CN1357578A - 银色珠光颜料 - Google Patents

银色珠光颜料 Download PDF

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CN1357578A
CN1357578A CN01143104A CN01143104A CN1357578A CN 1357578 A CN1357578 A CN 1357578A CN 01143104 A CN01143104 A CN 01143104A CN 01143104 A CN01143104 A CN 01143104A CN 1357578 A CN1357578 A CN 1357578A
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pigment
pearly
coating
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C·施密德特
A·海兰德
C·福诺弗
H－D·布鲁克纳
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Merck Patent GmbH
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Abstract

本发明涉及基于多层涂布的小片状底物的银色珠光颜料,包括至少一种层序(A)、一层高折射率涂层,由TiO2组成和厚度为5－200nm,(B)、一层无色涂层,其折射率n≤1.8和厚度10－300nm,(C)、一种高折射率涂层,由TiO2组成和其厚度为5－200nm,和任选(D)、一层外保护层。以及其在油漆、涂料、印刷油墨(包括保密印刷油墨)、塑料、陶瓷材料、玻璃及化妆品配方中的应用及用于生产颜料制剂及干型产品。

Description

银色珠光颜料
本发明涉及基于多层施涂的小片状底物的银色珠光颜料。
珠光或珠光效果颜料广泛用于工业，特别是用于汽车涂料、装饰涂料、塑料、漆料、油墨和化妆品配方。
珠光颜料由于在多种干扰色间随角度色变而呈现一种颜色间的相互作用，使这种颜料尤其适用于汽车涂层和防伪的应用场合。
已有技术披露了制取珠光颜料的方法，用此法可将高、低折射率的交替层施涂于细分的底物上。这种基于多层涂敷的小片状底物的颜料可见于例如U.S.4,434,010、JR H7-759、U.S.3,438,796、U.S.5,135,812、DE 44 05 494、DE 44 37 753、DE 195 16 181和DE 19515 988中所述。
在本说明书中，特别重要的是矿物性珠光颜料。珠光颜料是采用在无机小片状载体上涂以高折射率普通氧化层的方法而制备的。这些颜料的颜色是通过介质/氧化物或氧化物/底物界面上反射或透射光的选择波长的部分反射和干扰所引起的。
颜料的干扰色由氧化层的厚度确定。干扰银色颜料的色彩由单一(光学意义上的)高折射率层产生，此高折射率层的光学厚度致使可见光波长区在约500nm处反射(第一次)最大。人眼对约500nm的波长感知为绿色。但其最大点沿波长轴向的亮度曲线很宽，以致很多光在整个可见光区都被反射，使人眼所见到的只是非常明亮而无色。
薄层的光学规律-尤其在光学元件涂层中所熟悉的-预示在干扰最大值处的亮度比单层***增大约60％。干扰反射光分布会因此而变得非常显著，所以预期这样的多涂层***会有绿反射颜色。
现在已意外发现，对于TiO2高折射率层和透明底物小片上低折射率层的交替型的实际干扰***，感知的不是绿色，而是在某种层厚下感知为银色。
因此，本发明提供基于多层施涂小片状底物的银色珠光颜料，包括至少一种层序：
(A)、一层高折射率涂层，由Ti02组成和厚度为5-200nm，
(B)、一层无色涂层，其折射率n≤1.8和厚度10-300nm，
(C)、一层高折射率涂层，由TiO2组成和厚度为5-200nm，
和任选
(D)、一层外保护层。
按照本发明这种银色颜料在银色区内优于现有珠光颜料，因为：
-金属光泽更强，尤其从大锥度(steep)视角看，
-平视角透明度较高，和
-主色更明亮。
本发明还提供对本发明的银色颜料在油漆、涂料、印刷油墨、塑料、陶瓷材料、玻璃和化妆品配方中的应用，特别在印刷油墨方面的应用。按照本发明的颜料也可用于制备颜料制剂，及用于制备干型产品，例如粒料、片剂、丸粒、团块等。干型产品尤其适用于印刷油墨。
可用于按照本发明多层颜料的基底物是可进行选择性或非选择性吸收的小片状底物。优选底物是薄片硅酸盐。特别有用的是天然和/或合成云母、滑石、高岭土、小片状铁或铝氧化物、玻璃小片、SiO2小片、TiO2小片、石墨小片、无合成载体的小片、氮化钛、硅化钛、液晶聚合物(LCP)、全息颜料、BiOC1、小片状混合氧化物、例如FeTiO3、Fe2TiO5或其它类似材料。
基底物尺寸本身不是关键性的，尺寸可适应具体的最终用途。一般说来，这种小片状底物厚度在0.005-10μm之间，尤其在0.05-5μm之间。在另二维空间，一般延伸达到1-500μm之间，优选在2-200μm之间，尤其在5-60μm之间。
具有高折射率或低折射率的各层(A)、(B)和(C)的基底物厚度对该颜料的光学性质是主要的。为获得具有强珠光效果的银色颜料，对各层厚度必须彼此兼顾地精确加以调节。
层(A)或(C)的厚度为5-200nm，优选10-100nm，尤其20-70nm。Ti02层(A)和(C)可有相同或不同的厚度。层(B)厚度为10-300nm(纳米)，优选20-100nm，尤其30-80nm。
这种颜料可包含许多相同或不同的层系(layer packets)的组合，但优选是施涂仅一种层系(A)+(B)+(C)+任选(D)的底物。为了加强色度，按照本发明颜料可包含多至4个层系，但是，在这样情况下底物上所有各层的厚度不应超过3μm。优选的是，对小片状底物奇数层的最内和最外部涂以高折射率层。特别优选的是给出(A)(B)(C)顺序的三层光学干涉层的结构。
可用作为涂层(B)的无色低折射率材料，优选是金属氧化物或其对应氢氧化物，例如，SiO2、Al2O3、AlO(OH)、B2O3、MgF2、MgSiO3、或其混合物。尤其，层(B)是一层SiO2层。
按照本发明的颜料易于通过在细分的小片状底物上产生许多层具有精确限定厚度及光滑表面的高、低折射率干扰层而构成。
对这种金属氧化物层优选采用湿化学法施涂，例如采用为生产珠光颜料而开发的湿化学涂布法。这种方法被描述于，例如，DE14 67 468、DE 19 59 988、DE 20 09 566、DE 22 14 545、DE 22 15 191、DE 2244 298、DE 23 13 331、DE 25 22 572、DE 31 37 808、DE 31 37 809、DE 31 51 343、DE 31 51 354、DE 31 51 355、DE 32 11 602、DE 3235 017，或另外本领域技术人员已知的其它专利文件及刊物。
在湿涂布法中，底物颗粒被悬浮于水中，在适宜水解pH下与一种或多种可水解金属盐或硅酸盐溶液相混合，对底物颗粒的选择要使这种金属氧化物或氢氧化物可直接沉淀至小片上而不发生共沉淀。通常通过同时计量加入碱和/或酸的方法，来保持pH恒定。然后分离出颜料，在50-150℃下洗涤及干燥6-18小时，任选焙烧0.5-3小时，在这样情况下，焙烧温度可针对当前具体涂法进行最佳化。一般，焙烧温度在250-1000℃，优选在350-900℃之间。如果需要，可在涂布各涂料之后，分离出颜料，加以干燥及任选焙烧，接着再悬浮以沉淀另外各层。
此外，这种涂料也可在流化床反应器中通过气相涂布完成，而在这样情况下，例如，可适当变化采用EP 0 045 851及EP 0 106 235中所建议的生产珠光颜料的一些方法。
可通过改变涂布速率及所得层厚度使颜料的色彩在非常宽的范围内变化，只要使之具有所获得的银色效果。除纯定量方法外，还可通过在视觉或仪器控制下逼近所需颜色的方法，来达到对某些色彩的精确调整。
为增加对光、水及气候的稳定性，对准备生产的颜料进行后涂布或后处理通常总是可行的，这要视应用范围而定。可采用的后涂布或后处理包括，例如，DE-C 22 15 191、DE-A 31 51 354、DE-A 32 35017或DE-A 33 34 598中所描述的方法。此外，这种后涂布(层D)增强了化学稳定性，或使颜料易于处置，尤其将其掺入各种介质中。
本发明颜料是与多色彩体系匹配的，优选在涂料、油漆及印刷油墨领域。为生产印刷油墨、例如用于凹版印刷、苯胺印刷、胶版印刷、胶版叠印涂布(offset overprint coating)，有许多适宜粘合剂，尤其水溶性级的粘合剂，如下述公司所销售的，例如，BASF、Marabu、Proll、Sericol、Hartmann、Gebr.Schmidt、Sicpa、Aarberg、Siegberg、GSB-Wahl、Follmann、Ruco或Coates Screen INKS GmbH等。这些印刷油墨可以是水基或溶剂基的。此外，这种颜料也可用于纸及塑料的激光标志，及用于农业部门，例如用于大棚膜，以及例如防水布着色。
由于本发明银色颜料光泽出众与透明度高及色彩中性主色兼有，可用于不同涂布介质，达到特别鲜明的效果，例如化妆品配方，如指甲漆膜、口红、盒粉、凝胶、洗液、肥皂、牙膏、涂料，例如汽车涂料、工业涂料及粉末涂料，以及在塑料、陶瓷以及在嗜好部分用于窗色料。
显然，对于不同最终用途，这种多层颜料也可有效用于混合有机染料、有机颜料或其它颜料的混合物，例如透明及遮掩白色、彩色及黑色颜料及与小片状铁氧化物，有机颜料、全息颜料、LCP(液晶聚合物)及基于金属氧化物涂布云母及SiO2小片等的常规透明、着色及黑色的珠光颜料混合的混合物。这种多层颜料可与能大批供应的颜料和填料按任何比例混和。
按照本发明的颜料还可用于生产可流动颜料制剂及干型产品，尤其用于印刷油墨，包括按照本发明的一种或更多种颜料、粘合剂及任选一种或多种添加剂。
因此，本发明也提供颜料制剂的应用，诸如油漆、印刷油墨(包括保密印刷油墨)、涂料、塑料、陶瓷材料、玻璃及化妆品配方。
下文中的实施例是对本发明的更具体描述，而非对其限制。
实施例
实施例1
将2升软化水中100克颗粒尺寸10-60μm的云母加热至75℃。达到此温度后，在搅拌下将90克水中溶解3克SnCl4×5H2O的溶液逐渐计量加入该云母悬浮液中。用32％氢氧化钠水溶液保持其pH恒定在2.0。接着降低pH至1.8，在此pH下计量加入270克32％TiCl4的溶液，同时利用32％氢氧化钠水溶液保持pH恒定。然后提高pH至7.5，在此pH下逐渐计量加入270克硅酸钠溶液(13.5重量％SiO2)，同时利用10％HCl保持pH恒定在7.5。最后，在pH1.8下加入300克的32％TiCl4溶液。在pH 1.8下搅拌0.5小时后，滤出涂布过的云母颜料，加以洗涤，并在110℃干燥16小时。最后，在800℃焙烧该颜料1小时。
实施例2
将2升软化水中100克颗粒尺寸10-60μm的云母加热至75℃。达到此温度后，在强烈搅拌下将90克水中内含3克SnCl4×5H2O的溶液逐渐计量加入该云母悬浮液中。用32％氢氧化钠水溶液保持其pH恒定在2.0。接着降低pH至1.8，在此pH下计量加入380克32％TiCl4溶液，同时用32％氢氧化钠水溶液保持pH恒定。然后提高pH至7.5，在此pH下逐渐计量加入380克硅酸钠溶液(13.5重量％的SiO2)，同时用10％HCl保持pH恒定在7.5。最后，在pH1.8下加入380克的32％TiCl4溶液。在pH 1.8下搅拌0.5小时后，滤出涂布过的云母颜料，加以洗涤，并在110℃干燥16小时。最后，在800℃下焙烧该颜料1小时。
实施例3
将2升软化水中100克颗粒尺寸10-60μm的云母加热至75℃。达到此温度后，强烈搅拌下将90克水中内含3克SnCl4×5H2O的溶液逐渐计量加入该云母悬浮液中。用32％氢氧化钠水溶液保持其pH恒定在2.0。接着降低pH至1.8，在此pH下计量加入220克的32％TiCl4溶液，同时用32％氢氧化钠水溶液保持pH恒定。然后提高pH至7.5，在此pH下逐渐计量加入215g的硅酸钠溶液(13.5重量％SiO2)，同时用10％HCl保持pH恒定在7.5。最后，在pH1.8下加入300克的32％TiCl4溶液。在pH 1.8下搅拌2.5小时后，滤出涂布的云母颜料，加以洗涤，并在110℃干燥16小时。最后，在800℃焙烧该颜料1小时。
实施例4
将2升软化水中100克颗粒尺寸10-60μm的云母加热至75℃。达到此温度后，计量加入330克32％TiCl4溶液，同时用32％氢氧化钠水溶液保持pH恒定。然后提高pH至7.5，在此pH下逐渐计量加入270克的硅酸钠溶液(13.5重量％的SiO2)，同时用10％HCl保持pH为7.5恒定。最后，在pH2.2下加入250克的32％TiCl4溶液。在pH 2.2下搅拌5小时后，滤出涂布的云母颜料，加以洗涤，并在110℃干燥16小时。最后，在800℃焙烧该银色颜料1小时。
下表表明按照本发明颜料的比色数据与已有技术的银色颜料(按光泽22.50°/22.50°黑背景测定的Phyma Lab值)的比较：
颜料     L     a     b     C   光泽数   隐蔽能力
银色珠光颜料Iriodin103(TiO2云母颜料，颗粒尺寸10-60μm，Merck KGaA公司)  83.6   -1.4   -1.9    2.4    58.5     30.6
实施例1银色颜料  90.2   -8.1   -11.4   14.0    60.9     33.6
实施例2银色颜料  93.0   -5.5    13.0   14.1    61.3     37.0
实施例3银色颜料  79.2   -10.3   -23.3   25.5    59.8     25.4
实施例4干扰颜料  84.5   -8.1   -10.5   13.3    61.4     27.2

Claims (11)

1、基于多层施涂小片状底物的银色珠光颜料，包括至少一种层序：
(A)、一层高折射率涂层，由Ti02组成和其厚度为5-200nm，
(B)、一层无色涂层，其折射率n≤1.8和厚度10-300nm，
(C)、一层高折射率涂层，由TiO2组成和其厚度为5-200nm，
和任选
(D)一层外保护层。
2、按照权利要求1的珠光颜料，其特征在于该小片状底物是天然或合成云母，玻璃小片，Al2O3小片，SiO2小片或TiO2小片。
3、按照权利要求1或2的珠光颜料，其特征在于该层(B)基本上由二氧化硅、氧化铝、氟化镁、或其混合物组成。
4、按照权利要求1-3任一项的珠光泽颜料，其特征在于它们包括层序(A)+(B)+(C)多达四次。
5、按照权利要求1-4任一项的珠光颜料，其特征在于它们包括层序(A)+(B)+(C)仅一次。
6、按照权利要求1-5任一项的珠光颜料，其特征在于它们包括一层外保护层(D)，以增强对光、热及气候的稳定性。
7、用于制备按照权利要求卜6任一项的珠光颜料的方法，其特征在于该底物是用湿化学法通过金属盐在一种水介质中的水解分解作用加以涂布的。
8、按照权利要求1的珠光颜料在油漆、涂料、印刷油墨，包括保密印刷油墨、塑料、陶瓷材料、玻璃及化妆品配方中的应用及用于生产颜料制剂及干型产品。
9、颜料制剂，包括一种或多种粘合剂，任选一种或多种添加剂及按照权利要求1的一种或多种珠光颜料。
10、干型产品，诸如丸粒、颗粒、片粒、团粒，包括按照权利要求1的珠光颜料。
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CN100513492C (zh) * 2003-03-27 2009-07-15 默克专利股份有限公司 银色干涉颜料
WO2006015530A1 (fr) 2004-08-10 2006-02-16 Shantou Longhua Pearl Lustre Co., Ltd. Pigment ayant une dependance angulaire des couleurs d’interference et son procede de fabrication
CN102702793B (zh) * 2004-08-13 2014-12-24 默克专利股份有限公司 珠光颜料
CN101646626B (zh) * 2007-02-27 2012-08-22 巴斯夫欧洲公司 一种形成(金红石型)二氧化钛涂覆的片状颜料的方法
CN101903471A (zh) * 2007-12-19 2010-12-01 默克专利股份有限公司 具有导电性核的强着色和/或光学可变的颜料
CN101903471B (zh) * 2007-12-19 2014-04-16 默克专利股份有限公司 具有导电性核的强着色和/或光学可变的颜料
CN102292401A (zh) * 2009-08-19 2011-12-21 埃卡特有限公司 具有银干涉色和窄尺寸分布的高光泽多层效应颜料和其生产方法
CN110603296A (zh) * 2017-04-27 2019-12-20 日本板硝子株式会社 具有电磁波透射特性的光亮性颜料和包含该颜料的组合物以及涂装体
CN110603296B (zh) * 2017-04-27 2021-10-26 日本板硝子株式会社 具有电磁波透射特性的光亮性颜料和包含该颜料的组合物以及涂装体

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TW555815B (en) 2003-10-01
US20030205170A1 (en) 2003-11-06
US6840993B2 (en) 2005-01-11
CZ20014352A3 (cs) 2002-07-17
JP5667330B2 (ja) 2015-02-12
ES2625081T3 (es) 2017-07-18
KR20020045542A (ko) 2002-06-19
JP2013108089A (ja) 2013-06-06
CA2364327A1 (en) 2002-06-07
EP1213330B1 (de) 2017-02-15
MXPA01012594A (es) 2004-10-15
DE10061178A1 (de) 2002-06-20
JP2002194245A (ja) 2002-07-10
BR0105904A (pt) 2002-08-13

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