CN1982362B - 非卤素阻燃树脂组合物 - Google Patents
非卤素阻燃树脂组合物 Download PDFInfo
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- CN1982362B CN1982362B CN2006101693224A CN200610169322A CN1982362B CN 1982362 B CN1982362 B CN 1982362B CN 2006101693224 A CN2006101693224 A CN 2006101693224A CN 200610169322 A CN200610169322 A CN 200610169322A CN 1982362 B CN1982362 B CN 1982362B
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- Prior art keywords
- flame retardant
- thermoplastic resin
- mass parts
- carbon atom
- halogen flame
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 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 43
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 31
- 239000011342 resin composition Substances 0.000 title abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 25
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 150000001721 carbon Chemical group 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 11
- 150000004692 metal hydroxides Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
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- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 2
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- 229920005668 polycarbonate resin Polymers 0.000 claims 1
- 239000004431 polycarbonate resin Substances 0.000 claims 1
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- 238000012360 testing method Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
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- 239000004702 low-density polyethylene 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
- 238000000034 method Methods 0.000 description 2
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- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
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- SGQUHMXHLSTYIH-UHFFFAOYSA-N 2-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(CC)C1=CC=CC=C1 SGQUHMXHLSTYIH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了一种无需用过氧化物交联、具有优异可模塑性、而且还具有高阻燃性以通过UL-94标准的V-0级测试的非卤素阻燃热塑性树脂组合物。该非卤素阻燃热塑性树脂组合物包含下列组分成为一种均相共混物:(A)100质量份除聚碳酸酯和聚苯醚树脂之外的热塑性树脂,(B)10-300质量份的无机粉末,(C)1-50质量份具有特定结构的有机聚硅氧烷,以及(D)0.01-10质量份具有特定结构的有机化合物。
Description
发明背景
1.技术领域
本发明涉及一种非卤素阻燃树脂组合物,其在燃烧期间不产生卤素气体,证实具有高阻燃性,并且在环境安全方面优异。
2.背景技术
由于热塑性树脂是可燃的,因此已经提出了各种赋予阻燃性的技术以用于要求阻燃性的用途。众所周知,混合了在阻燃方面优异的诸如溴化合物的基于卤素的阻燃剂和锑氧化物与热塑性树脂的阻燃配方已被用作这样的技术。基于卤素的阻燃剂通过游离基俘获活性、产生卤素气体(不燃性气体)等发挥出优异的阻燃效果。然而,由于卤素气体对有机体有害,作为一个近期的问题,强烈希望出现具有非卤素配方的阻燃树脂组合物。
近年来,已经提出了各种采用金属氢氧化物,如采用氢氧化镁的技术,作为用于生产用于电线/电缆和片材的涂料绝缘体中的热塑性树脂的阻燃配方。金属氢氧化物具有低毒性、产生的烟气少、以及低腐蚀性的优点,并且通过在燃烧时释放结晶水发挥阻燃作用。
然而,由于该阻燃效果不强,例如,当作为添加对象的基料树脂是聚烯烃时,即使相对于100质量份的聚烯烃,混合了等量的100质量份,作为物质燃烧性(可燃性)指标之一的需氧指数,证实仅为30或更低的数值。
混合有例如已用表面处理剂,如硅烷偶联剂,表面处理过的金属氢氧化物与热塑性树脂的阻燃树脂组合物,已知作为用于采用金属氢氧化物的热塑性树脂的阻燃技术(参见日本专利公开号为No.2825500、日本专利公开号为No.3019225和日本专利公开号为No.
3072746的日本专利申请)。
然而,仅将表面处理的金属氢氧化物与热塑性树脂混合只能得到低且不足的需氧指数,由此,为了赋予热塑性树脂足够的阻燃性,有必要大量混入金属氢氧化物。
此外,除了上述那些以外,作为阻燃技术还报道过通过将金属氢氧化物和有机聚硅氧烷与热塑性树脂混合在一起的阻燃树脂组合物(参见日本专利审查公开号为No.H7-119324、日本专利公开号为No.3051211、日本专利公开号为No.3063759和日本专利申请公开号为No.H4-226551的日本专利申请)。尽管当金属氢氧化物和有机聚硅氧烷组合使用时提高了阻燃性,但是为了能够适应各种阻燃性规定,仍需要一种能够实现更高阻燃性的阻燃配方。
此外,最近,将金属氢氧化物、有机聚硅氧烷和添加剂与热塑性树脂混合在一起的非卤素阻燃树脂组合物已有所报道(参见日本专利申请公开号为No.2004-250676和日本专利申请公开号为No.2003-128939的日本专利申请)。尽管很明显,这些阻燃树脂组合物具有提高的阻燃性,需氧指数显示为48或更高的值,但是阻燃性仍然不足以通过UL-94和UL-VW1测试标准。
此外,将金属氢氧化物、高度聚合的有机聚硅氧烷、含有不饱和官能团的有机聚硅氧烷和自由基生成剂,与热塑性树脂混合的非卤素阻燃树脂组合物已有所报道(参见日本专利申请公开号为No.2003-034755的日本专利申请)。
尽管这种非卤素阻燃树脂组合物被赋予了足够的阻燃性以通过VW-1,但是由于它必须用过氧化物交联,因此不仅由于其低可流动性使得生产变得费力,而且它还存在可模塑性方面的问题。
发明内容
由此,本发明的目的是提供一种能够解决上述现有技术中问题的非卤素阻燃树脂组合物,换言之,提供一种无需用过氧化物交联、具有优异可模塑性、而且还具有高阻燃性以通过UL-94的V-0级的非卤
素阻燃树脂组合物。
作为解决上述问题而深入研究的结果,本发明人发现,含有下列组份(A)-(D)而无需混入有机过氧化物的树脂组合物具有超过想像的高阻燃效果,而且,还在可模塑性方面极为优异,实现了本发明的目的。
也就是说,本发明提供了一种非卤素阻燃树脂组合物,含有:
(A)100质量份的热塑性树脂(除了聚碳酸酯和聚苯醚);
(B)10-300质量份的无机粉末;
(C)1-50质量份的用下列平均单元式(1)表示的有机聚硅氧烷
RaSiO(4-a)/2 (1)
(在式(1)中,R表示羟基、具有1-10个碳原子的烷基、具有2-10个碳原子的链烯基或芳基,a表示1.9-2.1的数);以及
(D)0.01-10质量份的用下列化学式(2)、(3)或(4)表示的化合物:
(在式(2)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,Q表示氢原子或钠原子);以及
(在式(3)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,R2表示氢原子、羟基、具有1-20个碳原子的烷基、具有7-20个碳原子的烷基苯基、或者用下列给出的式(5)表示的基团),
(在式(4)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,R2表示氢原子、羟基、具有1-20个碳原子的烷基、具有7-20个碳原子的烷基苯基、或者用下列给出的式(5)表示的基团),
(在式(5)中,R3和R4分别表示氢原子、具有1-20个碳原子的烷基、具有2-20个碳原子的链烯基、具有7-20个碳原子非必要地包含一个氧原子的单价烃基、或者具有7-20个碳原子的烷基苯基)。
除了表现出高阻燃性以通过UL-94的V-0以外,本发明的非卤素阻燃树脂组合物还在可模塑性和相对于环境安全方面优越,具体而言,在作为用于制造阻燃电线、阻燃管、阻燃片材等方面的材料而言优越。
优选实施方式的说明
如上所述,本发明的非卤素阻燃树脂组合物含有组分(A)-(D)作为必要组份。下面将详细说明本发明。
对组份(A)的热塑性树脂没有具体限制,除了排除掉聚碳酸酯和聚苯醚,可以述及的有,例如,低密度聚乙烯、高密度聚乙烯、线性低密度聚乙烯、极低密度聚乙烯、超高分子量聚乙烯、聚丙烯、基于聚丙烯的弹性体、聚醋酸乙烯酯、乙烯-醋酸乙烯酯共聚物的皂化产物,例如,乙烯-醋酸乙烯酯共聚物和乙烯-乙烯醇共聚物、各种热塑性弹性体,例如,乙烯-丙烯酸酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酰胺共聚物、乙烯-甲基丙烯酸酯共聚
物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-甲基丙烯酸缩水甘油酯共聚物、乙烯-马来酸酐共聚物和离聚体、聚苯乙烯、基于苯乙烯的热塑性弹性体、ABS树脂、聚缩醛树脂、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯,等等。作为组份(A)的热塑性树脂可以单独使用或者可以两种或多种结合使用。
在上面给出的热塑性树脂中,具体而言,特别优选基于聚烯烃的树脂、基于聚醋酸乙烯酯的树脂以及基于苯乙烯的热塑性弹性体,例如,低密度聚乙烯、高密度聚乙烯、线性低密度聚乙烯、极低密度聚乙烯、超高分子量聚乙烯、聚丙烯、乙烯-丙烯酸乙酯共聚物、乙烯-醋酸乙烯酯共聚物、聚醋酸乙烯酯,因为它们与组份(B)的无机粉末(具体而言,金属氢氧化物)以及组份(C)的有机聚硅氧烷一起在提高本发明的阻燃性方面具有协同效果。
对本发明中作为组份(B)的无机粉末没有具体的限制,可以述及的有,例如,氢氧化铝、氢氧化镁、三氧化锑、五氧化锑、锑酸钠、四氧化锑、硼酸锌、锆化合物、钼化合物、碳酸钙、氧化硅、有机硅树脂粉末、硅橡胶粉末、滑石、丙烯酰基有机硅粉末、钛氧化物、叶蜡石、石英、硅藻土、黄铁矿、硫化煅烧石灰(sulfidized calcine)、石墨、膨润土、高岭土、活性碳、炭黑、锌氧化物、铁氧化物、大理石、电木粉、波特兰水泥、SiO2粉末、氮化硼、合成云母、玻璃珠、云母、丝云母,等等。金属氢氧化物特别优异,其中特别优选氢氧化镁、氢氧化铝和氢氧化钙。
此外,作为组份(B)的无机粉末可以是未处理的或用表面处理剂处理过的,所述表面处理剂为,例如,饱和脂肪酸、不饱和脂肪酸、钛酸酯偶联剂、硅烷偶联剂、硅氧烷低聚体、反应性硅油或热塑性树脂。
本发明中组份(B)的混合量为每100质量份组份(A)10-300质量份,优选地,50-150质量份。如果超过300质量份,则组合物的可流动性会过度降低,组合物1有时不适于使用,而如果少于10质量份,则不能获得足够的阻燃性。
本发明中组份(C)的有机聚硅氧烷是一种由平均单元式(1)表示的聚合物:
RaSiO(4-a)/2 (1)
在上述式(1)中,R表示羟基、具有1-10个、或优选1-8个碳原子的烷基、具有2-10个碳原子的链烯基或芳基,例如,甲基、乙基、丙基、丁基等,可以称为烷基,乙烯基、烯丙基、丁烯基等,可以称为链烯基,苯基、甲苯基等,可以称为芳基。
尽管组份(C)有机聚硅氧烷的分子结构具有一个优选为含有上述硅氧烷单元的直链的主链,但是如果它部分包含带有支链的分子结构,也无问题。因此,a表示1.9-2.1范围内的数,优选为1.95-2.05范围内的数。
组份(C)的有机聚硅氧烷具有一个数均聚合度,其为总硅氧烷单元重复数的数均值,优选在2,500-30,000范围内,更优选在3,000-15,000范围内。如果数均聚合度小于2,500,则有时由本发明树脂组合物获得的模制品的机械性能会降低。此外,如果数均聚合度的数值超过30,000,则本发明的树脂组合物的粘度会变得过高,制备过程中搅拌会变得困难。
作为组份(C)的有机聚硅氧烷的例子包括,具体而言,mR2SiO单元连接形成一个直链并且该分子链两端用R3SiO1/2单元封端的聚合物,如下式中所示。在这种情况下,m+2是数均聚合度,优选地为,2,500≤m+2≤30,000,如前所述。
R3SiO(R2SiO)mSiR3
此处,如上所述,R表示羟基、具有1-10个碳原子的烷基、具有2-10个碳原子的链烯基或芳基。尽管无论每个R是否相同或彼此不同无关紧要,但是,考虑到可模塑性,优选组份(C)有机聚硅氧烷中包含的全部R基团的至少80%是甲基。
组份(C)的混合量为每100质量份组份(A)1.0-50质量份,或优选1.5-30质量份,更优选2.0-20质量份。混合量小于1.0质量份,则不能表现出足够的阻燃性,而如果超过50质量份,则树脂组合物将
变得橡胶化,且本发明组份在树脂中的非均匀分散会导致阻燃性的下降。在本发明中,组份(C)可以两种或多种结合使用。
本发明中的组份(D)是用下列化学式(2)、(3)或(4)表示的化合物。
在式(2)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,Q表示氢原子或钠原子。
在式(3)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,R2表示氢原子、羟基、具有1-20个碳原子的烷基、具有7-20个碳原子的烷基苯基、或者用下列给出的式(5)表示的基团。
在式(4)中,R表示碳原子或氮原子,R1表示具有1-20个碳原子的烷基或具有7-20个碳原子的烷基苯基,R2表示氢原子、羟基、具有1-20个碳原子的烷基、具有7-20个碳原子的烷基苯基、或者用下列式(5)表示的基团。
在式(5)中,R3和R4分别表示具有1-20个碳原子的烷基、具有
2-20个碳原子的链烯基、具有7-20个碳原子非必要地包含一个氧原子的单价烃基、或者具有7-20个碳原子的烷基苯基。该具有7-20个碳原子非必要地包含一个氧原子的单价烃基是一个包含具有7-20个碳原子的单价烃基的基团,其中,包含羟基、羰基、醚基等。
具体而言,具有苯并三唑结构或苯并咪唑结构的下列化合物可称为组份(D)的例子。在由下列结构式所示的组份(D)化合物中,1H-苯并三唑、4-甲基-1H-苯并三唑和5-甲基-1H-苯并三唑表现出最佳的阻燃性能。
组份(D)的混合量为每100质量份组份(A)0.01-10质量份,或优选0.1-5质量份,更优选0.5-3质量份。混合量小于0.01质量份,则阻燃效果得不到提高。而如果超过10质量份混合量,则阻燃效果开始下降。在本发明中,组份(D)可以两种或多种结合使用。
在本发明中,通过再添加包含铂族元素的催化剂作为除上述组份(A)-(D)以外的组份(E),可以进一步提高阻燃效果。选自铂催化剂、钯催化剂和铑催化剂的一种或多种催化剂优选作为包含铂族元素的催化剂(E)。此外,组份(E)可以不单是铂族元素,更优选是络合态的铂族元素,并且,具体而言,特别优选用有机硅氧烷或醇改性的络合物。
优选地,每100质量份的组份(A)混合0.01-10质量份的组份(E)。尽管即使配方中省略组份(E),仍可以确保提高阻燃效果,但是,通过混合组份(E)可以进一步提高阻燃性。然而,如果超过10重量份,则有时会观察到由于形成络合物而导致的着色,而如果少于0.01质量份,则有时不能提高阻燃效果。
可以在不降低本发明非卤素阻燃树脂组合物性能的限度内根据其目的与其它添加剂混合。这类添加剂可以是氧化抑制剂、紫外吸收剂、稳定剂、相容剂、其它类型的非卤素阻燃剂、润滑剂、填料、粘合促
进剂和腐蚀抑制剂。
可用于本发明中的氧化抑制剂的例子包括:2,6-二叔丁基-4-甲基苯酚、正十八烷基-3-(3’,5’-二叔丁基-4-羟基苯基)丙酸酯、四[亚甲基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]甲烷、三-羟基甲基-氨基甲烷(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、4,4’-亚丁基双-(3-甲基-6-叔丁基苯酚)、三乙二醇-双[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、3,9-双{2-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧]-1,1-二甲基乙基}-2,4,8,10-四氧杂螺[5,5]十一烷、4,4-硫代双-(2-叔丁基-5-甲基苯酚)、2,2-亚甲基双-(6-叔丁基-甲基苯酚)、4,4-亚甲基双-(2,6-二叔丁基-苯酚)、1,3,5-三甲基-2,4,6-三羟基甲基-氨基甲烷(3,5-二叔丁基-4-羟基苄基)苯、三-羟基甲基-氨基甲烷壬基苯基亚磷酸酯、三-羟基甲基-氨基甲烷(2,4-二叔丁基苯基)亚磷酸酯、二硬脂基季戊四醇亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯、2,2-亚甲基双(4,6-二叔丁基苯基)辛基亚磷酸酯、四(2,4-二叔丁基苯基)-4,4’-亚联苯基-二膦酸酯、二尿基(diurayl)-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、季戊四醇四(3-月桂基硫代丙酸酯)、2,5,7,8-四甲基-2(4,8,12-三甲基癸基)苯并二氢吡喃-2-醇、5,7-二叔丁基-3-(3,4-二甲基苯基)-3H-苯并呋喃-2-酮、2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二戊基苯基丙烯酸酯、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯、四(亚甲基)-3-(十二烷基硫代丙酸酯)甲烷,等等。
可用于本发明中的稳定剂的例子包括各种基于金属皂的稳定剂,例如,硬脂酸镁、月桂酸钙、蓖麻醇酸钙、硬脂酸钙、月桂酸钡、蓖麻醇酸钡、硬脂酸钡、月桂酸锌、蓖麻醇酸锌和硬脂酸锌、来自基于月桂酸盐、基于马来酸盐化合物以及基于含巯基的化合物的各种基于有机锡化合物的稳定剂、各种基于铅的稳定剂如硬脂酸铅和三盐基硫酸铅、环氧化物如环氧化植物油、亚磷酸盐化合物如烷基烯丙基亚磷酸盐和三烷基亚磷酸盐、β-二酮化合物如二苯甲酰基甲烷和脱氢乙
酸、多元醇如山梨糖醇、甘露醇和季戊四醇、水滑石和沸石。
可用于本发明中的相容剂的例子包括丙烯酰有机聚硅氧烷共聚物、二氧化硅与有机聚硅氧烷的部分交联产物、硅氧烷粉末、MQ树脂、脱水马来酸化接枝改性聚烯烃、羧酸化接枝改性聚烯烃、聚烯烃接枝改性有机聚硅氧烷,等等。
此外,可用于本发明中的粘结促进剂的例子包括各种烷氧基硅烷等。
可用于本发明中的其它类型上述非卤素阻燃剂的例子包括硼酸锌、锡酸锌、各种基于磷的阻燃剂、可膨胀(expandable)石墨、三聚氰胺氰尿酸酯、氨基磺酸胍、光致氧化钛等。此外,填料的例子包括硅酸、碳酸钙、二氧化钛、炭黑、高岭土、煅烧粘土、硅酸铝、硅酸镁、硅酸钙、重晶石等。
本发明非卤素阻燃树脂组合物通过用捏合机,如Banbury混合机、加压捏合机或双螺杆挤出机等,均相捏合上述组份(A)-(D)(以及如果需要,进一步的组份(E))获得。对于捏合方法没有具体限制,只要它能够均匀捏合即可。对模塑方法也没有具体限制,例如,共混物捏合后造粒并将所获得的球粒通过合适的模塑方法进行模制,如通过膜式模制、压塑、砑光辊模制、挤塑等,以获得各种模塑制品。
本发明非卤素阻燃树脂组合物作为用于形成阻燃电线、阻燃电缆、阻燃管和阻燃片材特别优异。此外,它也可以广泛用于各种家用电气用途、OA器具、建筑材料等。
[实施例]
下面,本发明将通过实施例和对比例的方式进行详细说明,但是本发明的范围不限于这些实施例,只要本发明的范围不会因此而超出。注意,表1空格中给出的相应于各基本材料的数字表示在各实施例中配混的以质量份计的该基本材料的量。
[实施例1-18和对比例1-8]
按照表1或表2中所列的比例取用这些实施例各自的基本材料并在Laboplastomill(Toyo Seiki Co.Ltd.制造)中一起捏合。捏合条件取决于基料树脂的类型,并且当该基料树脂为用于过氧化物交联的(1)乙烯-醋酸乙烯酯共聚物树脂、(2)聚丙烯树脂、或(3)基于苯乙烯的热塑性弹性体或乙烯-醋酸乙烯酯共聚物树脂时,分别在(1)150℃/3分钟/30rpm、(2)190℃/3分钟/30rpm及(3)180℃/3分钟/30rpm的条件下进行捏合。该捏合的配混料通过挤出造粒后,通过对球粒在150℃、100kg/cm2下压塑1分钟,以制备用于评价阻燃性的样品试样。
<阻燃性评价方法>
对上述制备的样品试样(厚度:1/8英寸)进行UL规范的UL-94中规定的Horizontal Burning测试,以评价是否能通过V-0阻燃级别。结果示于表1和表2中。在表1中,通过V-0的那些用标记A表示,未通过的那些用标记B表示。
在上述测试中配混并在表1和2中用*1-*18标识的各基本材料表征如下。
*1:乙烯-醋酸乙烯酯共聚物(EVA)树脂(Evaflex 360,产品名,Mitsui-DuPont Polychemicals Co.,Ltd.生产)
*2:PM854X树脂(产品名,聚丙烯树脂,Sun Allomer Co.,Ltd.生产)
*3:SEPTON Compound CEOC3(产品名,基于苯乙烯的热塑性弹性体,Kuraray Co.,Ltd.生产)
*4:KISUMA 5A(产品名,脂肪酸处理的氢氧化镁,Kyowa ChemicalIndustry Co.,Ltd.生产)
*5:HIGILITE H42S(产品名,氢氧化铝,Showa Denko Co.,Ltd.生产)
*6:聚有机硅氧烷A(Shin-Etsu Chemical Co.,Ltd.生产)
[(CH3)3SiO1/2]2[(CH3)2SiO2/2]7000
*7:聚有机硅氧烷B(Shin-Etsu Chemical Co.,Ltd.生产)
[(CH3)3SiO1/2]2[(CH3)2SiO2/2]3000
*8:1H-苯并三唑(Wako Pure Chemical Industries Co.,Ltd.生产)
*9:甲基-1H-苯并咪唑(混合物,ToKyo Chemical Industry Co.,Ltd.生产)
*10:苯并咪唑(Wako Pure Chemical Industries Co.,Ltd.生产)
*11:TINUVIN 234(产品名,2-[2-羟基-3,5-双(二甲基苄基)苯基]-苯并三唑,Ciba Specialty Chemicals Co.,Ltd.生产)
*12:TINUVIN 238(产品名,2-(2’-羟基-3’,5’-二叔戊基)-苯并三唑,Ciba Specialty Chemicals Co.,Ltd.生产)
*13:TINUVIN 571(产品名,2-(2’-羟基-3’-十二烷基-5’-甲基苯基)-苯并三唑,Ciba Specialty Chemicals Co.,Ltd.生产)
*14:CAT-PL-56(产品名,含0.5%铂的铂催化剂,Shin-EtsuChemical Co.,Ltd.生产)
*15:PH滑石(产品名,滑石,6.0μm平均粒径,Takehara Kagaku
*16:聚有机硅氧烷C(Shin-Etsu Chemical Co.,Ltd.生产)
[(CH3)3SiO1/2]2[(CH3)2SiO2/2]800
*17:甲基乙烯基硅油(Shin-Etsu Chemical Co.,Ltd.生产)
[(CH3)3SiO1/2]2[(CH3)(CH2CH)SiO2/2]50[(CH3)2SiO2/2]200
*18:Nofmer BC(产品名,2,3-二甲基-2,3-二苯基丁烷,NipponOils & Fats Co.,Ltd.生产)
[表2]
(评价测试结果)
本发明的非卤素阻燃树脂组合物证实具有通过UL-94的V-0的高阻燃性,另外,其可模塑性也令人满意。
Claims (6)
1.一种非卤素阻燃热塑性树脂组合物,包含下列组分成为均相共混物:
(A)100质量份除聚碳酸酯树脂和聚苯醚树脂之外的无卤素热塑性树脂;
(B)10-300质量份的无机粉末;
(C)1-50质量份的用下列平均单元式表示的有机聚硅氧烷
RaSiO(4-a)/2
其中,R表示羟基、具有1-10个碳原子的烷基、具有2-10个碳原子的链烯基或者芳基,下标a表示1.9-2.1的数;以及
(D)0.01-10质量份的1H-苯并三唑、4-甲基-1H-苯并三唑或5-甲基-1H-苯并三唑。
2.根据权利要求1的非卤素阻燃热塑性树脂组合物,进一步含有0.01-10质量份含有铂族元素的催化剂。
3.根据权利要求1或2的非卤素阻燃热塑性树脂组合物,其中,作为组份(C)的有机聚硅氧烷具有2,500-30,000范围内的数均聚合度。
4.根据权利要求1或2的非卤素阻燃热塑性树脂组合物,其中,组份(A)选自基于聚烯烃的树脂、基于聚醋酸乙烯酯的树脂和基于聚苯乙烯的热塑性弹性体。
5.根据权利要求1或2的非卤素阻燃热塑性树脂组合物,其中组份(B)为金属氢氧化物。
6.由根据权利要求1至5任一项的非卤素阻燃热塑性树脂组合物成型的模塑制品。
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CN1982362A CN1982362A (zh) | 2007-06-20 |
CN1982362B true CN1982362B (zh) | 2012-06-27 |
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US (1) | US7745519B2 (zh) |
EP (1) | EP1798256B1 (zh) |
JP (1) | JP4674701B2 (zh) |
KR (1) | KR100943381B1 (zh) |
CN (1) | CN1982362B (zh) |
DE (1) | DE602006007425D1 (zh) |
TW (1) | TW200736317A (zh) |
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DE60219387T2 (de) * | 2001-05-16 | 2008-01-03 | Shin-Etsu Chemical Co., Ltd. | Halogenfreie flammhemmende Harzzusammensetzung |
KR100782231B1 (ko) * | 2007-01-25 | 2007-12-05 | 엘에스전선 주식회사 | 난연성 고분자 조성물 및 이를 이용하여 제조된 전선 |
JP2009120673A (ja) * | 2007-11-13 | 2009-06-04 | Shin Etsu Chem Co Ltd | 難燃性樹脂組成物 |
KR100952816B1 (ko) * | 2008-01-29 | 2010-04-14 | 엘에스전선 주식회사 | 난연성 절연재 제조용 조성물 및 전선 |
US8680397B2 (en) * | 2008-11-03 | 2014-03-25 | Honeywell International Inc. | Attrition-resistant high temperature insulated wires and methods for the making thereof |
US20100124663A1 (en) * | 2008-11-20 | 2010-05-20 | Alpha Technical Research Co. Ltd. | Resin composition and sheet using resin composition |
CN102471517B (zh) * | 2009-08-13 | 2015-05-13 | 旭化成化学株式会社 | 发泡珠粒、使用了该发泡珠粒的成型体和成型体的制造方法 |
US20110147038A1 (en) * | 2009-12-17 | 2011-06-23 | Honeywell International Inc. | Oxidation-resistant high temperature wires and methods for the making thereof |
CN102040773B (zh) * | 2010-12-07 | 2012-11-21 | 惠州市沃特新材料有限公司 | 一种塑料合金、其制备方法和应用 |
JP2013194080A (ja) * | 2012-03-16 | 2013-09-30 | Teijin Ltd | 難燃ポリエステル組成物及び難燃ポリエステル成形品 |
JP5800085B2 (ja) * | 2012-03-21 | 2015-10-28 | 日立化成株式会社 | 無機蛍光体含有ポリマー粒子、無機蛍光体含有ポリマー粒子の製造方法、及び太陽電池モジュール |
CN102817284B (zh) * | 2012-08-23 | 2014-12-03 | 浙江池河科技有限公司 | 一种人造革用离型层及离型纸 |
CN104066798A (zh) * | 2012-09-20 | 2014-09-24 | 住友电气工业株式会社 | 阻燃性树脂组合物、阻燃性热收缩管和阻燃性绝缘电线 |
DE102012022482A1 (de) | 2012-11-19 | 2014-05-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymerzusammensetzung mit verbesserter Langzeitstabilität, hieraus hergestellte Formteile sowie Verwendungszwecke |
CN103013246A (zh) * | 2012-12-19 | 2013-04-03 | 青岛华电高压电气有限公司 | 一种阻燃涂料 |
CN103013022B (zh) * | 2012-12-28 | 2015-04-08 | 四川鑫成新材料科技有限公司 | 高耐磨改性聚烯烃管道材料及其制备方法 |
DE102013005307A1 (de) | 2013-03-25 | 2014-09-25 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung von organischen Oxyimiden als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffzusammensetzung und hieraus hergestelltem Formteil |
JP2015048371A (ja) * | 2013-08-30 | 2015-03-16 | 日立金属株式会社 | ノンハロゲン樹脂組成物、絶縁電線及びケーブル |
DE102014210214A1 (de) | 2014-05-28 | 2015-12-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung von Oxyimid-enthaltenden Copolymeren oder Polymeren als Flammschutzmittel, Stabilisatoren, Rheologiemodifikatoren für Kunststoffe, Initiatoren für Polymerisations- und Pfropfprozesse, Vernetzungs- oder Kopplungsmittel sowie solche Copolymere oder Polymere enthaltende Kunststoffformmassen |
DE102014211276A1 (de) * | 2014-06-12 | 2015-12-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung von Hydroxybenzotriazol-Derivaten und/oder Hydroxy-Indazol-Derivaten als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffformmasse |
CN104031211A (zh) * | 2014-06-17 | 2014-09-10 | 常州天马集团有限公司(原建材二五三厂) | 无卤阻燃胶衣树脂及其制备方法 |
KR101721512B1 (ko) * | 2015-04-09 | 2017-03-31 | 엘에스전선 주식회사 | 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물 |
US20160340517A1 (en) * | 2015-05-21 | 2016-11-24 | Chestnut Springs Llc | Flame retardant compositions and processes for preparation thereof |
KR102006525B1 (ko) * | 2016-10-07 | 2019-08-01 | 엘에스전선 주식회사 | 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물 |
JP2019031601A (ja) * | 2017-08-07 | 2019-02-28 | 信越化学工業株式会社 | 付加硬化型シリコーン組成物及びシリコーンゴム硬化物 |
CN109485975A (zh) * | 2018-11-19 | 2019-03-19 | 成都市水泷头化工科技有限公司 | 一种阻燃高密度聚乙烯燃气输送管及制备方法 |
KR102151360B1 (ko) * | 2019-10-28 | 2020-09-02 | 엘에스전선 주식회사 | 케이블 개재용 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물 |
KR102151359B1 (ko) * | 2019-10-28 | 2020-09-02 | 엘에스전선 주식회사 | 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물 |
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-
2005
- 2005-12-14 JP JP2005360242A patent/JP4674701B2/ja active Active
-
2006
- 2006-12-07 EP EP06291886A patent/EP1798256B1/en not_active Ceased
- 2006-12-07 DE DE602006007425T patent/DE602006007425D1/de active Active
- 2006-12-13 TW TW095146719A patent/TW200736317A/zh not_active IP Right Cessation
- 2006-12-13 US US11/637,720 patent/US7745519B2/en not_active Expired - Fee Related
- 2006-12-13 KR KR1020060126830A patent/KR100943381B1/ko active IP Right Grant
- 2006-12-14 CN CN2006101693224A patent/CN1982362B/zh not_active Expired - Fee Related
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US3950301A (en) * | 1974-08-01 | 1976-04-13 | General Electric Company | Light stabilized polyester resin composition |
EP1441004A2 (en) * | 2003-01-27 | 2004-07-28 | Shin-Etsu Chemical Co., Ltd. | Halogen-free flame-retardant resin composition |
CN1651498A (zh) * | 2004-01-26 | 2005-08-10 | 信越化学工业株式会社 | 非卤素阻燃树脂组合物 |
Also Published As
Publication number | Publication date |
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TW200736317A (en) | 2007-10-01 |
JP2007161883A (ja) | 2007-06-28 |
DE602006007425D1 (de) | 2009-08-06 |
EP1798256B1 (en) | 2009-06-24 |
EP1798256A1 (en) | 2007-06-20 |
US20070135538A1 (en) | 2007-06-14 |
CN1982362A (zh) | 2007-06-20 |
JP4674701B2 (ja) | 2011-04-20 |
TWI375699B (zh) | 2012-11-01 |
KR20070063436A (ko) | 2007-06-19 |
US7745519B2 (en) | 2010-06-29 |
KR100943381B1 (ko) | 2010-02-18 |
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