CN115260650A - 含有至少一种金属颜料的塑料组合物、其制备方法和用途 - Google Patents
含有至少一种金属颜料的塑料组合物、其制备方法和用途 Download PDFInfo
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- CN115260650A CN115260650A CN202210931277.0A CN202210931277A CN115260650A CN 115260650 A CN115260650 A CN 115260650A CN 202210931277 A CN202210931277 A CN 202210931277A CN 115260650 A CN115260650 A CN 115260650A
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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Abstract
本发明涉及一种塑料组合物,其含有0.01‑25重量%的至少一种小片状金属颜料、0.01‑10重量%的至少一种光稳定剂和0.01‑2重量%的至少一种抗氧化剂,各自基于塑料组合物的重量比例计。
Description
本申请是中国专利申请201480056158.9的分案申请,该中国专利申请的申请日为2014年10月14日,发明名称是“含有至少一种金属颜料的塑料组合物、其制备方法和用途”。
技术领域
本发明涉及用小片状金属颜料着色的塑料组合物、其制备方法和用途。
背景技术
因为美观或技术原因被染成或涂成深色且暴露于日光的表面通常根据颜色深度在被或多或少加热时具有不利的性能。认为深色表面的阳光加热是极为不利的,例如在车辆内部中。深色表面在吸收太阳能的作用下被或多或少地加热,并且将这种吸收的热量作为热辐射和经由空气对流驱散入车辆的内部。另外,这些深色表面的较高储热容量导致例如车辆内部的加热。热容量和进入材料的热传导越高,在材料中储存的太阳能就越多。所以,经由加热辐射和空气对流缓慢地进行散热。
WO 02/12405 A2涉及一种扁平元件,其具有深色表面并显示减少的太阳能吸收,其中扁平元件的基材的反射度是在380-720nm的可见光范围内小于50%并且在720-1500nm的近红外范围内大于60%。基材的涂料是由在380-1500nm光谱范围具有大于70%透明度的粘合剂以及第一种颜料和/或第二种颜料组成的,所述第一种颜料使得涂料在可见光范围内具有小于50%的反射度和使得涂料在近红外光谱范围内具有大于50%的透明度,所述第二种颜料能使得涂料在可见光范围内具有小于50%的反射度和使得涂料在近红外光谱范围内具有大于40%的透明度。为了制备涂料,第一种颜料是有机颜料,其用量是基于配制剂总量计的0.2-20重量%。为了制备涂料,第二种颜料是无机颜料,例如被涂覆的小片状云母颜料,其用量是基于配制剂总量计的4-50重量%。尽管在可见光范围内被染成深色,但是扁平元件具有在近红外范围内的高反射度,从而降低在日光下的加热,这在即使具有深色表面也不会在日光下加热的应用中是所需要的。没有提到金属效应颜料用于着色。
WO 2006/058782 A1描述了一种具有低太阳能吸收性的深色扁平元件,即载体材料与在其中包埋的各组分的组合。此元件具有在400-700nm可见光波长范围内的平均反射度小于50%,在700-1000nm近红外波长范围内的平均反射度大于50%。载体材料可以是塑料。另外,被包埋的组分包括颜料和染料,但不是金属颜料。
WO 00/24833 A1公开了具有光谱选择性的涂料,特别是用于在机动车辆中的沉积表面,其含有:a)粘合剂,其具有在0.7-2.5μm近红外波长范围内的透射比为60%或更大,和在热红外波长范围内的透射比为40%或更大;b)第一种颜料,其在0.35-0.7μm波长范围内吸收40%或更多的可见光,在0.7-2.5μm近红外范围内具有40%或更大的反散射,并且在热红外波长范围内具有60%或更小的吸收率;c)第二种颜料,其在热红外波长范围内具有40%或更大的反散射和/或反射度。其中粘合剂可以选自热塑性材料,例如聚烯烃和聚乙烯基化合物。第一种颜料可以是无机颜料或有机颜料。另外,第二种颜料包括小片状金属或金属合金,例如铁。
WO 02/057374 A1公开了具有低太阳能吸收性的涂料。此涂料含有:a)粘合剂和/或粘合剂组合物,b)第一种颜料,其在300-2500nm波长范围范围内具有大于70%的透明度,选择其粒径以使它们在700-1500nm近红外波长范围内具有大于70%的高反散射,并且在5-50μm热红外范围内具有大于40%的吸收率;c)第二种颜料,其在400-700nm可见光波长范围内具有吸收光谱选择性,和/或在整个可见光波长范围内具有大于50%的吸收率,在70-1500nm近红外波长范围内具有大于50%的透明度,和在热红外范围内具有大于40%的吸收率;和/或d)第三种颜料,其在可见光光谱范围内具有吸收光谱选择性,和/或在整个可见光波长范围的吸收率大于50%,并且按照在近红外光谱范围内的反射度大于50%进行反射,和具有在热红外范围内的吸收率大于40%;e)填料。第一种和第三种颜料可以是无机颜料,第二种颜料是有机颜料,但没有提到金属颜料。
DE 25 44 245 A1提到了将IR-反射颜料引入模塑材料的可能性,其中颜料在加工期间大部分按照表面平行的方式排列成行。但是,根据EP 1 256 437 A1,粒子的排列并不能像在由例如其中均匀分散IR-反射颜料的挤出模塑材料时制备的塑性体那样好,例如在共挤出或涂清漆的单独层的情况下。根据EP 1 256 437 A1,这特别适合用于具有较复杂几何形状的塑性体,其与简单板材形状不同,并且用于其中在挤出期间出现不同熔体流动方向和剪切力的情况,这强制颜料粒子进入不同的排列,因此也使得它们暴露于总体较高的机械应力下。
EP 1 256 437 A1涉及一种制备可透光的IR-反射塑性体的方法,其全部或至少部分地由抗冲击热塑性材料组成,含有0.01-5重量%的由被金属氧化物涂覆的小片状载体颜料制成的反射粒子。
DE 100 10 538 A1描述了具有光谱选择性能的防污染涂料,其另外含有具有优良抗UV性能的粘合剂和第一种小片状粒子。所述小片状粒子在5-100μm的热红外波长范围内反射。第一种小片状粒子可以例如是选自铝、铝青铜、铁、铜、锌或锡的金属和/或金属合金。粘合剂可以例如选自热塑性材料,例如聚烯烃或聚乙烯基化合物。
EP 0 673 980 A2涉及着色的铁或铁合金颜料,其是在高温下在含氧气氛中获得的。这些颜料可以例如用于塑料中以模仿花岗岩效果。
EP 1 541 636 A1描述了一种热塑性塑料组合物,其含有0.1-15质量份的具有红外反射性能的无机颜料。无机颜料可以含有Fe、Cr、Mn、Cu、Co或Ni中的至少一种元素,并可以选自例如氧化物FeO、FeO(OH)、Fe2O3、CrO、Cr2O3、MnO或CuO。
EP 1 916 352 A2公开了屋顶产品,其含有两种共挤出的聚合物层,其中第一层在近红外范围内反射,第二层在此范围内是可透过的。这两层可以着色,其中金属颜料或被包封在二氧化硅中的金属小片可以用作太阳能反射材料。
WO 2012/075369 A1公开用于形成在近红外范围具有改进反射度的产品的组合物。例如铝、钴、铁、锰或锌的金属或金属合金可以用作红外反射颜料。
CN 102627828 A涉及一种塑料组合物,其含有0.1-2.0重量份的金属颜料、0.1-2.0重量份的红外-反射颜料、0.1-2.0重量份的润滑剂、0.1-1.0重量份的抗氧化剂、0.1-0.5重量份的调色剂。另外,铝或银粉末可以用作金属颜料;铁、铜或锌例如可以用作红外-反射颜料。
US 2008/0138609 A1公开了塑料组合物,其含有小于5重量%的红外-反射颜料。无机有色颜料用作红外-反射颜料,例如在US 6,036,763 A或US 6,174,360 B1中所描述的那些。
发明内容
本发明的目的是提供一种组合物,其本身在日光辐照下不会加热或仅仅轻微加热。此组合物的特征另外是其耐侯性。
此目的是通过提供一种塑料组合物实现的,其含有含量范围为0.01-25重量%的至少一种小片状金属颜料,含量范围为0.01-10重量%的至少一种光稳定剂,和含量范围为为0.01-2重量%的至少一种抗氧化剂,在每种情况下基于塑料组合物的重量比例计。
本发明塑料组合物的优选实施方案如下:
根据一个实施方案,在所述塑料组合物中,至少一种金属颜料是铁颜料或铝颜料。
根据上述任一个实施方案,在所述塑料组合物中,小片状金属颜料是被氧化硅、氢氧化硅和/或氧化硅水合物层涂覆的。
根据上述任一个实施方案,在所述塑料组合物中,小片状金属颜料是被氧化硅、氢氧化硅和/或氧化硅水合物层涂覆的铁颜料,其中铁颜料的铁芯具有在从20nm至小于100nm范围内的平均厚度。
根据上述任一个实施方案,在所述塑料组合物中,金属颜料的平均粒径D50是在1-100μm的范围内。
根据上述任一个实施方案,在所述塑料组合物中,塑料组分是选自聚丙烯(PP),PP共聚物,聚乙烯(PE),PE共聚物,HDPE,LDPE,LLDPE,聚苯乙烯(PS),苯乙烯/丙烯腈(SAN),高抗冲击聚苯乙烯(HIPS),丙烯腈-丁二烯-苯乙烯(ABS),丙烯腈-苯乙烯-丙烯酸酯(ASA),聚碳酸酯(PC),PC/ABS的聚合物共混物,PC/ASA的聚合物共混物,聚甲醛(POM),聚酰胺,聚酯,聚氨酯,聚甲基丙烯酸甲酯(PMMA),和它们的混合物。
根据上述任一个实施方案,在所述塑料组合物中,光稳定剂是位阻胺(HALS)和/或UV吸收剂。
另外,此目的是通过提供一种制备本发明塑料组合物的方法实现的。
本发明的主题另外是本发明塑料组合物用作膜、板或型材的用途。
本发明的目的另外通过至少一种被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的小片状铁颜料在根据上述任一个实施方案的塑料组合物中的用途实现。
具体实施方式
要用于本发明塑料组合物中的小片状金属颜料,其是任选被涂覆的,可以选自铁和/或铁合金颜料,铝和/或铝合金颜料,或它们的混合物。
任选被涂覆的铁和/或铁合金颜料优选用于本发明塑料组合物中。被涂覆的铁和/或铁合金颜料特别优选用于本发明塑料组合物中。
在本发明中,铁颜料表示小片状颜料具有的铁含量是≥95重量%,优选≥97重量%,特别优选≥99重量%,十分特别优选≥99.5重量%,在每种情况下基于颜料的总重量计。另外,碳或氧可以作为其它成分存在。
颜料的铁含量可以例如受制备方法和原料的影响。优选使用任选被涂覆的小片状铁颜料,其可以根据EP 1 251 152 A1、EP 1 251 153 A1或EP 2 157 138 A1从经还原处理的羰基铁粉末制备。
EP 1 251 152 A1公开了从经还原处理的羰基铁粉末制备的小片状铁颜料,其用于装饰领域中,例如塑料染色、涂料、印刷或化妆品中,和用于功能领域中,例如安全领域。
EP 1 251 153 A1描述了小片状的被金属氧化物涂覆的软质铁颜料,其是通过模塑从经还原处理的羰基铁粉末制备的。在装饰领域中,颜料用于例如清漆、油漆、塑料、印刷、玻璃、陶瓷和化妆品中。在功能领域中,利用特定的磁性性能、电导性、吸收雷达波的能力或电磁波容量。
EP 2 157 138 A1公开了薄的小片状铁颜料,其具有10-55nm的h50值和20-80nm的h90值。具有这种厚度分布的铁颜料具有高光泽度,并且具有深色或黑色。铁颜料可以例如用于涂料、油漆、清漆、印刷油墨、粉末涂料、塑料、化妆品配制剂中,和用于安全和安全印刷领域中。
在本发明中,铁合金颜料表示小片状颜料的铁含量是在从≥50重量%至<95重量%的范围内,优选在从≥60重量%至<95重量%的范围内,特别优选在从≥70重量%至<95重量%的范围内,十分特别优选在从≥80重量%至<95重量%的范围内,在每种情况下基于颜料的总重量计。在这里,可以考虑铬、钨、钼、钒、钴、镍、铌、硅、锰或它们的混合物用作合金成分。
金属颜料的任选存在的涂料含有以下物质或由以下物质组成:硅、钛和/或锆的金属氧化物、金属氢氧化物和/或金属氧化物水合物。或者,任选存在的涂料含有以下物质或由以下物质组成:聚丙烯酸酯,聚氨酯,聚碳酸酯,聚酯,或它们的混合物。任选存在的涂料优选含有硅的金属氧化物、金属氢氧化物和/或金属氧化物水合物,或由它们组成。
在一个实施方案中,用于本发明塑料组合物中的小片状金属颜料的金属芯具有14-500nm的平均厚度,优选21-340nm,特别优选36-280nm。
在特别优选的实施方案中,使用被SiO2涂覆的小片状铝和/或铁颜料。十分特别优选的是被SiO2涂覆的铁颜料且其具有小片状铁芯的平均厚度在从20nm至小于100nm的范围内,特别是25-60nm。用这种薄铁颜料着色的本发明塑料配制剂惊奇地具有深色固有颜色。发明人还未发现对此结论的解释。已经知道铁在可见光范围内的反射度小于铝;但是初始的深色固有颜色是令人惊奇的。即使在其中小片状铁颜料能非常好地按照与塑料表面的平面平行的方式取向的塑料应用中,也获得深色固有颜色。这是更令人惊奇的,因为取向平面平行的小片状铁颜料至少在掠射角上在可见范围内具有高的反射度。
因为铁效应颜料的厚度小,所以可以使用0.1-2.5重量%的较低浓度范围,优选0.15-2.3重量%,特别优选0.18-2.1重量%,在每种情况下基于塑料组合物的重量比例计。
如果要提供深色塑料组合物,则本发明塑料组合物优选仅仅含有铁颜料作为金属颜料,所述铁颜料优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆,而不是铝颜料。惊奇地证明,在此实施方案中,此塑料组合物的红外反射度足够高以防止在例如太阳能辐射情况下不利的明显升温。在这方面,这是令人惊奇的,因为已经知道铁的红外反射度显著低于铝的反射度,另外,仅仅用铁颜料着色的塑料组合物具有比用铝颜料着色的塑料组合物显著更深的颜色。
塑料的这种深色固有颜色与优异反射性能的组合可以有利地特别用于模塑部件中,例如用于汽车内部的深色部件中,例如仪表板、门装饰等,以及用于外部应用,例如塑料包层、塑料窗框、塑料管或由塑料制成的屋顶瓦。
深色固有颜色与优异反射性能的组合导致在太阳能辐射下的表面温升较小,这是在应用技术方面的性能分布中十分受关注的。含有常规黑色颜料和IR-反射颜料的塑料组合物在实现此性能分布方面是不能令人满意的。
在本发明中,术语“深色塑料组合物”表示大部分的可见光被本发明塑料组合物吸收,从而被人眼视为深色的。在这里,通过使用来自Konica Minolta的CR 310比色计进行扩散颜色检测,深色塑料组合物的亮度L*优选是≤60,特别优选≤50和十分特别优选≤40。虽然塑料组合物被人眼明确视为深色,但令人惊奇的是亮度检测值是高的,但是这可以通过金属颜料的反射度解释。深色塑料组合物即使在低着色情况下也是十分不透明的。
小片状金属颜料的平均厚度是参比硬化清漆膜检测的,其中颜料基本上与基材平面平行地排列。为此,用扫描电子显微镜(SEM)检测硬化清漆膜的横截面,其中检测100个颜料厚度并计算统计平均值,如WO2004087816A2第24页所述。
在另一个实施方案中,含有金属氧化物、金属氢氧化物和/或金属氧化物水合物的涂料或由它们组成的涂料可以含有含量范围为20-80重量%、优选30-70重量%和特别优选40-65重量%的至少一种有色颜料,在每种情况下基于金属颜料的总重量计。至少一种有色颜料可以分布在涂料中,或可以施用于涂层上,优选有色颜料分布在涂料中。涂料优选含有深色颜料,优选是粒子的形式,其在0.8-2.5μm的近红外(NIR)波长范围内具有低吸收率。特别优选的是具有平均初级粒径为10-1000nm、优选20-800nm和特别优选30-400nm的棕色和/或黑色颜料。可以用作有色颜料的是例如铁氧化物,铁-锰混合氧化物,铬-铁黑色Cr2O3(Fe),铬-铁棕色(Fe,Cr)2O3和/或(Zn,Fe)(Fe,Cr)2O4,CuCr2O4类型的铜-铬尖晶石,选自苝的有机有色颜料,或它们的混合物。这些颜料可以根据WO 2008/155038 A2所述制备。
WO 2008/155038 A2涉及深色的IR-辐射反射颜料,其具有小片状的金属IR-辐射反射芯。在芯周围的低IR-辐射吸收涂料包含在基质中、基质上和/或基质下的深色颜料。由铝、铜、锌、锡、钛、铁、银和/或这些金属的合金制成的小片状颜料优选用作小片状芯。
在本发明中,铝颜料表示具有铝含量为≥97重量%、优选≥98重量%、特别优选≥99重量%和十分特别优选≥99.5重量%的小片状颜料,在每种情况下基于颜料的总重量计。另外,金属铁或氧可以作为其它成分存在。
在本发明中,铝合金颜料表示具有铝含量为<97重量%、优选65-95重量%、特别优选70-90重量%和十分特别优选75-85重量%的小片状颜料,在每种情况下基于铝合金颜料的总重量计。一种或多种与铝不同的金属可以用作合金成分,优选铁、锰、铜、钒、铬、镍、钴、硅、镁、锌或钛。
用于本发明塑料组合物中的小片状金属颜料的平均粒径D50优选在1-100μm的范围内,更优选3-69μm,特别优选4-61μm,十分特别优选5-58μm。
在本发明中,平均粒径D50表示体积平均尺寸分布函数的累积频率分布的D50值,这是使用激光散射法获得的。D50值表示50%的金属颜料具有等于或小于此检测值的直径。相应地,D90值表示90%的金属颜料具有等于或小于此检测值的直径。另外,D10值表示10%的金属颜料具有等于或小于此检测值的直径。来自Quantachrome的装置(装置:Cilas 1064)优选用于检测和评价。
在另一个实施方案中,用于本发明塑料组合物中的金属颜料可以经过表面改性,这可以例如影响金属颜料的取向性能。一种或多种硅烷可以作为表面改性剂施涂。硅烷可以是烷基硅烷,其具有1-24个碳原子、优选6-18个碳原子的支化或未支化的烷基。
但是,硅烷也可以是有机官能硅烷,其使得可以与塑料结合。这些有机官能团也可以称为偶联基团或官能连接基团,优选选自羟基、氨基、丙烯酰基、甲基丙烯酰基、乙烯基、环氧基、异氰酸酯、氰基和它们的混合物。
优选用作表面改性剂且具有合适官能团的有机官能硅烷可以商购,例如由Evonik生产和以商品名“Dynasylan”销售。其它产品可以从Momentive(倍半硅烷)或从Wacker获得,例如GENIOSIL产品系列的标准硅烷和α-硅烷。
这些硅烷的例子是3-甲基丙烯酰氧基丙基三甲氧基硅烷(Dynasylan MEMO,Silquest A-174NT),乙烯基三(甲)乙氧基硅烷(分别是Dynasylan VTMO和VTEO,分别是Silquest A-151和A-171),甲基三(甲)乙氧基硅烷(分别是Dynasylan MTMS和MTES),3-巯基丙基三甲氧基硅烷(Dynasylan MTMO;Silquest A-189),3-环氧丙氧基丙基三甲氧基硅烷(Dynasylan GLYMO,Silquest A-187),三[3-(三甲氧基甲硅烷基)丙基]异氰脲酸酯(Silquest Y-11597),二[3-(三乙氧基甲硅烷基)丙基]四硫化物(Silquest A-1289),二[3-(三乙氧基甲硅烷基)丙基]二硫化物(Silquest A-1589),β-(3,4-环氧基环己基)乙基三甲氧基硅烷(Silquest A-186),二(三乙氧基甲硅烷基)乙烷(Silquest Y-9805),γ-异氰酸基(isocyanato)丙基三甲氧基硅烷(Silquest A-Link 35,GENIOSIL GF40),甲基丙烯酰氧基甲基三(甲)乙氧基硅烷(GENIOSIL XL 33,XL 36),(甲基丙烯酰氧基甲基)(甲)乙基二甲氧基硅烷(GENIOSIL XL 32,XL 34),(异氰酸基甲基)甲基二甲氧基硅烷,(异氰酸基甲基)三甲氧基硅烷,3-(三乙氧基甲硅烷基)丙基琥珀酸酐(GENIOSIL GF 20),(甲基丙烯酰氧基甲基)甲基二乙氧基硅烷,2-丙烯酰氧基乙基甲基二甲氧基硅烷,2-甲基丙烯酰氧基乙基三甲氧基硅烷,3-丙烯酰氧基丙基甲基二甲氧基硅烷,2-丙烯酰氧基乙基三甲氧基硅烷,2-甲基丙烯酰氧基乙基三乙氧基硅烷,3-丙烯酰氧基丙基三甲氧基硅烷,3-丙烯酰氧基丙基三丙氧基硅烷,3-甲基丙烯酰氧基丙基三乙氧基硅烷,3-甲基丙烯酰氧基丙基三乙酰氧基硅烷,3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷,乙烯基三氯硅烷,乙烯基三甲氧基硅烷(GENIOSIL XL 10),乙烯基三(2-甲氧基乙氧基)硅烷(GENIOSIL GF 58),乙烯基三乙酰氧基硅烷,或它们的混合物。
优选用作有机官能硅烷的是:3-甲基丙烯酰氧基丙基三甲氧基硅烷(DynasylanMEMO,Silquest A-174NT),乙烯基三(甲)乙氧基硅烷(分别是Dynasylan VTMO和VTEO,分别是Silquest A-151和A-171),甲基三(甲)乙氧基硅烷(分别是Dynasylan MTMS和MTES),β-(3,4-环氧基环己基)乙基三甲氧基硅烷(Silquest A-186),二(三乙氧基甲硅烷基)乙烷(Silquest Y-9805),γ-异氰酸基丙基三甲氧基硅烷(Silquest A-Link 35,GENIOSILGF40),甲基丙烯酰氧基甲基三(甲)乙氧基硅烷(GENIOSIL XL 33,XL 36),(甲基丙烯酰氧基甲基)(甲)乙基二甲氧基硅烷(GENIOSIL XL 32,XL 34),3-(三乙氧基甲硅烷基)丙基琥珀酸酐(GENIOSIL GF 20),乙烯基三甲氧基硅烷(GENIOSIL XL 10)和/或乙烯基三(2-甲氧基乙氧基)硅烷(GENIOSIL GF 58)。
在一个优选实施方案中,有机官能硅烷混合物含有至少一种氨基官能硅烷以及至少一种不含官能结合基团的硅烷。氨基官能团是能与在粘合剂中存在的大多数基团发生一种或多种化学相互作用的官能团。这可以包括共价键,例如与粘合剂的异氰酸酯或羧基官能团之间的共价键,或氢桥键,例如与OH或COOR官能团之间的氢桥键,或离子相互作用。所以,氨基官能团非常适合用于将颜料与不同粘合剂以化学方式结合的目的。
以下化合物优选用于此目的:3-氨基丙基三甲氧基硅烷(Dynasylan AMMO;Silquest A-1110),3-氨基丙基三乙氧基硅烷(Dynasylan AMEO),[3-(2-氨基乙基)氨基丙基]三甲氧基硅烷(Dynasylan DAMO,Silquest A-1120),[3-(2-氨基乙基)氨基丙基]三乙氧基硅烷,三氨基-官能三甲氧基硅烷(Silquest A-1130),二(γ-三甲氧基甲硅烷基丙基)胺(Silquest A-1170),N-乙基-γ-氨基异丁基三甲氧基硅烷(Silquest A-Link 15),N-苯基-γ-氨基丙基三甲氧基硅烷(Silquest Y-9669),4-氨基-3,3-二甲基丁基三甲氧基硅烷(Silquest A-1637),N-环己基氨基甲基甲基二乙氧基硅烷(GENIOSIL XL924),N-环己基氨基甲基三乙氧基硅烷(GENIOSIL XL 926),N-苯基氨基甲基三甲氧基硅烷(GENIOSIL XL973),或它们的混合物。
在另外优选的实施方案中,不含官能结合基团的硅烷是烷基硅烷。烷基硅烷优选具有式R(4-z)Si(X)z。其中,z是1-3的整数,R是取代或未取代的、未支化或支化的具有10-22个碳原子的烷基链,X表示卤素和/或烷氧基。优选的是具有至少12个碳原子烷基链的烷基硅烷。R也可以以环状方式与Si连接,在这种情况下z通常是2。
除了上述硅烷或硅烷混合物之外,也可以使用其它有机化学改性剂,例如取代或未取代的烷基,聚醚,硫醚,硅氧烷等和它们的混合物。
在本发明中,例如聚烯烃、聚苯乙烯、聚酯、聚醚、聚酰胺、聚(甲基)丙烯酸酯、热塑性聚氨酯、聚砜、聚缩醛、聚氯乙烯、它们的混合物或共聚物可以用作塑料组分。优选使用聚丙烯(PP),聚乙烯(PE),聚酰胺(PA),聚对苯二甲酸亚丁基酯(PBT),聚对苯二甲酸亚乙基酯(PET),二醇改性的聚对苯二甲酸亚环己基亚甲基酯(PCTG),聚砜(PSU),聚甲基丙烯酸甲酯(PMMA),热塑性聚氨酯(TPU),丙烯腈-丁二烯-苯乙烯(ABS),丙烯腈-苯乙烯-丙烯酸酯(ASA),丙烯腈-乙烯-丙烯-苯乙烯(AES),苯乙烯-马来酸酐(SMA)或高抗冲击聚苯乙烯(HIPS)。
在另一个实施方案中,以下塑料可以用于本发明塑料组合物中:
1.基于/衍生自单烯烃和二烯烃的聚合物,例如聚丙烯(PP),聚异丁烯(PIB),聚丁-1-烯,聚-4-甲基戊-1-烯(PMP),聚乙烯基环己烷(PVCH),聚异戊二烯或聚丁二烯,以及环烯烃的聚合物,例如环戊烯或降冰片烯,聚乙烯(任选地也交联),例如高密度聚乙烯(HDPE)、高密度高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、(VLDPE)和(ULDPE)。在此段中所述的单烯烃的聚合物,特别是聚乙烯和聚丙烯,可以使用各种方法制备:
a)自由基聚合(通常在高压和高温下进行)。
b)使用催化剂的催化聚合,催化剂通常含有元素周期表IVb、Vb、VIb或VIII族的一种或多种金属。这些金属通常具有一种或多种配体,通常是氧化物、卤化物、醇盐、酯、醚、胺、烷基化物、烯基化物和/或芳基化物,其可以是π-或σ-配位的。这些金属配合物可以自由存在或与基材粘合,通常是活化的氯化镁、氯化钛(III)、铝或氧化硅。这些催化剂可以能溶于或不溶于聚合介质中。催化剂可以作为本身使用或可以使用其它活化剂,通常是金属烷基化物、金属氢化物、金属-烷基卤化物、金属-烷基氧化物或金属-烷基氧丙环,其中所述金属来自元素周期表的Ia、IIa和/或IIIa族。活化剂可以另外用酯、醚和胺或甲硅烷基醚基团改性。这些催化剂体系通常称为菲利普(Phillips)、美孚印第安纳(Standard OilIndiana)、齐格勒-纳塔(Ziegler-Natta)、TNZ(DuPont)、金属茂催化剂或单点催化剂(SSC)。
2.在1)中所述聚合物的混合物,例如聚丙烯和聚异丁烯的混合物,聚丙烯和聚乙烯的混合物(例如PP/HDPE,PP/LDPE),以及不同类型聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃彼此的共聚物或它们与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)和它们与低密度聚乙烯(LDPE)的混合物,丙烯/丁-1-烯共聚物,丙烯/异丁烯共聚物,乙烯/丁-1-烯共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,乙烯/乙烯基环己烷共聚物,乙烯/环烯烃共聚物(例如乙烯/降冰片烯例如COC),乙烯/1-烯烃共聚物,其中1-烯烃是现场产生的;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烯共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物和它们的盐(离聚体),以及乙烯和丙烯和二烯例如己二烯、二环戊二烯或亚乙基降冰片烯的三元共聚物;以及这些共聚物彼此的混合物和它们与在1)中所述聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA,和交替或统计聚烯/一氧化碳共聚物,以及它们与其它聚合物例如聚酰胺的混合物。
4.烃树脂(例如C5-C9),包括其氢化改性形式(例如增粘剂),以及聚烯烃和淀粉的混合物。
上述均聚物和共聚物也可以具有任何立体结构,例如间同立构、全同立构、半全同立构或无规立构;其中无规立构聚合物是优选的。也包括立体嵌段聚合物。
5.聚苯乙烯,聚-(对-甲基苯乙烯),聚-(α-甲基苯乙烯)。
6.芳族均聚物和共聚物,其衍生自乙烯基芳族单体,包括苯乙烯、α-甲基苯乙烯,乙烯基甲苯的所有异构体,特别是对-乙烯基甲苯,乙基苯乙烯的所有异构体,丙基苯乙烯,乙烯基联苯,乙烯基萘和乙烯基蒽,和它们的混合物。均聚物和共聚物可以形成任何立体结构,其可以是间同立构、全同立构、半全同立构或无规立构,其中无规立构聚合物是优选的。包括立体嵌段聚合物。
a)含有上述乙烯基芳族单体和共聚单体的共聚物,共聚单体是乙烯、丙烯、二烯、腈、酸、马来酸酐、马来酰亚胺、乙酸乙烯酯和氯乙烯或丙烯酰基衍生物和它们的混合物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/乙烯(三元共聚物),苯乙烯/甲基丙烯酸烷基酯,苯乙烯/丁二烯/丙烯酸烷基酯,苯乙烯/丁二烯/甲基丙烯酸烷基酯,苯乙烯/马来酸酐,苯乙烯/丙烯腈/丙烯酸甲基酯;高抗冲击性苯乙烯共聚物和其它聚合物的混合物,例如聚丙烯酸酯,二烯聚合物或乙烯/丙烯/二烯三元共聚物;和苯乙烯嵌段共聚物,例如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯,或苯乙烯/乙烯/丙烯/苯乙烯。
b)基于在6.)中所述聚合物的氢化反应的氢化芳族聚合物,特别是聚环己基乙烯(PCHE),其通过无规立构聚苯乙烯的氢化反应制备,通常也称为聚乙烯基环己烷(PVCH)。
c)基于在6.a)中所述聚合物的氢化反应的氢化芳族聚合物。均聚物和共聚物可以具有任何立体结构,这可以是间同立构、全同立构、半全同立构或无规立构,其中无规立构聚合物是优选的。包括立体嵌段聚合物。
7.乙烯基芳族单体的接枝共聚物,例如苯乙烯或α-甲基苯乙烯,例如在聚丁二烯上接枝苯乙烯,在聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上接枝苯乙烯;在聚丁二烯上接枝苯乙烯和丙烯腈(或甲基丙烯腈);在聚丁二烯上接枝苯乙烯、丙烯腈和甲基丙烯酸甲基酯;在聚丁二烯上接枝苯乙烯和马来酸酐;在聚丁二烯上接枝苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;在聚丁二烯上接枝苯乙烯和马来酰亚胺;在聚丁二烯上接枝苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯;在乙烯/丙烯/二烯三元共聚物上接枝苯乙烯和丙烯腈;在聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上接枝苯乙烯和丙烯腈,在丙烯酸酯/丁二烯共聚物上接枝苯乙烯和丙烯腈,以及它们与在6)中所述共聚物的混合物,例如称为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素的聚合物,例如聚氯丁二烯,氯化弹性体,异丁烯-异戊二烯的氯化和溴化共聚物(卤素丁基橡胶),氯化或磺化氯化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均聚物和共聚物,特别是含卤素的乙烯基化合物的聚合物,例如聚氯乙烯(PVC)、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯,以及它们的共聚物,例如氯乙烯/偏二氯乙烯共聚物,氯乙烯/乙酸乙烯酯共聚物,或偏二氯乙烯/乙酸乙烯酯共聚物。
9.衍生自α,β-不饱和酸及其衍生物的聚合物,例如聚丙烯酸酯和聚甲基丙烯酸酯;聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈,用丙烯酸丁基酯冲击改性。
10.在9)中所述单体彼此的共聚物或与其它不饱和单体的共聚物,例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/乙烯基卤化物共聚物,或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和醇和胺或其酰基衍生物或缩醛的聚合物,例如聚乙烯基醇(PVOH),聚乙酸乙烯酯(PVAc),聚硬脂酸乙烯基酯,聚苯甲酸乙烯基酯,聚丙二酸乙烯基酯,聚乙烯基缩丁醛(PVB),聚烯丙基邻苯二甲酸酯或聚烯丙基三聚氰胺;以及它们与1)中所述烯烃的共聚物。
12.环醚的均聚物和共聚物,例如聚亚烷基二醇、聚氧化乙烯、聚氧化丙烯,或它们与二缩水甘油醚的共聚物。
13.聚缩醛,例如聚甲醛(POM),以及含有氧化乙烯作为共聚单体的那些聚甲醛;聚缩醛,其用热塑性聚氨酯(TPU)、丙烯酸酯或MBS改性。
14.聚苯醚(PPO)和聚苯硫醚,以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15.聚酰胺和共聚酰胺,其衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应的内酰胺,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,来自间苯二甲胺和己二酸的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸和/或对苯二甲酸形成的聚酰胺,具有或不具有弹性体作为改性剂,例如聚-2,4,4,-三甲基六亚甲基对苯二甲酰胺或聚-间-亚苯基-间苯二甲酰胺;以及所述聚酰胺与聚烯烃、烯烃共聚物、离聚体或化学键接或接枝的弹性体形成的嵌段共聚物;或与聚醚形成的共聚物,例如与聚乙二醇、聚丙二醇或聚丁二醇形成的共聚物;用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工期间缩合的聚酰胺(RIM聚酰胺体系)。
16.聚脲,聚酰亚胺,聚酰胺酰亚胺,聚醚酰亚胺,聚酯酰亚胺,聚乙内酰脲和聚苯并咪唑。
17.聚酯,其衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯,例如聚对苯二甲酸亚乙基酯,聚对苯二甲酸亚丁基酯,聚(1,4-二羟甲基环己烷对苯二甲酸酯),聚萘甲酸亚烷基酯(PAN)和聚羟基苯甲酸酯,以及基于/衍生自羟基封端的聚醚的嵌段共聚醚酯;以及用聚碳酸酯或MBS改性的聚酯。
18.聚苯醚和聚苯硫醚,以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
19.聚氨酯,其衍生自羟基封端的聚醚、聚酯或聚丁二烯以及芳族多异氰酸酯,以及它们的前体。
20.聚脲,聚酰亚胺,聚酰胺酰亚胺,聚醚酰亚胺,聚酯酰亚胺,聚乙内酰脲和聚苯并咪唑。
21.聚酯,其衍生自二羧酸和二醇和/或衍生自相应内酯的羟基羧酸,例如聚对苯二甲酸亚乙基酯,聚对苯二甲酸亚丁基酯,聚(1,4-二羟甲基环己烷对苯二甲酸酯),聚萘甲酸亚烷基酯(PAN)和聚羟基苯甲酸酯,和衍生自羟基封端的聚醚的嵌段共聚醚酯;以及用聚碳酸酯或MBS改性的聚酯。
22.聚碳酸酯和聚酯碳酸酯。
23.聚砜、聚醚砜和聚醚酮。
24.交联的聚合物,其衍生自醛以及酚、脲和三聚氰胺,例如苯酚/甲醛树脂,脲/甲醛树脂和三聚氰胺/甲醛树脂。
25.干燥和未干燥的醇酸树脂。
26.不饱和聚酯树脂,其衍生自饱和和不饱和二羧酸与多元醇的共聚酯,其中乙烯基化合物用作交联剂,以及具有低可燃性的含卤素改性形式。
27.可交联的丙烯酸树脂,其衍生自取代的丙烯酸酯,例如环氧基丙烯酸酯、聚氨酯丙烯酸酯或聚酯丙烯酸酯。
28.醇酸树脂、聚酯树脂和丙烯酸酯树脂,它们用三聚氰胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联。
29.交联的环氧树脂,其衍生自脂族、脂环族、杂环或芳族缩水甘油基化合物,例如双酚A和双苯酚F的二缩水甘油醚产物,其用常规硬化剂例如酸酐或胺交联,使用或不使用加速剂。
30.天然聚合物,例如纤维素、橡胶、明胶和它们的化学改性同系衍生物,例如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚,例如甲基纤维素;以及松香及其衍生物。
31.上述聚合物的混合物(聚合物共混物),例如PP/EPDM,聚酰胺/EPDM或ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PBTP/ABS,PC/ASA,PC/PBT,PVC/CPE,PVC/丙烯酸酯,POM/TPU,PC/TPU,POM/丙烯酸酯,POM/MBS,PPO/HIPS,PPO/PA 6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。
32.天然和合成有机材料,其完全是单体化合物或这些化合物的混合物,例如矿物油,动物和植物脂肪、油和蜡,或基于合成酯的油、脂肪和蜡(例如邻苯二甲酸酯,己二酸酯,磷酸酯或偏苯三酸酯),以及合成酯混合物与矿物油按照所有重量比率的混合物,通常是纺丝试剂,以及这些材料的水乳液。
33.天然或合成橡胶的水乳液,例如天然胶乳或羧基化苯乙烯/丁二烯共聚物的胶乳。
优选用作塑料组分的是聚丙烯(PP),PP共聚物,聚乙烯(PE),PE共聚物,HDPE,LDPE,LLDPE或其它聚烯烃,聚苯乙烯(PS),SAN,HIPS,丙烯腈-丁二烯-苯乙烯(ABS),ASA或其它苯乙烯共聚物,聚碳酸酯,聚合物共混物例如PC/ABS或PC/ASA,聚甲醛(POM),聚酰胺(PA6,PA6.6,PA11,PA12等),聚酯例如PET、PBT、聚氨酯、热塑性聚氨酯(TPU)、聚甲基丙烯酸甲酯(PMMA)以及其它丙烯酸酯聚合物,丙烯酸酯共聚物,聚氯乙烯(PVC),有机硅和弹性体。
除了所用的金属颜料之外,本发明塑料组合物还可以含有添加剂,例如颜料,染料,光稳定剂,抗氧化剂,共稳定剂例如酸捕捉剂(例如金属硬脂酸盐,水滑石,金属氧化物,金属钝化剂,亚磷酸酯),增塑剂,阻燃剂,或它们的混合物。
为了实现特定的颜色效果,着色剂和/或效应颜料和/或它们的混合物可以加入本发明塑料组合物中。着色剂和/或效应颜料和/或它们的混合物的用量是优选是0.01-10重量%、特别优选0.1-5重量%和十分特别优选1-5重量%,在每种情况下基于塑料组合物的重量比例计。
例如,效应颜料可以是基于以下的可商购的珠光颜料:基于天然云母小片,基于被涂覆的合成云母小片,例如来自ECKART GmbH的产品系列SYMIC,或基于被涂覆的玻璃小片,例如来自ECKART GmbH的产品系列LUXAN。代替或另外,可以使用任选经涂覆的基于铜或金青铜小片的金属效应颜料,例如产品系列STANDART、STAPA、SILVERSHINE,在每种情况下来自ECKART GmbH。着色剂也可以选自无机或有机颜料,以及有机染料,它们用以下颜色指数表征。
CI颜料白:4,5,7,
CI颜料黄:1,3,5,10,12,13,14,16,17,23,42,55,61,62,65,73,74,81,83,93,94,95,108,109,110,111,114,120,126,127,128,129,138,139,147,150,151,154,155,168,173,174,175,176,177,180,181,183,185,188,191,191:1,194,199,214,
CI溶剂黄:16,19,21,25,29,32,34,47,56,79,81,82,88,89,93,98,129,130,135,145,160:,162,174,
CI颜料橙:5,13,31,34,36,37,38,43,46,51,61,62,64,65,67,68,71,72,74,
CI溶剂橙:3,5,6,11,14,25,41,54,56,59,60,62,86,99,102,
CI颜料红:2,3,4,5,8,9,10,12,14,23,38,48:1,48:2,48:3,48:4,49,52,53:1,53:3,57:1,81,88,95,101,102,112,122,123,144,146,149,166,170,171,175,176,177,178,179,185,187,188,190,202,206,208,209,210,214,220,221,224,242,247,253,254,255,259,262,264,272,
CI溶剂红:1,7,23,24,27,49,52,109,111,118,119,122,125,127,130,132,135,160,179,181,195,
CI颜料棕:23,25,
CI溶剂棕:1,3,20,28,42,43,44,58,
CI颜料紫:15,16,19,23,29,32,37,42,
CI溶剂紫:2,8,9,13,24,36,
CI颜料蓝:15,15:1,15:3,29,56,60,61,
CI溶剂蓝:4,10,21,35,38,48,64,67,70,97,
CI颜料绿:7,36,
CI溶剂绿:3,5,7,28,
CI颜料黑:10,
CI溶剂黑:3,5,6,7,27,28,29,34,45,47。
如果需要深色塑料组合物,则它们可以通过将优选棕色和/或黑色有色颜料和/或棕色和/或黑色染料在至少一种小片状金属颜料存在下混合获得。与不含小片状金属颜料的塑料组合物相比,本发明塑料组合物在暴露于例如太阳能辐射时惊奇地显示仅仅非常低程度的表面升温。含有棕色和/或黑色颜料和/或棕色和/或黑色染料的塑料组合物通常暴露于高的热量增加状况,这是因为它们能强烈吸收太阳能辐射。
因为本发明塑料组合物也能用于外部应用或直接暴露于太阳光的应用,所以根据本发明加入至少一种光稳定剂和至少一种抗氧化剂。在这里,光稳定剂可以分类成UV吸收剂和位阻胺。
另外,以下化合物可以在本发明塑料组合物中用作光稳定剂:
UV吸收剂:
2-(2'-羟基苯基)-苯并三唑,例如:
■2-(2H-苯并三唑-2-基)-对-甲酚(CAS登记号[2440-22-4])
■2-(2H-苯并三唑-2-基)-4,6-二(1-甲基-1-苯基乙基)苯酚(CAS登记号[70321-86-7])
■2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5])
■2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1])
■2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚(CAS登记号[25973-55-1])
■2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(CAS登记号[3147-75-9])
■2,2′-亚甲基二-(6-(2H-苯并三唑-2-基)-4,1,3,3-四甲基丁基)苯酚(CAS登记号[103597-45-1])
■2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1])
■2-(2'-羟基-5'-甲基苯基)苯并三唑,2-(3',5'-二叔丁基-2'-羟基苯基)苯并三唑,2-(5'-叔丁基-2'-羟基苯基)苯并三唑,2-(2'-羟基-5'-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3',5'-二叔丁基-2'-羟基苯基)-5-氯苯并三唑,2-(3'-叔丁基-2'-羟基-5'-甲基苯基)-5-氯苯并三唑,2-(3'-仲丁基-5'-叔丁基-2'-羟基苯基)苯并三唑,2-(2'-羟基-4'-辛氧基苯基)苯并三唑,2-(3',5'-二-叔戊基-2'-羟基苯基)苯并三唑,2-(3',5'-二-(α,α-二甲基苄基)-2'-羟基苯基)苯并三唑,2-(3'-叔丁基-2'-羟基-5'-(2-辛氧基羰基乙基)苯基)-5-氯苯并三唑,2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羟基苯基)-5-氯苯并三唑,2-(3'-叔丁基-2'-羟基-5'-(2-甲氧基羰基乙基)苯基)-5-氯苯并三唑,2-(3'-叔丁基-2'-羟基-5'-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3'-叔丁基-2′-羟基-5'-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)苯并三唑,2-(3′-十二烷基-2'-羟基-5'-甲基苯基)苯并三唑,2-(3'-叔丁基-2'-羟基-5'-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2'-亚甲基-二[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基-苯酚];2-[3'-叔丁基-5'-(2-甲氧基羰基乙基)-2'-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯化产物;[R-CH2CH2-COO-CH2CH2-]2,其中R=3′-叔丁基-4'-羟基-5'-2H-苯并三唑-2-基-苯基;2-[2'-羟基-3'-(α,α-二甲基苄基)-5'-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2′-羟基-3'-(1,1,3,3-四甲基丁基)-5'-(α,α-二甲基苄基)苯基]苯并三唑。
2-羟基二苯酮,例如:
■2-羟基-4-(正-辛氧基)二苯酮(CAS登记号[1843-05-6])。
■4-羟基-、4-甲氧基-、4-辛氧基-、4-癸基氧基-、4-十二烷基氧基-、4-苄基氧基-、4,2',4'-三羟基-或2'-羟基-4,4'-二甲氧基衍生物。
■未取代或取代的苯甲酸的酯,例如水杨酸4-叔丁基-苯基酯,水杨酸苯基酯,水杨酸辛基苯基酯,二苯甲酰基间苯二酚,二(4-叔丁基苯甲酰基)间苯二酚,苯甲酰基间苯二酚,2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯,十六烷基-3,5-二叔丁基-4-羟基苯甲酸酯,十八烷基-3,5-二叔丁基-4-羟基苯甲酸酯,2-甲基-4,6-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯。
丙烯酸酯,例如:
■α-氰基-β,β-二苯基丙烯酸乙基酯或异辛基酯,α-甲氧基羰基肉桂酸甲基酯,α-氰基-β-甲基-对-甲氧基肉桂酸甲基酯或丁基酯,α-甲氧基羰基-对-甲氧基肉桂酸甲基酯,N-(β-甲氧基羰基-β-氰基乙烯基)-2-甲基二氢吲哚。
草酸二酰胺,例如:
■N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8])
■4,4'-二辛氧基-N,N‘-草酰二苯胺,2,2'-二乙氧基-N,N‘-草酰二苯胺,2,2'-二辛氧基-5,5'-二-叔丁酰二苯胺,2,2'-双十二烷基氧基-5,5'-二-叔丁酰二苯胺,2-乙氧基-2'-乙基-N,N‘-草酰二苯胺,N,N'-二(3-二甲基氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2'-N,N‘-乙酰二苯胺和它们与2-乙氧基-2'-乙基-5,4'-二-N,N‘-叔丁酰二苯胺的混合物,邻-和对-甲氧基-二取代的N,N‘-草酰二苯胺的混合物,以及邻-和对-乙氧基-二取代的N,N‘-草酰二苯胺的混合物。
2-(2-羟基苯基)-1,3,5-三嗪,例如:
■2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚(CAS登记号[174315-50-2]),3-(二芳基)[1,3,5]三嗪-2-基)-5-(烷氧基-取代的)-苯酚,2,4-二(2,4-二甲基苯基)-6-(2-羟基-4-异辛氧基苯基)-s-三嗪(CAS登记号[137759-38-7])
■2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2,4-二(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-二(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙基氧基]苯基}-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪。
甲脒化合物,例如:
■4-[[[甲基苯基氨基]亚甲基]氨基]苯甲酸乙基酯(CAS登记号[57834-33-0])
位阻胺,例如:
■二(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(CAS登记号[52829-07-9])
■二(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯+甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸酯(CAS登记号[41556-26-7和82919-37-7])
■二(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯,与1,1-二甲基乙基氢过氧化物和辛烷的反应产物(CAS登记号[129757-67-1])
■聚[[6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8])
■N,N’-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺,与2,4,6-三氯-1,3,5-三嗪的聚合物,与N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[192268-64-7])
■N,N”’-[1,2-乙二基-二[[[4,6-二-[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-丙烷二基]]二[N’,N”-二丁基-N’,N”-二(1,2,2,6,6-五甲基-4-哌啶基)-1,3,5-三嗪-2,4,6-三胺(CAS登记号[106990-43-6])
■N,N'-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺,与2,4,6-三氯-1,3,5-三嗪的聚合物,与3-溴-1-丙烯、N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物,被氧化,被氢化(CAS登记号[247243-62-6])
■丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0])
■二-(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-二(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯(CAS登记号[63843-89-0])
■Hostavin N30:2,2,4,4-四甲基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮和表氯醇的聚合物(CAS登记号[202483-55-4])
■Hostavin N20:2,2,4,4-四甲基-21-氧基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷(CAS登记号[64338-16-5])
■Cyassorb UV-3529:N,N'-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺,与吗啉-2,4,6-三氯-1,3,5-三嗪的聚合物(CAS登记号[193098-40-7])
■Uvinul 5050H用于PP:α-烯烃,C20-24,与马来酸酐的聚合物,与2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[152261-33-1])
■Uvinul 4050:1,6-六亚甲基-二[N-甲酰基-N-(2,2,6,6-四甲基哌啶-4-基)胺](CAS登记号[124172-53-8])
■二(2,2,6,6-四甲基哌啶-4-基)琥珀酸酯,二(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯,二(1-辛氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯,正丁基-3,5-二叔丁基-4-羟基苄基丙二酸-二(1,2,2,6,6-五甲基哌啶基)酯,1-羟基乙基-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合产物,N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-s-三嗪的直链或环状缩合产物,三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯,四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁四酸酯,1,1'-(1,2-乙二基)二(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂基氧基-2,2,6,6-四甲基哌啶,二(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,二(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯,二(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯,N,N'-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的直链或环状缩合产物,2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-二(3-氨基丙基氨基)乙烷的缩合产物,2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-二(3-氨基丙基氨基)乙烷的缩合产物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-硬脂基氧基-2,2,6,6-四甲基哌啶的混合物,N,N'-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合产物,1,2-二(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合产物(CAS登记号[136504-96-6]);1,6-二氨基己烷和2,4,6-三氯-1,3,5-三嗪和N,N-二丁基胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合产物(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷和表氯醇的反应产物,1,1-二(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N'-二-甲酰基-N,N'-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐/α-烯烃共聚物和2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
另外,自由基捕捉剂也可以在本发明塑料组合物中用作光稳定剂,以及镍化合物,例如2,2'-硫代二[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,例如1:1或1:2配合物,任选地具有其它配体例如正丁基胺、三乙醇胺或N-环己基二乙醇胺配合,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸单烷基酯的镍盐,例如甲基或乙基酯,酮肟的镍配合物,例如2-羟基-4-甲基苯基十一烷基酮肟,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,任选地具有其它配体。
以下物质优选用作UV吸收剂:
2-(2H-苯并三唑-2-基)-对-甲酚(CAS登记号[2440-22-4]),
2-(2H-苯并三唑-2-基)-4,6-二(1-甲基-1-苯基乙基)苯酚(CAS登记号[70321-86-7]),
2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),
2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1]),
2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚(CAS登记号[25973-55-1]),
2,2′-亚甲基二-(6-(2H-苯并三唑-2-基)-4,1,3,3-四甲基丁基)苯酚(CAS登记号[103597-45-1]),
N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8]),
2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1]),
2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚(CAS登记号[174315-50-2]),
3-(二芳基)[1,3,5]三嗪-2-基)-5-(烷氧基-取代的)苯酚,
2,4-二(2,4-二甲基苯基)-6-(2-羟基-4-异辛氧基苯基)-s-三嗪(CAS登记号[137759-38-7]),
4-[[[甲基苯基氨基]亚甲基]氨基]苯甲酸乙基酯(CAS登记号[57834-33-0])。
以下物质优选用作位阻胺:
二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),
二(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯+甲基1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(CAS登记号[41556-26-7和82919-37-7]),
癸烷二甲酸,二(2,2,6,6-四甲基-1-(辛氧基)-4-哌啶基)酯,与1,1-二甲基乙基氢过氧化物和辛烷的反应产物(CAS登记号[129757-67-1]),
聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),
N,N’-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺,与2,4,6-三氯-1,3,5-三嗪的聚合物,与N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[192268-64-7]),
N,N”’-[1,2-乙烷-二基-二[[[4,6-二-[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-丙烷二基]]二[N’,N”-二丁基-N’,N”-二(1,2,2,6,6-五甲基-4-哌啶基)-1,3,5-三嗪-2,4,6-三胺(CAS登记号[106990-43-6]),
丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),
二(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-二(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯(CAS登记号[63843-89-0]),
Hostavin N30(CAS登记号[202483-55-4]),
Hostavin N20:(CAS登记号[64338-16-5]),
Cyassorb UV-3529:(CAS登记号[193098-40-7]),
Uvinul 5050H用于PP:(CAS登记号[152261-33-1]),
Uvinul 4050(CAS登记号[124172-53-8])。
以下物质可以作为抗氧化剂加入本发明塑料组合物中:
1.1.烷基化单酚,例如2,6-二叔丁基-4-甲基苯酚,2-叔丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚,具有直链或支化侧链的壬基酚,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1'-甲基十一烷-1'-基)苯酚,2,4-二甲基-6-(1'-甲基十七烷-1'-基)苯酚,2,4-二甲基-6-(1'-甲基十三烷-1'-基)苯酚和它们的混合物。
1.2.烷基硫代甲基酚,例如2,4-二辛基硫代甲基-6-叔丁基苯酚,2,4-二辛基硫代甲基-6-甲基苯酚,2,4-二辛基硫代甲基-6-乙基苯酚,2,6-双-十二烷基硫代甲基-4-壬基苯酚。
1.3.氢醌和烷基化氢醌,例如2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二-叔戊基氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯基硬脂酸酯,二(3,5-二叔丁基-4-羟基苯基)己二酸酯。
1.4.生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚和它们的混合物(维生素E)。
1.5.羟基化硫代二苯基醚,例如2,2′-硫代二(6-叔丁基-4-甲基苯酚),2,2′-硫代二(4-辛基苯酚),4,4′-硫代二(6-叔丁基-3-甲基苯酚),4,4′-硫代二(6-叔丁基-2-甲基苯酚),4,4′-硫代二(3,6-二-仲戊基苯酚),4,4′-二(2,6-二甲基-4-羟基苯基)二硫醚。
1.6.亚烷基双酚,例如2,2'-亚甲基-二(6-叔丁基-4-甲基苯酚),2,2′-亚甲基-二(6-叔丁基-4-乙基苯酚),2,2'-亚甲基-二[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基-二(4-甲基-6-环己基苯酚),2,2′-亚甲基-二(6-壬基-4-甲基苯酚),2,2′-亚甲基-二(4,6-二叔丁基苯酚),2,2'-亚乙基-二(4,6-二叔丁基苯酚),2,2′-亚乙基-二(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基-二[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基-二[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基-二(2,6-二叔丁基苯酚),4,4'-亚甲基-二(6-叔丁基-2-甲基苯酚),1,1-二(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-二(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-二(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,乙二醇-二[3,3-二(3'-叔丁基-4'-羟基苯基)丁酸酯],二(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯,二[2-(3'-叔丁基-2'-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯,1,1-二-(3,5-二甲基-2-羟基苯基)丁烷,2,2-二(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-二-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-、N-和S-苄基化合物,例如3,5,3′,5'-四叔丁基-4,4′-二羟基二苄基醚,十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯,十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯,三(3,5-二叔丁基-4-羟基苄基)胺,二(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯,二(3,5-二-叔丁基-4-羟基苄基)硫化物,异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8.羟基苄基化丙二酸酯,例如双十八烷基-2,2-二(3,5-二叔丁基-2-羟基苄基)丙二酸酯,双-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯,双-十二烷基巯基乙基-2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸酯,二[4-(1,1,3,3-四甲基丁基)苯基]-2,2-二(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟基苄基化合物,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯,1,4-二(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。
1.10.三嗪化合物,例如2,4-二(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-二(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-二(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯,2,4,6-三(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯,二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯,双十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯,双十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯,3,5-二叔丁基-4-羟基苄基膦酸单乙基酯的钙盐。
1.12.酰基氨基苯酚,例如4-羟基-N-月桂酰苯胺,4-羟基-N-硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛基酯。
1.13.β-(3,5-二叔丁基-4-羟基苯基)丙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N′-二(羟基乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N'-二(羟基乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷、3,9-二[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰基氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N'-二(羟基乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.16.3,5-二叔丁基-4-羟基苯基乙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N′-二(羟基乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺,例如N,N'-二(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺,N,N'-二(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二酰胺,N,N′-二(3,5-二叔丁基-4-羟基苯基丙酰基)酰肼,N,N'-二[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰基氧基)乙基]草酰胺。
1.18.抗坏血酸(维生素C)。
1.19.胺类抗氧化剂,例如N-苯基苄基胺,与2,4,4-三甲基戊烯的反应产物(CAS登记号[192268-64-7]),N,N'-二-异丙基-对苯二胺,N,N'-二仲丁基-对苯二胺,N,N'-二(1,4-二甲基戊基)-对苯二胺,N,N'-二(1-乙基-3-甲基戊基)-对苯二胺,N,N'-二(1-甲基庚基)-对苯二胺,N,N'-二环己基-对苯二胺,N,N'-二苯基-对苯二胺,N,N'-二(2-萘基)-对苯二胺,N-异丙基-N'-苯基-对苯二胺,N-(1,3-二甲基丁基)-N'-苯基-对苯二胺,N-(1-甲基庚基)-N′-苯基-对苯二胺,N-环己基-N′-苯基-对苯二胺,4-(对-甲苯基磺胺酰基)二苯基胺,N,N′-二甲基-N,N′-二仲丁基-对苯二胺,二苯基胺,N-烯丙基二苯基胺,4-异丙氧基二苯基胺,N-苯基-1-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化的二苯基胺,例如p,p′-二-叔辛基二苯基胺,4-正丁基氨基苯酚,4-丁酰基氨基苯酚,4-壬酰基氨基苯酚,4-十二烷酰基氨基苯酚,4-十八烷酰基氨基苯酚,二(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲基氨基甲基苯酚,2,4'-二氨基二苯基甲烷,4,4'-二氨基二苯基甲烷,N,N,N',N'-四甲基-4,4'-二氨基二苯基甲烷,1,2-二[(2-甲基苯基)氨基]乙烷,1,2-二(苯基氨基)丙烷,(邻-甲苯基)双胍,二[4-(1',3'-二甲基丁基)苯基]胺,叔辛基化的N-苯基-1-萘基胺,单-和二-烷基化的叔丁基/叔辛基二苯基胺的混合物,单-和二-烷基化的壬基二苯基胺的混合物,单-和二-烷基化的十二烷基二苯基胺的混合物,单-和二-烷基化的异丙基/异己基二苯基胺的混合物,单-和二-烷基化的叔丁基二苯基胺的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并三嗪,吩噻嗪,单-和二-烷基化的叔丁基/叔辛基吩噻嗪的混合物,单-和二-烷基化的叔-辛基吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N',N'-四苯基-1,4-二氨基丁-2-烯,N,N-二(2,2,6,6-四甲基哌啶-4-基-六亚甲基二胺,二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯,2,2,6,6-四甲基哌啶-4-酮,2,2,6,6-四甲基哌啶-4-醇。
优选的抗氧化剂是季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),
3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),
3-(3,5-二叔丁基-4-羟基苯基)丙酸2-乙基戊基酯(CAS登记号[125643-61-0]),
亚乙基二(氧亚乙基)二(3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯)(CAS登记号[36443-68-2]),
N,N′-己烷-1,6-二基二(3-3,5-二叔丁基-4-羟基苯基丙酰胺)(CAS登记号[23128-74]),
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(CAS登记号[27676-62-6]),
N-苯基苯胺,与2,4,4-三甲基戊烯的反应产物(CAS登记号[192268-64-7]),
三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4]),
四(2,4-二叔丁基苯基)[1,1-二苯基]-4,4′-二基二亚膦酸酯(CAS登记号[119345-01-6]),
二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯;3,9-二(2,4-二(1,1-二甲基乙基)苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺(5.5)十一烷(CAS登记号[26741-53-7]),
二-2,4-二叔丁基苯基季戊四醇二亚磷酸酯(CAS登记号[26741-53-7]),
二[2,4-二(1,1-二甲基乙基)-6-甲基苯基]乙基酯磷酸(CAS登记号[145650-60-8])。
一般而言,可以将以下分类的所有增塑剂物质加入本发明塑料组合物中作为增塑剂:邻苯二甲酸酯;磷酸酯;己二酸、壬二酸、戊二酸和癸二酸的酯;脂肪酸酯,环氧化脂肪酸酯;柠檬酸酯;乙酸、丙酸和丁酸的酯;乙基丁酸和乙基己酸的酯;二醇酸酯;聚酯;卤代烃;脂族和芳族烃;苯甲酸酯;偏苯三酸酯;磺酸酯;磺酰胺;苯胺;醇;醚;酮;聚乙二醇;松香酸酯衍生物。这些物质的例子是:烷基磺酸酯(ASE),邻苯二甲酸丁基苄基酯(BBP),邻苯二甲酸丁基辛基酯(BOA),邻苯二甲酸二丁基酯(DBP),癸二酸二丁基酯(DBS),邻苯二甲酸二环己基酯(DCHP),邻苯二甲酸二辛基酯(DCP),邻苯二甲酸二癸基酯(DDP),邻苯二甲酸二乙基酯(DEP),邻苯二甲酸二庚基酯(DHP),邻苯二甲酸二己基酯(DHXP),邻苯二甲酸二异丁基酯(DIBP),己二酸二异癸基酯(DIDA),邻苯二甲酸二异癸基酯(DIDP),邻苯二甲酸二异庚基酯(DIHP),邻苯二甲酸二异己基酯(DIHXP),己二酸二异壬基酯(DINA),邻苯二甲酸二异壬基酯(DINP),己二酸二异辛基酯(DIOA),邻苯二甲酸二异辛基酯(DIOP),邻苯二甲酸二异戊基酯(DIPP),邻苯二甲酸二异十三烷基酯(DITDP),邻苯二甲酸二甲基酯(DMP),邻苯二甲酸二正辛基酯(DNOP),邻苯二甲酸二壬基酯(DNP),己二酸二辛基酯(DOA),间苯二甲酸二辛基酯(DOIP),邻苯二甲酸二辛基酯(DOP),癸二酸二辛基酯(DOS),对苯二甲酸二辛基酯(DOTP),壬二酸二辛基酯(DOZ),二苯基甲酚基磷酸酯(DPCF),二苯基辛基磷酸酯(DPOF),邻苯二甲酸二异十三烷基酯(DTDP),邻苯二甲酸双十一烷基酯(DUP),环氧化亚麻籽油(EPLO),环氧化大豆油(EPSO),庚基壬基十一烷基己二酸酯(HNUA),庚基壬基十一烷基邻苯二甲酸酯(HNUP),己基辛基癸基己二酸酯(HXODA),己基辛基癸基邻苯二甲酸酯(HXODP),壬基十一烷基己二酸酯(NUA),壬基十一烷基邻苯二甲酸酯(NUP),辛基癸基己二酸酯(ODA),辛基癸基邻苯二甲酸酯(ODP),正辛基癸基偏苯三酸酯(ODTM),磷酸三氯乙基酯(TCEF),磷酸三甲酚基酯(TCP),三异辛基偏苯三酸酯(TIOTM),磷酸三辛基酯(TOP),四辛基均苯四酸酯(TOPM),三辛基偏苯三酸酯(TOTM),磷酸三苯基酯(TPF),三(二甲苯基)磷酸酯(TXF),混合醇酯,芳基-烷基混合磷酸酯,乙酰基-三丁基柠檬酸酯,(丙烷,丁烷,戊烷和己烷)二醇与二羧酸(邻苯二甲酸、癸二酸、己二酸)的聚酯。增塑剂的用量优选是5-50重量%,基于塑料组合物的总重量计,与由PVC制成的塑料组分组合使用。
另外,阻燃剂可以加入本发明塑料组合物中。一般,可以加入以下分类的所有阻燃剂:有机溴和氯化合物;无机和有机磷化合物;卤化有机磷酸酯;氯化链烷烃,氯化脂环族化合物,无机阻燃剂;基于锑的阻燃剂;化合物;磷-氮化合物;氯化邻苯二甲酸衍生物。这些的例子是氢氧化铝,草酸铝,多磷酸胺,氧化锑,硼酸,四氟硼酸钠,硼酸锌,ZnS,ZnCl2,氢氧化镁,三聚氰胺,三聚氰胺氰脲酸酯,间苯二酚-二(二苯基磷酸酯),二溴苯乙烯,十溴二苯基醚,八溴二苯基醚,六溴二苯基醚,五溴二苯基醚,六溴二苯氧基乙烷,四溴邻苯二甲酸酐,四溴邻苯二甲酸二醇,四溴聚醚,亚乙基-二-四溴邻苯二甲酰亚胺,四溴双酚A(TBBA),TBBA-二(2,3-二溴丙基醚),TBBA-二(2-羟基乙基醚),TBBA-二(烯丙基醚),TBBA-二(2-乙基醚丙烯酸酯),TBBA-碳酸酯低聚物,基于TBBA的溴化环氧树脂,聚(二溴亚苯基醚),聚(五溴苄基丙烯酸酯),聚(三溴苯乙烯),六溴环十二烷,亚乙基-二(二溴降冰片烷-二-碳酰亚胺),二溴乙基二溴环己烷,二溴新戊二醇,三溴新戊基醇或三(三溴苯基)氰脲酸酯。阻燃剂的用量优选是0-60重量%,更优选5-50重量%,特别优选10-40重量%,十分特别优选20-30重量%,在每种情况下基于塑料组合物的总重量计。
塑料的特征是其低密度。通过添加用于本发明的金属颜料,本发明塑料组合物的密度仅仅轻微增加,优选增加小于5%。塑料组合物通常具有0.9-1.1g/cm3的密度(聚烯烃<1.0g/cm3)。
本发明塑料组合物可以存在于不同的应用中,例如用作箔或膜、带、板或作为型材。因为本发明塑料组合物也用于外部应用或直接暴露于阳光的应用,所以可以方便地加入至少一种光稳定剂以保护塑料组分。
在一个优选实施方案中,本发明塑料组合物含有含量范围为0.01-25重量%的至少一种金属颜料,含量范围为0.01-10重量%的至少一种光稳定剂,和含量范围为0.001-0.5重量%至少一种抗氧化剂,在每种情况下基于塑料组合物的重量比例计。本发明塑料组合物特别优选含有含量范围为0.1-15重量%、更优选0.5-15重量%的至少一种金属颜料,含量范围为0.05-10重量%、更优选0.7-7重量%的至少一种光稳定剂,和含量范围为0.008-0.4重量%、更优选0.01-0.3重量%的至少一种抗氧化剂,在每种情况下基于塑料组合物的重量比例计。
在一个特别优选的实施方案中,至少一种金属颜料和至少一种光稳定剂的用量匹配施涂的相应厚度。如果本发明塑料组合物作为厚度为10-100μm的箔或膜存在,则塑料组合物含有含量范围为0.5-15重量%的至少一种金属颜料,含量范围为0.01-10重量%的至少一种光稳定剂,以及含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于箔或膜的重量比例计。在一个优选实施方案中,厚度为10-100μm的箔或膜含有含量范围为0.7-13重量%、更优选1.1-13重量%、特别优选1.3-12重量%、十分特别优选1.6-11重量%的至少一种金属颜料,含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于箔或膜的重量比例计,以及至少一种光稳定剂,其中光稳定剂含有含量范围为1.1-7.3重量%、更优选1.4-6.9重量%、特别优选1.6-6.4重量%、十分特别优选2.1-5.2重量%的位阻胺(HALS)以及含量范围为0.005-1.9重量%、更优选0.007-1.7重量%、特别优选0.008-1.4重量%、十分特别优选0.01-1.1重量%的UV吸收剂,在每种情况下基于箔或膜的重量比例计。
如果本发明塑料组合物作为厚度为0.1-0.5mm的箔存在,则塑料组合物含有含量范围为0.5-10重量%的至少一种金属颜料,含量范围为0.01-7重量%的至少一种光稳定剂,以及含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于箔的重量比例计。在一个优选实施方案中,厚度为0.1-0.5mm的箔含有含量范围为0.5-8重量%、优选0.7-6.7重量%、更优选0.8-5.9重量%、十分特别优选0.9-5.1重量%的至少一种金属颜料,含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于箔的重量比例计,以及至少一种光稳定剂,其中光稳定剂含有含量范围为0.01-4重量%、优选0.05-3重量%、更优选0.07-2.7重量%、特别优选0.09-2.4重量%、十分特别优选0.1-2.2重量%的位阻胺(HALS)以及含量范围为0-2重量%、优选0-1.7重量%、更优选0-1.3重量%、十分特别优选0-1.1重量%的UV吸收剂,在每种情况下基于箔的重量比例计。
如果本发明塑料组合物是作为厚度为0.5-2mm的板存在,则塑料组合物含有含量范围为0.01-5重量%的至少一种金属颜料,含量范围为0.02-4重量%的至少一种光稳定剂,和含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于板的重量比例计。在一个优选实施方案中,厚度为0.5-2mm的板含有含量范围为0.01-4.3重量%、优选0.04-3.9重量%、更优选0.07-3.4重量%、特别优选0.09-3.2重量%、十分特别优选0.1-3重量%的至少一种金属颜料,含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于板的重量比例计,以及至少一种光稳定剂,其中光稳定剂含有含量范围为0.01-2.7重量%、优选0.02-2.3重量%、更优选0.03-1.9重量%、特别优选0.04-1.3重量%、十分特别优选0.05-1.1重量%的位阻胺以及含量范围为0.05-3.8重量%、优选0.07-3.1重量%、更优选0.08-2.6重量%、特别优选0.09-2.3重量%、十分特别优选0.1-2.1重量%的UV吸收剂,在每种情况下基于板的重量比例计。
如果本发明塑料组合物是作为厚度>2mm的型材存在,则塑料组合物含有含量范围为0.001-5重量%的至少一种金属颜料,含量范围为0.1-7重量%的至少一种光稳定剂,和含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于型材的重量比例计。在一个优选实施方案中,厚度>2mm的型材含有含量范围为0.001-3.9重量%、优选0.002-3.5重量%、更优选0.004-3.1重量%、特别优选0.008-2.6重量%、十分特别优选0.01-2.3重量%的至少一种金属颜料,含量范围为0.01-0.2重量%的至少一种抗氧化剂,在每种情况下基于型材的重量比例计,和至少一种光稳定剂,其中光稳定剂含有含量范围为0-0.9重量%、优选0-0.8重量%、更优选0-0.7重量%、特别优选0-0.6重量%、十分特别优选0-0.5重量%的位阻胺(HALS)以及含量范围为0.05-6.7重量%、优选0.1-6.4重量%、更优选0.15-6.1重量%、特别优选0.2-5.6重量%、十分特别优选0.25-5.2重量%的UV吸收剂,在每种情况下基于型材的重量比例计。
作为辐射到达土地表面的的阳光可以根据ASTM G 173-03(2012)“对于37°面向太阳表面的标准空气质量1.5直接正常和半球光谱太阳能辐射(Standard Air Mass1.5Direct Normal and Hemispherical Spectral Solar Irradiance for 37°Sun-Facing Tilted Surface)”基本上分成三个子范围:到达表面的能量的5%覆盖UV光谱范围(300-400nm),几乎43%覆盖可见范围(400-700nm)和52%覆盖NIR范围(700-2500nm)。
在所有立体角上的扩散反射是在280-2500nm的范围内使用与分光计连接的Ulbricht整合球检测的(装置:来自Perkin-Elmer的Lambda 1050)。考虑到ASTM G 173-03,总太阳能反射度(TSR)是在300-2500nm范围内计算的。
总太阳能反射度的值(TSR值)是十分重要的,因为其考虑到太阳能辐射的整个电磁波长光谱范围。但是,对于表面的加热,必须考虑由紫外、红外和可见光辐射组成的整个太阳能辐射。总太阳能反射度(TSR)是衡量被表面反射的辐射区域太阳能的比例的手段。这是被表面反射的太阳能辐射能量的比例。此值越高,反射的太阳能辐射就越强,所以在太阳光辐照后在涂层表面上能检测到的与环境温度相比的温升就越小。TSR值越小,表面的加热幅度就越大,并且TSR值越大,加热幅度就越低。所以,TSR值是与加热成反比的。
原则上,具有高反射系数的塑料的表面保持在直接太阳光辐射下基本上较冷。这抵抗了塑料的加热,并使得表面变热的程度较小。所以,“冷塑料”倾向于变形较少;它们显示改进的在加热下的尺寸稳定性。此事实开启了用于实现“冷塑料”的巨大潜力,即使在非常深色的情况下也是如此,这是用在本发明塑料组合物中的相应金属颜料实现的。高的TSR效率对应于低的NIR吸收,获得了较冷的塑料表面。
这种效果可以用于户外领域和用于汽车应用,例如车辆配件,和在车辆内部中的其它塑料部件,它们大幅度暴露于日光下。
本发明塑料组合物的加热速率相似地通过ASTM D 4803-97(Reapproved 2002)“用于预测在PVC建筑产品中的加热累积的标准检测方法”检测。
本发明塑料组合物可以使用所有常规塑料加工方法加工,例如注塑、吹塑(膜,中空体)、发泡、压延、铸塑、挤出和共挤出(多于一层)。在共挤出的情况下,本发明塑料组合物可以包含在一层或多个层中。本发明塑料组合物的各组分也可以分布在多个层中。例如,顶层可以含有HALS、UV吸收剂和抗氧化剂,第二层可以含有根据本发明使用的金属颜料和抗氧化剂或HALS、UV吸收剂、抗氧化剂,其中所用的金属颜料也可以存在于顶层中。
本发明的塑料组合物可以按照压实的形式存在,例如作为粒料。
根据本发明使用的金属颜料或颜料混合物可以以粉末形式作为基于颜料总重量计0-100重量%的活性材料存在,和/或作为例如粒料、颗粒材料、母料、与基于总重量计0-99重量%的活性材料混合。活性材料仅仅表示颜料,且不包括其它粘合剂、油或增塑剂。
丸粒、颗粒材料、母料、混合物等是通过将本发明的颜料/颜料混合物与所谓的载体材料一起压实制备的。
压实操作可以使用例如造粒盘、压片机、多孔辊、喷雾干燥器、挤出机(单螺杆或双螺杆挤出机)进行。
本发明颜料/本发明颜料混合物在粒料中的浓度范围符合技术要求,可以优选是0-99重量%,更优选5-90重量%,在每种情况下基于粒料总配制剂的总重量计。
为了造粒,可以使用多种分散助剂、蜡、树脂、塑料,例如天然和合成的树脂,例如醇酸树脂、羧基甲基和羧基乙基纤维素树脂,乙酸纤维素,乙酸丙酸纤维素(CAP)和乙酸丁酸纤维素(CAB),香豆素-茚树脂,环氧基酯,环氧基-三聚氰胺和环氧基-苯酚缩合物,乙基和甲基纤维素,乙基羟基乙基纤维素,羟基乙基纤维素,羟基丙基甲基纤维素,酮和马来酸树脂,松香树脂,三聚氰胺树脂,硝基纤维素树脂,苯酚和改性苯酚树脂,聚丙烯酰胺,聚碳酸酯,聚酰胺,聚酯,聚醚,聚乙烯或乙烯基树脂或它们的混合物。在这些聚合树脂中,以下是特别优选的:丙烯酸酯共聚物和丙烯酸酯树脂,聚丙烯腈和丙烯腈共聚物树脂,丁二烯和偏二氯乙烯的共聚物,丁二烯/苯乙烯共聚物,甲基丙烯酸酯和甲基丙烯酸甲酯共聚物,聚丁烯,聚异丁烯,聚乙酸乙烯酯,聚乙烯基醇,聚氯乙烯,聚乙烯基醚,聚乙烯基吡咯烷酮和聚苯乙烯树脂。其它共聚物包括苯乙烯/马来酸酐和苯乙烯/紫胶树脂,氯乙烯/乙酸乙烯酯,氯乙烯/乙烯基醚树脂和氯乙烯/偏二氯乙烯树脂。另外,可以使用天然树脂,例如阿拉伯树胶、杜仲胶、酪蛋白和明胶。优选的是醛树脂,例如来自BASF SE的Laropal系列(Ludwigshafen,德国)。另外,在这里考虑蜡作为粘合剂材料。在这里,例子是天然蜡,例如蜂蜡、小烛树蜡、巴西棕榈蜡、褐煤蜡和石蜡。也可以使用合成蜡,例如聚乙烯蜡。上述制剂可以很好地引入塑料中,且不会导致金属颜料例如铁效应颜料的不利聚集。
使用用于本发明塑料组合物中的所有成分以及塑料组分和任选地其它组分,使得它们占基于塑料组合物的重量比例计的100重量%。
在本发明塑料组合物中,金属颜料对相应塑料组分的不利影响,例如塑料组分在金属颜料存在下的较快分解,通过根据本发明优选同时存在光稳定剂和抗氧化剂得到缓解。这有利地适用于未涂覆的金属颜料和惊奇地适用于经涂覆的金属颜料。也可以经由金属颜料的涂料迁移和损害塑料组分的金属离子导致塑料组分的分解。本发明人认为应当优选选择光稳定剂或抗氧化剂以使得能与游离金属离子形成金属配合物。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有含量范围为0.01-10.1重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚丙烯(PP)、PP共聚物、聚乙烯(PE)、PE共聚物、HDPE、LDPE、LLDPE或其它聚烯烃,其中至少一种光稳定剂是选自聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),1,6-己二胺,N,N’-二(2,2,6,6-四甲基-4-哌啶基)-,与2,4,6-三氯-1,3,5-三嗪的聚合物,与N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[192268-64-7]),丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),Hostavin N30:2,2,4,4-四甲基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮和表氯醇的聚合物(CAS登记号[202483-55-4]),α-烯烃、C20-24,与马来酸酐的聚合物,与2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[152261-33-1]),2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),和/或它们的混合物,和其中至少一种抗氧化剂是选自季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4]),四(2,4-二叔丁基苯基)[1,1-二苯基]-4,4′-二基二亚膦酸酯(CAS登记号[119345-01-6]),二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,3,9-二(2,4-二(1,1-二甲基乙基)苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺(5.5)十一烷(CAS登记号[26741-53-7]),和/或它们的混合物,并且其中至少一种光稳定剂和至少一种抗氧化剂按照1:1至1:11的重量比率存在。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有含量范围为0.25-6.9重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚丙烯(PP)、PP共聚物、聚乙烯(PE)、PE共聚物、HDPE、LDPE、LLDPE或其它聚烯烃,其中至少一种光稳定剂是选自聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),1,6-己二胺,N,N’-二(2,2,6,6-四甲基-4-哌啶基)-与2,4,6-三氯-1,3,5-三嗪的聚合物,与N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[192268-64-7]),丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),Hostavin N30(CAS登记号[202483-55-4]),α-烯烃,C20-24,与马来酸酐的聚合物,与2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[152261-33-1]),2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),和/或它们的混合物,和其中至少一种抗氧化剂是选自季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4]),四(2,4-二叔丁基苯基)[1,1-二苯基]-4,4′-二基二亚膦酸酯(CAS登记号[119345-01-6]),二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,3,9-二(2,4-二(1,1-二甲基乙基)苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺(5.5)十一烷(CAS登记号[26741-53-7]),和/或它们的混合物,并且其中至少一种金属颜料和至少一种光稳定剂按照1:11至1:11的重量比率存在,优选重量比率为5:1至1:5。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有含量范围为0.1-4.6重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚丙烯(PP)、PP共聚物、聚乙烯(PE)、PE共聚物、HDPE、LDPE、LLDPE或其它聚烯烃,其中至少一种光稳定剂是选自聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),1,6-己烷二胺,N,N’-二(2,2,6,6-四甲基-4-哌啶基)-与2,4,6-三氯-1,3,5-三嗪的聚合物,与N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[192268-64-7]),丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),Hostavin N30(CAS登记号[202483-55-4]),α-烯烃,C20-24,与马来酸酐的聚合物,与2,2,6,6-四甲基-4-哌啶胺的反应产物(CAS登记号[152261-33-1]),2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),和/或它们的混合物,和其中至少一种抗氧化剂是选自季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4]),四(2,4-二叔丁基苯基)[1,1-二苯基]-4,4′-二基二亚膦酸酯(CAS登记号[119345-01-6]),二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,3,9-二(2,4-二(1,1-二甲基乙基)苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺(5.5)十一烷(CAS登记号[26741-53-7]),和/或它们的混合物,并且其中至少一种光稳定剂和至少一种抗氧化剂按照11:1至1:11的重量比率存在。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有含量范围为0.01-5.1重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚苯乙烯(PS)、SAN、HIPS、丙烯腈-丁二烯-苯乙烯(ABS)、ASA、其它苯乙烯共聚物、聚碳酸酯、聚合物共混物例如PC/ABS或PC/ASA、聚甲醛(POM)、聚酰胺(PA6,PA6.6,PA11,PA12等)、聚酯例如PET、PBT、聚氨酯、热塑性聚氨酯(TPU)、聚甲基丙烯酸甲酯(PMMA)以及其它丙烯酸酯聚合物、丙烯酸酯共聚物或其它工业热塑性材料,其中至少一种光稳定剂是选自聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),1,3,5-三嗪-2,4,6-三胺,N,N”'-1,2-乙二基二(N-(3-((4,6-二(丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基)-1,3,5-三嗪-2-基)氨基)丙基)-N',N”-二丁基-N′,N”-二(1,2,2,6,6-五甲基-4-哌啶基)-1,3,5-三嗪-2,4,6-三胺(CAS登记号[106990-43-6]),二(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-二(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯(CAS登记号[63843-89-0]),2-(2H-苯并三唑-2-基)-4,6-二(1-甲基-1-苯基乙基)苯酚,丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),(CAS登记号[70321-86-7]),2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1]),2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1]),2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚(CAS登记号[174315-50-2]),3-(二芳基)[1,3,5]三嗪-2-基)-5-(烷氧基-取代的)苯酚,N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8]),和/或它们的混合物,和其中至少一种抗氧化剂是选自季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),3-(3,5-二叔丁基-4-羟基苯基)丙酸2-乙基戊基酯(CAS登记号[125643-61-0]),亚乙基二(氧亚乙基)二(3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯)(CAS登记号[36443-68-2]),N,N′-己烷-1,6-二基二(3-3,5-二叔丁基-4-羟基苯基丙酰胺)(CAS登记号[23128-74]),三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4])和/或它们的混合物,并且其中至少一种金属颜料和至少一种光稳定剂按照1:11至11:1的重量比率,优选重量比率为3:1至1:3。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有含量范围为0.1-4.3重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚苯乙烯(PS)、SAN、HIPS、丙烯腈-丁二烯-苯乙烯(ABS)、ASA、其它苯乙烯共聚物、聚碳酸酯、聚合物共混物例如PC/ABS或PC/ASA、聚甲醛(POM)、聚酰胺(PA6,PA6.6,PA11,PA12等)、聚酯例如PET、PBT、聚氨酯、热塑性聚氨酯(TPU)、聚甲基丙烯酸甲酯(PMMA)以及其它丙烯酸酯聚合物、丙烯酸酯共聚物或其它工业热塑性材料,其中至少一种光稳定剂是选自聚[[6-(1,1,3,3-四甲基丁基)氨基]-1,3,5-三嗪-2,4-二基][(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]](CAS登记号[71878-19-8]),二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯(CAS登记号[52829-07-9]),1,3,5-三嗪-2,4,6-三胺,N,N”′-1,2-乙二基二(N-(3-((4,6-二(丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基)-1,3,5-三嗪-2-基)氨基)丙基)-N′,N”-二丁基-N′,N”-二(1,2,2,6,6-五甲基-4-哌啶基)-1,3,5-三嗪-2,4,6-三胺(CAS登记号[106990-43-6]),二(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-二(1,1-二甲基乙基)-4-羟基苯基]甲基]丁基丙二酸酯(CAS登记号[63843-89-0]),2-(2H-苯并三唑-2-基)-4,6-二(1-甲基-1-苯基乙基)苯酚,丁二酸二甲基酯,与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(CAS登记号[65447-77-0]),(CAS登记号[70321-86-7]),2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1]),2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1]),2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚(CAS登记号[174315-50-2]),3-(二芳基)[1,3,5]三嗪-2-基)-5-(烷氧基-取代的)苯酚,N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8]),和/或它们的混合物,和其中至少一种抗氧化剂是选自季戊四醇四(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)(CAS登记号[6683-19-8]),3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(CAS登记号[2082-79-3]),3-(3,5-二叔丁基-4-羟基苯基)丙酸2-乙基戊基酯(CAS登记号[125643-61-0]),亚乙基二(氧亚乙基)二(3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯)(CAS登记号[36443-68-2]),N,N′-己烷-1,6-二基二(3-3,5-二叔丁基-4-羟基苯基丙酰胺)(CAS登记号[23128-74]),三(2,4-二叔丁基苯基)亚磷酸酯(CAS登记号[31570-04-4]),和/或它们的混合物,并且其中至少一种光稳定剂和至少一种抗氧化剂按照11:1至1:11的重量比率存在。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有0.01-8.9重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚氯乙烯(PVC)和其它氯乙烯基聚合物,其中至少一种光稳定剂是选自2-(2H-苯并三唑-2-基)-对-甲酚(CAS登记号[2440-22-4]),2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1]),2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚(CAS登记号[25973-55-1]),2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1]),N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8]),2-羟基-4-(正-辛氧基)二苯酮(CAS登记号[1843-05-6]),和/或它们的混合物,和其中至少一种抗氧化剂是选自烷基锡稳定剂或有机锡稳定剂和/或它们的混合物,和其中至少一种光稳定剂和至少一种抗氧化剂按照11:1至1:11的重量比率存在。
在另一个实施方案中,本发明涉及一种塑料组合物,其含有0.01-7.2重量%的至少一种小片状金属颜料,优选被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的铁颜料,并含有至少一种光稳定剂以及至少一种抗氧化剂,其中塑料组分包括聚氯乙烯(PVC)和其它氯乙烯基聚合物,其中至少一种光稳定剂是选自2-(2H-苯并三唑-2-基)-对-甲酚(CAS登记号[2440-22-4]),2-(5-氯-2H-苯并三唑-2-基)-6-(1,1-二甲基乙基)-4-甲基苯酚(CAS登记号[3896-11-5]),2,4-二叔丁基-6-(5-氯苯并三唑-2-基)苯酚(CAS登记号[3864-99-1]),2-(2H-苯并三唑-2-基)-4,6-二叔戊基苯酚(CAS登记号[25973-55-1]),2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚,支化和直链的(CAS登记号[23328-53-2/125304-04-3/104487-30-1]),N-(2-乙氧基苯基)-N'-(2-乙基苯基)乙烷二酰胺(CAS登记号[23949-66-8]),2-羟基-4-(正-辛氧基)二苯酮(CAS登记号[1843-05-6]),和/或它们的混合物,和其中至少一种抗氧化剂是选自烷基锡稳定剂或有机锡稳定剂,和/或它们的混合物,并且其中至少一种金属颜料和至少一种光稳定剂按照1:11至11:1的重量比率存在,优选重量比率为6:1至1:6。
实施例
以下实施例更详细地描述本发明,但是不限制本发明。所有百分比都理解为重量%。
I.制备本发明的塑料组合物以及对比例的塑料组合物。
实施例
将实施例和对比例的颜料分别与根据表1各自使用的塑料组分混合并挤出。使如此得到的母料进行注塑加工以形成板(表面积100x 70mm;厚度2mm)。
为了制备10重量%母料,此方法如下所示:
粉末形式的颜料:
将870g的颗粒形式的相应塑料、100g的相应粉末颜料、20g的相应光稳定剂和10g的相应抗氧化剂在转鼓式混合机中混合,然后在双螺杆挤出机(来自Labtech,Bangkok;直径20mm,28L/D)中在约230℃加工温度下加工形成颗粒材料。
糊料形式的颜料:
将845g的颗粒形式的相应塑料、125g的相应颜料糊料(具有颜料含量为80重量%,基于糊料的总重量计)、20g的相应光稳定剂和10g的相应抗氧化剂在转鼓式混合机中混合,然后在双螺杆挤出机(来自Labtech,Bangkok;直径20mm,28L/D)中在约230℃加工温度下加工形成颗粒材料。
粒料形式的颜料:
将845g的颗粒形式的相应塑料、125g的相应颜料制剂(粒料)(具有颜料含量为80重量%,基于粒料的总重量计)、20g的相应光稳定剂和10g的相应抗氧化剂在转鼓式混合机中混合,然后在双螺杆挤出机(来自Labtech,Bangkok;直径20mm,28L/D)中在约230℃加工温度下加工形成颗粒材料。
如果在制备母料期间另外加入着色剂,则按照比例减少相应的塑料组分。
如此得到的母料颗粒材料被稀释到颜料含量为5.0重量%、2.5重量%、1重量%、0.5重量%、0.25重量%和0.1重量%,基于板的重量比例计。然后将此母料颗粒材料在相应物质的特定加工温度(例如对于PP是260℃)下用注塑机(Arburg 221K-75-250)加工形成具有上述尺寸的板。
表1
在表1中使用的金属颜料可以根据EP 1 251 152 A1、EP 1 251 153 A1、EP 2 157138 A1或WO 2008/155038 A2所述制备。在表1中使用的小片状铝或不锈钢颜料可以选自产品系列STAPA、STANDART或STAY STEEL的颜料,其适合用于塑料,在每种情况下来自ECKARTGmbH。
“被SiO2涂覆”表示金属颜料可以被氧化硅、氢氧化硅和氧化硅水合物的层覆盖。
实施例41:将本发明塑料组合物转变成压实形式(粒料)
将700g的来自实施例1的塑料组合物均匀地与300g的来自Clariant聚烯烃蜡Licocene PP 6102在转鼓式混合机中混合。
将此混合物在双螺杆挤出机中(来自Labtech,Bangkok;直径20mm,28L/D)在140℃温度下挤出。挤出物是70%粒料,可以在冷却后直接用于塑料染色(挤出、注塑)。
II表征实施例和对比例的塑料组合物
IIa检测在280-2500nm范围内的扩散反射
将实施例和对比例的板在250-2500nm波长范围内用UV-Vis-NIR分光计(PerkinElmer,Lambda 1050)检测。不含外加颜料的PP板用作参比。根据ASTM G173–03进行评价。
表2
与来自对比例的塑料组合物不同,根据本发明实施例1、3和40的塑料组合物的特征在于具有极高的总太阳能反射度(TSR),即使在低的金属颜料浓度下也是如此。同时,本发明塑料组合物在低的金属颜料浓度下也显示极高的不透明性。这种特定的性能使得特别可以制备薄的太阳能反射性且不透明的应用形式,例如厚度为10-100μm的膜,其可以用于农业用箔、温室膜或热保护膜。在厚度大于0.5mm的应用中,极好的TSR也可以用非常小的添加量实现。这种效果可以用于户外领域和用于汽车应用,例如车辆配件和在大部分暴露于日光的车辆内部中的其它塑料部件。
IIb不透明性
目测评价来自实施例和对比例的染色塑料板的不透明性(在每种情况下的厚度是2mm)。在这里,将塑料板置于黑白色的不透明性表格上(Byko-Chart 2853,来自BykGardner),使得塑料板的一半处于黑色背景上,另一半处于白色背景上。
如果不再能经由塑料板区分在表格中的黑色和白色部份,则将塑料板归为不透明的。结果列在表2中。
IIc粒径检测
金属效应颜料和对比例颜料的尺寸分布曲线是使用来自Quantachrome的装置(装置:Cilas 1064)根据生产指南检测。为此,将约1.5g颜料悬浮在异丙醇中,在超声浴中处理300秒(装置:Sonorex IK 52,来自Bandelin),然后用巴氏移液管放在检测装置的样品准备池中并检测数次。所得的平均值是从各个检测结果计算的。散射光信号的评价是根据Fraunhofer方法进行的。
在本发明中,平均尺寸D50表示体积平均尺寸分布函数的累积频率分布的D50值,这通过激光散射方法获得。D50值表示50%的金属颜料具有等于或小于此值的直径,例如20μm。相应地,D90值表示90%的颜料具有等于或小于相应值的直径。另外,D10值表示10%的颜料具有等于或小于相应值的直径。
IId本发明塑料组合物的加热速率
塑料组合物的加热速率相似地按照ASTM D 4803–97(Reapproved2002)检测。
表3
根据实施例1的本发明塑料组合物加热的程度明显小于对比例4和5的塑料组合物。这在来自实施例1、对比例4和对比例5的塑料组合物被人眼视为深色的情况下是特别令人感兴趣的。
Claims (13)
1.一种塑料组合物,其特征在于:
塑料组合物含有含量范围为0.01-25重量%的至少一种小片状金属颜料,含量范围为0.01-10重量%的至少一种光稳定剂,和含量范围为0.01-2重量%的至少一种抗氧化剂,在每种情况下基于塑料组合物的重量比例计,
其中至少一种小片状金属颜料是铁和/或铁合金颜料。
2.根据权利要求1的塑料组合物,其特征在于小片状金属颜料是被氧化硅、氢氧化硅和/或氧化硅水合物层涂覆的。
3.根据权利要求1或2的塑料组合物,其特征在于小片状金属颜料是被氧化硅、氢氧化硅和/或氧化硅水合物层涂覆的铁颜料,其中铁颜料的铁芯具有在从20nm至小于100nm范围内的平均厚度。
4.根据权利要求1或2的塑料组合物,其特征在于金属颜料的平均粒径D50是在1-100μm的范围内。
5.根据权利要求1或2的塑料组合物,其特征在于塑料组分是选自聚丙烯(PP),PP共聚物,聚乙烯(PE),PE共聚物,聚苯乙烯(PS),苯乙烯/丙烯腈(SAN),丙烯腈-丁二烯-苯乙烯(ABS),丙烯腈-苯乙烯-丙烯酸酯(ASA),聚碳酸酯(PC),PC/ABS的聚合物共混物,PC/ASA的聚合物共混物,聚甲醛(POM),聚酰胺,聚酯,聚氨酯,聚甲基丙烯酸甲酯(PMMA),和它们的混合物。
6.根据权利要求5的塑料组合物,其特征在于聚乙烯是HDPE、LDPE或LLDPE。
7.根据权利要求5的塑料组合物,其特征在于聚苯乙烯是高抗冲击聚苯乙烯(HIPS)。
8.根据权利要求1或2的塑料组合物,其特征在于光稳定剂是位阻胺(HALS)和/或UV吸收剂。
9.一种制备根据权利要求1-8中任一项的塑料组合物的方法,其特征在于此方法包括以下步骤:
a)将至少一种金属颜料、至少一种光稳定剂和至少一种抗氧化剂与塑料组分混合,
b)挤出此混合物,
c)将来自步骤b)的挤出物注塑形成板。
10.根据权利要求1或2的塑料组合物,其特征在于塑料组合物是以颗粒形式存在的。
11.根据权利要求1-8中任一项的塑料组合物用作膜或型材的用途。
12.根据权利要求11的用途,其中型材是板。
13.至少一种被氧化硅、氢氧化硅和/或氧化硅水合物涂覆的小片状铁颜料用于根据权利要求1-8中任一项的塑料组合物中的用途。
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PCT/EP2014/072048 WO2015055674A1 (de) | 2013-10-14 | 2014-10-14 | Kunststoffzusammensetzung umfassend wenigstens ein metallpigment, verfahren zur herstellung und verwendung |
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EP3058021B1 (de) | 2019-09-04 |
US10208201B2 (en) | 2019-02-19 |
WO2015055674A1 (de) | 2015-04-23 |
ES2755324T3 (es) | 2020-04-22 |
US20160237275A1 (en) | 2016-08-18 |
EP3058021A1 (de) | 2016-08-24 |
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