CN102656217A - 包括发泡型防火涂层的阻燃聚酰胺铸件 - Google Patents
包括发泡型防火涂层的阻燃聚酰胺铸件 Download PDFInfo
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- CN102656217A CN102656217A CN2010800576196A CN201080057619A CN102656217A CN 102656217 A CN102656217 A CN 102656217A CN 2010800576196 A CN2010800576196 A CN 2010800576196A CN 201080057619 A CN201080057619 A CN 201080057619A CN 102656217 A CN102656217 A CN 102656217A
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Abstract
本发明涉及包含发泡型防火涂层的阻燃聚酰胺铸件。具有优异阻燃性的所述铸件在聚酰胺基质中包含至少一种阻燃体系，并在所述铸件的至少一个表面上具有发泡型防火涂层。
Description
技术领域
本发明涉及包含发泡型防火涂层的基于聚酰胺的阻燃模制品。具有优异阻燃性的这些制品在聚酰胺基质中包含至少一种阻燃体系，并在所述模制品的至少一个表面上具有发泡型防火涂层。
背景技术
基于聚酰胺树脂的组合物用于通过由通用术语“模制”表示的各种成形过程来制备制品。这些制品用于众多技术领域。其中，电学或电子系统组件的生产是需要特殊性质的主要应用。因此，这些组件必须具有优异的机械性能以及化学耐性和电绝缘性，尤其是高的阻燃性。
基于聚酰胺树脂的组合物的阻燃性已经研究了很久。因此，所使用的主要阻燃剂是红磷和卤代化合物，例如二溴酚、多溴二苯、多溴二苯醚和溴化聚苯乙烯。从大约二十年前，已经开发新的阻燃剂种类，例如属于三嗪类的含氮有机化合物，如三聚氰胺或其衍生物，例如氰尿酸三聚氰胺以及最近的磷酸三聚氰胺、多磷酸三聚氰胺和焦磷酸三聚氰胺，单独使用或与有机和/或无机膦酸盐或次膦酸盐组合。
所述最后一类阻燃剂的优点在于所涉及化合物不含卤素或红磷的事实。这是因为含有卤素或红磷的阻燃剂可以在燃烧聚酰胺组合物期间或甚至在制备所述组合物期间产生毒气。然而，获得满意的阻燃性所需的一些基于三聚氰胺的化合物的含量非常高，尤其对于含有纤维形式(例如玻璃纤维)的增强填料的组合物而言。这种高浓度的三聚氰胺化合物具有某些缺点，尤其是在制备组合物期间，例如产生含三聚氰胺的化合物的蒸汽，或在制备模制品期间，例如通风管阻塞和在模具中沉淀。
同样地，新的基于有机磷的阻燃体系非常昂贵，且需要大量使用以获得良好的阻燃性。
此外，聚酰胺基质中的过高含量的阻燃剂导致其机械性能受损。
因此需要制备包含阻燃剂(特别是有机磷化合物)的含量的阻燃聚酰胺组合物，所述含量相对低或，无论如何，明显低于常规用于获得良好阻燃性能力的含量。
发明内容
完全出乎意料地，申请人公司表明，可以通过对所述聚酰胺制品涂覆发泡型防火涂层来制备具有优异阻燃性的聚酰胺制品，同时使用少量阻燃剂。
因此，本发明涉及基于聚酰胺的制品，其通过阻燃体系获得阻燃性并包含发泡型防火涂层。
因此本发明的主题是通过成型包含至少一种阻燃体系的聚酰胺组合物而获得的阻燃制品，所述制品至少在其一部分表面上包含发泡型防火涂层。
在本发明含义内，应理解发泡型防火涂层是指一种材料涂层，其区别特征在于所述涂层在超过某温度情况下膨胀。因此，所述材料尤其具有延迟燃烧传播的性质。
应理解表面是指本发明聚酰胺制品的表面层。表面通常是由边界或分界线定义的部分。取决于制品及其复杂性，表面特别可以是平的、凹的和/或凸的。
聚酰胺
本发明制品通过成型基于聚酰胺的组合物而获得，也就是说含有至少一种聚酰胺的组合物。
聚酰胺选自由线性二羧酸和线性或环状二胺缩聚而获得的聚酰胺，例如PA 6.6、PA 6.10、PA 6.12、PA 12.12、PA 4.6或MXD 6，或由芳族二羧酸和线性或芳族二胺缩聚而获得的聚酰胺，例如聚对苯二甲酰胺、聚间苯二甲酰胺和聚芳酰胺，以及由氨基酸本身缩聚而获得的聚酰胺，氨基酸可通过水解打开内酰胺环而产生，例如PA 6、PA 7、PA 11或PA 12。
本发明组合物也可以包含尤其来源于上述聚酰胺的共聚酰胺，或这些聚酰胺或共聚酰胺的混合物。
优选的聚酰胺是聚(己二酰己二胺)、聚己内酰胺、或聚(己二酰己二胺)和聚己内酰胺的共聚物和混合物。
通常使用分子量适于注模过程的聚酰胺，尽管也可以使用具有较低粘性的聚酰胺。也可以使用具有较高分子量的聚酰胺，尤其是在挤出或挤出/吹塑类型的转化过程方面。
聚酰胺基质特别可以是含有星型或H型大分子链的聚合物，适当的话也可以是含有线型大分子链的聚合物。含有这种星型或H型大分子链的聚合物例如在文献FR 2 743 077、FR 2 779 730、US 5 959 069、EP 0 632 703、EP 0682 057和EP 0 832 149中描述。
根据本发明另一个具体的替代形式，本发明聚酰胺基质可以是无规树型的聚合物，优选具有无规树型结构的共聚酰胺。具有无规树型结构的这些共聚酰胺及其制备方法特别在文献WO 99/03909中描述。本发明基质也可以是含有线型热塑性聚合物和上述星型、H型和/或树型热塑性聚合物的组合物。本发明基质也可包含文献WO 00/68298中描述的那些种类的超支化的共聚酰胺。本发明组合物也可包含上述线型、星型、H型和树型热塑性聚合物和超支化共聚酰胺的任意组合。
本发明组合物可包含相对于组合物总重量的20至99重量％，优选20至80重量％，更优选50至70重量％的聚酰胺。
除聚酰胺外，组合物基质还可以包含一种或多种其他聚合物，特别是热塑性聚合物。
所述组合物还可以包含增强填料，尤其选自下组：玻璃纤维、无机填料(例如高岭土、滑石或钙硅石)和可脱落填料。相对于组合物的总重量，增强填料的重量浓度有利地为1至50重量％，优选15至50重量％。尤其可以使用玻璃纤维和无机填料例如硅灰石的混合物。
本发明组合物也可包含通常用于被用来制备模制品的基于聚酰胺的组合物中的任何添加剂。因此，可以提及的实例是添加剂、热稳定剂、U.V.稳定剂、抗氧化剂、润滑剂、颜料、染料、增塑剂或改变冲击强度的试剂。举例来说，抗氧化剂和热稳定剂例如是碱金属卤化物、卤化铜、位阻酚化合物或芳族胺。U.V.稳定剂通常是苯并三唑、二苯甲酮或HALS。
对改变冲击强度的试剂类型没有限制。通常它是可用于该目的的弹性聚合物。合适的弹性体的实例是乙烯/丙烯酸酯/马来酸酐聚合物、乙烯/丙烯/马来酐聚合物或任选用马来酸酐接枝的EPDM(乙烯/丙烯/二烯单体)聚合物。相对于组合物的总重量，弹性体的重量浓度有利地为0.1至15％。
本发明组合物通过通常在单螺杆或双螺杆挤出机中，在足以保持聚酰胺树脂作为熔融介质的温度下混合各种成分而获得。通常，所得混合物以杆状挤出，其切成片以形成颗粒。可以通过在热状态或冷状态下通过混合将阻燃剂一起或单独添加至聚酰胺。
化合物和添加剂的添加可以通过将这些化合物以纯净的形式或在树脂(例如聚酰胺树脂)中的浓缩混合物形式添加至熔融聚酰胺中来进行。
所得颗粒用作原材料送至用于制备制品的进料过程中，例如注射、注模、挤出和挤出/吹塑过程。
本发明制品尤其可以是挤出或注射制品。
因此，本发明组合物尤其适于制备用于电学或电子连接件领域的制品，例如断路器、开关、连接器等的组件。
PA基质中的阻燃剂
本发明的阻燃体系可以包含任何类型的阻燃剂，即可能降低火焰传播和/或具有阻燃性的化合物，其是本领域技术人员所熟知的。这些阻燃剂通常用于阻燃组合物，尤其在例如专利US 6 344 158、US 6 365 071、US 6 211 402和US 6 255 371中描述，以引用方式引用于此。
有利地，所述阻燃体系包含至少一种选自下组的阻燃剂：
*含磷阻燃剂，例如：
-氧化膦，例如三苯基氧化膦、三(3-羟基丙基)氧化膦和三(3-羟基-2-甲基丙基)氧化膦，
-膦酸及其盐和次膦酸及其盐，例如，次膦酸的锌盐、镁盐、钙盐、铝盐或锰盐，尤其是二乙基次膦酸的铝盐或二甲基次膦酸的锌盐，
-环状膦酸酯，例如环状二膦酸酯，例如Antiblaze 1045，
-有机磷酸酯，例如磷酸三苯酯，
-无机磷酸盐，例如聚磷酸铵和聚磷酸钠，
-红磷，例如，不管是稳定化或涂层形式、作为粉末或以原批形式。
*含氮有机化合物类型的阻燃剂，例如，三嗪、氰尿酸和/或异氰尿酸、三聚氰胺或其衍生物，例如氰尿酸三聚氰胺、草酸三聚氰胺、酞酸三聚氰胺、硼酸三聚氰胺、硫酸三聚氰胺、磷酸三聚氰胺、多磷酸三聚氰胺和/或焦磷酸三聚氰胺、由三聚氰胺(例如蜜勒胺、蜜白胺和氰尿酰胺(melon))缩合的产物、三(羟乙基)异氰尿酸酯、苯代三聚氰胺、胍、尿囊素和甘脲，
*含卤化衍生物的阻燃剂，例如：
-溴衍生物，例如，PBDPO(多溴二苯醚)、BrPS(多溴苯乙烯和溴化聚苯乙烯)、聚(五溴苄基丙烯酸酯)、溴化茚满、十四溴二苯氧基苯(Saytex 120)、1，2-双(五溴苯基)乙烷或来自Albemarle的Saytex 8010、四溴双酚A和溴化环氧低聚物。尤其可以提及聚二溴苯乙烯的溴化衍生物，例如来自Chemtura的PDBS-80；溴化聚苯乙烯，例如来自Albemarle的Saytex HP 3010或来自Dead Sea Bromine Group的FR-803P、来自Dead Sea Bromine Group的阻燃剂十溴二苯醚(DBPE)或FR-1210、八溴二苯醚(OBPE)、来自Dead Sea BromineGroup的2，4，6-三(2，4，6-三溴苯氧基)-1，3，5-三嗪或FR-245、来自Dead SeaBromine Group的聚(五溴苄基丙烯酸酯)或FR-1025以及含有四溴双酚A的环氧末端的低聚物或聚合物，例如来自Dead Sea Bromine Group的F-2300和F2400，
-氯化化合物，例如，氯化脂环族化合物，例如Dechlorane Plus(由OxyChem销售，参加CAS 13560-89-9)。
这些化合物可单独或组合使用，有时协同使用。尤其优选含磷化合物，例如氧化膦、膦酸或其盐或次膦酸或其盐和环状膦酸酯与含氮衍生物，例如蜜白胺、蜜勒胺、磷酸三聚氰胺、多磷酸三聚氰胺、焦磷酸三聚氰胺或聚磷酸铵的协同组合。
组合物可包含相对于组合物总重量的5到40重量％的阻燃剂。
发泡型防火涂层
发泡型防火涂层是其区别特征在于其在加热情况下转变的产品。在冷状态下，膜的厚度通常为0.1到4mm。加热至180℃到300℃的温度，所述产品膨胀并转变为泡沫，通常厚度达到30到40mm。这些涂层根据所述领域所用的常规方法使用，尤其经由喷枪或刷子使用，但在其施加阶段需要非常精确，以确保保护层是均匀的。吸引人的外观的维持是这类保护层的主要优点，其可以实现一个小时的保护时间，甚至对于一些溶液，可实现一个半小时到两小时的保护时间。发泡型防火涂层还具有有利的耐用性且可在内部或外部使用。由于这些多种优点以及规则的变化，发泡型防火涂层经历主要发展。
事实上为金属结构销售的所有发泡型防火涂层(其也适用于本发明)由四种主要成分组成：
-酸源：能释放酸的化合物，例如，磷酸，当其经历升温时。通常使用聚磷酸铵(APP)或磷酸三聚氰胺，
-碳源：含有能与酸反应的羟基的有机化合物，例如，羟基，通常为季戊四醇，
-发泡剂：在加热作用下释放使磷/碳结构膨胀的大量不可燃气体的化合物，例如，三聚氰胺，
-和，最后，粘合剂：一种物质，通常为液体物质，与或不与溶剂组合，其捕获颜料或添加剂颗粒并在干燥后形成固体膜。例如，所述物质特别可以是丙烯酸树脂或环氧树脂。所述粘合剂是涂层的基础元素，其使所述涂层特性化。
发泡型防火涂层可以选自下组：水性涂层、丙三氧基涂层(glycerocoating)、纤维素涂层、乙烯基涂层、丙烯酸涂层、聚氨酯涂层和环氧涂层。
本发明所用的涂层优选是油漆或清漆；例如，能与聚合物基质良好粘合的软的、水基的、无光泽的、透明的发泡清漆。
普遍接受的导致发泡发展的机制如下。第一步，在温度升高作用下酸源分解，例如释放磷酸，其与碳源剂反应形成磷酸酯和水。随后这些酯分解并导致磷/碳结构的形成，一般称为焦炭。由于这些反应发生在超过100℃的温度下，所释放的水立即转化为蒸汽。所述蒸汽和发泡剂分解的气体将磷/碳结构转化为泡沫。粘合剂将帮助捕获分解气体并将对膨胀程度和组成泡沫的小室的尺寸有着显著影响，并因此对发泡结构的阻燃性能有着显著影响。
认为制品的待处理表面和发泡型防火涂层之间的粘合是要点。通常，机械粘合模型与特定粘合模型不同，其完全涵盖除纯机械锚定以外的现象。从后者中选择扩散理论，和热机吸附理论，或润湿理论。也存在电学或化学粘合模型。
机械粘合由孔隙中的机械锚定和基质的碰撞产生。通过扩散的粘合由表面平面分子的相互扩散产生，其通过称为厚的间期或分界面的转变区域的产生来反映。通过相互扩散的粘合基于两种基本标准：热力学标准：大分子必须是互溶或相容的，以及动力标准：大分子必须具有足够的流动性，因此温度很重要。当这两种状态组合时，大分子链发生互相渗透。引起破裂所需的力一方面与通过分界面的链数成比例，另一方面，与大分子的平均渗透深度成比例。例如，这种理论在粘合相容性聚合物的情况下被证实是明确的。
润湿理论由Sharpe和Schonhorn介绍。根据该理论，粘合归因于存在于分界面的范德瓦尔斯类型的分子间力。这些分子间键是弱的和不定向的。它们在大约分子间距离具有作用范围。因为该理由，为了使其变成确定的，有必要使两种表面密切接触。通常，良好粘合的标准本质上就是润湿性标准。
为了增加制品的待处理表面和发泡型防火涂层之间的粘合，例如可以通过等离子体处理或通过火焰处理预先处理所述表面。基质特别可以通过火焰处理来预先处理，从而提高油漆或清漆类型的发泡型防火涂层与聚合物的粘合质量。火焰处理在于使待处理表面暴露于加热氧化；在碳氢化合物燃烧期间产生氧化焰。用于火焰处理的优化参数例如是：火焰和表面之间的距离为8.8cm，火焰处理装置的速度为200m/s，样品在火焰前面通过三次并使用甲烷作为燃烧气体。
作为发泡型防火涂层，尤其可以提及以下产品：
-来自Flame Seal Products的FX-100
-Nullifire(例如，S607-油漆)
-Unitherm 19010-清漆
-A650P-Comus清漆
-Char 17-来自Iris Vernici s.r.l.，Italy的清漆
-来自Firetherm Intumescent and Insulation Supplies Ltd.，Kent，UnitedKingdom的Firesteel；
-来自Altex Coatings Ltd.，Bay of Plenty，New Zealand的Firetex；
-来自AD Fire Protection Systems Ltd.，Ontario，Canada的A/DFirefilm
-来自Nippon Paint Company，Osaka，Japan的Taikalitt；
-来自Eagle Specialized Coatings and Protected Environments，Division ofDW Pearce Enterprises Ltd.，British Columbia，Canada的Safecoat产品。
发泡型防火涂层施加于本发明制品的至少一部分表面上。所述涂层将尤其施加于很可能与强热(特别是火焰)接触的表面部分。
尤其优选使用不含阻燃剂的发泡型防火涂层，例如可以原料形式用于本发明聚酰胺组合物的那些。
本发明也涉及制备阻燃制品的方法，其中在任选进行处理表面以增加表面和涂层之间的粘合的步骤后，将发泡型防火涂层施加于制品的至少一部分表面上。
在说明书中使用特定语言，以促进本发明原理的理解。然而，应理解使用所述特定语言不预期对本发明范围的限制。本技术领域的技术人员根据其自身常识尤其可预期修改和改进。
术语“和/或”包括含义“和”、“或”和与该术语有关元素的所有其他可能的组合。
本发明的其他细节或优点将根据仅作为指示给出的以下实施例而变得更加明确。
具体实施方式
实验部分
所使用材料
所述测试在未使用过的聚酰胺6，6、加有2％的插入的硅酸盐纳米填料(Nanofil SE3010 from Sud-Chemie)的聚酰胺6，6、加有30％的玻璃纤维(Vetrotex 983)的聚酰胺6，6、和加有30％的玻璃纤维和2％的纳米填料的聚酰胺6，6上进行。
将阻燃剂添加至一些制剂中：
-FR1：次膦酸铝(来自Clariant的OP 1230)
-FR2：1，2-双(五溴苯基)乙烷(来自Albemarle的Saytex 8010)
使用3种涂层：发泡油漆Nullifire S607HB(Nullifire)，以及两种发泡清漆，A650P(SEPV-Comus)和Pyroplast HW(Rustifrance)。
沉淀涂层的过程
沉淀过程分两步进行：预处理和沉淀步骤。在约1000℃的温度下通过火焰处理预先处理基质从而提高以下步骤期间发泡型防火涂层与聚合物的粘合的质量。火焰处理在于使待处理表面暴露于加热氧化；在碳氢化合物燃烧期间产生氧化焰。在之前研究期间优化的火焰处理参数是：火焰和表面之间的距离为8.8cm，火焰处理装置的速度为200m/s，样品在火焰前面通过三次并使用甲烷作为燃烧气体。
发泡型防火涂层的施加采用刷子进行或可通过喷雾进行。
划痕试验显示，火焰处理可以改善涂层与聚合物的粘合。这在采用Elcometer
107切割器的方格(cross hatch)试验中观察到。给出粘合的定性评价的这种试验在于采用具有分开一毫米的六个或十一个齿状物的切割器划基质表面，从而刻画出25或100个正方形的方格图，取决于切割器的齿状物数目，所述正方形大小为1mm2。随后粘合剂的标准化片与其接触，所述粘合剂片在90±30秒后移除。移除粘合剂后检查方格表面，有可能对作为撕掉涂层数目的函数的基质的粘合性能进行分类。进行所述试验的同时观察标准的ASTM D 3359-02“Standard Test Methods for Measuring Adhesionby Tape Test”。
阻燃性的测量
按常规进行以百分比表示的LOI(极限氧指数(Limiting Oxygen Index))和UL94试验。
灼热金属丝试验装置可以测量GWFI(灼热金属丝可燃性指数)。GWFI在于模拟热震和在于评价由完全相同的材料产生的火焰的点燃风险和自动熄灭能力。该方法在于在给定温度(550、650、750、850、960℃)下以0.8至1.2N的给定力将热金属丝和/或灼热金属丝的末端施加于60mm x 60mm试验样品30s，和在于在移除金属丝后测量火焰的熄灭时间。
所述产品的特征在于移除灼热金属丝后，3个连续试验样品自动熄灭的温度低于30s。
在试验期间，必须记录以下各项：
-从施加灼热金属丝的末端开始直到试验样品或规定的底层点燃瞬间的时间(ti)。
-从施加灼热金属丝的末端开始直到施加期间或之后火焰熄灭瞬间的时间(te)。
-任何火焰的最大高度，然而，不考虑可在约1s内产生高火焰的火焰开始出现时。
-试验样品是否通过试验，因为点燃的较大部分被灼热金属丝带走。
-置于样品下的底层中任何火焰的出现(这要求在较低温度下在3个新的试验样品上进行新的试验)。
必须在施加灼热金属丝期间观察试验样品。必须记录点燃时间(ti)，即施加金属丝的末端开始和试验样品形成火焰时间之间的时间。
锥形量热计是尤其可以获得通过样品燃烧发出的热量变化、易燃性、失重、烟雾不透明度和试验期间发出的CO/CO2水平的装置。所述样品水平放置并经受受控水平的辐照。所述试验在提取器的存在下在开放环境中进行。所述样品在环境空气中经受由截锥体发出的热通量(热通量为0至100kW/m2)，从而不干扰火焰。热释放率根据氧消耗量热学原理来评估。与该体系偶联的多个分析器可以评估失重、烟雾不透明度(消光系数k)和燃烧期间的CO和CO2含量(红外线分析仪)。点燃时间通过该试验测量。
结果
试验结果在下表中给出：
表1
表2
表3
由此观察到，与通常使用的阻燃聚酰胺组合物比较，在其至少一部分表面上包含发泡型防火涂层的本发明阻燃制品具有好的多的阻燃性。
Claims (12)
1.通过成型包含至少一种阻燃体系的聚酰胺组合物而获得的阻燃制品，所述制品至少在其一部分表面上包含发泡型防火涂层。
2.如权利要求1所述的制品，其特征在于所述组合物还包含增强填料。
3.如权利要求1或2所述的制品，其特征在于所述聚酰胺组合物的阻燃体系包含至少一种选自下组的含磷阻燃剂：氧化膦、膦酸及其盐、次膦酸及其盐、环状膦酸酯、有机磷酸酯、无机磷酸盐和红磷。
4.如权利要求1至3任一项所述的制品，其特征在于所述聚酰胺组合物的阻燃体系包含至少一种选自下组的含氮有机化合物类型的阻燃剂：三嗪类、氰尿酸和异氰尿酸、三聚氰胺及其衍生物、草酸三聚氰胺、酞酸三聚氰胺、硼酸三聚氰胺、硫酸三聚氰胺、磷酸三聚氰胺、多磷酸三聚氰胺和焦磷酸三聚氰胺、由三聚氰胺缩合的产物、三(羟乙基)异氰尿酸酯、苯代三聚氰胺、胍、尿囊素和甘脲。
5.如权利要求1至4任一项所述的制品，其特征在于所述聚酰胺组合物的阻燃体系包含至少一种选自下组的含溴化衍生物的阻燃剂：PBDPO(多溴二苯醚)、BrPS(多溴苯乙烯和溴化聚苯乙烯)、聚(五溴苄基丙烯酸酯)、溴化茚满、十四溴二苯氧基苯、1，2-双(五溴苯基)乙烷、四溴双酚A和溴化环氧低聚物。
6.如权利要求1至5任一项所述的制品，其特征在于所述组合物包含相对于组合物总重量的5到40重量％的阻燃剂。
7.如权利要求1至6任一项所述的制品，其特征在于所述发泡型防火涂层包含酸源、碳源、发泡剂和粘合剂。
8.如权利要求1至7任一项所述的制品，其特征在于所述发泡型防火涂层选自下组：水性涂层、丙三氧基涂层、纤维素涂层、乙烯基涂层、丙烯酸涂层、聚氨酯涂层和环氧涂层。
9.如权利要求1至8任一项所述的制品，其特征在于所述发泡型防火涂层是油漆或清漆。
10.如权利要求1至9任一项所述的制品，其特征在于所述制品是挤出制品或注射制品。
11.制备如权利要求1至10任一项所述的制品的方法，其中在任选进行处理表面以增加表面和涂层之间的粘合的步骤后，将发泡型防火涂层施加于所述制品的至少一部分表面上。
12.如权利要求11所述的方法，其中表面和涂层之间的粘合的增加通过等离子体处理或火焰处理完成。
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| GB2492142A (en) * | 2011-06-23 | 2012-12-26 | Michael James Drane | Method of protecting fire unstable material from heat and flame damage |
| DE102012100628A1 (de) * | 2012-01-25 | 2013-07-25 | Ebm-Papst Mulfingen Gmbh & Co. Kg | Schaufelrad mit Intumeszenz-Beschichtung |
| EP2671907A1 (de) * | 2012-06-06 | 2013-12-11 | Georg Fischer Rohrleitungssysteme AG | Flammgeschütztes Kunststoff-Rohrleitungssystem |
| DE102014008830A1 (de) * | 2014-06-20 | 2015-12-24 | Mann + Hummel Gmbh | Sensoreinrichtung, Filteranordnung und Verfahren zum Herstellen derselben |
| CH711604B1 (de) * | 2015-10-02 | 2019-07-15 | Ems Patent Ag | Polyamid-basierte Komponenten mit verbessertem Brandverhalten. |
| US20200115551A1 (en) | 2016-12-22 | 2020-04-16 | Dsm Ip Assets B.V. | Improved heat and electrically resistive thermoplastic resin compositions |
| CN111785563B (zh) * | 2020-08-21 | 2023-08-22 | 湖北大禹汉光真空电器有限公司 | 一种用于真空灭弧室的耐高温主屏蔽筒及其制作方法 |
| CN118488988A (zh) * | 2021-12-28 | 2024-08-13 | Sabic环球技术有限责任公司 | 包含物体和层的制品 |
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- 2010-10-15 CN CN201510883176.0A patent/CN105295084A/zh active Pending
- 2010-10-15 WO PCT/EP2010/065553 patent/WO2011045426A1/fr active Application Filing
- 2010-10-15 EP EP16152782.5A patent/EP3112403A1/fr not_active Withdrawn
- 2010-10-15 CN CN2010800576196A patent/CN102656217A/zh active Pending
- 2010-10-15 BR BR112012008800-9A patent/BR112012008800B1/pt not_active IP Right Cessation
- 2010-10-15 US US13/502,074 patent/US20120276391A1/en not_active Abandoned
- 2010-10-15 EP EP10781849.4A patent/EP2488574B1/fr not_active Not-in-force
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| US20070275617A1 (en) * | 2006-05-25 | 2007-11-29 | Wp Ip, Llc | Decorative flame barrier surface covering |
| EP1935894A1 (de) * | 2006-12-12 | 2008-06-25 | Clariant International Ltd. | Carboxyethyl(alkyl)phoshinsäure-Alkylestersalze |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109320745A (zh) * | 2016-08-02 | 2019-02-12 | 南通凯英薄膜技术有限公司 | 一种阻燃耐高温聚酰亚胺复合板及其应用 |
| CN113597366A (zh) * | 2019-03-18 | 2021-11-02 | 阿科玛法国公司 | 用于3d打印的阻燃聚酰胺和共聚酰胺 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2488574B1 (fr) | 2016-01-27 |
| FR2951452A1 (fr) | 2011-04-22 |
| EP3112403A1 (fr) | 2017-01-04 |
| WO2011045426A1 (fr) | 2011-04-21 |
| EP2488574A1 (fr) | 2012-08-22 |
| FR2951452B1 (fr) | 2012-07-27 |
| BR112012008800B1 (pt) | 2022-10-11 |
| KR101424898B1 (ko) | 2014-07-31 |
| CN105295084A (zh) | 2016-02-03 |
| US20120276391A1 (en) | 2012-11-01 |
| BR112012008800A2 (pt) | 2020-02-04 |
| KR20120066656A (ko) | 2012-06-22 |
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