CN1193333A - 片状二氧化钛颜料 - Google Patents

片状二氧化钛颜料 Download PDF

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CN1193333A
CN1193333A CN97190517A CN97190517A CN1193333A CN 1193333 A CN1193333 A CN 1193333A CN 97190517 A CN97190517 A CN 97190517A CN 97190517 A CN97190517 A CN 97190517A CN 1193333 A CN1193333 A CN 1193333A
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pigment
titanium dioxide
titanium
aqueous solution
sheet
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S·安德斯
G·鲍尔
G·布伦纳
D·布鲁克纳
A·海兰德
M·昆茨
K·奥斯特里德
G·普法弗
M·施迈尔茨
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Merck Patent GmbH
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Abstract

片状无基体的二氧化钛颜料,该颜料是通过将一种可加热水解的钛化合物的水溶液固化在连续的带上、剥离所形成的层、通过湿法工艺用二氧化钛在无中间干燥或有中间干燥的条件下涂覆所获得的二氧化钛片、分离、干燥以及将所获得的材料煅烧而获得的。

Description

片状二氧化钛颜料
本发明涉及基于片状二氧化钛的非常薄的二氧化钛珠光颜料。
含有二氧化钛的珠光颜料已经被人们使用了多年。它们根据层状基体原理而构成，其采用云母作为唯一的基体。
人们已经知道有两种主要的方法用于沉积二氧化钛层。第一种方法是如US3087828中所说、通过向云母悬浮液中加入用硫酸酸化的硫酸氧钛溶液进行沉积并且通过加热到100℃进行水解，涂层的厚度和相应的干涉色根据所存在的硫酸氧钛量而预先确定。
第二种方法是如DE2009566中所说进行沉积。在这种情况下，将云母悬浮液加热到约50-100℃，特别是70-80℃，慢慢加入一种钛盐水溶液，通过同时加入一种碱，如氨水溶液或碱金属氢氧化物溶液而pH值基本保持不变，约为0.5-5，特别是1.5-2.5。当达到所需的二氧化钛沉积层厚度时，停止加入钛盐溶液。
云母的一个缺点在于在形成二氧化钛的过程中，它会诱导锐钛转变，尽管人们经常需要的是金红石转变，后一种转变具有更高的折射率和更好的性能。因此必须通过加入外来离子，特别是锡(IV)离子来引起金红石转变。
例如在DE2214545和2522572中描述了这种方法，其中通过在云母附近或在二氧化钛层之间引入二氧化锡而引起金红石反应。但是，已知还有其它一些方法可以采用，例如根据CS208578可以引入氧化锌或根据DE1959998向二氧化钛层之间引入铁(III)，这些方法均可导致金红石层。
云母颜料广泛用于印刷和涂料工业、用于化妆品和用于聚合物工业中。它们以干涉颜色和高光泽而著称。但是云母颜料不适宜形成极薄的层，其原因在于作为颜料金属氧化物层的基体，云母的厚度已经为200-1200nm。另一个缺点是由片尺寸决定的一定比例的云母片的厚度有时在平均值附近变化较大。此外，云母是一种天然存在的矿物，它含有某些外来杂质离子。此外还需要在工业上非常昂贵和费时的操作步骤。这些步骤包括研磨和分级。
基于厚云母片并且用金属氧化物涂覆的珠光颜料由于其边缘厚度而具有明显的分散量，特别是在细颗粒尺寸分布低于20微米时。
人们提出采用通过将玻璃熔体轧制而后研磨而获得的玻璃薄片作为云母的替代物。基于这种材料的干涉颜料确实显示出比普通的基于云母的颜料更好的颜色效果。但是它存在这样一个缺点，即该玻璃片具有非常大的约10-15微米的平均厚度和非常宽的厚度分布(通常在4-20微米之间)，而干涉颜料的厚度一般为不大于3微米。
EP0384596公开了一种方法，其中在480-500℃下向水合碱金属硅酸盐中加入空气射流，形成壁厚较小的气泡；然后将气泡破碎并获得厚度小于3微米的片状碱金属硅酸盐基体。但是该方法较昂贵并且所获得的片的厚度分布较宽。
DE1136042公开了一种制备元素周期表中IV和V族和铁族金属片状氧化物或水合氧化物的连续带方法。在该方法中，如果合适，可以在连续带上首先涂覆例如一层硅氧烷隔离层以有助于该金属氧化物层随后脱开。然后涂覆可转化成所需的金属氧化物的金属的可水解化合物溶液的液体膜并且将该膜干燥而后用一种振动装置将其脱开。所获得的片的层厚度为0.2-2微米，对此没有给出具体的实施例。
EP0240952和EP0236952提出制备多种片状材料，包括二氧化硅，氧化铝和二氧化钛的连续带方法。在该方法中，通过一种辊系统将厚度一定的片状材料的前体的液体薄膜涂覆在光滑的带上；将该膜干燥并与该带脱开，形成片状颗粒。然后将该颗粒煅烧，如果需要并研磨和分级。
通过EP0240952中所说的方法获得的片的厚度相对固定，这是因为例如该膜可以通过一种辊系统非常均匀地涂覆到连续的带上，在其实施例中，片的厚度为0.3-3.0微米。根据实施例1，通过将这种辊部分浸入装有该前体的贮存容器中而首先用该前体润湿第一个辊。该膜由该辊转移到以相同方向转动的第二个辊上，第二个辊与第一个辊非常靠近。最后由该第二个辊将该膜压在该连续的带上。
但是其缺点在于采用非常昂贵的前体材料，并且特别是要增加场地的安全性，这在使用有机化合物时是必须要提出的。一般要使该前体完全化学转化成所需的金属层必须将该膜和该带材料高温加热。除了在这种情况下会使该带材料产生相当高的热应力以外，较高的能量消耗和对工艺速度的限定还会对该方法产生非常不利的影响。
W093/08 237公开了由二氧化硅的片状基质组成的片状颜料，该基质包括可溶的和不可溶的着色剂并且其上涂覆了一层或多层金属氧化物或金属反射层。该片状基质是通过将水玻璃固化在连续的带上而制得的。
DE1273098描述了通过将ZnS、MgF2、ZnO、CaF2和TiO2膜汽相沉积在连续带上而制备珍珠颜料的过程。但是与在US4879140中所说的方法(其中通过由SiH4和SiCl4等离子沉积而获得具有Si和SiO2层的片状颜料)相类似，这种方法还会在设备上花费非常大。
尽管存在多种努力，但至今人们尚不能开发出一种较为经济的制备层厚度低于500nm的非常薄的片状二氧化钛颜料的方法。
本发明的目的在于提供一种高光泽度的二氧化钛珠光颜料，其层厚度低于500nm并且层厚度偏差低于10％，这种颜料实际上不含有外来离子并且是金红石或锐钛矿形式。
根据本发明，该目的是通过片状无基体的二氧化钛颜料而实现的，该颜料是通过将一种可加热水解的钛化合物的水溶液固化在连续的带上、剥离所形成的层、通过湿法工艺用另一种二氧化钛在无中间干燥或有中间干燥的条件下涂覆所获得的二氧化钛片、分离、干燥以及将所获得的材料煅烧而获得的。
所用的可加热水解的钛化合物优选地是四氯化钛水溶液。在这些溶液中的钛盐的浓度为7-30％重量，优选地为8-15％重量。
根据本发明，该目的还通过制备该新型颜料的方法而实现，其中-将片状二氧化钛前体作为薄层涂覆到连续的带上，-干燥固化该液体膜，在此期间二氧化钛通过化学反应由该前体形成，-将所形成的层从该带上剥离并进行冲洗，-在中间干燥之后或没有干燥的条件下，将所形成的二氧化钛片悬浮在水中并用另一种二氧化钛进行涂覆，以及-将经过涂覆的颗粒从水悬浮液中分离、干燥以及如果需要进行煅烧。
干燥以后，该二氧化钛处于锐钛矿状态。通过在600℃以上的温度下煅烧，可以在无外来离子存在的条件下将其转变成金红石形式。由此可以获得一种高度纯净的金红石型二氧化钛颜料，相对于基于云母的常规二氧化钛颜料来说，这种颜料在许多方面均是优越的。
如果要将锡引入二氧化钛基体中，则从110℃开始在干燥过程中发生向金红石的转变。
本发明还涉及该新型颜料在带颜料的涂料、印刷油墨、塑料、化妆品和陶瓷及玻璃釉料中的运用。
为此，它们还可以用作与市售颜料，如无机和有机吸收颜料、金属颜料和LCP颜料的混合物。
该新型颜料由片状二氧化钛组成。这些片的厚度为10-500nm，优选地为40-300nm。其它两个尺寸的范围为2-200微米，特别是5-50微米。
该新型颜料可以在两阶段工艺中制备。在第一个阶段中，借助于连续带制备片状二氧化钛。
首先参照图1来描述该带方法。
在辊系统2上导转的连续带1移动通过涂覆机3，在该涂覆机用前体薄膜涂覆。可以采用辊式涂覆机和流动单元作为合适的涂覆机。带速度为2-400米/分钟，优选地为5-200米/分钟。
为了达到均匀润湿该塑料带，一般向该涂覆溶液中加入一种市售润湿剂或通过火焰、电晕处理或电离处理而使该带表面活化。
经过涂覆的带而后移过干燥区4，在该区中，涂层在30-200℃的温度下干燥。可以采用市售红外、环境空气喷射器和UV干燥器作为干燥器。
在经过干燥区以后，将该带导过具有适当剥离介质，如完全软化的水的剥离浴，在该浴中，经过干燥的涂层从该带上剥离。利用一些附加的装置如喷射器、刷子或超声波来帮助进行剥离操作。
在再涂覆之前，将该带在后干燥器6中干燥。
该连续的带应由化学稳定的、耐热的塑料制成，以确保其有适当的寿命和较高的干燥温度。适用于此的材料是聚对苯二甲酸乙二醇酯(PET)或其它的聚酯和聚丙烯酸酯。
膜的宽度一般为几厘米-二米或更多米。其厚度为10微米-几毫米，这两个参数可以根据特定的需要而最佳化。
连续带工艺的更进详细的描述可以从US3138475、EP0240952和W093/08237中获知。
从该带上剥离的二氧化钛片再通过已知的方法在第二个阶段中用另一种二氧化钛进行涂覆，在此之前可以不干燥。优选地采用在US3553001中所说的方法。
可以将一种钛盐水溶液慢慢加入到加热至50-100℃，优选地为70-80℃的二氧化钛片的悬浮液中，通过同时加入一种碱。例如氨水溶液或碱金属氢氧化物水溶液而将pH值保持在约0.5-5，特别是在约1.5-2.5下不变。当二氧化钛沉积物的厚度达到所需的值时，停止加入钛盐溶液。
这种方法也称为滴定法，其特点在于可以避免钛盐过量。这一点是通过这样一种方法实现的，即单位时间内向水解液中仅仅加入用水合二氧化钛均匀涂覆所需的钛盐量以及单位时间内可以被要涂覆的颗粒的可获得表面所吸附的量。因此，不会形成没有沉积在要涂覆的表面上的水合二氧化钛颗粒。每分钟加入的钛盐的量约为0.01-2×10-4摩尔钛盐/平方米要涂覆的表面。
此外，该二氧化钛片上还可以在干燥以后，在流化床反应器中通过气相涂覆用另一种二氧化钛进行涂覆，例如可以适当采用在EP0045851和EP0106235中所说的用于制备珠光颜料的技术。
该新型颜料还可以用低溶解度的牢固粘接的无机或有机着色剂涂覆。优选地采用色淀颜料，特别是铝色淀颜料。为此，可以沉积氢氧化铝层并且在第二步中用色淀颜料进行涂覆。在DE2429762和DE2928287中更详细地描述了该方法。
另外优选的是用配合盐颜料，特别是氰基高铁酸盐配合物，例如普鲁士兰或特恩布尔兰进行涂覆，例如在EP0141173和DE2313332中所说。
该新型颜料还可以用有机染料进行涂覆，特别是用酞菁染料或金属酞菁染料和/阴丹士染料进行涂覆，如DE4009567中所述。为此，制备该颜料在该染料溶液中的悬浮液然后将其与染料微溶或不可溶解的溶剂混合在一起。
还可以采用金属硫化物或金属硫化物水合物和碳黑来进行另外的涂覆。
还可以对该颜料进行后涂覆或后处理，它们可以进一步提高该颜料对光、气候和化学品的稳定性或有利于该颜料的操作各方面，特别是将其导入到各种介质中。例如可能的后涂覆或后处理工艺可以是在DE-C-2215191、DE-A-3151354、DE-A-3235017或DE-A-3334598中所说的工艺。
这些另外涂覆的物质可以在颜料总量的约0.5-5％，特别是1-3％重量。
该颜料可以以常规方式用于带颜料的食品、涂科、印刷油墨、塑料、化妆品和陶瓷和玻璃釉料中。但是由于它基本上可以挡住330nm以下的所有紫外辐射，因此它还可以在化妆品中作于UV防护或用于工业运用中。因此该颜料明显优于市售防光过滤材料。
颜料在这些配方中的浓度为0.1-30％重量，优选地为1-10％重量。
该新型颜料在UV辐射方面的防护作用可以与Luxelen Silk D(一种市售防晒霜，制造商：Presperse，Inc.)相比。为此，将该颜料(层厚度为130nm)和对比产品引入NC大漆中(颜料浓度为1.7％)，将该大漆用刮刀涂覆到玻璃板上。干燥以后，将该膜从基体上剥离并用带有内置式积分球(放大的Specacarol光阑，30nm)的PE Lambda 19仪器测定其在200-2500nm内的透光率、反射率和吸收率。含有该新型颜料的膜的透光率在330nm以下为0％，在350nm处为5％，在380nm处为35％，在400nm处为40％。因此在350nm以下的UV辐射透过性远远低于对比产品的。
该新型颜料代表在珠光颜料中在厚度方面可以获得的最理想状态。
在这种情况下，片的厚度对应于在光学上起作用的二氧化钛层的所需层厚度，而在常规的珠光颜料的情况下，片的厚度要大25倍。这是因为在该功能层中加入了基体，如云母的层厚度。
由此而在工业应用方面导致了固有的优点，这是任何其它常规的珠光颜料所不能达到的。
举例来说，可以以更薄的涂层进行涂覆并且可以减少所需的颜料量，这是因为由不存在“填料”载体材料，该颜料更具光学活性。
采用下面的实施例来进一步描述本发明而不是要对它进行限制。实施例1
通过反向旋转涂覆辊用20％四氯化钛溶液涂覆聚对苯二甲酸乙二醇酯循环带(宽度：0.3米，速度：20米/分钟)。该涂覆溶液含有0.3％重量表面活性剂(DISPERSE-AYD W-28，制造商：DANIEL PRODUCTSC0MPANY)。在该带上的水膜通过将其放入70℃热空气中而在干燥阶段干燥并且在填充了去离子水的剥离盒中从该带上剥离。而后过滤该片状二氧化钛颗粒并用去离子水进行冲洗。这些片具有银光泽并且层厚度为100±10nm。为了涂覆另一种二氧化钛，可以将它们分散在去离子水中。
将2升二氧化钛片分散液(固体含量：15克二氧化钛)加热到75℃并用稀盐酸调整到pH2.2。
以3毫升/分钟的速度将40％四氯化钛水溶液加入并且将pH用32％氢氧化钠仍保持在2.2下不变。
连续加入四氯化钛，直到达到所需的第一或更高级的干涉色。将获得的颜料过滤，用去离子水冲洗直到没有盐，干燥并将其在750℃下煅烧。其颜色性能不会随着煅烧温度的变化而有很大变化，这是因为在约600℃开始并在750℃时结束的锐钛矿-金红石转变反应起作很重要的作用。实施例2防晒乳液组成成分A：液体石蜡            20.0％
   十六烷醇            1.5％
   蜂蜡                6.0％
   硬脂酸              20.0％
   PEO(5.5)十六醚      1.5％
   山梨醣醇单硬脂酸酯  2.5％成分B：10％氢氧化钠        1.0％
   去离子水            36.5％成分C  甘油醇              6.0％
   二氧化钛颜料        5.0％制备过程：
将该颜料分散在甘油醇中。将成分A和B分别加热到75℃并借助于高速搅拌机以凝胶形式混合。最后在50℃下，将成分C乳化在A和B的乳化液中

Claims (8)

1.片状无基体的二氧化钛颜料，该颜料可通过以下方法制得，即将一种可加热水解的钛化合物的水溶液固化在连续的带上、剥离所形成的层、通过湿法工艺用另一种二氧化钛在无中间干燥或有中间干燥的条件下涂覆所获得的二氧化钛片、分离、干燥以及煅烧所获得的材料。
2.权利要求1的二氧化钛颜料，其特征在于该可加热水解的钛化合物的水溶液是四氯化钛的水溶液。
3.用于制备根据权利要求1和2的二氧化钛颜料的方法，其特征在于-将一种可加热水解的钛化合物的水溶液作为薄层涂覆到连续的带上，-干燥固化该液体膜，在此期间二氧化钛通过化学反应由该溶液形成，-将所形成的层从该带上剥离并进行冲洗，-在中间干燥之后或没有干燥的条件下，将所形成的二氧化钛片悬浮在水中并用另一种二氧化钛进行涂覆，以及-将经过涂覆的颗粒从水悬浮液中分离、干燥以及如果需要进行煅烧。
4.根据权利要求3的二氧化钛颜料，其特征在于该可加热水解的钛化合物的水溶液是四氯化钛的水溶液。
5.根据权利要求3和4的方法，其特征在于该另一层二氧化钛通过CVD法在流化床反应器中涂覆到二氧化钛片上。
6.根据权利要求1和2的颜料在涂料、印刷油墨、塑料、化妆品和陶瓷及玻璃釉料以及食品中作为颜料和作为防晒霜的用途。
7.根据权利要求6的用途，其特征在于该颜料以与市售颜料的混合物使用。
8.用根据权利要求1和2的颜料着色的涂料、印刷油墨、塑料、化妆品、陶瓷及玻璃。
CN97190517A 1996-05-09 1997-04-25 片状二氧化钛颜料 Expired - Fee Related CN1083865C (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347091C (zh) * 2000-02-04 2007-11-07 昭和电工株式会社 超微粒子混晶氧化物及其制造方法和用途

Families Citing this family (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT910549E (pt) * 1996-07-08 2002-04-29 Rhodia Chimie Sa Particulas de dioxido de titanio processo para a sua preparacao e sua utilizacao nos cosmeticos vernizes e revestimentos de superficie
DE19707805A1 (de) * 1997-02-27 1998-09-03 Merck Patent Gmbh Multischicht-Interferenzpigment mit absorbierender Mittelschicht
AU743389B2 (en) * 1997-09-02 2002-01-24 Ishihara Sangyo Kaisha Ltd. Fine hollow powder,thin flaky titanium oxide powder obtained by pulverization of the fine hollow powder and processes for producing the same
DE19817286A1 (de) * 1998-04-18 1999-10-21 Merck Patent Gmbh Mehrschichtiges Perlglanzpigment auf Basis eines opaken Substrates
DE19831869A1 (de) * 1998-07-16 2000-01-20 Merck Patent Gmbh Farbgebung mit Perlglanzpigmenten im Lebensmittel- und Pharmabereich
US6157489A (en) * 1998-11-24 2000-12-05 Flex Products, Inc. Color shifting thin film pigments
US6150022A (en) 1998-12-07 2000-11-21 Flex Products, Inc. Bright metal flake based pigments
US6284032B2 (en) * 1999-03-09 2001-09-04 Merck Patent Gmbh Multilayer interference pigments
US6987590B2 (en) * 2003-09-18 2006-01-17 Jds Uniphase Corporation Patterned reflective optical structures
US20070195392A1 (en) * 1999-07-08 2007-08-23 Jds Uniphase Corporation Adhesive Chromagram And Method Of Forming Thereof
US6761959B1 (en) 1999-07-08 2004-07-13 Flex Products, Inc. Diffractive surfaces with color shifting backgrounds
US7667895B2 (en) * 1999-07-08 2010-02-23 Jds Uniphase Corporation Patterned structures with optically variable effects
US7047883B2 (en) 2002-07-15 2006-05-23 Jds Uniphase Corporation Method and apparatus for orienting magnetic flakes
US6241858B1 (en) 1999-09-03 2001-06-05 Flex Products, Inc. Methods and apparatus for producing enhanced interference pigments
US6524381B1 (en) 2000-03-31 2003-02-25 Flex Products, Inc. Methods for producing enhanced interference pigments
US6545809B1 (en) 1999-10-20 2003-04-08 Flex Products, Inc. Color shifting carbon-containing interference pigments
EP1252027A1 (en) * 2000-01-21 2002-10-30 Flex Products, Inc. Optically variable security devices
US11768321B2 (en) 2000-01-21 2023-09-26 Viavi Solutions Inc. Optically variable security devices
US6572964B2 (en) 2000-02-04 2003-06-03 Showa Denko K.K. Ultrafine mixed-crystal oxide, production process and use thereof
AU2001278446A1 (en) 2000-06-15 2001-12-24 Merck Patent G.M.B.H A method for producing sphere-based crystals
DE10034332A1 (de) * 2000-07-14 2002-01-24 Beiersdorf Ag Visualisierung von Sonnenschutzmitteln auf der Haut
US6586098B1 (en) 2000-07-27 2003-07-01 Flex Products, Inc. Composite reflective flake based pigments comprising reflector layers on bothside of a support layer
US6686042B1 (en) 2000-09-22 2004-02-03 Flex Products, Inc. Optically variable pigments and foils with enhanced color shifting properties
US6569529B1 (en) 2000-10-10 2003-05-27 Flex Product, Inc. Titanium-containing interference pigments and foils with color shifting properties
US6565770B1 (en) 2000-11-17 2003-05-20 Flex Products, Inc. Color-shifting pigments and foils with luminescent coatings
US6572784B1 (en) 2000-11-17 2003-06-03 Flex Products, Inc. Luminescent pigments and foils with color-shifting properties
JP2004514558A (ja) 2000-11-30 2004-05-20 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 乳白色効果を有する粒子
US20020160194A1 (en) * 2001-04-27 2002-10-31 Flex Products, Inc. Multi-layered magnetic pigments and foils
US6808806B2 (en) * 2001-05-07 2004-10-26 Flex Products, Inc. Methods for producing imaged coated articles by using magnetic pigments
US6627212B2 (en) * 2001-06-26 2003-09-30 Engelhard Corporation Use of effect pigments in ingested drugs
US7625632B2 (en) * 2002-07-15 2009-12-01 Jds Uniphase Corporation Alignable diffractive pigment flakes and method and apparatus for alignment and images formed therefrom
US6692830B2 (en) 2001-07-31 2004-02-17 Flex Products, Inc. Diffractive pigment flakes and compositions
US6841238B2 (en) 2002-04-05 2005-01-11 Flex Products, Inc. Chromatic diffractive pigments and foils
US6497998B1 (en) 2001-08-16 2002-12-24 Eastman Kodak Company Oriented polyolefin imaging element with nacreous pigment
US6544713B2 (en) 2001-08-16 2003-04-08 Eastman Kodak Company Imaging element with polymer nacreous layer
US6544714B1 (en) 2001-08-16 2003-04-08 Eastman Kodak Company Nacreous photographic packaging materials
US6569593B2 (en) 2001-08-16 2003-05-27 Eastman Kodak Company Oriented polyester imaging element with nacreous pigment
US6596447B2 (en) 2001-08-16 2003-07-22 Eastman Kodak Company Photographic element with nacreous overcoat
US6596451B2 (en) 2001-08-16 2003-07-22 Eastman Kodak Company Nacreous imaging element containing a voided polymer layer
US6599669B2 (en) 2001-08-16 2003-07-29 Eastman Kodak Company Imaging element with nacreous pigment
US6497986B1 (en) 2001-08-16 2002-12-24 Eastman Kodak Company Nacreous satin imaging element
DE10204789A1 (de) 2002-02-06 2003-08-14 Merck Patent Gmbh Inhibitoren des Integrins alpha¶v¶beta6
US6626989B1 (en) 2002-05-16 2003-09-30 Engelhard Corporation Rutile titanium dioxide effect pigments and production thereof
US7934451B2 (en) 2002-07-15 2011-05-03 Jds Uniphase Corporation Apparatus for orienting magnetic flakes
US20100208351A1 (en) * 2002-07-15 2010-08-19 Nofi Michael R Selective and oriented assembly of platelet materials and functional additives
US11230127B2 (en) 2002-07-15 2022-01-25 Viavi Solutions Inc. Method and apparatus for orienting magnetic flakes
US7674501B2 (en) * 2002-09-13 2010-03-09 Jds Uniphase Corporation Two-step method of coating an article for security printing by application of electric or magnetic field
US7645510B2 (en) * 2002-09-13 2010-01-12 Jds Uniphase Corporation Provision of frames or borders around opaque flakes for covert security applications
US9458324B2 (en) 2002-09-13 2016-10-04 Viava Solutions Inc. Flakes with undulate borders and method of forming thereof
US9164575B2 (en) * 2002-09-13 2015-10-20 Jds Uniphase Corporation Provision of frames or borders around pigment flakes for covert security applications
US8025952B2 (en) 2002-09-13 2011-09-27 Jds Uniphase Corporation Printed magnetic ink overt security image
KR101015030B1 (ko) * 2002-10-16 2011-02-16 시바 홀딩 인크 환원성 안료
US7169472B2 (en) 2003-02-13 2007-01-30 Jds Uniphase Corporation Robust multilayer magnetic pigments and foils
MXPA05008491A (es) * 2003-02-20 2006-02-22 Bpsi Holdings Inc Sistemas de recubrimiento de pelicula nacarada y substratos recubiertos con la misma.
DE102004032799A1 (de) * 2003-07-21 2005-02-17 Merck Patent Gmbh Effektpigmente mit einheitlicher Form und Grösse
US20070048416A1 (en) * 2003-07-21 2007-03-01 Engelhard Corporation Use of Effect Pigments in Ingested Drugs
US7550197B2 (en) * 2003-08-14 2009-06-23 Jds Uniphase Corporation Non-toxic flakes for authentication of pharmaceutical articles
US7014700B2 (en) * 2004-01-13 2006-03-21 Engelhard Corporation Highly reflective interference pigments with dark absorption color
US7118622B2 (en) * 2004-05-19 2006-10-10 Engelhard Corporation Organic dyes suitable for use in drugs and cosmetics laked onto a platy titanium dioxide pigment
TWI402106B (zh) 2005-04-06 2013-07-21 Jds Uniphase Corp 印記於含有可印記菲涅耳結構之成型磁場中之動態外觀變化光學裝置（ｄａｃｏｄ）
JP4789508B2 (ja) * 2005-05-25 2011-10-12 トヨタ自動車株式会社 シルバー発色の真珠光沢顔料の製造方法
KR20080032083A (ko) * 2005-06-10 2008-04-14 시바 스페셜티 케미칼스 홀딩 인크. 플라즈마 토치를 사용하는 입자의 처리방법
AU2006202315B2 (en) * 2005-06-17 2011-01-27 Viavi Solutions Inc. Covert security coating
WO2007021999A2 (en) 2005-08-10 2007-02-22 Mars, Incorporated Marbled surface chocolate product
CN101282804B (zh) 2005-08-12 2012-03-21 唐维科（1198）公司 制备金属薄片的方法
CA2564764C (en) * 2005-10-25 2014-05-13 Jds Uniphase Corporation Patterned optical structures with enhanced security feature
AU2006249295A1 (en) * 2005-12-15 2007-07-05 Jds Uniphase Corporation Security device with metameric features using diffractive pigment flakes
CA2592667C (en) * 2006-07-12 2014-05-13 Jds Uniphase Corporation Stamping a coating of cured field aligned special effect flakes and image formed thereby
DE102006044076A1 (de) * 2006-09-20 2008-03-27 Merck Patent Gmbh Photokatalytisch aktive Beschichtung
US20100029788A1 (en) * 2006-09-29 2010-02-04 John Pelesko Wet edible pearlescent film coatings
US7927416B2 (en) 2006-10-31 2011-04-19 Sensient Colors Inc. Modified pigments and methods for making and using the same
EP2099312B1 (en) * 2006-12-14 2016-05-04 Sensient Colors LLC Pearlescent pigment compositions and methods for making and using the same
WO2009024471A1 (en) * 2007-08-20 2009-02-26 Basf Se Process for preparing platelet-like pigments comprising a nitrogen doped carbon coating
JP5706159B2 (ja) 2007-08-23 2015-04-22 センシエント カラーズ エルエルシー 自己分散型顔料ならびにその製造方法および使用
CA2697490C (en) * 2007-08-24 2016-04-19 Mars, Incorporated Apparatus and method of applying edible pearlescent coating to a food product
AU2008219354B2 (en) * 2007-09-19 2014-02-13 Viavi Solutions Inc. Anisotropic magnetic flakes
AU2008316507A1 (en) 2007-10-26 2009-04-30 Basf Se Security element
DE102007058601A1 (de) 2007-12-04 2009-06-10 Merck Patent Gmbh Sicherheitspigment
US7449287B1 (en) 2008-01-30 2008-11-11 Eastman Kodak Company Pearlescent textured imaging supports
JP2009193069A (ja) 2008-02-13 2009-08-27 Jds Uniphase Corp 光学的な特殊効果フレークを含むレーザ印刷用の媒体
WO2009135784A1 (en) * 2008-05-09 2009-11-12 Basf Se Pearlescent pigments coated with a metal oxide/hydroxide layer and an acrylic copolymer
KR20110135989A (ko) 2009-04-07 2011-12-20 센션트 컬러스 엘엘씨 자가-분산 입자 및 그의 제조 및 사용 방법
CN102714265A (zh) 2009-12-30 2012-10-03 默克专利有限公司 作为水分子的扩散屏障的浇铸组合物
CA3123564C (en) 2012-01-12 2023-12-19 Vladimir P. Raksha Article with a dynamic frame formed with aligned pigment flakes
US9482800B2 (en) 2013-06-10 2016-11-01 Viavi Solutions Inc. Durable optical interference pigment with a bimetal core
KR101764564B1 (ko) * 2017-04-11 2017-08-02 신상순 유약 첨가 분쇄물, 유약 첨가 분쇄물 제조 방법 및 도자기 제작 방법.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138475A (en) * 1959-11-14 1964-06-23 Jenaer Glaswerk Schott & Gen Filler and meterial with an artificial pearly gloss and method of producing the same
US3340006A (en) * 1963-05-01 1967-09-05 Corning Glass Works Method of producing thin flakes of metal oxide
US3395203A (en) * 1965-07-06 1968-07-30 Koppers Co Inc Method of making titanium dioxide nacreous pigment
US3582382A (en) * 1967-07-20 1971-06-01 Nihon Koken Kogyo Co Ltd Method of producing nacreous pigment
JPH01264932A (ja) * 1988-04-15 1989-10-23 Ishihara Sangyo Kaisha Ltd 顔料性針状二酸化チタン及びその製造方法
EP0649816B1 (en) * 1993-10-22 1998-07-15 Ishihara Sangyo Kaisha, Ltd. Dendrite or asteroidal titanium dioxide micro-particles and process for producing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100347091C (zh) * 2000-02-04 2007-11-07 昭和电工株式会社 超微粒子混晶氧化物及其制造方法和用途

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TW406121B (en) 2000-09-21
DE59704951D1 (en) 2001-11-22
CZ5098A3 (cs) 1998-04-15
CN1083865C (zh) 2002-05-01
US5858078A (en) 1999-01-12
KR19990028852A (ko) 1999-04-15
DE19618564A1 (de) 1997-11-13
CA2226509A1 (en) 1997-11-20
EP0837911A1 (de) 1998-04-29
JPH11509888A (ja) 1999-08-31
WO1997043346A1 (de) 1997-11-20
BR9702236A (pt) 1999-02-23
MX9800263A (es) 1998-04-30

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