CN116891631A - 具有高断裂强度的聚酰胺模塑材料及由其制备的模塑件 - Google Patents
具有高断裂强度的聚酰胺模塑材料及由其制备的模塑件 Download PDFInfo
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- CN116891631A CN116891631A CN202310313748.6A CN202310313748A CN116891631A CN 116891631 A CN116891631 A CN 116891631A CN 202310313748 A CN202310313748 A CN 202310313748A CN 116891631 A CN116891631 A CN 116891631A
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- polyamide
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 132
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- 239000000203 mixture Substances 0.000 claims description 60
- 239000000975 dye Substances 0.000 claims description 35
- -1 PA614 Polymers 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 22
- 239000006229 carbon black Substances 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 11
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- 239000003381 stabilizer Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 claims description 9
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
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- VJUKWPOWHJITTP-UHFFFAOYSA-N 81-39-0 Chemical compound C1=CC(C)=CC=C1NC1=CC=C2C3=C1C(=O)C1=CC=CC=C1C3=CC(=O)N2C VJUKWPOWHJITTP-UHFFFAOYSA-N 0.000 claims description 7
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- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 6
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001000 anthraquinone dye Substances 0.000 claims description 3
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 3
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- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 3
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 claims description 3
- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 claims description 2
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- DGLNOYZGIXHXJB-UHFFFAOYSA-N benzoyl 3-amino-2-hydroxybenzoate Chemical class C(C1=CC=CC=C1)(=O)OC(C1=C(C(=CC=C1)N)O)=O DGLNOYZGIXHXJB-UHFFFAOYSA-N 0.000 description 1
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- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及具有高断裂能的聚酰胺模塑材料和由其制成的模塑件,其特别适用于汽车零件或电子装置的可见部件。除了优异的断裂能之外,聚酰胺模塑材料还具有同样优异的钢琴亮漆饰面和高的耐摩擦性。
Description
技术领域
本发明涉及具有高断裂能的聚酰胺模塑材料和由其制备的模塑件,其特别适用于汽车零件或电子设备的可见部件。除了优异的断裂能之外,聚酰胺模塑材料还具有同样优异的钢琴亮漆饰面和高的耐摩擦性。
背景技术
EP 1930373 A2涉及透明的模塑件,其选用聚酰胺模塑材料制成,其物理性能,特别是透明度和动态阻力均优于聚碳酸酯。构成这些模塑材料的透明聚酰胺由至少两个脂肪族二胺和至少两个芳香族二羧酸以及内酰胺(如有必要)形成。然而,提及的由这些透明聚酰胺与其他聚酰胺制成的混合物,在实施例中没有使用。
EP 3336131 A1涉及基于透明的脂环族聚酰胺的透明聚酰胺模塑材料,其可用于例如外壳部件,也可用于家用行业、体育用品或玩具领域,并且具有高的断裂伸长率。模塑材料还可以包含其他聚合物,特别是聚酰胺。
EP 3450481 A1涉及具有高光泽度和高缺口冲击强度的聚酰胺模塑材料。该模塑材料是基于非晶或微晶共聚酰胺6I/6T/MACMI/MACMT/PACMI/PACMT/Y或PA 6I/6T/MACMI/MACMT/Y制成的,其中Y代表内酰胺或ω-氨基酸,其用由乙烯、丙烯和1-丁烯制成的官能化共聚物进行冲击改性。作为共混组分的脂肪族聚酰胺未被提及。
EP 3502164 A1涉及聚酰胺模塑材料,其基于特定的非晶聚酰胺和特定的半结晶聚酰胺的混合物,并且其以非常好的抗应力开裂性为特征,同时以非常好的光学性能为特征,特别是高透光率和低雾度。半结晶聚酰胺是长链脂肪族聚酰胺。
EP 3502191 A1涉及聚酰胺模塑材料,其基于特定的非晶或微晶聚酰胺和半结晶聚酰胺PA616、PA516、PA1016的混合物,并且其以非常好的抗应力开裂性为特征,同时以非常好的光学性能为特征。
EP 2055743 A1描述了由聚酰胺混合物制成的模塑材料的用途,所述聚酰胺混合物包含脂肪族均聚酰胺或共聚酰胺和透明的均聚酰胺或共聚酰胺,如有必要,还包含填料或增强材料和添加剂。所提出的用途是制造用于饮用水的模塑件,特别是容器或管道,在其预期用途中,至少加工的模塑材料的区域基本上直接暴露在饮用水中。在实施例中,仅将PA12用作脂肪族聚酰胺。
全部的脂肪族聚酰胺,如聚酰胺66确实具有高机械阻力,然而,它们是结晶的。微晶化合物折射或散射光线;因此,由于丁达尔效应,模塑材料是丝质的,或者具有条纹外观。因此,结晶聚酰胺模塑材料具有过低的透明度和过高的雾度,以至于不能由其制备视觉上美观和高质量的部件,并且在安装状态下可见。
发明内容
因此,现有技术以前没有解决提供聚酰胺模塑材料的问题,该聚酰胺模塑材料在高能量吸收之后仅丧失其尺寸稳定性(基于断裂能来确定),并因此具有更高的安全级别,特别是对于类似冲击的机械载荷,同时还具有优良的外观。由以这种方式制得的模塑材料制成的模塑件特别用作汽车零件或电子设备中的可见部件。同时,聚酰胺模塑材料优选具有所谓的钢琴亮漆饰面,从而传达出最暗的黑色搭配高光泽的印象。还优选的是,聚酰胺模塑材料另外并同时具有针对磨损影响的高稳定性,因此是耐磨的。
用根据权利要求1的本发明的模塑材料和根据专利权利要求13的模塑件解决了这个问题。从属专利权利要求因而提供了有利的改进。
术语的定义
聚酰胺及其单体的符号和缩写
在本发明的意义上,术语“聚酰胺”(缩写PA)理解为总括术语;其包含均聚酰胺和共聚酰胺。聚酰胺及其单体的所选命名和缩写对应于DIN EN ISO标准16396-1:2015中定义的那些。本文使用的缩写作为单体的IUPAC名称的同义词在下文中使用,具体地,本申请中出现了以下单体缩写:MACM指双(4-氨基-3-甲基环己基)甲烷(也称为3,3'-二甲基-4,4'-二氨基二环己基甲烷,CAS编号6864-37-5)、PACM指双-(4-氨基环己基)甲烷(也称为4,4'-二氨基二环己基甲烷,CAS编号1761-71-3)、TMDC指双-(4-氨基-3,5-二甲基环己基)甲烷(也称为3,3',5,5'-四甲基-4,4'-二氨基二环己基甲烷,CAS编号65962-45-0)、T指对苯二甲酸(CAS编号100-21-0)、I指间苯二甲酸(CAS编号121-95-5)、BAC指1,4-双(氨基甲基)环己烷(CAS编号2549-93-1)。
量
根据本发明的聚酰胺模塑材料包含组分a)至d),或优选仅由组分a)至d)组成。因此该规定适用于组分a)至d)的总和为聚酰胺模塑材料的100重量%。单独的组分a)至d)的量指示的固定范围应当理解为可以在指定范围内选择每个单独组分的任意量,只要满足严格的规定,即组分a)至d)的总和为聚酰胺模塑材料的100重量%。
非晶或微晶聚酰胺
根据DIN EN ISO 11357-3(2018)的差示扫描量热法(DSC),非晶或微晶聚酰胺在20K/分钟的加热速率下,优选表现出不超过25J/g、特别优选不超过22J/g、并最特别优选为0J/g至20J/g的熔融热。
微晶聚酰胺除了具有玻璃化转变温度外,还具有熔点。然而,其具有尺寸很小的微晶的形貌,使得由其制造的厚度为2mm的平板仍然是透明的,即根据ASTM D 1003-21(2021)测量的透光率为至少88%或至少90%,并且其雾度为最多3%。
与微晶聚酰胺相比,非晶聚酰胺没有熔融热,或者只有非常低的、几乎无法检测到的熔融热。根据DIN EN ISO 11357-3(2018)的差示扫描量热法(DSC),非晶聚酰胺在20K/分钟的加热速率下,优选表现出不超过5J/g、特别优选不超过3J/g、并最特别优选为0J/g至1J/g的熔融热。非晶聚酰胺由于其非晶形态而不具有熔点。
在本发明的意义上,根据DIN EN ISO 11357-3(2018)的差示扫描量热法(DSC),半结晶聚酰胺是在20K/分钟的加热速率下,优选表现出不超过25J/g、特别优选不超过30J/g、并最特别优选为0J/g至35J/g的熔融热的那些聚酰胺。由半结晶聚酰胺制造的厚度为2mm的平板是不透明的,即根据ASTM D 1003-21(2021)分别测量的透光率低于88%和/或其雾度高于5%。
透明聚酰胺
在本发明的意义上,透明聚酰胺被定义为根据ASTM D 1003-21(2021)测量的厚度为2mm的平板具有至少88%或至少90%的透光率和最多5%、优选最多3%的雾度。如果透明聚酰胺如下所述,则总是指非晶或微晶聚酰胺,其在透明度和熔融热方面满足上述定义。
本发明因此涉及聚酰胺模塑材料,其包含以下组分或优选由以下组分组成:
a)93.0重量%至99.9重量%的混合物M,其由以下组分组成:
15.0重量%至50.0重量%的至少一种聚酰胺X和
50.0重量%至85.0重量%的至少一种聚酰胺Y,所述聚酰胺Y选自PA6、PA66、PA6/66、PA610、PA612、PA614、PA616、PA6/12及其混合物;
b)0.05重量%至5.0重量%的添加剂;
c)0.01重量%至2.0重量%的着色剂;
d)可能地,除组分a)至c)之外的成分;
其中所述至少一种聚酰胺X选自聚酰胺,所述聚酰胺至少包含由单体单元A、B、C、D和/或E衍生的酰胺键合的聚酰胺单元AC、BC和E、或AC、BC、AD和BD、或AC和E,其中单体单元A、B、C、D和E具有以下定义:
A:至少一种脂环族二胺;
B:至少一种非环状脂肪族二胺;
C:至少一种芳香族二羧酸;
D:至少一种脂肪族二羧酸;
E:至少一种α,ω-氨基羧酸或至少一种内酰胺;
其中组分X和Y的总和占混合物M的100重量%,以及组分a)、b)、c)和d)的总和为100重量%。
出人意料地,发现与现有技术中已知的聚酰胺组合物相比,根据本发明的聚酰胺模塑材料具有极高的能量吸收,因此相对于机械载荷,例如由于拉伸应力或类似冲击的机械载荷的影响,其失效时间更晚。因此,根据本发明的聚酰胺模塑材料在安全性方面优于现有技术的组合物。同时,该聚酰胺模塑材料具有优良的外观,因此可用于高质量的应用,例如在安装状态下可见的部件,例如在车辆内部。
聚酰胺混合物
包含在根据本发明的聚酰胺模塑材料中的聚酰胺混合物M包含15.0重量%至50.0重量%的聚酰胺X和50.0重量%至85.0重量%的聚酰胺Y。因此组分X和Y的重量比合计混合物M的100重量%。优选的是,混合物中聚酰胺X的量小于聚酰胺Y的量,即,相对于混合物,聚酰胺X的量小于50重量%。同样地,优选聚酰胺Y的量大于50重量%。
聚酰胺混合物M优选由15.0重量%至45.0重量%、优选20.0重量%至42.0重量%、特别优选25.0重量%至38.0重量%的至少一种聚酰胺X和互补比例的聚酰胺Y,即55.0重量%至85.0重量%,优选58.0重量%至80.0重量%,特别优选62.0重量%至75.0重量%的至少一种聚酰胺Y组成。
聚酰胺X
聚酰胺X是透明的聚酰胺,相对于聚酰胺X中单体的总量,其优选包含至少50摩尔%的仅具有脂肪族结构单元的单体。聚酰胺X优选为非晶或微晶的。
仅具有脂肪族结构单元的单体的至少50摩尔%可以为脂肪族二胺、脂肪族二羧酸、脂肪族内酰胺或脂肪族氨基羧酸。因此,聚酰胺X由至少50摩尔%的仅具有脂肪族结构单元的单体和不超过50摩尔%的含有芳香族结构单元的单体组成。
还优选的是,聚酰胺X是透明的并具有至少88%或至少90%的透明度和最多5%、优选最多3%的雾度(分别使用随后阐述的测量方法测定)。
根据本发明的一个优选实施方案,聚酰胺X是非晶的。
根据本发明的另一个优选实施方案,聚酰胺X包含至少一种具有芳香族结构单元的单体。
根据ISO 307:2007在20℃下、100ml含0.5g聚合物的间甲酚溶液中测量的,聚酰胺X优选具有1.35至2.40、特别优选1.40至1.90、更特别优选1.45至1.80的相对黏度。
例如,具有至少聚酰胺单元AC、BC和E的聚酰胺的相对黏度优选为1.50至1.75,特别是1.59至1.64。
例如,具有至少聚酰胺单元AC、BC、AD和BD的聚酰胺的相对黏度优选为1.60至1.85,特别是1.70至1.75。
例如,具有至少聚酰胺单元AC和E的聚酰胺的相对黏度优选为1.40至1.65,特别是1.51至1.57。
对于聚酰胺X,单体单元A至E优选彼此独立地选自
A:(脂环族二胺):双-(4-氨基-3-甲基-环己基)-甲烷(MACM)、双(4-氨基-环己基)甲烷(PACM)、双-(4-氨基-3,5-二甲基-环己基)-甲烷(TMDC)及其混合物;
B:(非环状脂肪族二胺):1,6-己二胺、2-甲基-1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,12-十二烷二胺,优选地选自1,6-己二胺和1,10-癸二胺;
C:(芳香族二羧酸)选自对苯二甲酸、间苯二甲酸及其混合物,优选对苯二甲酸和间苯二甲酸的混合物;
D:(脂肪族二羧酸):己二酸、壬二酸、1,10-癸二酸、1,12-十二烷二酸、1,14-十四烷二酸、1,16-十六烷二酸、环己烷-1,3-二羧酸、环己烷-1,4-二羧酸及其混合物;
E:(α,ω-氨基羧酸或内酰胺)选自α,ω-氨基己酸、α,ω-氨基十一酸、α,ω氨基十二酸、己内酰胺、月桂内酰胺及其混合物。
根据另一个优选实施方案,聚酰胺X的聚酰胺单元AC包括至少两个不同的,优选正好两个不同的脂环族二胺,特别是双-(4-氨基-3-甲基-环己基)甲烷(MACM)和双(4-氨基-环己基)甲烷(PACM)。
另外优选的是,聚酰胺X必须含有聚酰胺单元AC和BC。
类似优选的是,聚酰胺X不包含任何单体单元D。
特别优选的是,聚酰胺X包含聚酰胺单元AC、BC和E,聚酰胺X最特别优选由聚酰胺单元AC、BC和E组成。
进一步有利的是,相对于单体的总量,聚酰胺X包含超过30摩尔%、优选超过40摩尔%、更特别超过42摩尔%、特别优选为30摩尔%至50摩尔%或40摩尔%至50摩尔%或42摩尔%至50摩尔%的具有芳香族结构单元的单体。
特别是,聚酰胺X选自PA6I/6T/MACMI/MACMT/PACMI/PACMT/12、PA6I/6T/MAC MI/MACMT/MACM12/612、PAMACMI/12、PAMACMT/12、PA10I/MACMI/MACM10/1010、PA10T/MACMT/MACM10/1010、PA10I/10T/MACMI/MAMT/MACM10/1010PA MACMI/MACMT、PA MACMI/MACMT/12、PAMACMI/MACMT/MACM12、PA6I/6T/MACMI/MACMT、PA6I/6T/MACMI/MACMT/12、PA6I/612/MACMI/MACM12、PA6T/612/MACMT/MACM12、PA6I/6T/612/MACMI/MACMT/MACM12、PA6I/6T/MACMI/MAC MT/-PACMI/PACMT/MACM12/PACM12及其混合物。
聚酰胺Y
聚酰胺Y为至少一种非环状脂肪族二胺。聚酰胺Y选自PA6、PA66、PA6/66、PA610、PA612、PA614、PA616、PA6/12及其混合物。
根据ISO 307:2007在20℃下、100ml含1.0g聚合物的硫酸溶液中测量的,聚酰胺Y优选具有2.10至3.60、特别优选2.30至3.50、更特别优选2.40至2.80的相对黏度。
出人意料地,观察到首先通过选择和组合特定的聚酰胺X和Y获得的断裂能的改善,同时获得能够使模塑材料适合于高质量部件的视觉外观。
添加剂(b)
根据本发明的模塑材料包含作为组分b)的至少一种添加剂,其优选地选自有机和无机稳定剂,特别是抗氧化剂、抗臭氧剂、热稳定剂、光稳定剂、UV稳定剂、UV吸收剂或UV阻滞剂、润滑剂、脱模剂及其混合物和组合。
相对于组分a)至d)的总和,至少一种添加剂的量为0.05重量%至5.0重量%、优选0.10重量%至3.0重量%、还优选0.20重量%至2.5重量%和特别优选0.25重量%至2.3重量%。
在稳定剂用作至少一种添加剂的情况下,其可以根据一个优选实施方案从以下组中选择:
·一价铜或二价铜的化合物,特别是一价铜或二价铜与有机酸或无机酸或与一元酚或二元酚的盐,一价铜或二价铜的氧化物,或铜盐与氨、胺、酰胺、内酰胺、氰化物或膦的络合物,优选氢卤酸、氢氰酸的Cu(I)盐或Cu(II)盐,或脂肪族羧酸的铜盐,其中一价铜化合物特别优选CuCl、CuBr、CuI、CuCN和Cu2O,以及二价铜化合物特别优选CuCl2、CuSO4、CuO、乙酸铜(II)或硬脂酸铜(II),或这些化合物的混合物,其中这些铜化合物如此使用或优选以浓缩物的形式使用。浓缩物被理解为聚合物,其化学性质优选与聚酰胺X或Y相同或基本上相同,该浓缩物含有高浓度的铜盐或铜化合物(母粒)。更特别优选的是,铜化合物用于与其他金属卤化物结合使用,包括碱卤化物,如NaI、KI、NaBr、KBr,其中金属卤化物与铜的摩尔比为0.5至20、优选1至10、特别优选2至7;
·基于二级芳香胺的稳定剂;
·基于空间位阻酚的稳定剂;
·亚磷酸酯和亚膦酸酯;
·选自N,N’-草酰胺、羟苯基三嗪、羟苯基苯并三唑、二苯甲酰基甲烷、氨基羟基苯甲酰基苯甲酸酯、羟基二苯甲酮、受阻胺光稳定剂(HALS),以及
·上述稳定剂的混合物。
根据本发明可以使用的基于二级芳香胺的稳定剂的特别优选实例为苯二胺与丙酮的加合物(Naugard A)、苯二胺与亚油酸的加合物、Naugard 445、N,N'-二萘基-对-苯二胺、N,N'-二萘基-对-苯二胺、或其两种或多于两种的混合物。
根据本发明可以使用的基于空间位阻酚的稳定剂的优选实例为N,N'-六亚甲基-二-3-(3,5-二-叔丁基-4-羟苯基)-丙酰胺、二-(3,3-二-(4'-羟基-3'-叔丁基苯基)-丁酸)-二醇酯、2,1'-硫代乙基二-(3-(3,5-二-叔丁基-4-羟基苯基)-丙酸酯、4,4'-亚丁基-二-(3-甲基-6-叔丁基苯酚)、三亚乙基二醇-3-(3-叔丁基-4-羟基-5-甲基苯基)-丙酸酯,或两种或多于两种这些稳定剂的混合物。
优选的亚磷酸酯或亚膦酸酯为三苯基亚磷酸酯、二苯基烷基亚磷酸酯、苯基二烷基亚磷酸酯、三(壬基苯基)亚磷酸酯、三月桂基亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂酰基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)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、双异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)-季戊四醇二亚磷酸酯、三硬脂基山梨醇三亚磷酸酯、四-(2,4-二叔丁基苯基)-4,4’-联苯基双亚膦酸酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧磷杂环辛烷、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧磷杂环辛烷、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯和双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯。更特别优选为三[2-叔丁基-4-硫代(2’-甲基-4’-羟基-5’-叔丁基-丁基)-苯基-5-甲基]苯基亚磷酸酯和三(2,4-二叔丁基苯基)亚磷酸酯((PAR24:来自Clariant的商用产品,Basel)。
热稳定剂的一个优选实施方案包括Irgatec NC 66(可从BASF获得)和基于CuI与KI的铜稳定剂的组合。仅基于CuI与KI的热稳定剂是特别优选的。
根据另一优选实施方案,组分(b)的热稳定剂选自酚基热稳定剂、亚磷酸酯基热稳定剂、胺基热稳定剂或其混合物或其组合,其中特别是组分C优选选自以下组:3-(3,5-二-叔丁基-4-羟基苯基)丙酸、四(3-(3',5'-二叔丁基-4-羟基苯基)-丙酸)季戊四醇酯、N,N'-六亚甲基-二[3-(3,5-二-叔丁基-4-羟苯基)丙酰胺]、三(2,4-二叔丁基苯基)亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯或其混合物。
优选的有机稳定剂为酚化合物和/或亚磷酸酯化合物,例如Irganox 245、Irganox1010、Irganox 1098、Hostanox PAR 24、Anox 20或Irgafos 168。特别优选的组分(D)为Irganox1010(CAS 6683-19-8,酚类抗氧化剂)和Anox 20(CAS 6683-19-8,酚类抗氧化剂)以7:3的比例的混合物和2重量份Hostanox PAR24(CAS:3157004-4,三(2,4-二叔丁基苯基)亚磷酸酯)的10重量份混合物。
优选的紫外线稳定剂为,例如,选自N-(2-乙氧基苯基)-N'-(2-乙基苯基)草酰胺(Tinuvin312)、2-(4,6-二苯基-1,3,5三嗪-2-基)-5-己氧基苯酚(Tinuvin 1577)、2-(4,6-二芳基-1,3,5-三嗪-2-基)-5-(烷氧基取代基)-苯酚(Tinuvin 1600)、2-叔丁基-6-(5-氯苯并三唑-2-基)-4-甲基苯酚(Tinuvin 326)、2-(苯并三唑-2-基)-4,6-双(2-苯基丙烷-2-基)苯酚(Tinuvin 234)、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(Tinuvin 770DF)、2-(2-羟基苯基)-苯并三唑衍生物(Tinuvin Carboprotect)、2-(苯并三唑-2-基)-4,6-双(2-甲基丁烷-2基)苯酚(Tinuvin 328)、2-(苯并三唑-2-基)-6-[[3-(苯并三唑-2-基)-2-羟基-5-(2,4,4-三甲基戊烷-2-基)苯基]甲基]-4-(2,4,4-三甲基戊烷-2-基)苯酚(Tinuvin360)、聚[[6-[(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二醇][(2,2,6,6-四甲基-4-哌啶基)-亚氨基]-1,6-己二基[(2,2,6,6-四甲基-4-哌啶基)-亚氨基]])(Chimasorb944FD)、1-(4-甲氧基苯基)-3-(4-叔丁基苯基)丙烷-1,3-二酮(Parsol 1789)及其混合物。
加工助剂的一个优选实施方案为具有10个至44个碳原子,优选具有14个至44个碳原子的脂肪酸的铝盐、碱金属盐、碱土金属盐、酯或酰胺,其中优选金属离子Na、Mg、Ca和Al,特别优选Ca或Mg。特别优选的金属盐为硬脂酸镁、硬脂酸钙和褐煤酸钙,以及硬脂酸铝。脂肪酸可以是一元或二元的。列举的实例为:壬酸、棕榈酸、月桂酸、十七烷酸、十二烷二酸、二十二烷酸,特别优选硬脂酸、癸酸以及褐煤酸(具有30个至40个碳原子的脂肪酸的混合物)。根据另一个优选的实施方案,加工助剂硬脂酸钙、甘油单硬脂酸酯、Abril 1033或ACRAWAXC是合适的。
着色剂(c)
组分c)为着色剂或着色剂的混合物,其适合于将聚酰胺模塑材料着色成黑色。黑色着色和视觉外观是基于视觉评估进行的。着色剂可以是有机或无机染料或颜料。染料是通常不散射光的着色剂,但它们会吸收特定可见光波长的光。染料在聚合物基质中通常在一定浓度下是可溶的。颜料是有机或无机染料,通常以离散的、不溶于水的颗粒存在于聚合物基质中。将某种染料指定为颜料或染料取决于聚合物基质、染料浓度以及结晶度、温度和其他因素。关于本发明,优选的着色剂在聚酰胺模塑材料中以使模塑制品着色所需的浓度溶解,其中这些着色剂也可以与炭黑结合使用。
根据本发明,着色剂的用量和组合足以将模塑材料染成黑色且基本上不透明。所用着色剂的具体用量取决于其在热塑性基质中的溶解度和消光系数,以及其是否与一种或多于一种其他着色剂结合使用。
相对于组分a)至d)的总和,组分c)的比例优选为0.05重量%至2.0重量%。根据本发明的一个优选实施方案,分别相对于成分a)至d)的总和,组分c)的比例为0.08重量%至1.5重量%,特别优选为0.10重量%至1.0重量%。
合适的着色剂一般在可见光波长范围内具有高的消光系数和高的热稳定性。因此,如果在230℃至300℃的温度注塑或挤压期间,在着色模塑材料的制备和加工期间没有观察到明显的色移或热降解,则着色剂的热稳定性高。此外,着色剂不影响或降解聚合物,这可能会导致不可接受的机械特征的损失或在模塑过程中形成气态副产品。
合成着色剂通常从煤焦油或石油中间体中获得。许多不同类型的染料可用于热塑性材料。颜色指数列出了许多不同化学类别的着色剂,其中,例如,亚硝基、硝基、单偶氮、重氮、三偶氮、多偶氮、偶氮、二苯乙烯、类胡萝卜素、二苯甲烷、三芳基甲烷、氧杂蒽、喹啉、吖啶、次甲基、噻唑、吲达胺、靛酚、吖嗪、嗪、噻嗪、硫磺、内酯、氨基酮、羟基酮、蒽醌、靛蓝和酞菁染料、苯胺黑、炭黑和无机颜料。
着色剂或着色剂组合优选选自吡唑啉酮着色剂、芘酮着色剂和蒽醌着色剂、次甲基着色剂、偶氮着色剂和香豆素类着色剂和/或包含金属的颜料,如无机颜料和偶氮金属络合物着色剂、甲亚胺着色剂或次甲基着色剂、甲亚胺着色剂、喹吖啶酮着色剂、二嗪着色剂、异吲哚着色剂、异吲哚啉酮着色剂、苝着色剂、酞菁着色剂、吡咯并吡咯着色剂和硫靛着色剂,并且可能会补充炭黑。
无机颜料的实例为三氧化锑、五氧化二锑、碱式碳酸铅、碱式硫酸铅或硅酸铅、锌钡白、二氧化钛(锐钛矿型、金红石型)、氧化锌、硫化锌、金属氧化物如普鲁士蓝、铬酸铅、硫铬酸铅、钛酸铬锑、氧化铬、氧化铁、钴蓝、亚铬酸钴蓝、钴镍灰、锰蓝、锰紫、钼铬橙、钼铬红、钛酸锑镍、群青,以及金属硫化物如三硫化二锑、硫化镉、硒化镉、硅酸锆、锆钒蓝、锆镨黄。分散染料适合作为,例如,聚合物可溶性染料,如蒽醌系列的那些,例如烷基氨基、氨基、芳基氨基、环己基氨基、羟基、羟基氨基或苯巯基蒽醌,以及偶氮染料的金属络合物,特别是单偶氮染料的1:2铬络合物或钴络合物,以及来自苯并噻唑、香豆素、嗪或噻嗪系列的荧光着色染料。
特别优选的是,至少一种着色剂选自有机染料,特别是蒽醌染料、芘酮染料、苯胺黑、炭黑、及其混合物和组合。
至少一种着色剂c)优选包含至少一种随后列出的着色剂,并且至少一种着色剂c)特别优选选自随后列出的着色剂组,随后以颜色索引通用名称(CIGN)列出:
溶剂绿3(CAS编号128-80-3),溶剂绿28(CAS编号28198-05-2),溶剂红52(CAS编号81-39-0),溶剂红111(CAS编号82-38-2),溶剂红135(CAS编号20749-68-2),溶剂红169(CAS编号27354-18-3),溶剂红179(CAS编号89106-94-5),溶剂红207(CAS编号10114-49-5),分散红22(CAS编号2944-28-7),还原红41(CAS编号522-75-8)、溶剂橙60(CAS编号61969-47-9)、溶剂橙63(CAS编号16294-75-0)、溶剂紫13(CAS编号81-48-1)、溶剂紫14(CAS编号8005-40-1)、溶剂紫50、分散蓝73(CAS编号12222-78-5)、溶剂蓝97(CAS编号12222-78-5)。CAS61969-44-6),溶剂蓝101(CAS编号6737-68-4),溶剂蓝104(CAS编号116-75-6),溶剂蓝138(CAS编号110157-96-5),分散黄160(CAS编号75216-43-2),溶剂黄84(CAS编号12239-76-8),溶剂黄93(CAS编号4702-90-3),溶剂黄98(CAS编号12671-74-8),溶剂黄163(CAS编号13676-91-0),溶剂黄160:1(CAS编号35773-43-4)及其混合物。这些着色剂具有良好的热稳定性。
具有酞菁结构的优选着色剂为,例如,颜料蓝15:1(CAS编号147-14-8)、颜料蓝15:3(CAS编号147-14-8)、颜料蓝16(CAS编号574-93-6)和颜料绿7(CAS编号1328-53-6)。
其他优选的组分c)为溶剂棕53(CAS编号64696-98-6)、颜料棕23(CAS编号35869-64-8)、颜料棕24(CAS编号68186-90-3)、颜料棕(CAS编号6992-11-6)、颜料橙68(CAS编号42844-93-9)、溶剂橙60(CAS编号61969-47-9)、溶剂橙63(CAS编号16294-75-0)和颜料棕6(CAS编号52357-70-7)。
特别优选的染料为溶剂红52、溶剂红135、溶剂红179、溶剂紫13、溶剂紫14、溶剂紫36、溶剂紫50、分散蓝73、溶剂黄93、溶剂绿3、分散黄160、溶剂蓝97以及含有上述至少一种染料的混合物。
特别优选选自以下染料混合物的着色剂:
·溶剂绿3和溶剂红179
·溶剂红52和溶剂蓝97
·溶剂绿3、溶剂蓝97和溶剂红179
·溶剂绿3、溶剂红52和溶剂红179
其中染料混合物还可以包含炭黑。相对于染料混合物,染料混合物优选包含最高50重量%炭黑。相对于染料混合物,染料混合物特别优选包含20重量%至50重量%炭黑。
作为着色剂,最特别优选的是以下组分的混合物:
20重量%至40重量%的溶剂绿3
0重量%至20重量%的溶剂红52
15重量%至35重量%的溶剂红179
40重量%至60重量%的炭黑
其中各组分的总和占混合物(组分c)的100重量%。相对于组分a)至d)的总和,着色剂混合物(c)的量优选为0.7重量%至0.8重量%。
优选使用具有<200nm的粒度分布d90的类型的炭黑(这意味着至少90%的颗粒小于200nm)。例如,可以通过扫描透射电子显微镜(STEM)来测定粒度分布。这些类型的炭黑为,例如,Color Black FW 1beads、Corax N115、Black Pearls 1100、Black Pearls 1150或Black Pearls 880。
着色剂的存在,特别是在上述量和质量的情况下,使得能够提供基于透明聚酰胺的聚酰胺模塑材料,其以黑色钢琴亮漆饰面为特征。
添加剂(d)
根据本发明的聚酰胺模塑材料还可以包含,例如,相对于组分a)至d)的总和的0重量%至10重量%的添加剂(组分d)。
根据本发明的一个优选实施方案,分别相对于成分a)至d)的总和,聚酰胺模塑材料中组分d)的比例为0重量%至5.0重量%,特别优选为0.10重量%至2.0重量%。
另一个优选实施方案提供了至少一种添加剂d),其选自单体,特别是内酰胺、软化剂、冲击强度改性剂、缩合催化剂、链调节剂,特别是单官能羧酸或胺、消泡剂、防黏连剂、天然层状硅酸盐、合成层状硅酸盐、纳米级填料及其混合物。
可以由根据本发明的聚酰胺模塑材料制成的模塑制品,所述模塑制品特别选自汽车、摩托车、露营车或移动房屋的内部和外部部件,建筑和立面部件,装饰结构框架,操作按钮或杠杆,盖子,可见表面,背光部件,移动电话、平板电脑的孔,电子装置的壳体,车辆、家用装置、容器、车辆钥匙、休闲和户外产品的装饰部件。
具体实施方式
将在以下实施例的基础上更详细地说明根据本发明的主题,而不希望将所述主题局限于本文所示的特定实施方案。在本申请的范围内使用了以下测量方法:
雾度、透明度
使用来自BYK Gardner的Haze Gard Plus测量装置,使用CIE光源C在23℃下,根据ASTM D1003-21在2mm厚的板(60mm×60mm表面)上测量透明度和雾度。
相对黏度,ηrel
相对黏度根据ISO 307(2007)在20℃下测定。为此目的,将0.5g聚合物颗粒称量加入100ml间甲酚中,根据RV=t/t0计算相对黏度(RV),该计算基于标准的第11章进行。
拉伸弹性模量
拉伸弹性模量和拉伸强度的测定是根据ISO 527(2012)在23℃的温度下,在根据ISO/CD 3167(2003)标准制备的ISO拉伸棒(A1型,尺寸170×20/10×4)上,以1毫米/分钟的拉伸速率进行的。
屈服应力和屈服伸长率
屈服应力和屈服伸长率的测定是根据ISO 527(2012)在23℃的温度下,在根据ISO/CD3167(2003)标准制备的ISO拉伸棒(A1型,尺寸170×20/10×4mm)上,以50毫米/分钟的拉伸速率进行的。
断裂应力和断裂伸长率
断裂应力和断裂伸长率的测定是根据ISO 527(2012)在23℃的温度下,在根据ISO/CD 3167(2003)标准制备的ISO拉伸棒(A1型,尺寸170×20/10×4mm)上,以50毫米/分钟的拉伸速率进行的。
根据Charpy的冲击强度
根据Charpy的冲击强度的测定是根据ISO 179/2*eU(1997,*2=工具变量)在23℃的温度下,在根据ISO/CD 3167(2003)标准制备的ISO拉伸棒(B1型,尺寸80×10×4mm)上进行的。
根据Charpy的缺口冲击强度
根据Charpy的冲击强度的测定是根据ISO 179/2*eA(1997,*2=工具变量)在23℃的温度下,在根据ISO/CD 3167(2003)标准制备的ISO拉伸棒(B1型,尺寸80×10×4mm)上进行的。
光泽度60%
使用Minolta Multi Gloss 268装置,在尺寸为60×60×2mm的板上,根据ISO2813(2015)在60°的角度和23℃的温度下测定光泽度。光泽度水平以无量纲光泽度单位(GU)表示。在干燥的环境中在室温下,即在硅胶上,在注塑后将干燥状态的测试样品储存至少48小时。
调湿处理
调湿处理是根据ISO 527(2012)进行的。因此,测试样品在23℃±2℃和50°±10°相对湿度下储存16小时。
断裂能
根据ISO 527(2012),断裂能由拉伸试验的应力-应变曲线下的表面积来表示。
耐摩擦性
测试装置:根据DIN EN ISO 105-X12的摩擦掉色测定计或可设置必要测试条件的其他测试设备(测试力:9N,测试路径:104mm±3mm)
测试头:根据DIN 55654:2015的摩擦适配器C
测试装置/摩擦介质:根据DIN 55654:2015的抛光纸:磨料颗粒由氧化铝制成,半开放铺展,颗粒5μm,颗粒充分与柔性挤出的PES膜树脂胶黏(例如,3MTM261X1))。抛光纸的切割精确至25mm的宽度和最小75mm的长度。
光泽度测量装置:使用反射计以20°的角度进行光泽度测量(根据DIN EN ISO2813:2015)
样品制备:为进行测试,最小样品尺寸必须为150mm×100mm。
如上所述建立条件。
试验方法:
1.调湿处理
2.在流动的温水下清洗
3.在刮擦前测量光泽度。光泽度的测量是以20°的测量角度进行的。
4.摩擦/刮擦:在每次摩擦步骤之前夹入新的摩擦介质。一个摩擦步骤包括5个双冲程。摩擦在9N的负载下进行。如果摩擦痕迹不均匀(有条纹、有瑕疵),则必须进行重复测试。
5.摩擦后,样品在室温下储存24小时。
6.测量摩擦痕迹处的光泽度。光泽度测量装置的校准由此进行,使得测量方向相对于摩擦方向成90°。应注意使光泽度测量装置的测量开口与负载表面接触。在该情况下,不测量摩擦痕迹的前10mm和后10mm。
耐摩擦性表示为相对于初始光泽水平的光泽度的相对变化(%)。测量角度为20°。光泽度的相对变化计算如下:
(初始光泽度-摩擦后的光泽度)×100/初始光泽度
实施例和比较例中使用的材料汇总于表1。
表1
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根据本发明的聚酰胺模塑材料(实施例)列于下表2和4中,非根据本发明的模塑材料(比较例)列于表3和5中,并示出分别测定的测量值。有关量的信息以重量份数表示。
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用根据本发明实施例1至11和比较例1至9的化合物获得的测量值列于下表4和表5中。
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从实施例中可以清楚地看出,需要聚酰胺X和Y的特定组合才能获得高断裂能值。同时,不仅可以达到理想的视觉效果(钢琴黑),而且耐磨性也可以因此得到出人意料的提高。
Claims (19)
1.一种聚酰胺模塑材料,其包含以下组分或优选由以下组分组成:
a)93.0重量%至99.9重量%的混合物M,其由以下组分组成:
15.0重量%至50.0重量%的至少一种聚酰胺X和
50.0重量%至85.0重量%的至少一种聚酰胺Y,其选自PA6、PA66、PA6/66、PA610、PA612、PA 614、PA 616、PA6/12及其混合物;
b)0.05重量%至5.0重量%的至少一种添加剂;
c)0.01重量%至2.0重量%的至少一种着色剂;
d)不同于组分a)至c)的可能成分;
其中所述至少一种聚酰胺X选自聚酰胺,所述聚酰胺至少包含由单体单元A、B、C、D和/或E衍生的酰胺键合的聚酰胺单元AC、BC和E、或AC、BC、AD和BD、或AC和E,其中单体单元A、B、C、D和E具有以下定义:
A:至少一种脂环族二胺;
B:至少一种非环状脂肪族二胺;
C:至少一种芳香族二羧酸;
D:至少一种脂肪族二羧酸;
E:至少一种α,ω-氨基羧酸或至少一种内酰胺;
其中组分X和Y的总和占混合物M的100重量%,以及组分a)、b)、c)和d)的总和为100重量%。
2.根据权利要求1所述的聚酰胺模塑材料,其特征在于包含0.10重量%至3.0重量%的至少一种添加剂(b)和/或包含0.05重量%至2.0重量%的至少一种着色剂(c)和/或包含0重量%至5.0重量%的成分(d)。
3.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于单体单元A至E分别彼此独立地选自
A:脂环族二胺,其选自双-(4-氨基-3-甲基-环己基)-甲烷(MACM)、双(4-氨基-环己基)甲烷(PACM)、双-(4-氨基-3,5-二甲基-环己基)-甲烷(TMDC)及其混合物;
B:非环状脂肪族二胺,其选自1,6-己二胺、2-甲基-1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,12-十二烷二胺,优选地选自1,6-己二胺和1,10-癸二胺;
C:芳香族二羧酸,其选自对苯二甲酸、间苯二甲酸及其混合物,优选对苯二甲酸和间苯二甲酸的混合物;
D:脂肪族二羧酸,其选自己二酸、壬二酸、1,10-癸二酸、1,12-十二烷二酸、1,14-十四烷二酸、1,16-十六烷二酸、环己烷-1,3-二羧酸、环己烷-1,4-二羧酸及其混合物;
E:α,ω-氨基羧酸或内酰胺,其选自α,ω-氨基己酸、α,ω-氨基十一酸、α,ω-氨基十二酸、己内酰胺、月桂内酰胺及其混合物。
4.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于所述聚酰胺单元AC包含至少两种不同的,优选正好两种不同的脂环族二胺,特别是双-(4-氨基-3-甲基-环己基)甲烷(MACM)和双(4-氨基-环己基)甲烷(PACM)。
5.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于混合物M由以下组分组成
15.0重量%至45.0重量%,优选20.0重量%至42.0重量%,特别优选25.0重量%至38.0重量%的至少一种聚酰胺X和
55.0重量%至85.0重量%,优选58.0重量%至80.0重量%,特别优选62.0重量%至75.0重量%的至少一种聚酰胺Y。
6.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于相对于单体的总量,聚酰胺X包含超过30摩尔%、优选超过40摩尔%、特别是超过42摩尔%、特别优选为30摩尔%至50摩尔%或40摩尔%至50摩尔%或42摩尔%至50摩尔%的具有芳香结构单元的单体。
7.根据前述权利要求中任一项所述的聚酰胺模塑材料,其中聚酰胺X选自PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12、PA6I/6T/MACMI/MACMT/MACM12/612、PA MACMI/12、PAMACMT/12、PA10I/MACMI/MACM10/1010、PA 10T/MACMT/MACM10/1010、PA 10I/10T/MACMI/MAMT/MACM10/1010、PA MACMI/MACMT、PA MACMI/MACMT/12、PAMACMI/MACMT/MACM12、PA 6I/6T/MACMI/MACMT、PA 6I/6T/MACMI/MACMT/12、PA6I/612/MACMI/MACM12、PA 6T/612/MACMT/MACM12、PA6I/6T/612/MACMI/MACMT/MACM12、PA 6I/6T/MACMI/MACMT/PACMI/PACMT/MACM12/PACM12及其混合物。
8.根据权利要求1至6中任一项所述的聚酰胺模塑材料,其特征在于聚酰胺模塑材料不含PAMACMI/12。
9.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于聚酰胺X具有分别根据ASTM-D1003-21在尺寸为60×60×2mm的板上测量的至少88%的透明度和最多5%的雾度。
10.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于着色剂(c)选自有机染料,特别是蒽醌染料、芘酮染料、苯胺黑、炭黑、及其混合物和组合。
11.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于着色剂包含或组成为炭黑和至少一种选自吡唑啉酮、芘酮和蒽醌、次甲基、偶氮和香豆素类染料的染料和/或含有金属的颜料的组合,所述颜料如无机颜料和偶氮染料、甲亚胺染料或次甲基染料、甲亚胺着色剂、喹吖啶酮着色剂、二嗪着色剂、异吲哚着色剂、异吲哚啉酮着色剂、苝着色剂、酞菁着色剂、吡咯并吡咯着色剂和硫靛着色剂和苯胺黑的金属络合物。
12.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于相对于染料组合,组合中炭黑的比例为20重量%至50重量%。
13.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于着色剂由以下组分组成
炭黑、溶剂绿3、溶剂红52和溶剂红179,或
炭黑和Polysynthren Black H(溶剂黑27,CAS编号72812-34-1),其中相对于着色剂,炭黑的比例为20重量%至50重量%。
14.根据权利要求1至10中任一项所述的聚酰胺模塑材料,其特征在于着色剂包含或组成为至少两种选自吡唑啉酮染料、芘酮染料和蒽醌染料、次甲基染料、偶氮染料和香豆素类染料的染料和/或包含金属的颜料的组合,但不含炭黑,所述颜料如无机颜料和偶氮染料、甲亚胺染料或次甲基染料、甲亚胺着色剂、喹吖啶酮着色剂、二嗪着色剂、异吲哚着色剂、异吲哚啉酮着色剂、苝着色剂、酞菁着色剂、吡咯并吡咯着色剂和硫靛着色剂和苯胺黑的金属络合物。
15.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于着色剂由溶剂绿3、溶剂红179和溶剂蓝97的组合组成。
16.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于至少一种添加剂(b)选自有机和无机稳定剂,特别是抗氧化剂、抗臭氧剂、热稳定剂、光稳定剂、UV稳定剂、UV吸收剂或UV阻滞剂、润滑剂、脱模剂及其混合物和组合。
17.根据前述权利要求中任一项所述的聚酰胺模塑材料,其特征在于包含至少一种与添加剂b)和着色剂c)不同的成分,并且所述成分选自软化剂、冲击强度改性剂、缩合催化剂、链调节剂,特别是单官能羧酸或胺、消泡剂、防黏连剂、天然层状硅酸盐、合成层状硅酸盐、纳米级填料及其混合物。
18.根据权利要求1至16中任一项所述的聚酰胺模塑材料,其特征在于聚酰胺模塑材料不含冲击强度改性剂。
19.包含或优选组成为根据权利要求1至18中任一项所述的聚酰胺模塑材料的模塑件,模塑件特别选自汽车、摩托车、露营车或移动房屋的内部和外部部件,建筑和立面部件,装饰结构框架,操作按钮或杠杆,盖子,可见表面,背光部件,移动电话、平板电脑的孔,电子装置的壳体,车辆、家用装置、容器、车辆钥匙、休闲和户外产品的装饰部件。
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