CN113825792A - 用于激光焊接应用的具有高激光透射率的黑色聚酰胺组合物 - Google Patents

用于激光焊接应用的具有高激光透射率的黑色聚酰胺组合物 Download PDF

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CN113825792A
CN113825792A CN202080035676.8A CN202080035676A CN113825792A CN 113825792 A CN113825792 A CN 113825792A CN 202080035676 A CN202080035676 A CN 202080035676A CN 113825792 A CN113825792 A CN 113825792A
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polyamide composition
polyamide
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hexamethylenediamine
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王焕冰
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BASF SE
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Abstract

聚酰胺组合物，包括(i)至少一种脂族聚酰胺或半芳族聚酰胺或其混合物；(ii)玻璃纤维；(iii)最高达8重量％的量的至少一种非纤维增强材料；(iv)至少一种单偶氮络合物类型的黑色染料；(v)任选地一种或多种其他添加剂。

Description

用于激光焊接应用的具有高激光透射率的黑色聚酰胺组合物
技术领域
本发明涉及一种产生模制件的聚酰胺组合物，该模制件在使用激光焊接技术制备制品时表现出高激光透射性，同时保持令人满意的机械性能。该制品可用于特定的汽车应用，例如过滤器外壳、谐振器、排气控制阀、门锁部件和显示部件。
背景技术
作为连接塑料的工具，激光仍然相对较新，但这种工业应用很可能会变得如激光打标和激光切割一样成熟。迄今为止，使用激光焊接的材料主要是塑料膜，并且该工艺最近才扩展到用于批量生产零件的三维组件的连接。
与传统焊接方法(如加热工具焊接、振动焊接或超声波焊接)相比，热塑性塑料的激光焊接工艺技术具有许多优势：
-不产生粉尘
-良好的美学效果，无明显疤痕
-连接组件上没有机械应力
-对有限区域施加少量热量
-可焊接具有不同刚度的零件
-非接触式(无熔体粘性，组件上无标记)
-可修复焊缝
-可焊接不同黏度的材料
在激光焊接中，两种塑料通常通过将对激光半透明的上层塑料与对激光不半透明的下层塑料粘合在一起而相互结合。此处，激光束穿过塑料的上层而保持不变并到达下层，它被吸收并释放出热能。释放的热能熔化塑料材料，从而在激光束的冲击点将其粘合至上层。
然而，该方法的缺点是不能加工使用吸收染料或颜料着色或包含吸收填料的塑料组合物，因为填料或染料或用于着色的颜料总是各自地立即吸收激光，因此不产生连接。
在汽车工业的许多应用中，需要黑色热塑性材料。然而，即使仅存在少量着色剂或颜料，激光焊接性能也会显著恶化。炭黑和苯胺黑是黑色材料中最常用的黑色着色剂。然而，炭黑表现出在宽波长范围内高的激光吸收率，即使是少量也是如此。苯胺黑较合适，但仍不能满足激光焊接应用中对激光透明组件的要求。因此，仍然需要用于激光焊接应用的改进的黑色聚酰胺组合物，其对980nm和1064nm(为激光焊接中最常用的两种激光波长)的光具有高激光透射率。
US 2002/0002225 A1公开了一种黑色热塑性模塑组合物，其包含由非吸收性、非黑色聚合物可溶性染料制成的染料组合，其产生对激光半透明或透明的黑色热塑性模塑组合物。染料为喹酞酮(chinophthalone)或蒽醌(anthrachinone)染料。
US 2003/0039837 A1公开了一种用于激光焊接的制造树脂产品，包括：第一透射激光束的树脂组件包括吸收波长小于700nm的可见光并透射800nm至1200nm波长范围内的激光束的激光束透射黑色着色剂，以及第二吸收激光束的树脂组件包括吸收激光束的黑色着色剂，其中所述第一树脂组件通过透射穿过所述树脂组件并被所述第二树脂组件吸收的激光束接合到所述第二树脂组件。根据某些实施方案，所述透射激光束的黑色着色剂为单偶氮络合物染料。
本发明的一个目的是通过提供一种具有令人满意的机械性能和在980nm和1064nm处的改进的激光透射率的纤维填充聚酰胺材料来弥补上述缺点，用于生产用于激光焊接应用的黑色激光透明部件。
发明内容
该目的是通过提供一种聚酰胺组合物来实现的，该组合物包含
(i)至少一种脂族聚酰胺或半芳族聚酰胺或其混合物；
(ii)玻璃纤维；
(iii)最高达8重量％的量的至少一种非纤维增强材料；
(iv)至少一种单偶氮络合物类型的黑色染料；
(v)任选地一种或多种其他添加剂。
本发明人惊奇地发现，如果标准短切玻璃纤维和非纤维增强材料(优选玻璃珠)的混合物而不是单独的标准短切玻璃纤维用作增强填料，则聚酰胺组合物在980nm和1064nm处的激光透射率显著提高。同时，聚酰胺组合物的机械性能保持在高水平。
下文更详细地描述本发明的聚酰胺组合物的组分。
本发明的聚酰胺组合物包含(i)至少一种脂族聚酰胺或半芳族聚酰胺，优选包含衍生自六亚甲基二胺和己二酸的缩聚反应的重复单元。该至少一种脂族聚酰胺可任选地包含衍生自可与六亚甲基二胺和己二酸共聚的单体的其他脂族重复单元。
优选地，所述至少一种脂族聚酰胺具有通过凝胶渗透色谱法(GPC)测定的10,000至30,000g/mol，特别是12,000至24,000g/mol的数均分子量(Mn)。
优选地，脂族聚酰胺选自六亚甲基二胺和己二酸的均聚物(PA6.6)、ε-己内酰胺的均聚物(PA6)或六亚甲基二胺、己二酸和ε-己内酰胺的共聚物(PA6.6/6)以及这些脂族聚酰胺的共混物的混合物。如果脂族聚酰胺是包含衍生自ε-己内酰胺的重复单元的共聚物，则这些重复单元以1至30mol％，优选5至20mol％，特别是7至15mol％的量存在，基于所述至少一种脂族聚酰胺的总重量计。聚酰胺的其余组分优选由衍生自摩尔比为1:1的六亚甲基二胺和己二酸的重复单元组成。
如果所述至少一种脂族聚酰胺选自六亚甲基二胺、己二酸和ε-己内酰胺的共聚物(PA6.6/6)，则仅衍生自六亚甲基二胺和己二酸的重复单元占至少一种脂族聚酰胺的40至70重量％，优选为45.0至67.5重量％，基于聚酰胺组合物的总重量计。
半芳族聚酰胺优选包含衍生自六亚甲基二胺、己二酸和至少一种芳族二羧酸的缩聚反应的重复单元。
一般而言，半芳族聚酰胺包含至少5mol％的量的衍生自至少一种芳族二羧酸的重复单元，基于半芳族聚酰胺的总重量计。在本发明的一个更优选的实施方案中，半芳族聚酰胺包含5至50mol％，尤其是10至30mol％的量的衍生自至少一种芳族二羧酸的重复单元，基于至少一种半芳族聚酰胺的摩尔组成计。
半芳族聚酰胺优选由脂族二胺、脂族二羧酸、芳族二胺和/或芳族二羧酸的缩聚反应获得。在进一步优选的实施方案中，半芳族聚酰胺可由脂族二胺、脂族二羧酸和芳族二羧酸的缩聚获得。
优选的脂族二胺包括六亚甲基二胺和/或5-甲基五亚甲基二胺。在一个特别优选的实施方案中使用六亚甲基二胺。
在一个特别优选的实施方案中，使用己二酸作为脂族二羧酸。
在本发明的一个优选的实施方案中，半芳族聚酰胺包含0mol％至90mol％的量的衍生自脂族二羧酸(特别是衍生自己二酸)的重复单元，基于衍生自二羧酸的重复单元的总量计，更优选40mol％至80mol％的衍生自二羧酸的重复单元，而衍生自二羧酸的重复单元的其余部分衍生自芳族二羧酸。
在一个特别优选的实施方案中，至少一种芳族二羧酸选自对苯二甲酸和间苯二甲酸。
在本发明的进一步优选的实施方案中，衍生自至少一种芳族二羧酸的至少一种重复单元衍生自对苯二甲酸，任选与至少一种其他芳族二羧酸组合，特别是与间苯二甲酸组合。优选地，至少一种衍生自对苯二甲酸的重复单元包含于至少一种衍生自至少一种脂族二羧酸(特别是己二酸)的重复单元的组合中，并且任选地进一步与至少一种衍生自至少一种其他芳族二羧酸(尤其是间苯二甲酸)的重复单元组合。
在本发明的一个特别优选的实施方案中，半芳族聚酰胺包含衍生自以下的重复单元
(a)10至60mol％的量的对苯二甲酸或间苯二甲酸，基于衍生自二羧酸的重复单元的总量计，和
(b)40至90mol％的量的己二酸，基于衍生自二羧酸的重复单元的总量计；
其中对苯二甲酸或间苯二甲酸和己二酸的总量总计最高达衍生自二羧酸的重复单元的量的100mol％。
在本发明的另一个特别优选的实施方案中，半芳族聚酰胺包含衍生自以下的重复单元
(a)10至60mol％的量的对苯二甲酸，基于衍生自二羧酸的重复单元的总量计，和
(b)40至90mol％的量的间苯二甲酸，基于衍生自二羧酸的重复单元的总量计；
其中对苯二甲酸和间苯二甲酸的总量总计最高达衍生自二羧酸的重复单元的量的100mol％。
在本发明的又一个特别优选的实施方案中，半芳族聚酰胺包含衍生自以下的重复单元
(a)10至60mol％的量的对苯二甲酸和至少一种其他芳族二羧酸，基于衍生自二羧酸的重复单元的总量计，和
(b)40至90mol％的量的己二酸，基于衍生自二羧酸的重复单元的总量计；
其中己二酸、对苯二甲酸和至少一种另外的芳族二羧酸的总量总计最高达衍生自二羧酸的重复单元的量的100mol％，并且其中对苯二甲酸占10至60mol％，基于衍生自芳族二羧酸的重复单元的总量计，并且至少一种其他芳族酸(特别是间苯二甲酸)占40至90mol％，基于衍生自芳族二羧酸的重复单元的总量计。
因此，在本发明的一个优选的实施方案中，聚酰胺组合物包含至少一种半芳族聚酰胺，其选自六亚甲基二胺、己二酸和对苯二甲酸和/或间苯二甲酸的均聚物和/或共聚物。
在本发明的一个特别优选的实施方案中，至少一种半芳族聚酰胺选自六亚甲基二胺、己二酸和对苯二甲酸的共聚物(PA6.6/6.T)；六亚甲基二胺、己二酸和间苯二甲酸的共聚物(PA6.6/6.I)；六亚甲基二胺、对苯二甲酸和间苯二甲酸的共聚物(PA6.T/6.I)；六亚甲基二胺、己二酸、对苯二甲酸和间苯二甲酸的共聚物(PA6.6/6.T/6.I)以及这些半芳族聚酰胺的混合物。
优选地，至少一种半芳族聚酰胺具有通过凝胶渗透色谱法(GPC)测定的10,000g/mol至30,000g/mol，特别是12,000g/mol至24,000g/mol的数均分子量(Mn)。
聚酰胺(i)通常以30至80.89重量％，优选50至78.88重量％的量存在于聚酰胺组合物中，基于聚酰胺组合物的总重量计。
本发明的聚酰胺组合物进一步包含(ii)玻璃纤维。所用的玻璃纤维可以是短切玻璃纤维或连续玻璃纤维。如果使用短切玻璃纤维，则在通过将组分(i)至(v)混合来制备聚酰胺组合物之前，玻璃纤维优选具有1mm至8mm的长度和5μm至20μm的直径。在与熔融聚合物混合和捏合期间，纤维断裂并且在聚酰胺组合物中的平均长度为200至600μm。优选具有基本圆形横截面的玻璃纤维。
至少一种非纤维增强材料(iii)选自玻璃珠、玻璃片和磨碎的玻璃纤维。在本发明的一个优选实施方案中，非纤维增强材料优选是直径为3至120μm，更优选10μm至60μm的玻璃珠，和/或长度小于250μm以及直径小于20μm的磨碎的玻璃纤维。
因此，在本发明的一个特别优选的实施方案中，聚酰胺组合物包含至少(ii)一种选自玻璃纤维的纤维增强填料和(iii)一种选自玻璃珠的非纤维增强材料。
玻璃珠可以是实心玻璃珠或空心玻璃珠。优选实心玻璃珠。这些玻璃珠是众所周知的，特别是在Plastics Additives Handbook,Hanser，第4版，第537-538页中被提及。
玻璃珠的平均直径通常为1μm至2mm，优选为3至500μm，更优选为3和120μm，特别优选为10μm和60μm。
玻璃珠可以包括涂层，例如特别是硅烷涂层。
玻璃纤维(ii)通常以15至55重量％，优选20至50重量％，更优选25至40重量％的量存在于聚酰胺组合物中，基于聚酰胺组合物的总重量计。
至少一种非纤维增强材料(iii)通常以0.1至8重量％，优选1至8重量％，更优选1至6重量％，并且特别优选1至5重量％的量存在于聚酰胺组合物中，基于聚酰胺组合物的总重量计。
本发明的聚酰胺组合物包含(iv)至少一种单偶氮络合物类型的黑色染料。单偶氮络合物染料可概括为以下通式：
Figure BDA0003351761520000061
式中，A代表任选地具有取代基的芳族残基，B代表任选地具有取代基的萘酚衍生物残基。M为金属，P+为阳离子，q为0-2的整数，K为0-2的整数。
作为前述单偶氮络合物染料的抗衡离子P+，基于H+的阳离子；NH4 +、碱金属(Na、K等)、基于有机胺的阳离子(脂肪伯胺、脂肪仲胺、脂肪叔胺)；可以使用季铵离子。
作为上述单偶氮络合物染料的中心金属M，可以使用各种金属。作为更优选的金属，可以使用具有二价至四价原子值的金属。作为具体的实例，可以使用Zn、Sr、Cr、Cu、Al、Ti、Fe、Zr、Ni、Co、Mn、B、Si和Sn。
通过改变上述单偶氮络合染料的结构，可以获得黄、红、蓝、紫和黑等多种颜色。上述单偶氮络合物染料具有高耐热性和耐光性，热塑性树脂的成型性和色调优异。例如，通式表示的单偶氮络合染料是通过将A-N＝N-B单偶氮染料金属化而得到的。A-N＝N-B单偶氮染料是对A组分进行重氮化和在B组分上偶联得到的化合物。当吡唑啉酮衍生物或乙酰乙酰苯胺衍生物用作B组分时，得到黄红色单偶氮络合物染料，以萘酚衍生物为B组分时，得到蓝黑色单偶氮络合物染料。使用萘酚作为B组分的单偶氮复合染料在YAG激光附近显示出高透射特性。换而言之，通过单独使用上述单偶氮络合物染料或将其与至少一种具有较短波长吸收峰的染料混合，可以获得在近YAG激光(1000-1200nm)的整个区域具有优异透射性的黑色着色剂，同时在800-1200nm范围内具有良好的透射性。然而，每种染料的掺入比例可根据染料的色调、所用树脂和所用浓度(或树脂的厚度)适当调整。
单偶氮络合物染料的具体实例如下。这些仅代表可以使用的更广泛的染料选择：
黑色染料：
C.I.溶剂黑21、22、23、27、28、29、31
C.I.酸性黑52、60、99；
蓝色染料：C.I.酸性蓝167；
紫色染料：C.I.溶剂紫21。
至少一种单偶氮络合物类型(iv)的黑色染料优选以0.01至2重量％，优选0.02至1重量％，更优选0.05至0.5重量％的量存在于聚酰胺组合物中，基于聚酰胺组合物的总重量计。
聚酰胺组合物进一步包含(v)一种或多种其他添加剂，包括通常用于聚酰胺组合物中的所有添加剂。优选地，至少一种添加剂选自热稳定剂、脱模剂、阻燃剂、增韧改性剂和促进组分混合或组合物成型的添加剂。特别优选的实施方案包含热稳定剂和脱模剂作为添加剂。热稳定剂可选自铜盐、铁盐、磷酸盐稳定剂、芳族胺和/或酚类抗氧化剂。
至少一种添加剂通常以0.1至20重量％的量存在，基于聚酰胺组合物的总重量计。在一个实施方案中，添加剂以0.1至5重量％，优选0.1至2重量％的量存在，并且包括脱模剂和热稳定剂。在另一个实施方案中，添加剂以0.1至20重量％的量存在并且包括热稳定剂、脱模剂、阻燃剂、增韧改性剂和促进组分混合的添加剂。
因此，在本发明的一个实施方案中，本发明涉及一种聚酰胺组合物，其包含
(i)31至80.89重量％，优选50至78.88重量％的至少一种脂族聚酰胺或半芳族聚酰胺或其混合物，基于聚酰胺组合物的总重量计；
(ii)15至55重量％，优选20至50重量％的玻璃纤维，基于聚酰胺组合物的总重量计；
(iii)1至8重量％，优选1至6重量％的至少一种非纤维增强材料，基于聚酰胺组合物的总重量计；
(iv)0.01至2重量％，优选0.02至1重量％的至少一种单偶氮络合物类型的黑色染料，基于聚酰胺组合物的总重量计；
(v)0.1至20重量％，优选0.1至5重量％的一种或多种其他添加剂，基于聚酰胺组合物的总重量计。
本发明的聚酰胺组合物通常通过在双螺杆挤出机或单螺杆挤出机中混合聚酰胺和不同负载量而制备。
将聚酰胺组合物挤出为棒状，将其切割以形成颗粒。
聚酰胺组合物在23℃下的挠曲强度(根据ISO 178)优选>250MPa，更优选>260MPa(如实验部分所述确定)。
聚酰胺组合物在23℃下的拉伸强度DAM(根据ISO 527-2/1A)优选>160MPa，更优选>170MPa(如实验部分所述确定)。
聚酰胺组合物在23℃下的简支梁无缺口冲击强度(charpy unnotched impactstrength)(根据ISO 179/1eU)优选>30kJ/m2，更优选>40kJ/m2，特别是>40kJ/m2(如实验部分所述确定)。
聚酰胺组合物在23℃下的简支梁缺口冲击强度(根据ISO 179/1eA)优选>8kJ/m2，特别是>10kJ/m2(如实验部分所述确定)。
聚酰胺组合物在1.82mPa(根据ISO 75/Af)下优选具有>230℃，特别是>240℃的热变形温度(如实验部分所述确定)。
优选通过注射模塑工艺由本发明的聚酰胺组合物制备模塑制品。
适用于激光焊接的模制树脂产品可以通过包括挤出成型和注射成型的任何方法获得。激光焊接仅要求使由所用激光的透射性树脂制成的成型品与由所用激光的吸收性树脂制成的成型品紧密接触。如果需要，可以进一步对粘合表面施加压力。
用于焊接本发明的模制树脂产品的有用激光器可以是在近红外区域具有光发射的任何激光器。特别地，优选发射波长为800-1200nm的光的激光器，特别优选二极管激光器和YAG激光器。激光可以单独使用或彼此组合使用，如激光操作领域的技术人员将理解的。激光发射可以是连续的或脉冲的，优选连续发射。
对于进行激光焊接的树脂材料，提供一种激光透射性树脂材料和另一种激光吸收性树脂材料。通过将激光穿过透射树脂材料照射至附着在其上的吸收性树脂材料上，积累在吸收性树脂材料的接触表面上的激光能量加热并熔化接触区域。透射性树脂材料也通过传热被加热/熔化，从而使树脂材料容易且牢固地结合在一起。激光可以直接照射焊接区域或者可以使用诸如镜子或光纤的光学设备引导至接触区域。这些和其他技术可根据个别焊接操作适当采用，并由本领域技术人员选择。
选择激光的强度、密度和照射面积，以适当地进行接合面的加热和熔化。这些以这样的方式进行调整，以获得产生的粘合具有感兴趣的应用所需的强度。如果太弱，则不能实现充分的加热熔化。相反，如果它太强，则可能导致树脂降解。
本发明涉及置于彼此接触的两个模制品(分别是透射激光和吸收激光)的接合部分，其中聚焦和透射预定量的激光束，熔化和粘合接合部分。如果要焊接多个点、线或面，可以依次移动激光照射接合面，或者可以使用多个激光源同时照射。
本发明的其他优点和细节将从以下仅出于说明目的给出的实施例中变得显而易见。
实施例
制备聚酰胺组合物：
制备几种聚酰胺组合物作为实施例和比较实施例。
以下组分用作起始材料：
组分(i)：PA6.6均聚物
组分(ii)：平均长度为4.5mm，平均直径为10μm的玻璃纤维短切原丝(T435R购自Taishan)
组分(iii)：平均直径为20μm的实心玻璃珠(购自Sovitec的Microperl 050-20-215)
组分(iv)：单偶氮络合物染料溶剂黑27
组分(v)：热稳定剂和脱模母料(购自Solvay的MM9549C)
本发明的用于模塑的组合物通过在双螺杆型挤出机ZSK 18W中以12kg/h的速率和等螺杆300rev/min的旋转速度在265℃至340℃的温度范围内通过混合制备，取决于各种组分的配方和如下表1中公开的量。
通过注射成型制备不同尺寸和厚度的板。
确定以下特性：
拉伸模量、拉伸强度和拉伸伸长率：
拉伸模量和拉伸强度根据ISO 527-2/1A测定。数值以MPa为单位给出。根据ISO527-2/1A测定拉伸伸长率。数值以％给出。
弯曲模量和弯曲强度：
根据ISO 178使用尺寸为80×10mm和厚度为4mm的试样来确定最大载荷下的弯曲强度。数值以MPa给出。
简支梁无缺口冲击强度：
简支梁无缺口冲击强度根据ISO 179/1eU用尺寸为80×10mm和厚度为4mm的试样测定。数值以kJ/m2给出。
简支梁缺口冲击强度：
简支梁缺口冲击强度根据ISO 179/1eA用尺寸为80×10mm和厚度为4mm的测试样品测定。在试样的宽边上制作了一个0.8mm宽的U形缺口。缺口深度为试样厚度的1/3。边缘勾勒出的凹口根部具有<0.1mm的弯曲半径。数值以kJ/m2给出。
热变形温度：
热变形温度在1.82MPa下根据ISO 75/Af确定。值以℃给出。
980和1064nm处的激光透射率：
激光透射率通过具有60×60mm大小的测试板的紫外-可见分光光度计(MettlerEvolution 220)测定。
颜色L*、a*、b*值，2mm：
颜色L*、a*、b*值是通过台式分光光度计(型号Ci7800，由
Figure BDA0003351761520000111
Inc.制造)在颜色测试模式下使用90×60×2mm扁平试样测定的。
测试结果：
实施例E1至E3和比较实施例例C1至C3的测试结果总结在表1中。
Figure BDA0003351761520000121
表1显示了标准玻璃纤维和玻璃珠之间的协同效应。在30重量％的增强填料量下，分别用玻璃珠代替1重量％、2重量％和5重量％的标准玻璃纤维，显著提高了聚酰胺板在980nm和1064nm处的激光透射率。这种效果对3.2mm板最为显著。同时，保持了良好的机械性能水平。然而，使用20重量％的标准玻璃纤维和10重量％的玻璃珠，聚酰胺板的激光透射率和机械性能都会下降。使用15重量％的标准玻璃纤维和15重量％的玻璃珠，聚酰胺板的激光透射率和机械性能进一步下降。

Claims (12)

1.聚酰胺组合物，包括
(i)至少一种脂族聚酰胺或半芳族聚酰胺或其混合物；
(ii)玻璃纤维；
(iii)最高达8重量％的量的至少一种非纤维增强材料；
(iv)至少一种单偶氮络合物类型的黑色染料；
(v)任选一种或多种其他添加剂。
2.根据权利要求1的聚酰胺组合物，其中所述至少一种脂族聚酰胺选自六亚甲基二胺和己二酸的均聚物(PA6.6)；ε-己内酰胺的均聚物(PA6)；六亚甲基二胺、己二酸和ε-己内酰胺的共聚物(PA6.6/6)；六亚甲基二胺和癸二酸的均聚物(PA6.10)以及这些脂族聚酰胺的混合物。
3.根据权利要求1或2的聚酰胺组合物，其中所述半芳族聚酰胺选自六亚甲基二胺和己二酸与对苯二甲酸和/或间苯二甲酸的均聚物和/或共聚物。
4.根据权利要求3的聚酰胺组合物，其中所述至少一种半芳族聚酰胺选自六亚甲基二胺、己二酸和对苯二甲酸的共聚物(PA6.6/6.T)；六亚甲基二胺、己二酸和间苯二甲酸的共聚物(PA6.6/6.I)；六亚甲基二胺、对苯二甲酸和间苯二甲酸的共聚物(PA6.T/6.I)；六亚甲基二胺、己二酸、对苯二甲酸和间苯二甲酸的共聚物(PA6.6/6.T/6.I)以及这些半芳族聚酰胺的混合物。
5.根据权利要求1至4中任一项的聚酰胺组合物，其中所述至少一种非纤维增强材料选自玻璃珠、玻璃片和磨碎的玻璃纤维。
6.根据权利要求1至5中任一项的聚酰胺组合物，其中所述至少一种非纤维增强材料为玻璃珠。
7.根据权利要求1至6中任一项的聚酰胺组合物，其中所述单偶氮络合物类型的黑色染料为C.I.溶剂黑27。
8.根据权利要求1至7中任一项的聚酰胺组合物，其中所述至少一种添加剂选自着色剂、脱模剂、阻燃剂、增韧改性剂和促进组分混合或组合物成型的添加剂。
9.根据权利要求1至8中任一项的聚酰胺组合物，其包含
(i)31至80.89重量％的至少一种脂族聚酰胺或半芳族聚酰胺或其混合物，基于聚酰胺组合物的总重量计；
(ii)15至55重量％的玻璃纤维，基于聚酰胺组合物的总重量计；
(iii)1至8重量％的至少一种非纤维增强材料，基于聚酰胺组合物的总重量计；
(iv)0.01至2重量％的至少一种单偶氮络合物类型的黑色染料，基于聚酰胺组合物的总重量计；
(vi)0.1至20重量％的一种或多种其他添加剂，基于聚酰胺组合物的总重量计。
10.根据权利要求1至9中任一项的聚酰胺组合物，其包含
(ii)20至50重量％的玻璃纤维，基于聚酰胺组合物的总重量计；
(iii)1至8重量％的至少一种非纤维增强材料，基于聚酰胺组合物的总重量计。
11.根据权利要求1至10中任一项的聚酰胺组合物，其包含
(i)50至78.88重量％的至少一种脂族聚酰胺或半芳族聚酰胺或其混合物，基于聚酰胺组合物的总重量计；
(ii)20至50重量％的玻璃纤维，基于聚酰胺组合物的总重量计；
(iii)1至6重量％的至少一种非纤维增强材料，基于聚酰胺组合物的总重量计；
(iv)0.02至1重量％的至少一种单偶氮络合物类型的黑色染料，基于聚酰胺组合物的总重量计；
(v)0.1至5重量％的一种或多种其他添加剂，基于聚酰胺组合物的总重量计。
12.由根据权利要求1至11中任一项所述的聚酰胺组合物获得的模制品。
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