CN1103086A - 表面改性颜料及其用作着色塑料的变黄抑制剂 - Google Patents

表面改性颜料及其用作着色塑料的变黄抑制剂 Download PDF

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CN1103086A
CN1103086A CN94115627A CN94115627A CN1103086A CN 1103086 A CN1103086 A CN 1103086A CN 94115627 A CN94115627 A CN 94115627A CN 94115627 A CN94115627 A CN 94115627A CN 1103086 A CN1103086 A CN 1103086A
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M·斯彻拉姆·马斯
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Abstract

本发明涉及以TiO2颜料或带TiO2涂层的片晶状基体为主成分的表面改性颜料，且其表面涂有一层碱土金属硼酸盐或者碱金属和/或碱土金属复硼酸盐，本发明涉及在塑料和塑料系统中使用该物作为变黄抑制剂。

Description

本发明涉及以TiO2颜料或带TiO2涂层的片晶状基体为主成分的表面改性颜料，且其表面涂有一层碱土金属硼酸盐和/或碱金属和/或碱土金属复硼酸盐，本发明涉及在塑料和塑料系统中使用该物作为变黄抑制剂。
工业上适用的塑料通常含有若干添加剂以改进使用性能，例如增塑剂、填料、稳定剂、抗氧化剂、。润滑剂、脱模剂、抗静电剂、着色剂以及另外的添加剂。
时常发现，一方面，主要是着色剂之间，另一方面是稳定剂和抗氧化剂之间出现不希望有的反应，大概由于稳定剂和/或抗氧化剂分子扩散到颜料颗粒表面而导致往往即使在暗中也进行的发黄反应。尤其在浅色颜料的情况下这种发黄反应导致令人讨厌的效果并明显削弱对该塑料系统美的感受。
为避免变黄反应的先有技术建议的确导致变黄稳定性的提高，但在完全抑制塑料变黄方面没有成功。例如，EP0492223描述一种方法，其中借助颜料表面的硅烷化降低TiO2的反应性。在使用有色氧化物层，完全改变打底的带TiO2涂层的颜料显色性能的情况下，更为严重的是，当时落在表面的金属氧化物层往往正在高表面活性的时候，涂敷另外的金属氧化物层同样具有缺点。
EP0520313A2中公开的用碱土金属的钛酸盐处理TiO2层随后煅烧的方法并没有彻底抑制着色塑料的变黄反应。
因此，本发明的一个目的是提供以TiO2为主成分的表面改性颜料，在混入塑料中时即使期限延长，该TiO2也的确不引起变黄反应。
现在已经意想不到地发现，用碱土金属硼酸盐和/或碱金属和/或碱土金属复硼酸盐涂敷的TiO2颜料或带TiO2涂层的片晶状基体在抑制塑料的发黄反应方面是高度有效的。
本发明从而提供以TiO2或带TiO2涂层的片晶状基体为主成分的表面改性颜料，其特征在于，它们已经用一层碱土金属硼酸盐和/或碱金属和/或碱土金属复硼酸盐进行后涂敷。
本发明另外提供一种生产本发明颜料的方法，其特征在于，向TiO2颜料或带TiO2涂层的片晶状基体的水溶液中同时添加一种水溶性碱金属和/或碱土金属盐和一种水溶性硼一氧化合物，条件是引起硼酸盐或复硼酸盐的沉积，在此之后，涂敷的颜料被分离开，洗涤并任选地烘干或煅烧。
本发明另外提供本发明的颜料作塑料的变黄抑制剂用途。
适用于后涂敷的基体，一方面是广泛用作白色颜料的不透明非片晶状TiO2颜料，另一方面是粒径小于100nm的透明非片晶状型TiO2，后者日益被用作化妆品及工程中的紫外线吸收剂。
因此按照本发明的颜料也是以粒径1-10，000nm的非片晶状TiO2颜料为主成分。合格的基体包括，特别是由下列物质组成的片晶状及优选是透明或半透明的基体：例如，片型硅酸盐诸如云母、滑石或高岭土、玻璃、二氧化硅或合成陶瓷片，合成的无载体片晶或其类似矿物。
也可使用金属片晶例如铝片晶或片晶状金属氧化物例如片晶状氧化铁或氯氧化铋。片晶状基体的厚度通常是0.1-5μm，特别是0.2-4.5μm。长与宽的尺寸通常是1-250μm，特别是2-200μm。
原则上有两种方法可实现TiO2在片晶状基体上的沉积，DE1467468中所述的硫酸盐法和DE2009566中所述的氯化物法。在上两法中TiO2都是以锐钛矿型沉积在片晶状基体上的。DE2214545描述了TiO2以金红石型沉积的方法。与锐钛矿型相比，金红石型的折射率较高，因此带金红石涂层的片晶状基体的光泽明显高于锐钛矿型TiO2云母颜料因而往往是优选的。
本文指出的基体上涂敷TiO2的方法只是作为实例提及和只是用来具体说明本发明的。在本文中明确描述的其它方法事实上也能使用，例如化学气相淀积法等。如果不进行另外的工序，涂敷TiO2后的基体通常被分离开，洗涤并任选地烘干或煅烧。
在涂敷TiO2层之前，片晶状基体最初也可以涂敷一种或多种由下列物质组成的其它金属氧化物层，例如氧化铬、氧化铁、氧化锆、氧化铝、氧化锡和/或另外的金属氧化物。由于此法不需要高剪切力，因此也非常适合于涂敷珠光颜料。
能够使用任何常规的珠光颜料，例如涂了有色或无色金属氧化物涂层的云母，这些金属氧化物如TiO2、Fe2O3、SnO2、Cr2O3、ZnO以及其它金属氧化物，它们单独或混合在单层或在各邻接层中。例如根据下列德国专利和专利申请，这些颜料都是已知的：1467468、1959998、2009566、2214545、2215191、2244298、2313331、2522572、3137808、3137809、3151343、3151354、3151355、3211502和3235017。这些颜料也是市场上买得到的例如E.Merck，Darmstadt公司，商标Iriodin
Figure 941156273_IMG1
。
所用的基体最好是这样一些颜料，即在其TiO2层底下有不多于两层，特别是只有一层或者没有另外的金属氧化物层。
为生产碱土金属/碱金属硼酸盐层，已把一种水溶性碱土金属盐或一种水溶性碱土金属和/或碱金属盐的混合物以及一种水溶性硼-氧化合物添加到非片晶状TiO2或带TiO2涂层的片晶状基体的水悬液中。
合格的碱土金属和碱金属盐包括特别是碱土金属/碱金属氯化物，还有碱土金属/碱金属硝酸盐以及其它水溶性化合物。所用的硼-氧化合物主要是多硼酸盐。其中特别是碱金属硼酸盐，因为通常它们易溶于水。所用的具体化合物是四硼酸二钠，Na2B4O7·10H2O（硼砂）。
对反应溶液的温度要求不是很严格的，通常为20-80℃，而可取的是在稍高温度下，最好是40-80℃，进行沉淀反应，因为硼砂的溶解度随着溶剂的温度而提高。沉淀通常在pH3-12下进行。
为进行涂敷，TiO2的水悬液或带TiO2涂层片晶状基体的水悬液同时与碱金属/碱土金属盐的水溶液和硼酸盐的水溶液混合。硼酸盐的弱碱性会使pH少量增加，可借助添加稀酸，优选是无机酸特别是盐酸使pH不费力地保持恒定。碱金属/碱土金属盐和硼酸盐最好按所要沉淀的硼酸盐的化学计量摩尔比添加，也就是例如就沉淀CaB4O7（＝CaO·2B2O3）而论，为2mol B2O3/1molCaO;就沉淀Ca2B6O11（＝2CaO·3B2O3）而论，为3mol B2O3/2mol CaO。碱金属/碱土金属盐与硼酸盐的摩尔比最好是1∶1-1∶3。
使用1mol碱土金属氯化物和1mol碱金属四硼酸盐结果用下列反应式表示。但这只是作为实例和只是用来具体说明而不是限制本发明的。
碱土金属硼酸盐和碱土金属和/或碱金属复硼酸盐只是微溶或者不溶的，结果是上述化合物沉淀在基体上。将这样后涂敷的颜料分离开，洗涤并任选地烘干或煅烧。
带硼酸盐涂层的颜料在高于500℃，最好是800-1000℃下干燥，特别是煅烧引起一个多级脱水过程，该过程导致TiO2一方面形成一种晶状高折射的变体，另一方面形成一种由晶状碱土金属硼酸盐或碱土金属/碱金属复硼酸盐组成的薄涂层。这一过程可用下式说明：
沉淀最好以这样的方式进行，以使煅烧工序留下一层几毫微米厚的较薄碱土金属/碱金属硼酸盐层，因为这一薄表面层对基体的光学性能仅有轻微的影响，如果有的话，这种影响往往是不希望有的。根据本发明的颜料计算，硼酸盐层的重量比最好是0.1-20%（重量），特别是0.2-10%（重量）。
与其它稳定化方法截然不同，用本发明颜料着色的塑料或塑料系统，即使期限延长，也没有任何变黄现象。
下列各实施例是用来具体说明而不是限制本发明的。
实施例1
把10.7kg粒径5-15μm的云母悬浮在280l水形成悬浮液，并调节pH到2.2。然后以约16l/h的速度添加约30%的TiCl4水溶液中同时用约30%NaOH使pH保持在2.2。在已经获得银白的干扰色之后，计量添加截止，随后搅拌混合物达半小时。用稀NaOH调节pH达6.7之后，开始以15l/h的速度同时计量添加下列两种溶液：882g Na2B4O7·10H2O溶于15lH2O的溶液;350gCaCl2·2H2O溶于15l H2O的溶液。滤出反应产物，烘干并在850℃煅烧。
实施例2：对照实施例（EP0520313）
起初按照实施例1制备一种银白色珠光颜料。用稀NaOH把pH调到9之后以15l/h的速度同时计量添加下列两种溶液：410g CaCl2·2H2O溶于10lH2O;0.6lH2O2（30%）溶于9.4lH2O。滤出反应产物，烘干并在850℃煅烧。
实施例3：对照实施例（EP0520313）
起初按照实施例1制备一种银白色球光颜料。然后改进0.63kg固态Na2（C2O4），pH由2.2升至4.5。然后以15l/h的速度计量添加入0.63kgCaCl2·2H2O在15l水里的溶液，同时保持pH基本恒定。滤出反应产物，烘干并在850℃煅烧。
实施例4：对照实施例
重复实施例1以制备银白色珠光颜料。滤出未经后涂敷的产物，烘干并在850℃煅烧。
实施例5：
将11kg粒径为5-15μm的云母悬浮到280l水中，调节pH值为2.2。然后以约16l/n的速经加入浓度接近30%的TiCl4水溶液，同时用约30%NaOH使pH值保持在2.2。达到银白色干涉色后，中止测量，随后搅拌混合物0.5小时。用稀NaOH调节pH值至6.7后，开始以15l/h的速率进行同时测量的添加600g Na2B4O7×10H2O在15lH2O中的溶液和235gCaCl2×2H2O在15lH2O中的溶液。滤出反应产物，在850℃干燥煅烧。
测定表面反应性
用下列测试方法来表明带涂层颜料导致塑料系统变黄达到的程度：
称出150mg颜料，与5ml棓酸丙酯在2-丙醇中的1%溶液混合摇匀，搁置15分钟。转移到一个专用的圆形比色杯之后，使溶液放置1分钟用Johne & Reilhofer装置在45°/0°下测定其CIELAB值。为测定空白值，把150mg颜料悬浮在5ml1-丙醇中并作如上测定。用棓酸丙酯所得的测量结果作空白值校正。
用作表面反应性的度量标准是b值的变化（＝主色调色向黄色的移动）。△b正值越大表示变黄越强烈。如果b值不变，就没看到发黄。
表1
实施例1  实施例2  实施例  实施例4  实施例5
△b  -0.1  1.5  5.8  15.0  0.3
表1中的测量结果具体说明，本发明的颜料彻底抑制了塑料变黄。

Claims (12)

1、表面改性颜料，其特征在于二氧化钛颜料或带二氧化钛涂层的片晶状基体已经后涂敷一层碱土金属硼酸盐或者碱金属和/或碱土金属复硼酸盐。
2、权利要求1的表面改性颜料的制备方法，其特征在于向二氧化钛颜料或带二氧化钛涂层的片晶状基体的水溶液中，同时添加一种水溶性碱金属和/或碱土金属盐和一种水溶性硼一氧化合物，条件是引起硼酸盐或复硼酸盐的沉积，后涂敷的颜料被分离开，洗涤并任选地烘干或煅烧。
3、按照权利要求1的表面改性颜料，其特征在于根据总颜料重量计算，硼酸盐的用量为0.1-20%（重量）。
4、按照权利要求1的表面改性颜料，其特征在于该片晶状基体是云母。
5、按照权利要求1的表面改性颜料，其特征在于该片晶状基体是二氧化硅片。
6、按照权利要求1的表面改性颜料，其特征在于该片晶状基体是一种珠光颜料。
7、按照权利要求2的方法，其特征在于水溶性硼一氧化合物是一种多硼酸盐。
8、按照权利要求2的方法，其物特征在于该硼一氧化合物是四硼酸二钠。
9、按照权利要求2的方法，其特征在于该碱金属和碱土金属盐与硼一氧化合物是按摩尔比使用的。
10、按照权利要求2的方法，其特征在于该后涂敷工序是在20-80℃的温度下进行的。
11、按照权利要求1的含有表面改性颜料的塑料系统。
12、按照权利要求1的表面改性颜料用于抑制塑料变黄。
CN94115627A 1993-09-02 1994-09-01 表面改性颜料及其用作着色塑料的变黄抑制剂 Pending CN1103086A (zh)

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