CN1133866A - 灰色干涉颜料及其生产方法 - Google Patents

灰色干涉颜料及其生产方法 Download PDF

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CN1133866A
CN1133866A CN95120163A CN95120163A CN1133866A CN 1133866 A CN1133866 A CN 1133866A CN 95120163 A CN95120163 A CN 95120163A CN 95120163 A CN95120163 A CN 95120163A CN 1133866 A CN1133866 A CN 1133866A
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A·斯蒂芬
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Merck Patent GmbH
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Abstract

一种干涉颜料，该颜料是小片状底物用二氧化钛进行涂覆后再用铜和锰的氧化物涂覆，因而所制得的颜料粉末的色彩为暗灰色。

Description

灰色干涉颜料及其生产方法
本发明涉及暗灰色干涉颜料，此类颜料具有很好的光亮度，这些颜料是以涂有二氧化钛的小片状底物为基础，并且还涂覆铜和锰的氧化物，本发明还涉及这些颜料的生产方法。
金属粉可用作户外涂料特别是汽车表面涂层的颜料，例如，铝粉用作颜料可获得银灰色的涂层，然而金属特别是铝用于水性硝基漆中有其不足之处，因为金属在含水体系中会发生化学反应。确切地说，这些金属与水接触会产生危险数量的氢，这种漆在不同的气候条件下还会发生外观变化。因此，难以制得具有重现性能的涂料。
为了克服这些不足，可用各种聚合物涂覆金属粉，就象EP—A—0393579(对照.U.S.5039343)所公开的方法。然而，当金属颜料与以云母片为底物的颜料混合用于水基清漆时，云母片锋利的边缘会破坏金属表面的涂层，进而产生氢。因此，在这些应用场合或其他应用场合，需找到传统的金属颜料的替代品。
另外，人们知道在某种颜料中并用炭黑可达到特殊的色彩效果。但炭黑的沉淀常是不定量的，而某些炭黑则以凝结的方式沉淀在底物材料上，这就造成所得颜料的遮盖力欠佳。另一不足是当用配制涂料体系的有机溶剂悬浮炭黑涂覆的颜料时，所并用的炭黑常常渗出。
为了消除对能造成配制困难的炭黑的需求并在专用配方中取代铝粉，对暗灰色粉末颜料就有很大的需求，这种颜料可产生的任意的干涉色，并可调制出各种暗黑的色彩。
通过对本说明书及所附权利要求的进一步研读，专业人员将会了解到本发明的其余目地和优点。
令人惊奇的是，业已发现在TiO2涂覆的小片状底物表面形成黑色的复合金属氧化物，CuxMn3-xO4(X＝1.4或1.5)，可以制得暗灰色粉状干涉颜料。
本发明的暗灰色颜料显著地减少干涉互补色的显现。而且这种颜料具有非常纯正的色彩和极佳的遮盖力。
利用上述金属氧化物组分涂覆小片状底物已有报道。JP05—271569报道了以涂覆铜和锰氧化物的TiO2/云母颜料所制得的黑色颜料，但还需用氧化铬。此外，JP04—249584曾报道，为了提高耐紫外光消色的能力，可在云母或TiO2/云母上沉积至少一种带色的Co、Fe、Ni、Cu和/或Mn的氧化物和/或第二层Ce和Sb的氧化物。
因而，本发明涉及具有任意干涉色的暗灰色粉末颜料，这种颜料由小片状底物二氧化钛与一种铜和锰的氧化物组成。
本发明还涉及这种干涉颜料的制备方法，其中金属氧化物，CuxMn3-xO4(X＝1.4或1.5)，是在TiO2涂覆的小片状底物上形成，具体方法是以适当的方式把水溶性的铜盐和锰盐加到小片状底物的水基悬浮液中，以便在TiO2涂覆底物的内部和表面形成带水的氧化物，然后将所得颜料分离、洗涤、干燥并进行焙烧，制成最终产品。
在这种方法中，任何常用的小片状底物均可使用，层状硅酸盐和氧化物或用氧化物涂覆的材料则更为适用，因为它们在表面上带有反应性的-OH基团。例如，云母、滑石、白土、陶土、绢云母或其他类似的矿物质，再如小片状氧化铁，氧氯化铋和铝粉或金属氧化物涂覆的铝粉。用含有带色或无色金属氧化物如TiO2、Fe2O3、SnO2、Cr2O3、ZnO等涂覆的云母，无论这些氧化物是单独涂覆还是混匀后进行单层涂覆或者用不同氧化物进行多层依次涂覆，都十分适于实施再涂覆。这些所谓的珠光颜料在以下专利中已有报道，例如德国专利说明书和专利申请1467468，1959998 2009566，2214545，2215191，2244298，2313331，2522572，3137808，3137809，3151354，3151355，3211602和3235017，而且已有商业化制品，例如E.Merck，Darmstadt出品的商品名为IriondinR的产品。
最优选的小片状底物有云母，以及合成云母，各种片状玻璃粉、陶瓷粉、SiO2粉、人造粉和珠光颜料。本发明中，小片状底物的直径优选为1～200μm，更优选为5～60μm，其厚度为0.1～10μm，优选为0.5～1.5μm。
本发明的方法很容易实施，制备过程是把小片状底物的水基悬浮液与涂覆剂混合，可以将定量的铜和锰化合物同时或依次加入到悬浮液中，最好是在往小片状底物的水基悬浮记中加入钛盐的同时首先加入锰盐，然后加入铜盐的水溶液或固态铜盐，特别适宜的盐是卤化盐、硝酸盐和硫酸盐，氯化盐则最为可取。铜和锰氧化物聚积到悬浮记中小片状底物上的沉积过程受pH值和温度条件的影响。
提供颜色的各种固态化合物或化合物溶液可以在用钛盐涂覆的过程中，同时或依加入，也可以在涂覆到达所需最终色度以后加入。最好是在加钛盐的同时加入锰盐，以确保在最低的焙烧温度下能形成最佳的金红石结构的TiO2和色泽。
一种优选的制备方法是在涂覆含水氧化物之前产生一层SnO2，以促进金红石TiO2的形成，SnO2的存在会改善颜料在更高焙烧温度下的稳定性，从而拓宽颜料所能达到的颜色范围，SnO2的用量相当于初始底物重量的0.1～2.0％，优选为0.5～1.5％。
对于以上步骤所需的条件，专业人员是了解的，还可以从有关教科书中查找。经过沉积之后，分离出已涂覆的颜料，经洗涤后于80～150℃烘干并在空气中在500～750℃，最好是在600～750℃的条件下，焙烧30～60分钟。
铜锰氧化物的含量相当于初始底物重量的2.5～20％，优选为10～20％，最优选为10～15％。
铜锰的比例可以大范围的变动，优选的金属盐摩尔比是2∶1到1∶2，最好是1∶1的混合物。直此比例之外，颜料会呈现所不希望的淡棕色，当比例为1∶1时，CuCl2·2H2O的最少用量为底物的3％。当比例为1∶2时，CuCl2·2H2O的最少用量是底物的5％，而当比例为2∶1时则为10％，普遍的专业人员可根据所需要的产物含量组成按常规方法确定起始物料的浓度和金属化合物的相对用量。
焙烧温度最好高于600℃，但高于750℃则会对颜料产生不利影响。
一个预料之外的结果是同时加入锰和钛化合物会影响TiO2涂层中金红石结构的形成。
按照本发明制得的颜料为暗灰色粉末，光亮度极佳，具有清晰的干涉色和强遮盖力。各种所需要的干涉色都可获得。这种暗灰色粉末的优点是显著减少干涉互补色的显现。所制备的颜料可与适量的白色颜料如TiO2颜料混合，得到类似于铝粉的产品，但也可以获得其它色调的灰色。这样的暗色减少了配制暗化涂料配方时对炭黑的需求。
这种颜料可以部分地取代金属粉，特别是铝粉。这种颜料具有足够的耐候性，可做为室外涂料特别是用于汽车车身涂料的着色剂，而且保留了很好的分散性，对主体颜料的色调和光译没有任何不良影响，这种颜料还可通过其它涂层来提高耐候性，例如EP—B—0268918(对照U.S.4828623或EP—A—0342533)所报道的水合氧化锆涂层或Al2O3/SiO2涂层。
本发明的珠光颜料不但可用于室外涂料，还可用于其它许多室外材料，例如塑料。
另外，这种颜料可用于釉底料，珐琅，搪瓷和陶瓷的着色。新颜料的遮盖力优于传统的颜料如E.Merck，Darmstadt制造的银白色颜料。
当干涉色为银色时，这些暗灰色粉末的特性可模仿铝粉的外观，从而使这种新颜料具有迄今为止其它产品都没有的优点。
可以相信，即使不进行更详细的说明，专业人员也可以通过前述内容充分地利用本专利。因此，以下优选的实施例只能理解为对本专利的具体说明，而不能视为是对本专利其它权利范围的限定。
在前文及以下实施例中，所有温度都是指未经校正的摄氏温度；另外，除非特别注明，所有份数和百分比都是指重量数。
前文如下文援引的申请书、专利、和出版物的内容都做为本文的参考文献。
实施例
实施例1—云母＋TiO2(金红石)＋CuxMn3-xO4(X＝1.4，1.5)
用60ml/10％HCl稀释2.2m160％的SnCl4溶液。将17.4gMn-C144H2O溶于TiCl4溶液(340gTiCl4/升水)该溶液用于涂覆云母底物，TiCl4溶液的用量取决于所要求的最终干涉色度。把100g云母(颗粒大小10-60μm)加入1.51去离子水，搅拌并升温至75℃。用10％HCl将PH调至1.8，在45分钟内把预先配好的SnCl4溶液加入淤浆中，同时滴加20％NaOH溶液以保持PH值为1.8。在75℃下搅拌悬浮液15分钟，然后用20％NaOH溶液将PH调升到2.2。将TiCl4/MnCl2·4H2O溶液滴加到淤浆中，同时以20％的NaOH溶液维持PH为2.2。TiCl4的起始滴加速度为大约每小时10ml，15分钟后以15分钟为间隔将滴加速度逐渐增加到每小时15ml，每小时20ml，每小时40ml，每小时60ml，最后到达每小时80ml直至滴加完毕，(此时出现的黄色表明一部分锰已进入水合TiO2基体)全部TiCl4/MnCl2·4H2O溶液加完后，淤浆在75℃下再搅拌15分钟。加入15.0gCuCl2·2H2O，再搅15分钟，用2％Na2CO3/20％NaOH溶液将PH值缓慢地调升至9.5。在75℃下将悬浮液搅拌0.5h，将淤浆过滤，洗涤，于110℃烘干并在600～750℃于空气中焙烧30分钟。
粉末和X-射线衍射测定表明，晶体中存在TiO2金红石异形体和CuxMn3-xO4(X＝1.4，1.5)。
实施例2—云母＋TiO2(锐钛矿)＋CuxMn3-xO4(X＝1.4，1.5)
将100g云母(颗粒尺寸10～60μm)加入1.5升去离子水中，搅拌并加热至75℃。用10％HCl将PH调至2.2，按要求往淤浆中滴加一定量的TiCl4溶液(340gTiCl4/升水)以便达到所需要的最终干涉色度。滴加过程中同时请加20％NaOH溶液以保持PH值为2.2加完TiCl4溶液后，于75℃搅动淤浆15分钟。加入15.0gCuCl2·2H2O和17.4g MnCl2·4H2O并继续搅拌15分钟。以2％Na2CO3/20％NaOH溶液将PH值缓慢地调升至9.5并在75℃下搅拌0.5小时。将淤浆过滤、洗涤、于110℃干燥16小时后在空气中于600～700℃焙烧30分钟。
X—射线衍射表明，粉末中存在TiO2锐钛矿异形体和CuxMn3-xO4(X＝1.4，1.5)。
实施例3—云母＋TiO2(锐钛矿)＋CuxMn3-xO4(X＝1.4，1.5)
将100g云母(颗粒尺寸10～60μm)加入1.5升去离子水中，搅拌并加热至75℃。用10％HCl将PH调至2.2，往淤浆中加入TiCl4/MnCl2·4H2O溶液(17.4g MnCl2·4H2O溶于为达到所需的最终干涉色度而需要的全部TiCl4溶液(340gTiCl4/升水)中所得到的溶液)，同时滴加20％NaOH溶液来保持PH仍为2.2。(此时出现的黄色表明锰已进入水合TiO2基体)，全部TiCl4/MnCl2·4H2O溶液加完后，在75℃搅拌15分钟，加入15.0gCuCl2·2H2O，再搅拌15分钟。用2％Na2CO3/20％NaOH溶液将PH值缓迈地调升至9.5并在75℃下搅拌0.5小时。然后将淤浆过滤、洗涤、于110℃干燥16小时，并且在空气中于600～700℃焙烧30分钟。温度为600～650℃时只生成TiO2锐钛矿异形体，温度为650至700℃时形成金红石异形体占优势的金红石/锐钛矿晶体复合产物。产物仍然显示CuxMn3-xO4(X＝1.4，1.5)晶体的衍射图形。
实施例4—云母＋TiO2(锐钛矿)＋CuxMn3-xO4(X＝1.4，1.5)
将100g云母(颗粒尺寸10～60μm)加入1.5升去离子水中，搅拌并加热至75℃。用10％HCl将PH调至2.2，加入TiCl4/MnCl2·4H2O溶液(17.4gMnCl2·4H2O溶于为达到所需的最终干涉色度而需要的全部TiCl4溶液(340gTiCl4/升水)]，同时滴加20％NaOH溶液来保持PH仍为2.2。(此时出现的黄色表明锰已进入水合TiO2基体)，溶液呈显淡兰色表明铜未进入基体)，加完TiCl4/MnCl2·4H2O/CuCl2·2H2O溶液加完后，在75℃搅拌15分钟，用2％Na2CO3/20％NaOH溶液将PH值缓慢地调升至9.5并在75℃再搅拌0.5小时。然后将淤浆过滤、洗涤、于110℃干燥16小时，并且在空气中于600～700℃焙烧30分钟。温度为600～650℃时只生成TiO2锐钛矿异形体，温度为650～700℃时形成金红石异形体占优势的金红石/锐钛矿晶体复合产物。产物仍然显示CuxMn3-xO4(X＝1.4，1.5)晶体的衍射图形。
色彩数值
本发明所制得的CuxMn3-xO4(X＝1.4，1.5)涂覆的TiO2(金红石)/云母颜料，是以暗灰色为主色调的粉末，它们的色彩数值是根据实验室方法(DIN 5053)测定的，测定结果按TiO2层的厚度不同依次列于下表：
                                           表I色彩数值
TiO2(金红石)/云母＋CuxMn3-xO4(x＝1.4，1.5) 45°黑背景 22.5°黑背景 45°白背景
    L       a     b     L      a     b     L     a     b
银色     24.54     -0.57     -3.09     60.00     -2.40     -5.21     29.74     -0.83     -2.10
    24.76     -0.66     -3.02     59.90     -2.44     -5.08     29.27     -0.84     -2.18
    26.26     -0.86     -2.62     60.14     -2.39     -4.08     30.71     -0.98     -2.11
    26.40     -0.96     -2.68     54.36     -1.12     -7.04     31.06     -1.05     -1.83
    26.51     -1.02     -2.69     60.09     -3.01     -4.68     30.88     -1.04     -1.81
金色     19.70     -1.00      5.89     53.27     -2.98      14.75     26.87     -1.08      2.47
    19.87     -1.01      5.97     52.95     -2.98      14.63     27.11     -1.14      2.54
    21.63     -1.39      6.39     50.92     -2.98      14.00     26.69     -1.61      4.09
    22.54     -1.43      8.50     53.13     -3.27      17.15     28.75     -160      5.57
    22.53      1.42      8.48     53.09     -3.29      17.19     28.75     -1.57      5.48
红色     14.97      3.73     -0.24     40.72     8.23      1.99     26.70      0.35      1.37
    15.01      3.76     -0.21     40.75     8.21      1.98     26.63      0.31      1.37
    15.07      4.04      0.28     39.83     8.13      2.80     23.16      1.14      0.34
    15.66      4.97      1.50     40.16     9.14      3.18     24.63      1.03      1.36
    15.68      4.97      1.51     40.06     9.11      3.24     24.77      0.96      1.37
紫色     13.07      5.56     -7.95     37.91     11.87     -14.09     25.86      1.02     -1.66
    13.07      5.54     -7.92     37.89     11.77     -13.97     27.38      0.86     -1.37
    11.57      6.67     -8.38     34.79     12.85     -14.21     18.88      2.87     -4.55
    12.56      8.16      10.11     35.00     14.06     -16.99     24.26      1.98     -3.53
    12.58      8.18     -10.14     35.05     14.10     -17.04     24.11      2.07     -3.65
兰色     13.24      1.57     -11.99     38.33     4.59     -24.41     24.14      0.04     -4.56
    13.25      1.52     -11.90     38.47     4.54     -24.35     24.21     -0.04     -4.38
    14.34      0.62     -12.18     38.30     1.23     -24.46     21.07      0.10     -6.87
    13.33      0.57     -12.48     36.15     1.11     -20.70     24.30     -0.38     -5.14
    13.36      0.56     -12.53     36.17     1.08     -20.65     24.35     -0.42     -5.04
兰绿色     15.87     -3.52     -4.60     45.52    -8.22     -10.93     26.42     -2.18     -1.61
    15.85     -3.53     -4.57     45.63    -8.36     -10.79     26.76     -2.26     -1.49
    15.19     -2.88     -5.26     41.65    -8.43     -7.97     24.00     -1.50      0.72
    15.47     -4.64     -5.35     40.38    -8.44     -9.24     26.64     -2.78     -1.31
    15.44     -4.62     -5.32     40.50    -8.47     -9.30     26.47     -2.77     -1.31
绿色     18.81     -3.92     -1.14     47.38    -11.10      3.15     27.72     -2.52      0.47
    17.72     -3.86     -1.18     47.41    -11.10      3.14     27.57     -2.52      0.44
    19.68     -4.73      0.26     46.63    -11.64      3.18     28.36     -2.77      2.97
    21.33     -7.44      1.04     47.94    -13.76      2.17     32.82     -4.35      3.21
    21.42     -7.52      1.06     48.04    -13.87      2.13     32.50     -4.54      3.19
本发明所制得的CuxMn3-xO4(X＝1.4，1.5)涂覆的TiO2(金红石)/云母颜料，是以暗灰色为主色调的粉末，其元素组成的数值按TiO2层的厚度不同依次列于下表：
表II元素组成
TiO2(金红石/云母＋CuxMn3-xO4(x＝1.4，1.5) ％TiO2 ％SnO2 ％Cu ％Mn
 实验值  计算值  实验值  计算值 实验值 计算值  实验值  计算值
银色  20.5  19.5  1.2  O.9  3.9  3.9  3.3  3.4
 19.7  18.3  1.1  0.9  4.0  4.O  3.3  3.4
金色  28.1  28.1  1.O  0.8  3.4  3.5  2.9  3.0
 31.0  29.6  O.9  0.8  3.3  3.4  2.8  2.9
红色  32.9  32.8  1.0  O.8  3.2  3.3  2.7  2.8
 34.9  32.9  0.9  0.8  3.1  3.3  2.7  2.8
紫色  34.9  34.2  O.9  0.8  3.2  3.2  2.7  2.8
 36.7  35.1  0.8  0.8  3.0  3.2  2.6  2.7
兰色  37.3  38.5  O.8  O.7  2.9  3.0  2.4  2.6
 40.6  38.4  0.8  0.7  2.9  3.0  2.4  2.6
兰绿色  42.3  42.4  0.7  0.7  2.8  2.8  2.3  2.4
 44.5  42.4  O.7  O.7  2.7  2.8  2.3  2.4
绿色  44.6  45.0  0.7  O.6  2.7  2.7  2.2  2.3
 44.6  42.6  O.7  O.7  2.7  2.7  2.3  2.4
本发明所制得的TiO2(金红石)/云母＋涂覆于TiO2(金红石)/云母表面的CuxMn3-xO4(X＝1.4，1.5)所组成的颜料，是以暗灰色为主色调的粉末，其遮盖力列于下表：
颜料                        遮盖层的大致厚度
IriodinR9103              101μm
本发明的紫色干涉颜料       18μm
本发明的兰—绿干涉颜料     23μm
*在Dupont的CronarR1860J系统中测定表光(mass—tone)，浓度为1g颜料比10g1860J材料。

Claims (10)

1.一种干涉颜料，其组成是涂覆有二氧化铁和铜与锰的复合氧化物的小片状底物，这种颜料粉末的色彩是暗灰色。
2.根据权利要求1的颜料，其中铜锰氧化物的用量是初始底物重量的2.5％至20％。
3.根据权利要求1的颜料，其中铜对锰摩尔比率的范围为2∶1至1∶2。
4.根据权利要求1的颜料，其中二氧化铁是锐铁矿异形体。
5.根据权利要求1的颜料，其中二氧化铁是金红石异形体。
6.根据权利要求1的颜料，其中小片状底物是云母，人造云母，各种片状玻璃粉、陶瓷粉、人造粉或珠光颜料。
7.根据权利要求1的颜料，其中底物是SnO2涂覆的云母。
8.根据权利要求1的干涉颜料的制造方法，其中铜和锰复合氧化物是在TiO2涂覆的小片状底物上形成的，其特征是将水溶性的铜盐和锰盐同时或依次加入小片状底物的水基悬浮液，这些盐在用钛盐涂覆底物的过程中加入或是在用TiO2涂覆底物之后加入，以便使得含水氧化物在底物的表面和内部沉积，然后将被涂覆的颜料分离、洗涤、干燥并在空气中焙烧。
9.根据权利要求8的方法，其特征在于所述颜料的焙烧温度为500～750℃。
10.在含有暗灰色粉末颜料的涂料、塑料、釉底料、珐琅、搪瓷或陶瓷材料中，其改进在于其中的颜料是权利要求1的颜料。
CN95120163A 1994-12-29 1995-12-25 灰色干涉颜料及其生产方法 Pending CN1133866A (zh)

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US5693134A (en) 1997-12-02
EP0719843B1 (en) 2002-03-27
DE69526050D1 (de) 2002-05-02
KR960022867A (ko) 1996-07-18
DE69526050T2 (de) 2002-11-07

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