将包含其的树脂组合物加热至熔融温度以上,则通过HBCD的分解而生成的HBr会使树脂着色而使质量劣化,另外,也可引起促进制造装置等的腐蚀这样的问题。此外,发泡体的废料及制造发泡体时产生的废料理想的是作为新的发泡体的制造用原料再利用,在废料中包含HBCD这样的热稳定性低的阻燃剂的情况下,在将废料熔融时,发生着色,或者促进解聚。因此,含有HBCD的发泡体存在难以再利用这样的问题。
从该观点考虑,最近正研究代替HBCD而将其他溴系阻燃剂用于挤出发泡苯乙烯系树脂发泡体。作为该溴系阻燃剂,提出了四溴双酚A-双(2,3-二溴-2-甲基丙基醚)。该阻燃剂具有与HBCD匹敌的阻燃效果,但为了进一步提高热稳定性,也提出了并用其他阻燃剂,例如并用四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯等。基于此,在维持优异的阻燃效果的同时,也抑制阻燃剂的分解,不易引起树脂的劣化(例如,参照专利文献1~专利文献3等)。
现有技术文献
专利文献
专利文献1:日本专利特开2010-275528号公报
专利文献2:日本专利特开2012-107227号公报
专利文献3:日本专利特开2012-136674号公报
发明内容
发明欲解决的技术问题
然而,在近年来的使用苯乙烯系发泡成形体的各种用途中,需要进一步提高所述发泡体的阻燃性及耐热性。从这样的观点考虑,开发用于进一步提高发泡体的阻燃性及耐热性的阻燃剂、或者开发用于制造苯乙烯系树脂发泡体的树脂组合物成为当务之急。
本发明是鉴于上述情况而完成,其目的在于提供一种可用于制造具有优异的阻燃性及耐热性的发泡成形体的发泡苯乙烯树脂用阻燃剂组合物、阻燃性发泡苯乙烯系树脂组合物及其挤出发泡成形体。
用在解决问题的技术手段
本发明人等为了达成上述目的而反覆进行了深入研究,结果发现通过至少组合特定的阻燃剂以及磷酸酯系化合物从而能够达成上述目的,至此完成了本发明。
即,本发明例如包含以下项中记载的主题。
项1
一种发泡苯乙烯树脂用阻燃剂组合物,至少包含下述的成分(B1)、成分(C)及成分(D),
(B1)四溴双酚A-双(2,3-二溴-2-甲基丙基醚)、
(C)锌改性水滑石、及
(D)磷酸酯系化合物,
相对于所述成分(B1)及所述成分(D)的总量,含有10质量%~98质量%的所述成分(B1)。
项2
如项1所述的发泡苯乙烯树脂用阻燃剂组合物,其中,所述成分(D)为选自由脂肪族磷酸酯、芳香族磷酸酯及芳香族亚磷酸酯所组成的组中的至少一种。
项3
如项1或项2所述的发泡苯乙烯树脂用阻燃剂组合物,其中,除了所述成分(B1)以外,也含有成分(B2)作为阻燃剂,所述成分(B2)包含选自由四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯、三(三溴苯氧基)三嗪及溴化环氧低聚物所组成的组中的至少一种。
项4
如项1至项3中任一项所述的发泡苯乙烯树脂用阻燃剂组合物,其中,相对于所述成分(B1)及所述成分(C)的总量,所述成分(B1)的含有比例为80质量%~99质量%。
项5
一种阻燃性发泡苯乙烯系树脂组合物,包含:如项1至项4中任一项所述的发泡苯乙烯树脂用阻燃剂组合物、以及成分(A)苯乙烯系树脂。
项6
如项5所述的阻燃性发泡苯乙烯系树脂组合物,其中,相对于100质量份所述成分(A),包含0.05质量份以上且10质量份以下的所述成分(D)。
项7
一种挤出发泡成形体,为如项5或项6所述的阻燃性发泡苯乙烯系树脂组合物的挤出发泡成形体。
项101
一种阻燃性发泡苯乙烯系树脂组合物,至少包含下述的成分(A)~成分(D),
(A)苯乙烯系树脂、
(B1)四溴双酚A-双(2,3-二溴-2-甲基丙基醚)、
(C)锌改性水滑石、及
(D)磷酸酯系化合物,
相对于所述成分(B1)及所述成分(D)的总量,包含10质量%~98质量%的所述成分(B1)。
项102
如项101所述的阻燃性发泡苯乙烯系树脂组合物,其中,所述成分(D)为选自由脂肪族磷酸酯、芳香族磷酸酯及芳香族亚磷酸酯所组成的组中的至少一种。
项103
如项101或项102所述的阻燃性发泡苯乙烯系树脂组合物,其中,作为阻燃剂,除了所述成分(B1)以外,也含有成分(B2),所述成分(B2)包含选自由四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯、三(三溴苯氧基)三嗪及溴化环氧低聚物所组成的组中的至少一种。
项104
如项101至项103中任一项所述的阻燃性发泡苯乙烯系树脂组合物,其中,相对于100质量份所述成分(A),包含0.05质量份以上且10质量份以下的所述成分(D)。
项105
如项101至项104中任一项所述的阻燃性发泡苯乙烯系树脂组合物,其中,相对于所述成分(B1)及所述成分(C)的总量,所述成分(B1)的含有比例为80质量%~99质量%。
项106
一种挤出发泡成形体,其中,是项101至项105中任一项所述的阻燃性发泡苯乙烯系树脂组合物的挤出发泡成形体。
发明效果
通过使用本发明的发泡苯乙烯树脂用阻燃剂组合物,从而能够制造具有优异的阻燃性及耐热性的挤出发泡成形体。另外,使用包含该发泡苯乙烯树脂用阻燃剂组合物的阻燃性发泡苯乙烯系树脂组合物获得的挤出发泡成形体具有优异的阻燃性及耐热性。
具体实施方式
以下,对本发明的实施方式进行详细说明。再者,在本说明书中,关于“含有”及“包含”的表达,包括“含有”、“包含”、“实质上包含”及“仅包含”这样的概念。
1.发泡苯乙烯树脂用阻燃剂组合物
本发明的发泡苯乙烯树脂用阻燃剂组合物至少包含下述的成分(B1)、成分(C)及成分(D)。
(B1)四溴双酚A-双(2,3-二溴-2-甲基丙基醚);
(C)锌改性水滑石;及
(D)磷酸酯系化合物
特别是在本发明的发泡苯乙烯树脂用阻燃剂组合物中,相对于所述成分(B1)及所述成分(D)的总量,含有10~98质量%的所述成分(B1)。
通过在苯乙烯树脂中含有本发明的发泡苯乙烯树脂用阻燃剂组合物作为阻燃剂,从而能够制造具有优异的阻燃性及耐热性的挤出发泡成形体。
以下,将本发明的发泡苯乙烯树脂用阻燃剂组合物仅简称为“阻燃剂组合物”,将包含本发明的发泡苯乙烯树脂用阻燃剂组合物的阻燃性发泡苯乙烯系树脂组合物仅简称为“苯乙烯系树脂组合物”,进而,将使用该苯乙烯系树脂组合物而获得的所述挤出发泡成形体仅简称为“发泡成形体”。
<成分(B1)>
阻燃剂组合物中所含的成分(B1)为四溴双酚A-双(2,3-二溴-2-甲基丙基醚),且为起到作为阻燃剂的作用的成分。即,成分(B1)为溴系阻燃剂。
成分(B1)可以通过公知的方法制造而得,或者也可以从市售品等获取成分(B1)。
<其他阻燃剂>
阻燃剂组合物只要不阻碍本发明的效果,也可包含成分(B1)以外的阻燃剂,在该情况下,有时也会提高阻燃性及耐热性。作为成分(B1)以外的阻燃剂,可以列举成分(B1)以外的溴系阻燃剂。以下,将该溴系阻燃剂简称为“成分(B2)”。
作为成分(B2),例如可以列举:四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯、三(三溴苯氧基)三嗪、四溴双酚S-双(2,3-二溴丙基醚)、四溴双酚F-双(2,3-二溴丙基醚)、四溴双酚A、六溴苯、五溴甲苯、聚溴二苯基醚、聚溴二苯基乙烷、双聚溴苯氧基乙烷、三(三溴苯氧基)三嗪、聚溴苯基茚满、聚五溴苄基丙烯酸酯、亚乙基双四溴邻苯二甲酰亚胺、三(三溴新戊基)磷酸酯、溴化环氧低聚物等。成分(B2)可为单独使用一种,也可以使用两种以上。
从阻燃剂组合物的发泡成形体的阻燃性及耐热性容易提高的方面考虑,成分(B2)优选包含选自由四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯、三(三溴苯氧基)三嗪及溴化环氧低聚物所组成的组中的至少一种。
在阻燃剂组合物包含成分(B1)以及成分(B2)这两者的情况下,两者的含有比例并无特别限定。例如,相对于成分(B1)及成分(B2)的总质量,成分(B1)的含有比例可以设为20质量%~100质量%。相对于成分(B1)及成分(B2)的总质量,成分(B1)的含有比例优选为25质量%以上,更优选为30质量%以上,进一步优选为35质量%以上,特别优选为40质量%以上。另外,相对于成分(B1)及成分(B2)的总质量,成分(B1)的含有比例优选为95质量%以下,更优选为90质量%以下,进一步优选为80质量%以下。
阻燃剂组合物可以包含成分(B1)及成分(B2)以外的阻燃剂,例如可以广泛列举公知的阻燃剂。在阻燃剂组合物包含成分(B1)及成分(B2)以外的阻燃剂的情况下,其含有比例也并无特别限定,可以在不妨碍本发明的效果的范围内适当调节。从成本不易增加的观点考虑,相对于成分(B1)及成分(B2)的总质量,该阻燃剂的含有比例可以设为10质量%以下,优选为5质量%以下,更优选为1质量%以下。阻燃剂组合物中所含的阻燃剂可以仅为成分(B1)及成分(B2)。
<成分(C)>
阻燃剂组合物中所含的成分(C)是锌改性水滑石。通过使阻燃剂组合物包含成分(C),从而能够进一步提高成分(B1)等阻燃剂的效果,能够进一步提高苯乙烯系树脂组合物的发泡成形体的阻燃性及耐热性。例如,成分(C)具有促进成分(B1)等阻燃剂分解的作用。
锌改性水滑石例如可以列举利用Zn置换水滑石Mg6Al2(OH)16(CO3)·4H2O的一部分Mg而得的层状双氢氧化物。一般而言,锌改性水滑石可以由下述通式(1)表示。
[MgaZnbAlx(OH)2]x+(An-)x/n·mH2O
在式(1)中,0.5≦a+b<1.0,0<x≦0.5,a+b=1-x,m为正数。另外,A为n价阴离子(n=1~4,优选为1或2),优选的是An-为碳酸根离子(CO3 2-)。
如式(1)所表示的那样,锌改性水滑石通过金属双氢氧化物的作为基本层的正电荷、及作为中间层的阴离子的负电荷,而使化合物整体呈电中性。
锌改性水滑石可以通过公知的制造方法获得,或者也能够从市售品获取。作为市售品,可列举:由协和化学工业公司提供的“ZHT-4A”(Mg3ZnAl2(OH)12CO3·mH2O)、由堺化学工业公司提供的“STABIACE HT-7”(Mg3.5Zn0.5Al2(OH)12CO3·mH2O)等。再者,Mg及Zn相对于Al的原子比与这些市售品不同的锌改性水滑石可以通过被称为共沈淀法的公知方法由Mg、Zn及Al的水溶性盐合成。
锌改性水滑石可以单独使用一种,也可以使用两种以上。
锌改性水滑石可以利用表面处理剂处理。在该情况下,锌改性水滑石容易均匀地分散在苯乙烯系树脂中,而容易发挥锌改性水滑石的作用。表面处理剂的种类并无特别限定,例如可以列举:硬脂酸、油酸、月桂酸等高级脂肪酸;硬脂酸钠、油酸钠等高级脂肪酸金属盐;月桂基苯磺酸钠等阴离子表面活性剂;乙烯基三乙氧基硅烷、γ-甲基丙烯酰基丙基三乙氧基硅烷等硅烷偶联剂;异丙基三异硬脂酰基钛酸酯、异丙基十三烷基苯磺酰基钛酸酯等钛酸酯偶联剂;甘油单硬脂酸酯、甘油单油酸酯等甘油脂肪酸酯;硬脂酸酰胺等高级脂肪酸酰胺;蜡类等。
在阻燃剂组合物中,成分(C)及成分(B1)的含有比例并无特别限定,例如,相对于成分(B1)及成分(C)的总量,可以将成分(B1)的含有比例设为80质量%~99质量%。在该情况下,成分(B1)的阻燃剂的效果容易提高。相对于成分(B1)及成分(C)的总量,成分(B1)的含有比例优选为82质量%以上,更优选为84质量%以上,进一步优选为86质量%以上。另外,相对于成分(B1)及成分(C)的总量,成分(B1)的含有比例优选为98质量%以下,更优选为97质量%以下,进一步优选为96质量%以下。
<成分(D)>
阻燃剂组合物中所含的成分(D)为磷酸酯系化合物。通过使阻燃剂组合物包含成分(D),从而能够进一步提高成分(B1)等阻燃剂的效果,能够进一步提高苯乙烯系树脂组合物的发泡成形体的阻燃性及耐热性。
再者,磷酸酯系化合物包括磷酸酯及亚磷酸酯。
磷酸酯系化合物的种类并无特别限定,例如可以广泛列举公知的磷酸酯系化合物。其中,从苯乙烯系树脂组合物的发泡成形体的阻燃性及耐热性容易提高的方面考虑,磷酸酯系化合物优选为选自由脂肪族磷酸酯、芳香族磷酸酯及芳香族亚磷酸酯所组成的组中的至少一种,进一步优选为选自由脂肪族磷酸酯及芳香族磷酸酯所组成的组中的至少一种。
作为脂肪族磷酸酯,可以含有卤素,也可以不含卤素。作为不含卤素的脂肪族磷酸酯,可以列举:三甲基磷酸酯、三乙基磷酸酯、三丁基磷酸酯、三(2-乙基己基磷酸酯)、三(2-乙基己基磷酸酯)、三丁氧基乙基磷酸酯、单异癸基磷酸酯等三烷基磷酸酯,此外,也可以列举2-丙烯酰氧基乙酸磷酸酯、2-甲基丙烯酰氧基乙酸磷酸酯等。作为含有卤素的脂肪族磷酸酯,可以列举:三(三溴新戊基)磷酸酯、三(氯乙基)磷酸酯、三(氯丙基磷酸酯)、三(二氯丙基磷酸酯)、四(2-氯乙基)亚乙基二磷酸酯、四(2-氯乙基)二氯异戊基二磷酸酯、双(三溴新戊基)二氯丙基磷酸酯、单溴新戊基二(氯丙基)磷酸酯、二(单溴新戊基)氯丙基磷酸酯、单溴新戊基二(氯乙基)磷酸酯、二(单溴新戊基)氯乙基磷酸酯等。其中,脂肪族磷酸酯优选为含有卤素的脂肪族磷酸酯,特别优选为三(三溴新戊基)磷酸酯。
作为芳香族磷酸酯,可以含有卤素,也可以不含卤素。作为不含卤素的芳香族磷酸酯,可以列举:三苯基磷酸酯、三甲苯基磷酸酯、三-二甲苯基磷酸酯、三(异丙基苯基)磷酸酯、三(苯基苯基)磷酸酯、三萘基磷酸酯、甲苯基二苯基磷酸酯、二甲苯基二苯基磷酸酯、二苯基(2-乙基己基)磷酸酯、甲苯基二-2,6-二甲苯基磷酸酯、二苯基(2-丙烯酰氧基乙基)磷酸酯、二苯基(2-甲基丙烯酰氧基乙基)磷酸酯、间苯二酚双(二苯基磷酸酯)、间苯二酚双(二-二甲苯基磷酸酯)、间苯二酚双(二甲苯基磷酸酯)、双酚A双(二苯基磷酸酯)、双酚A双(二-二甲苯基磷酸酯)、双酚A双(二甲苯基磷酸酯)、叔丁基化苯基磷酸酯。作为含卤素的芳香族磷酸酯,可以列举:三(溴苯基)磷酸酯、双(三溴新戊基)苯基磷酸酯、双(三溴新戊基)甲苯基磷酸酯等。其中,芳香族磷酸酯优选为三苯基磷酸酯及/或三甲苯基磷酸酯。
在本发明中,在(D)成分为芳香族亚磷酸酯的情况下,该芳香族亚磷酸酯可以列举由下述式(2)表示的化合物。
[化1]
式(2)中,R1-5是指在芳香环的5个碳原子上分别键合有R1、R2、R3、R4及R5。式(2)中,R6-10是指在芳香环的5个碳原子上分别键合有R6、R7、R8、R9及R10。式(2)中,R11-15是指在芳香环的5个碳原子上分别键合有R11、R12、R13、R14及R15。R1~R15相同或不同,是指碳数3以下的烷基或氢原子。
该芳香族亚磷酸酯也可以不含卤素。作为不含卤素的芳香族亚磷酸酯,可以列举三苯基亚磷酸酯、三甲苯基亚磷酸酯、三-二甲苯基亚磷酸酯、三(异丙基苯基)亚磷酸酯、二苯基甲苯基亚磷酸酯、二苯基二甲苯基亚磷酸酯等。其中,芳香族亚磷酸酯优选为三苯基亚磷酸酯及/或三甲苯基亚磷酸酯。
成分(D)的磷酸酯系化合物可以利用公知的制造方法获得、或者也能够从市售品获取。
磷酸酯系化合物可以单独使用一种,也可以使用两种以上。
在阻燃剂组合物中,成分(D)及成分(B1)的含有比例并无特别限定,例如,相对于成分(B1)及成分(D)的总量,可以将成分(B1)的含有比例设为10质量%~98质量%。在该情况下,成分(B1)的阻燃剂的效果容易提高。相对于成分(B1)及成分(D)的总量,成分(B1)的含有比例优选为20质量%以上,更优选为25质量%以上,进一步优选为30质量%以上,特别优选为40质量%以上。另外,相对于成分(B1)及成分(D)的总量,成分(B1)的含有比例优选为95质量%以下,更优选为80质量%以下,进一步优选为75质量%以下,特别优选为70质量%以下。
阻燃剂组合物可以包含除了脂肪族磷酸酯、芳香族磷酸酯及芳香族亚磷酸酯以外的磷酸酯化合物。在该情况下,相对于磷酸酯化合物的总质量,其含有比例为10质量%以下,优选为5质量%以下,更优选为1质量%以下。
<成分(E)>
除了成分(A)~成分(D)以外,阻燃剂组合物例如也可以包含热稳定剂作为成分(E)。再者,也可以是,阻燃剂组合物不含成分(E),而后述的苯乙烯系树脂组合物包含成分(E)。热稳定剂可以进一步提高发泡成形体的热稳定性。
热稳定剂的种类并无特别限定,例如可以广泛列举可用于发泡成形体的公知的热稳定剂。作为热稳定剂,例如可以列举:亚磷酸酯化合物、硫醚化合物、受阻酚化合物、受阻胺化合物、有机锡化合物、磷酸酯及水滑石等。其中,作为成分(E)的热稳定剂的亚磷酸酯化合物是指,成分(D)所包含的亚磷酸酯化合物以外的化合物。即,作为成分(E)的热稳定剂的亚磷酸酯化合物为由上述式(2)表示的化合物以外的亚磷酸酯化合物。
作为该热稳定剂的亚磷酸酯化合物,例如可以列举:三甲基亚磷酸酯、三乙基亚磷酸酯、三丁基亚磷酸酯、三(2-乙基己基)亚磷酸酯、三硬脂基亚磷酸酯等三烷基亚磷酸酯,此外,也可以列举:2-乙基己基二苯基亚磷酸酯、异癸基二苯基亚磷酸酯等烷基烯丙基亚磷酸酯、三(2,4-二-叔丁基苯基)亚磷酸酯、三壬基苯基亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯、亚磷酸双[2,4-双(1,1-二甲基乙基)-6-甲基苯基]乙酯、四(2,4-二-叔丁基苯基)[1,1-联苯基]-4,4'-二基双亚膦酸酯、双(壬基苯基)季戊四醇二亚磷酸酯、双硬脂基季戊四醇二亚磷酸酯、双(2,6-二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、2,2'-亚甲基双(4,6-二-叔丁基-1-苯基氧基)(2-乙基己氧基)磷、四(十三烷基)-4,4'-亚丁基-双(2-叔丁基-5-甲基苯基)二亚磷酸酯、六-十三烷基-1,1,3-三(3-叔丁基-6-甲基-4-氧基苯基)-3-甲基丙烷三亚磷酸酯、单(二壬基苯基)单-对壬基苯基亚磷酸酯、三(单壬基苯基)亚磷酸酯、四烷基(C=12~16)-4,4'-亚异丙基-(双苯基)二亚磷酸酯等。
作为硫醚化合物,例如可列举:二月桂基-3,3'-硫代二丙酸酯、二肉豆蔻基-3,3'-硫代二丙酸酯、二硬脂基-3,3'-硫代二丙酸酯、季戊四醇四(3-月桂基硫代丙酸酯)、二-十三烷基-3,3'-硫代二丙酸酯、2-巯基苯并咪唑等。
作为受阻酚化合物,例如可以列举:1,6-己二醇-双[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、三乙二醇-双[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯]、甘油三[3-(3,5-二-叔丁基-4-羟基苯基)-丙酸酯]、季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯、硫代二亚乙基双[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、N,N'-己烷-1,6-二基双[3-(3,5-二-叔丁基-4-羟基苯基)丙酰胺]、2,4-二甲基-6-(1-甲基十五烷基)苯酚、二乙基[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸酯、二乙基双[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸钙、3,3',3”,5,5',5”-六-叔丁基-a,a',a”-(均三甲苯-2,4,6-三基)三-对甲酚、4,6-双(辛基硫基甲基)-邻甲酚、亚乙基双(氧基亚乙基)双[3-(5-叔丁基-4-羟基-间甲苯基)丙酸酯]、六亚甲基双[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]、1,3,5-三(3,5-二-叔丁基-4-羟基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、1,3,5-三[(4-叔丁基-3-羟基-2,6-二甲苯基)甲基]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、2,6-二-叔丁基-4-(4,6-双(辛基硫基)-1,3,5-三嗪-2-基氨基)苯酚等。
受阻胺化合物的例子可以列举:4-苯甲酰氧基-2,2,6,6-四甲基哌啶、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)-2-(3,5-二-叔丁基-4-羟基苄基-2-正丁基丙二酸酯、四(2,2,6,6-四甲基-4-哌啶基-1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯等。
有机锡化合物的例子可以列举二月桂酸二辛基锡、马来酸二辛基锡等。
在阻燃剂组合物中,成分(E)的含量并无特别限定,在不妨碍本发明的效果的范围内可以设为适当的量。例如,相对于成分(B1)的总质量,成分(E)的含量为0.1质量%~50质量%,优选为1质量%~30质量%。
<成分(F)>
除了成分(A)~成分(D)以外,阻燃剂组合物例如也可以包含阻燃增强剂作为成分(F)。再者,也可以是,阻燃剂组合物不含成分(F),而后述的苯乙烯系树脂组合物包含成分(F)。阻燃增强剂可进一步提高发泡成形体的热稳定性。
阻燃增强剂的种类并无特别限定,例如可以广泛列举可用于发泡成形体的公知的阻燃增强剂。作为阻燃增强剂,例如可以列举:过氧化异丙苯、氢过氧化异丙苯、二-叔丁基过氧化物、二-叔己基过氧化物、2,5-二甲基-2,5-二(叔丁基过氧化物)-己炔-3、过氧化二异丙苯、2,3-二甲基-2,3-二苯基丁烷等,此外,也可以列举:酞菁铁、酞菁锰、酞菁钴等酞菁金属络合物、沸石等。
在阻燃剂组合物中,成分(F)的含量并无特别限定,在不妨碍本发明的效果的范围内可以设为适当的量。例如,相对于成分(B1)的总质量,成分(F)含量为0.1质量%~15质量%,优选为1质量%~10质量%。
<成分(H)>
除了成分(A)~成分(D)以外,阻燃剂组合物例如也可以包含发泡成核剂作为成分(H)。再者,也可以是,阻燃剂组合物不含成分(H),而后述的苯乙烯系树脂组合物包含成分(H)。发泡成核剂容易形成苯乙烯系树脂组合物的发泡成形体的气泡,气泡直径的调整也容易,因此容易有助于发泡成形体的强度等的调节。
发泡成核剂的种类并无特别限定,例如可以广泛列举可用于发泡成形体的公知的发泡成核剂。作为发泡成核剂,例如可以列举滑石、膨润土、高岭土、云母、二氧化硅、黏土、硅藻土等无机材料。
<其他成分>
阻燃剂组合物除了所述各成分以外,也可以在不损害本发明的效果的范围内,包含其他各种成分。在阻燃剂组合物包含其他成分的情况下,其含有比例并无特别限定,例如,相对于所述(B1)、成分(C)及成分(D)的总质量而为10质量%以下,优选为5质量%以下,更优选为1质量%以下。
阻燃剂组合物的制备方法并无特别限定,例如可以与公知的阻燃剂组合物的制备方法同样。
2.阻燃性发泡苯乙烯系树脂组合物
对于本发明的阻燃性发泡苯乙烯系树脂组合物(苯乙烯系树脂组合物),除了包含所述阻燃剂组合物以外,还包含成分(A)苯乙烯系树脂。即,本发明的发泡苯乙烯树脂用阻燃剂组合物包含成分(A)、成分(B1)、成分(C)及成分(D)。
(A)苯乙烯系树脂
(B1)四溴双酚A-双(2,3-二溴-2-甲基丙基醚)
(C)锌改性水滑石
(D)磷酸酯系化合物
本发明的苯乙烯系树脂组合物能够通过在挤出机内熔融,同时将发泡剂压入熔融物中并挤出成形从而形成发泡体,该发泡体具有优异的阻燃性及耐热性。即,根据本发明的苯乙烯系树脂组合物,能够制造具有优异的阻燃性及耐热性的挤出发泡成形体。
苯乙烯系树脂组合物中所含的成分(A)是苯乙烯系树脂。该苯乙烯系树脂是苯乙烯系树脂组合物的主要成分,即,为发泡成形体中的主要成分。
苯乙烯系树脂的种类并无特别限定,例如可以广泛使用用于发泡成形用的公知的苯乙烯系树脂。
作为苯乙烯系树脂,例如可以列举苯乙烯单体的均聚物、苯乙烯与其他单体的共聚物。作为其他单体,例如可以列举:对甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、对-叔丁基苯乙烯、α-甲基苯乙烯、α-甲基-对甲基苯乙烯、1,1-二苯基乙烯、对-(N,N-二乙基胺基乙基)苯乙烯、对-(N,N-二乙基氨基甲基)苯乙烯等苯乙烯系聚合性单体。其他单体可以为单独一种,也可组合两种以上。
构成苯乙烯系树脂的单体单元可以包含50质量%以上的苯乙烯单体,优选为70质量%以上,更优选为80质量%以上,进一步优选为90质量%以上,特别优选为95质量%以上。苯乙烯系树脂可以为聚苯乙烯的均聚物。
苯乙烯系树脂只要不妨碍本发明的效果,也可以含有其他成分。其他成分例如可以列举橡胶状聚合物。作为橡胶状聚合物,例如可以列举:聚丁二烯、聚异戊二烯、苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯共聚物、丙烯腈-丁二烯共聚物、苯乙烯-异丁烯-丁二烯系共聚物、丁二烯-(甲基)丙烯酸酯共聚物、苯乙烯-丁二烯嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、丁基橡胶、乙烯-α-烯烃系共聚物(乙烯-丙烯橡胶)、乙烯-α-烯烃-聚烯共聚物(乙烯-丙烯-二烯橡胶)、硅酮橡胶、丙烯酸系橡胶、氢化二烯系橡胶(氢化苯乙烯-丁二烯嵌段共聚物、氢化丁二烯系聚合物等)等。
苯乙烯系树脂中所含的橡胶状聚合物可以为一种,也可以为两种以上。在苯乙烯系树脂组合物中包含橡胶状聚合物的情况下,相对于构成苯乙烯系树脂的单体成分,其含有比例优选为30质量%以下,更优选为20质量%以下,进一步优选为10质量%以下。
苯乙烯系树脂的分子量等并无特别限定,可根据目的用途等,在能够发泡成形的范围内调节为适当的分子量,例如,可设为与公知的发泡成形体同样的范围。
苯乙烯系树脂只要不妨碍本发明的效果,可以还包含其他添加剂。作为添加剂,例如可列举:光稳定剂、抗氧化剂、防腐剂、表面活性剂、无机粒子等填充剂、颜料、着色剂、防霉剂等。这些添加剂中的一种或两种以上可以包含在苯乙烯系树脂中。在苯乙烯系树脂包含其他添加剂的情况下,相对于苯乙烯系树脂总质量,其含有比例优选为10质量%以下,更优选为5质量%以下,进一步优选为1质量%以下。
苯乙烯系树脂的制造方法并无特别限定,例如,能够通过利用公知的方法制造,来获得作为成分(A)的苯乙烯系树脂。或者,苯乙烯系树脂例如可以从市售品等获取。
苯乙烯系树脂组合物中所含的成分(B1)的含量并无特别限定。从容易提高阻燃性及耐热性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(B1)的含量例如可以设为0.05质量份以上,优选设为0.1质量份以上,更优选设为0.5质量份以上,进一步优选设为0.9质量份以上,特别优选设为1质量份以上。另外,从容易提高阻燃性及耐热性的方面考虑,相对于每100质量份上述苯乙烯系树脂,苯乙烯系树脂组合物中所含的成分(B1)的含量可以设为20质量份以下,优选设为18质量份以下,更优选设为10质量份以下,进一步优选设为5质量份以下,更进一步优选设为4质量份以下,特别优选设为3质量份以下。
在苯乙烯系树脂组合物包含成分(B1)以及成分(B2)这两者的情况下,从容易提高苯乙烯系树脂组合物的发泡成形体的阻燃性及耐热性的方面考虑,相对于每100质量份苯乙烯系树脂,成分(B1)及成分(B2)的总质量例如优选为0.1质量份以上且20质量份以下。相对于每100质量份苯乙烯系树脂,成分(B1)及成分(B2)的总质量优选设为1质量份以上,更优选设为1.5质量份以上,进一步优选设为2质量份以上,特别优选设为2.5质量份以上。另外,相对于每100质量份上述苯乙烯系树脂,成分(B1)及成分(B2)的总量优选设为10质量份以下,更优选设为9质量份以下,进一步优选设为8质量份以下,特别优选设为6质量份以下。
在苯乙烯系树脂组合物中,成分(C)的含量并无特别限定。例如,从容易提高阻燃性及耐热性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(C)的含量可以设为0.001质量份以上,优选设为0.01质量份以上,更优选设为0.05质量份以上,进一步优选设为0.08质量份以上,特别优选设为0.1质量份以上。另外,从容易提高阻燃性及耐热性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(C)的含量可以设为5质量份以下,优选设为1质量份以下,更优选设为0.8质量份以下,进一步优选设为0.5质量份以下,特别优选设为0.3质量份以下。
在苯乙烯系树脂组合物中,成分(D)的含量并无特别限定。例如,从容易提高阻燃性及耐热性的方面考虑,在苯乙烯系树脂组合物中,相对于每100质量份上述苯乙烯系树脂,优选为包含0.05质量份以上且10质量份以下的成分(D)。相对于每100质量份苯乙烯系树脂,成分(D)的含量优选设为0.1质量份以上,更优选设为0.5质量份以上,进一步优选设为0.55质量份以上,特别优选设为0.8质量份以上。另外,相对于每100质量份上述苯乙烯系树脂,成分(D)的含量优选设为8质量份以下,更优选设为6质量份以下,进一步优选设为4质量份以下,特别优选设为3质量份以下。
在苯乙烯系树脂组合物中包含成分(E)的情况下,其含量并无特别限定。例如,从容易提高发泡成形体的热稳定性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(E)的含量可以设为0.001质量份以上,优选设为0.01质量份以上,更优选设为0.02质量份以上,进一步优选设为0.03质量份以上。另外,从容易提高发泡成形体的热稳定性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(E)的含量优选设为1质量份以下,更优选设为0.8质量份以下,进一步优选设为0.6质量份以下,特别优选设为0.4质量份以下。
在苯乙烯系树脂组合物中包含成分(F)的情况下,其含量并无特别限定。例如,从容易提高发泡成形体的阻燃性的方面考虑,相对于每100质量份上述苯乙烯系树脂,成分(F)的含量优选设为0.01质量份以上且0.5质量份以下。
在苯乙烯系树脂组合物中包含成分(H)的情况下,其含量并无特别限定。例如,相对于每100质量份上述苯乙烯系树脂,成分(H)含量可以设为0.1质量份以上且5质量份以下。
除了所述各成分以外,苯乙烯系树脂组合物也可以包含各种成分。例如,可以包含作为后述的(G)成分的发泡剂。发泡剂可以在后述的苯乙烯系树脂组合物的发泡工序中调配至苯乙烯系树脂组合物中,或者也可以在使苯乙烯系树脂组合物发泡之前预先将发泡核剂调配至苯乙烯系树脂组合物中。
此外,在不损害本发明的效果的范围内,苯乙烯系树脂组合物可包含各种添加剂。作为添加剂,例如可以列举:光稳定剂、紫外线吸收剂、紫外线稳定化剂、重金属惰性剂、耐冲击改良剂、着色剂、润滑剂、防滴落剂、结晶成核剂、抗静电剂、增容剂等公知的树脂添加剂。在苯乙烯系树脂组合物包含添加剂的情况下,其含有比例例如相对于苯乙烯系树脂的质量而可以设为10质量%以下,优选为5质量%以下,更优选为1质量%以下,特别优选为0.1质量%以下。
苯乙烯系树脂组合物的制备方法并无特别限定,例如可以设为与公知的发泡用苯乙烯系树脂组合物的制备方法相同。例如,能够通过以规定的混合比例混合阻燃剂组合物、(A)成分以及其他视需要添加的一种以上的成分来制备苯乙烯系树脂组合物。
苯乙烯系树脂组合物例如能够通过各种发泡方法来形成发泡成形体。例如,能够通过使苯乙烯系树脂组合物挤出发泡,来获得苯乙烯系树脂组合物的挤出发泡成形体。
制造挤出发泡成形体的方法并无特别限定,例如可以广泛采用公知的制造方法。例如,挤出发泡成形体能够通过包括下述挤出发泡成形工序的制造方法来制造。
挤出发泡工序:将苯乙烯系树脂组合物在挤出机内熔融混合,将作为成分(G)的发泡剂(G)压入挤出机内,接着,从挤出机模口向大气中挤出的工序。
利用该挤出发泡工序使苯乙烯系树脂发泡成形,获得苯乙烯系树脂组合物的挤出发泡成形体。
在挤出发泡工序中,可以按任意顺序向挤出机内供给成分(A)、成分(B1)、成分(C)、及成分(D),在挤出机内熔融混合,进行发泡成形。或者,可以将各成分中的一些或全部预先混合形成混合物后,将该混合物供给至挤出机内。
作为发泡剂,例如可以广泛使用发泡成形中使用的公知的发泡剂。具体而言,可以例示:丙烷、丁烷、异丁烷、戊烷、环戊烷、己烷、环己烷、1-氯-1,1-二氟乙烷、单氯二氟甲烷、单氯-1,2,2,2-四氟乙烷、1,1-二氟乙烷、1,1,1,2-四氟乙烷、1,1,3,3,3-五氟丙烷、二氯甲烷、1,2-二氯乙烷、二甲基醚、二乙基醚、乙基甲基醚等挥发性有机发泡剂;水、氮气、二氧化碳等无机发泡剂;偶氮化合物等化学发泡剂等。发泡剂可以单独使用或并用两种以上。
发泡剂的调配量可以根据所期望的发泡体的性能及所采用的成形方法等适当设定。例如,相对于100质量份苯乙烯系树脂,可以将发泡剂设为0.01质量份~20质量份,优选为0.1质量份~10质量份,更优选为0.5质量份~5质量份。
如上所述获得的苯乙烯系树脂组合物的挤出发泡成形体至少包含成分(A)、成分(B1)、成分(C)及成分(D)。因此,该挤出发泡成形体具有优异的阻燃性及耐热性。因此,挤出发泡成形例如可以用于要求高阻燃水平的各种用途。
[实施例]
以下,通过实施例对本发明进行更具体的说明,但本发明并不限于这些实施例的方式。
实施例及比较例中所使用的原料如下所述。
<成分(A)>
(A)苯乙烯系树脂
·GP-PS(PS日本公司制造的“PSJ聚苯乙烯G9305”)
<成分(B1)>
四溴双酚A-双(2,3-二溴-2-甲基丙基醚)(第一工业制药公司制造的“PyroguardSR-130”)
<成分(B2)>
·B2-1:四溴双酚A-双(2,3-二溴丙基醚)(第一工业制药公司制造的“PyroguardSR-720N”)
·B2-2:三(2,3-二溴丙基)异氰脲酸酯(第一工业制药公司制造的“PyroguardSR-750”)
·B2-3:三(三溴苯氧基)三嗪(第一工业制药公司制造的“Pyroguard SR-245”)
·B2-4:溴化环氧低聚物(Nipponsteel Chemical&Material公司制造的“YDB-406”)
<其他阻燃剂>
·B2-5:六溴环十二烷(第一工业制药公司制造的“Pyroguard SR-103”)
<成分(C)>
(C)锌改性水滑石
·C-1:Mg3.5Zn0.5Al2(OH)12CO3·mH2O(堺化学工业公司制造的“STABIACE HT-7”)
·C-2:Mg3ZnAl2(OH)12CO3·mH2O(协和化学工业公司制造的“ZHT-4A”)
<不含锌的水滑石>
·C-3:Mg4.3Al2(OH)12.6CO3·mH2O(协和化学工业公司制造的“DHT-4A”)
<成分(D)>
(D)磷酸酯化合物
·D-1:三苯基磷酸酯(大八化学公司制造的“TPP”)
·D-2:三甲苯基磷酸酯(大八化学公司制造的“TCP”)
·D-3:三苯基亚磷酸酯(大八化学公司制造的“TP-I”)
·D-4:三(三溴新戊基)磷酸酯(大八化学公司制造的“CR-900”)
·D-5:三甲苯基亚磷酸酯(大八化学公司制造的“TXP”)
·D-6:无卤素系磷酸酯(大八化学公司制造的“DAIGUARD-1000”)
·D-7:甲苯基二-2,6-二甲苯基磷酸酯(大八化学公司制造的“PX-110”)
·D-8:间苯二酚双(二苯基磷酸酯)(大八化学公司制造的“CR-733S”)
·D-9:双酚A双(二苯基磷酸酯)(大八化学公司制造的“CR-741”)
·D-10:间苯二酚双(二-二甲苯基磷酸酯)(大八化学公司制造的“PX-200”)
<成分(E)>
(E)热稳定剂
双(2,6-二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯(ADEKA公司制造的“Adekastab PEP-36”)
<成分(F)>
(F)阻燃增强剂
·F-1:2,3-二甲基-2,3-二苯基丁烷(日油公司制造的“Nofmer BC-90”)
·F-2:合成沸石(东曹公司制造的“Zeorum A-3”)
<成分(G)>
(G)发泡剂
·G-1:异丁烷
·G-2:二甲基醚
<成分(H)>
(H)发泡成核剂
·滑石MS(日本滑石工业(股)制造)
(实施例1)
以后述表1中所示的调配比例将除发泡剂以外的各成分投入至口径65mm的挤出机中,将机内加热至200℃熔融并塑化,继续混炼,从而在挤出机内制备苯乙烯系树脂组合物。挤出机使用了从口径65mm串联连结至口径90mm的两段式挤出机。各成分的调配比例如表1所示,使成分(A)为100质量份,使成分(B1)为1.2质量份,使作为成分(B2)的B2-1为1.8质量份,使作为成分(C)的C-1为0.1质量份,使作为成分(D)的D-1为1.0质量份,使成分(E)为0.05质量份。
接着,通过其他生产线向65mm挤出机前端(与口径90mm的挤出机的模口为相反侧)压入规定量的发泡剂,通过口径90mm的挤出机将树脂温度(机内温度)冷却至120℃。如表1所示,作为成分(G)的发泡剂,使G-1为3质量份,且使G-2为3质量份(相对于每100质量份苯乙烯系树脂)。其后,通过从设置在口径90mm的挤出机前端的厚度方向为2.5mm、宽度方向为45mm的长方形剖面的模唇向大气中挤出树脂组合物,从而获得长方体状的苯乙烯系树脂的挤出发泡成形体。
(实施例2~实施例31)
将各成分的种类以及调配量如表1及表2所示地进行变更,除此以外,通过与实施例1同样的方法获得挤出发泡成形体。
(比较例1~比较例10)
将各成分的种类以及调配量如后述表3所示地进行变更,除此以外,通过与实施例1同样的方法获得挤出发泡成形体。
(评价方法)
<阻燃性>
根据日本工业标准(Japanese Industrial Standards,JIS)K-7201测定氧指数,并基于下述判断基准来评价阻燃性能。
〇:氧指数为29以上,具有优异的阻燃性。
×:氧指数低于29,不具有优异的阻燃性。
<耐热性>
根据各实施例及比较例中获得的发泡成形体的黄变程度(YI:黄色指数),来评价发泡成形体的耐热性。具体而言,将试验中的挤出发泡成形体用切割器进行切片而切成板,在用双轴辊压缩之后,用粉碎机进行粉碎。将粉碎物投入Labo Plastomill中,在200℃下熔融混炼,然后迅速取出,通过冷却压制机(press)成形为3.2mm厚的板状。将如此所获得的板状成形品通过220℃的热压制机加热40分钟后,通过冷却压制机进行冷却。将冷却后的板状成形品溶解于二氯甲烷中使其达到10质量%,将溶解液通过0.45μm的过滤器,并将过滤后的溶解液作为耐热试验样品。通过使用了分光光度计(日本电色工业(股)制造的SE-6000)的透过法测定该样品的YI值。
表1及表2示出各实施例中所使用的各成分的调配比例、以及所获得的发泡成形体的评价结果。
[表1]
[表2]
表3示出各比较例中所使用的各成分的调配比例、以及所获得的发泡成形体的评价结果。
[表3]
如根据表1而明确地,各实施例中制备出的苯乙烯系树脂的挤出发泡体具有优异的阻燃性,另外,由于YI值低,因此耐热性也优异。与此相对,各比较例中制备出的苯乙烯系树脂的挤出发泡体未由包含全部成分(A)~成分(D)的组合物形成,因此无法满足阻燃性及耐热性这两者。由以上可知,由包含成分(A)~成分(D)的阻燃性发泡苯乙烯系树脂组合物获得的挤出发泡体具有优异的阻燃性及耐热性。
Claims (7)
1.一种发泡苯乙烯树脂用阻燃剂组合物,其特征在于,
至少包含下述的成分(B1)、成分(C)及成分(D),
(B1)四溴双酚A-双(2,3-二溴-2-甲基丙基醚)、
(C)锌改性水滑石、及
(D)磷酸酯系化合物,
相对于所述成分(B1)及所述成分(D)的总量,含有10质量%~98质量%的所述成分(B1)。
2.如权利要求1所述的发泡苯乙烯树脂用阻燃剂组合物,其中,
所述成分(D)为选自由脂肪族磷酸酯、芳香族磷酸酯及芳香族亚磷酸酯所组成的组中的至少一种。
3.如权利要求1或2所述的发泡苯乙烯树脂用阻燃剂组合物,其中,
除了所述成分(B1)以外,也含有成分(B2)作为阻燃剂,
所述成分(B2)包含选自由四溴双酚A-双(2,3-二溴丙基醚)、三(2,3-二溴丙基)异氰脲酸酯、三(三溴苯氧基)三嗪及溴化环氧低聚物所组成的组中的至少一种。
4.如权利要求1至3中任一项所述的发泡苯乙烯树脂用阻燃剂组合物,其中,
相对于所述成分(B1)及所述成分(C)的总量,所述成分(B1)的含有比例为80质量%~99质量%。
5.一种阻燃性发泡苯乙烯系树脂组合物,其特征在于,
包含:权利要求1至4中任一项所述的发泡苯乙烯树脂用阻燃剂组合物、以及成分(A)苯乙烯系树脂。
6.如权利要求5所述的阻燃性发泡苯乙烯系树脂组合物,其中,
相对于100质量份所述成分(A),包含0.05质量份以上且10质量份以下的所述成分(D)。
7.一种挤出发泡成形体,其特征在于,
是权利要求5或6所述的阻燃性发泡苯乙烯系树脂组合物的挤出发泡成形体。
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