CN1382748A - 有色颜料 - Google Patents
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Abstract
本发明涉及基于多层涂覆的片晶状基材的有色颜料,其特征在于它包含:(A)折射指数n>1.8且层厚为20-500nm的涂层,(B)折射指数n≤1.8且层厚为10-100nm的无色涂层,(C)折射指数n>1.8且层厚为20-500nm的无色涂层,(D)粒径为1-500nm的吸收性颜料颗粒的覆盖物,和可有可无(E)外保护层,及其在油漆、涂料、印刷油墨、塑料、陶瓷材料、玻璃中、在化妆品配方中、用于激光标记和用于生产颜料制剂和干制剂的用途。
Description
本发明涉及基于多层涂覆的片晶状基材的有色颜料。
光泽或效果颜料用于许多工业领域,尤其是汽车油漆、装饰涂料、塑料、表面涂料、印刷油墨和化妆品配方的领域。
不具有“硬”金属光泽的基于透明片晶状基材的光泽颜料是WO93/12182的主题。云母片覆盖有高折射指数金属氧化物层,例如TiO2、和非选择性吸收层。根据TiO2层厚,这些颜料在垂直观察时具有某种干涉颜色,它随着倾斜视角的增加变得越来越弱,最后减少为灰色或黑色。该干涉颜色不会改变,但观察到颜色饱和度的下降。
JP1992/93206要求基于玻璃片或云母颗粒的光泽颜料,它覆盖有不透明金属层和交替的SiO2和TiO2层。
EP0753545A2公开了基于至少部分可透过可见光的多层涂覆的、高折射指数、非金属、片晶状基材的角异色性光泽颜料,该颜料具有包含无色、低折射指数涂层和能够选择或非选择性吸收的反射涂层的至少一层组合。
已有技术的已知多层颜料在某些情况下由具有较小或没有透光性的层材料构成并因此仅以非常有限的方式与吸收颜料结合使用。另外,这些颜料的干涉颜色高度取决于视角,这在大多数场合中是不理想的。此外,这些颜料在某些情况下非常难以制备或再生。
本发明的目的是提供具有高着色强度的彩色多层颜料,它没有明显的角异色性,以其有利的应用性能为特点且同时可以简单方式制备。
现已惊人地发现能产生特定颜色效果的基于多层涂覆的片晶状基材的有色颜料,它具有一定排列的光学功能层和由吸收颜料组成的外层。
具有有色颜料颗粒的颜料公开于,例如,德国专利2313332和德国专利3334596。其中所述的颜料基于涂有金属氧化物层并随后涂有普鲁士蓝的片晶状基材。但已有技术的颜料不是多层颜料。按照本发明的彩色多层颜料以其极高的色度C(“着色强度”)、高遮盖力、高干涉颜料的色纯度和非常强的光泽区别于已有技术颜料,而且不同于已有技术的角异色性颜料,该干涉颜色具有较小或没有角度依赖性。
因此本发明涉及基于多层涂覆的片晶状基材的有色颜料,特征在于,它包含:
(A)折射指数n>1.8且层厚为20-500nm的涂层,
(B)折射指数n≤1.8且层厚为10-100nm的无色涂层,
(C)折射指数n>1.8且层厚为20-500nm的无色涂层,
(D)粒径为1-500nm的吸收性颜料颗粒的覆盖物,和
可有可无的
(E)外保护层。
本发明还涉及本发明颜料在油漆、涂料、印刷油墨、塑料、陶瓷材料、玻璃中和用于激光标记的应用。本发明颜料因颜色强度高而特别适用于生产颜料制剂和用于生产干制剂,如粒剂、碎片、粒料、团块、等。干制剂特别适用于制备印刷油墨和涂料。
适用于本发明有色颜料的基材是透明片晶状基材。优选的基材是叶硅酸盐。特别合适的基材是天然和/或合成云母、滑石、高岭土、片晶状氧化铁或氧化铝、玻璃片、SiO2片晶、TiO2片晶、石墨片晶、合成的无载体的片晶、BiOCl或其它的相当材料。
基材的尺寸本身并不关键且可与相应应用场合相配。一般来说,片晶状基材的厚度为0.05-5μm,尤其是0.1-4.5μm。在两个其它区域的大小通常为1-250μm,优选2-200μm,尤其是5-60μm。基材上的各个层厚对颜料的光学性能是重要的。层(B)尤其明显影响颜色性能。层(B)与层(A)和(C)相比应该较薄。层(A)或(C)和(B)之间的比率优选为2∶1-5∶1。如果层(B)低于100纳米,色调对视角的依赖性下降使得仅可看见本发明颜料的干涉颜色,即,没有观察到在许多强干涉颜色之间的角度依赖性随角异色。
对于高颜色强度的颜料,各个层厚必须相互间精确调节。
本发明的干涉颜料具有交替的高折射指数层(A)或(C)和低折射指数层(B)。高折射指数层(A)或(C)的折射指数层n>1.8,优选n≥2.0。
层(A)优选由TiO2,ZrO2,SnO2,ZnO,BiOCl,Ce2O3,Fe2O3,Fe3O4,Cr2O3,Ti低氧化物(氧化态小于4至2的部分还原的TiO2,如低氧化物Ti3O5,Ti2O3直至TiO),氧氮化钛和氮化钛,CoO,Co3O4,VO2,V2O3,NiO,CoAl2O4,BiVO4,Ce2S3,MoS2或其混合物或组合组成,如果需要,氧化物混合物也可为还原形式。层(A)特别优选为无色层,尤其是TiO2层。此时的TiO2可以是金红石或锐钛矿型,优选金红石。
层(A)的厚度为20-500nm,优选30nm-400nm和尤其是40-350nm。
适用于涂层(B)的无色低折射指数材料优选为金属氧化物或相应的水合氧化物,例如SiO2,Al2O3,AlO(OH),B2O3,MgF2,MgSiO3或所述金属氧化物的混合物。层(B)优选由SiO2,MgF2或Al2O3或其混合物组成。
对于本发明颜料的光学性能,层(B)非常薄很有利。层(B)的厚度为10-100nm,优选10-90nm和尤其是20-80nm。
层(C)优选由TiO2,ZrO2,ZnO,SnO2,Ce2O3,BiOCl或其混合物或组合组成。层(C)特别优选为TiO2层。此时的TiO2可以是金红石或锐钛矿型,优选金红石。
层(C)的厚度为20-500nm,优选30-400nm和尤其是40-350nm。
层(D)由粒径为1-500nm,优选2-400nm,尤其是3-300nm的吸收性颜料颗粒组成。合适的颜料颗粒是有机和无机有色颜料,普鲁士蓝,钒酸铋,针铁矿和磁铁矿。合适的无机有色颜料尤其是赤铁矿,氧化铬和氢氧化铬,铝酸钴,群青,铬/铁混合氧化物,尖晶石,如,Tenards蓝,硫化或硒化镉,铬酸盐颜料和炭黑。在合适的有机有色颜料中,特别应该提及喹吖啶酮,苯并咪唑酮,酞菁铜,偶氮颜料,阴丹士林,1,4-二酮吡咯并吡咯,萘环酮,二苯并[cd,jk]芘-5,10-二酮,酞菁,蒽醌,靛蓝,硫靛及其衍生物、和胭脂红。
层(D)尤其由普鲁士蓝,磁铁矿,胭脂红和/或硫靛组成。
层(D)中的有色颜料的重量比例为基于总颜料的0.1-50%重量,优选0.5-30%重量和尤其是1-20%重量。层(D)的厚度为1-500nm,优选3-400nm和尤其是5-300nm。
用高折射指数层(A),低折射指数层(B),另一高折射指数层(C)和吸收层(D)涂覆的基材导致有色颜料的形成,其颜色、光泽和遮盖力可在宽限度内变化。
特别优选的有色颜料具有以下层序:
基材+TiO2(A)+SiO2(B)+TiO2(C)+普鲁士蓝(D)
基材+TiO2(A)+SiO2(B)+TiO2(C)+磁铁矿(D)
基材+TiO2(A)+SiO2(B)+TiO2(C)+硫靛(D)
基材+TiO2(A)+SiO2(B)+TiO2(C)+胭脂红(D)
基材+Fe2O3(A)+SiO2(B)+TiO2(C)+普鲁士蓝(D)
基材+TiO2(A)+SiO2(B)+TiO2(C)+铝酸钴(D)
本发明颜料容易通过在细分的片晶状基材上形成具有精确厚度的高和低折射指数干涉层和光滑表面而制成。
金属氧化物层优选通过湿化学法施用,可以使用开发用于生产珠光颜料的湿化学涂布法。这种方法描述于,例如DE1467468,DE1959988,DE2009566,DE2214545,DE2215191,DE2244298,DE2313331,DE2522572,DE3137808,DE3137809,DE3151343,DE3151354,DE3151355,DE3211602,DE3235017或其它专利文件以及其它本领域熟练技术人员已知的出版物。
在湿涂的情况下,将基材颗粒悬浮在水中,然后将一种或多种可水解金属盐在适合水解的pH下加入,以此选择后者使得金属氧化物或金属氧化物水合物直接沉淀到小片上而不发生二次沉淀。pH通常通过同时计量加入碱或酸而保持恒定。将颜料随后分离出,洗涤并干燥,然后视需要点燃,点燃温度可根据每次的涂层进行优化。一般来说,点燃温度为250-1000℃,优选350-900℃。如果需要,可在施用单个涂层之后将颜料分离出,干燥并视需要点燃,然后再悬浮以沉淀其它层。
涂布也可在流化床反应器中通过气相涂布进行,例如可相应地使用在EP0045851和EP0106235中提出的用于生产珠光颜料的工艺。
Ti低氧化物层可例如通过使用氨、氢或烃和烃/氨混合物还原TiO2层而制成,例如描述于EP-A-0332071,DE1951696.8和DE1951697.7。
颜料的色调可通过选择不同的覆盖量或由其得到的层而在宽限度内变化。某些色调的细调可在纯数量选择之外通过在视觉或测量技术控制下接近所需颜色而实现。
为了增加光、水和气候稳定性,通常可建议根据应用领域将成品颜料进行后涂覆或后处理。合适的后涂覆或后处理是,例如,描述于德国专利2215191,DE-A3151354,DE-A3235017,DE-A3334598,DE4030727Al,EP0649886A2,WO97/29059,WO99/57204,US5,759,255的方法。这种后涂覆(层E)进一步增加了颜料的化学稳定性或简化了颜料的处理,尤其是加入各种介质中。
本发明颜料可与优选来自油漆、涂料和印刷油墨领域的大量颜色体系相容。为了生产印刷油墨,大量粘结剂,尤其是水溶性级粘结剂是合适的,例如由BASF,Marabu,Pr_ll,Sericol,Hartmann,Gebr.Schmidt,Sicpa,Aarberg,Siegberg,GSB-WahI,Follmann,Ruco orCoates Screen INKS GmbH感光。印刷油墨可以是水基的或溶剂基的。该颜料还适用于纸和塑料的激光标记、以及用于农业领域,例如用于温室覆盖,和例如用于遮篷的着色。
毋庸置疑,对于各种场合,该多层颜料也可有利地以与有机染料、有机颜料或其它颜料,例如透明和遮盖性白色、彩色和黑色颜料、以及与片晶状氧化铁、有机颜料、全息颜料、LCP(液晶聚合物)和基于金属氧化物涂覆云母和SiO2片的常规透明、彩色和黑色光泽颜料、等的混合物形式使用。该多层颜料可与市售颜料和填料以任何比率混合。
本发明颜料进一步适用于生产可流动的颜料制剂和干制剂。颜料制剂和干制剂的区别在于,它包含一种或多种本发明颜料、粘结剂和可有可无的一种或多种添加剂。
本发明因此还涉及该颜料在配方如油漆、印刷油墨、涂料、塑料、陶瓷材料、玻璃中,在化妆品配方中,用于激光标记和用于生产颜料制剂和干制剂的应用。
以下实施例用于更详细说明本发明而非进行限定。
实施例
实施例1
步骤1.1
将100克粒径为10-60μm的云母悬浮在2升软化水中并在剧烈搅拌下加热至80℃。将270毫升TiCl4溶液(400克TiCl4/升)在pH=2.2下计量到该悬浮液中。该pH随后使用氢氧化钠溶液(32%)调节至7.5,然后在该pH下计量加入222毫升钠水玻璃溶液(13.5% SiO2)。在该加料过程中,pH使用氢氯酸(10%)保持恒定。随后在pH2.2下计量加入270毫升TiCl4溶液(400克TiCl4/升)。在TiCl4溶液的加料过程中,pH分别使用NaOH溶液(32%)保持恒定。对于处理,将颜料过滤出,用软化水洗涤,在110℃下干燥并在850℃下点燃30分钟。
步骤1.2(用普鲁士蓝覆盖)
将130克来自步骤1.1的干涉红色颜料悬浮在2升软化水中并在剧烈搅拌下加热至70℃。在该温度下,使用硫酸(10%)将pH调节至pH7.0。在该pH下,计量加入由2.6克FeSO4×7H2O,0.06克硫酸(约97%)和65克软化水组成的溶液。在该加料过程中,pH使用氢氧化铵溶液(10%)保持恒定。随后在约70分钟内计量加入3.64克K4[Fe(CN)6]×3H2O在195克软化水中的溶液,然后将该混合物再搅拌30分钟。在整个反应过程中,将空气(4-6升/小时)吹入该悬浮液。颜料在吸滤器上过滤出,用软化水洗涤,在100℃下干燥12小时并筛分(网眼宽度100μm),得到具有强红色珠光的蓝色颜料粉末。
实施例2
步骤2.1
将100克粒径为10-60μm的云母悬浮在2升软化水中并在剧烈搅拌下加热至80℃。将200毫升TiCl4溶液(400克TiCl4/升)在pH=2.2下计量到该悬浮液中。该pH随后使用氢氧化钠溶液(32%)调节至7.5,然后在该pH下计量加入212毫升钠水玻璃溶液(13.5% SiO2)。在该加料过程中,pH使用氢氯酸(10%)保持恒定。随后在pH2.2下计量加入220毫升TiCl4溶液(400克TiCl4/升)。在TiCl4溶液的加料过程中,pH分别使用NaOH溶液(32%)保持恒定。对于处理,将颜料过滤出,用软化水洗涤,在110℃下干燥并在850℃下点燃30分钟。
步骤2.2(用普鲁士蓝覆盖)
将130克来自步骤2.1的干涉金色颜料悬浮在2升软化水中并在剧烈搅拌下加热至70℃。在该温度下,使用硫酸(10%)将pH调节至pH7.0。在该pH下,计量加入由2.6克FeSO4×7H2O,0.06克硫酸(约97%)和65克软化水组成的溶液。在该加料过程中,pH使用氢氧化铵溶液(10%)保持恒定。随后在约70分钟内计量加入3.64克K4[Fe(CN)6]×3H2O在195克软化水中的溶液,然后将该混合物再搅拌30分钟。在整个反应过程中,将空气(4-6升/小时)吹入该悬浮液。颜料在吸滤器上过滤出,用软化水洗涤,在100℃下干燥12小时并筛分(网眼宽度100μm),得到具有强金色珠光的蓝色颜料粉末。
实施例3
步骤3.1
将100克粒径为10-60μm的云母悬浮在2升软化水中并在剧烈搅拌下加热至80℃。将300毫升TiCl4溶液(400克TiCl4/升)在pH=2.2下计量到该悬浮液中。该pH随后使用氢氧化钠溶液(32%)调节至7.5,然后在该pH下计量加入222毫升钠水玻璃溶液(13.5% SiO2)。在该加料过程中,pH使用氢氯酸(10%)保持恒定。随后在pH2.2下计量加入300毫升TiCl4溶液(400克TiCl4/升)。在TiCl4溶液的加料过程中,pH分别使用NaOH溶液(32%)保持恒定。对于处理,将颜料过滤出,用软化水洗涤,在110℃下干燥并在850℃下点燃30分钟。
步骤3.2(用普鲁士蓝覆盖)
将130克来自步骤3.1的干涉紫色颜料悬浮在2升软化水中并在剧烈搅拌下加热至70℃。在该温度下,使用硫酸(10%)将pH调节至pH7.0。在该pH下,在45分钟内计量加入由2.6克FeSO4×7H2O,0.06克硫酸(约97%)和65克软化水组成的溶液。在该加料过程中,pH使用氢氧化铵溶液(10%)保持恒定。随后在约70分钟内计量加入3.64克K4[Fe(CN)6]×3H2O在195克软化水中的溶液,然后将该混合物再搅拌30分钟。在整个反应过程中,将空气(4-6升/小时)吹入该悬浮液。颜料在吸滤器上过滤出,用水洗涤,在100℃下干燥12小时并筛分(网眼宽度100μm),得到具有紫色珠光的蓝色颜料粉末。
实施例4(用普鲁士蓝覆盖)
将130克来自实施例1/步骤1.1的干涉紫色颜料悬浮在2升软化水中并在剧烈搅拌下加热至70℃。在该温度下,使用硫酸(10%)将pH调节至pH7.0。在该pH下,在6小时内计量加入由31.2克FeSO4×7H2O,0.8克硫酸(约97%)和780克软化水组成的溶液。在该加料过程中,pH使用氢氧化铵溶液(10%)保持恒定。随后在约70分钟内计量加入43.7克K4[Fe(CN)6]×3H2O在2.3升软化水中的溶液,然后将该混合物再搅拌30分钟。在整个反应过程中,将空气(4-6升/小时)吹入该悬浮液。颜料在吸滤器上过滤出,用水洗涤,在100℃下干燥12小时并筛分(网眼宽度100μm),得到具有紫色珠光的深蓝色颜料粉末。
实施例5(用磁铁矿覆盖)
将130克来自实施例2/步骤2.1的金色干涉颜料悬浮在2升软化水中并加热至75℃。在用氢氧化钠溶液(32%)将pH调节至pH8.0之后,计量加入18克FeSO4×7H2O和3.0克KNO3以及1毫升硫酸(20%)在50毫升软化水中的溶液。在该加料过程中,将氮气恒定通入该悬浮液(130升/小时),并使用氢氧化钠溶液(32%)将pH保持在pH=8.0。将产物过滤出,用水洗涤,在110℃下干燥4小时并筛分(网眼宽度100μm),得到具有金色珠光的灰色颜料粉末。
应用实施例
实施例A:指甲漆
2.00%的来自实施例2的颜料(1)
98.00%的触变指甲漆基料1348(甲苯、乙酸乙酯、乙酸丁酯、硝基纤维素、甲苯磺酰基酰胺/-甲醛树脂、邻苯二甲酸二丁酯、异丙醇、十八烷鎓(stearalkonium)水辉石、樟脑、丙烯酸酯共聚物、二苯酮-1)(2)
供料来源:
(1)Merck KGaA
(2)国际漆S.A.
实施例B:眼影相A30.00% 来自实施例2的颜料(1)49.50% 滑石(1)7.50% 马铃薯淀粉(马铃薯)(2)2.50% 硬脂酸镁(1)相B9.14% 硬脂酸异丙醇酯(3)0.53% 肉豆蔻酸鲸蜡基酯(1)0.53% ewalin 1751(矿脂)(4)0.20% 香料Elegance#79228 D MF(香料)(5)0.10% 4-羟基苯甲酸丙酯(对羟基苯甲酸丙酯)(1)
将相A的组分均匀混合。将熔融相B随后在搅拌下加入粉末混合物中。粉末在40-50巴下压制。
供料来源:
(1)Merck KGaA
(2)Südst_rke GmbH
(3)Cognis GmbH
(4)H.Erhard Wagner GmbH
(5)Haarmann&Reimer GmbH
实施例C:唇膏相A15.00% 来自实施例2的颜料(1)相B8.75% 蜂蜡白(白蜂蜡)(1)5.25% paracera C 44(copernicia cerifera(巴西棕榈
蜡,地蜡)(2)3.50% 羊毛脂(羊毛脂)(3)5.60% 肉豆蔻酸异丙醇酯(香料)(4)2.10% 石蜡粘稠物(液体石蜡(矿物油))(1)0.05% Oxynex_K液体(PEG-8,生育酚、肉豆蔻酸抗坏血
基酯、抗坏血酸、柠檬酸)(1)0.10% 4-羟基苯甲酸丙酯(对羟基苯甲酸丙酯)(1)59.45% 蓖麻油(蓖麻)(3)相C0.20% 香料Tendresse# 75418C(香料)(5)
将相B的组分加热至75℃并熔化。加入相A的颜料,然后将所有物质充分搅拌。该唇膏组合物随后与来自相C的香料在一个受热至65℃的铸塑装置中搅拌15分钟。将该匀质熔体倒入预热至55℃的铸塑模具中。该模具随后冷却,并将铸塑物在冷却时取出。
供料来源:
(1)Merck KGaA
(2)Paramelt
(3)Henry Lamotte GmbH
(4)Cognis GmbH
(5)Haarmann & Reimer GmbH
Claims (11)
1.基于多层涂覆的片晶状基材的有色颜料,其特征在于,它包含:
(A)折射指数n>1.8且层厚为20-500nm的涂层,
(B)折射指数n≤1.8且层厚为10-100nm的无色涂层,
(C)折射指数n>1.8且层厚为20-500nm的无色涂层,
(D)粒径为1-500nm的吸收性颜料颗粒的覆盖物,和
可有可无的
(E)外保护层。
2.根据权利要求1的有色颜料,其特征在于,所述片晶状基材是天然和/或合成云母、玻璃片晶、Al2O3片晶、SiO2片晶、或TiO2片晶。
3.根据权利要求1或2的有色颜料,其特征在于,层(A)由TiO2、ZrO2、ZnO或BiOCl组成。
4.根据权利要求1-3之一的有色颜料,其特征在于,层(B)由SiO2、MgF2或Al2O3、或其混合物组成。
5.根据权利要求1-4之一的有色颜料,其特征在于,所述吸收性颜料颗粒是普鲁士蓝、磁铁矿、胭脂红和/或硫靛。
6.根据权利要求1-5之一的有色颜料,其特征在于,层(A)和层(C)具有相同的组成。
7.根据权利要求6的有色颜料,其特征在于,层(A)和层(C)由TiO2组成。
8.用于制备根据权利要求1的有色颜料的方法,其特征在于,片晶状基材的涂覆利用湿化学法通过金属盐在水介质中的水解或通过CVD或PVD法而进行。
9.根据权利要求1的有色颜料在油漆、涂料、印刷油墨、塑料、陶瓷材料、玻璃中、在化妆品配方中、用于激光标记和用于生产颜料制剂和干制剂的用途。
10.包含一种或多种粘结剂、可有可无的一种或多种添加剂和一种或多种根据权利要求1的有色颜料的颜料制剂。
11.干制剂如粒料、粒剂、碎片或团块,包含根据权利要求1的具有高着色强度的干涉颜料。
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DE2001120179 DE10120179A1 (de) | 2001-04-24 | 2001-04-24 | Farbige Pigmente |
DE10120179.6 | 2001-04-24 |
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EP (1) | EP1254928A1 (zh) |
JP (1) | JP2003055575A (zh) |
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- 2001-04-24 DE DE2001120179 patent/DE10120179A1/de not_active Withdrawn
-
2002
- 2002-04-08 EP EP20020007357 patent/EP1254928A1/de not_active Withdrawn
- 2002-04-18 TW TW91107995A patent/TWI303263B/zh active
- 2002-04-23 JP JP2002120302A patent/JP2003055575A/ja active Pending
- 2002-04-23 CN CNB021180954A patent/CN1230473C/zh not_active Expired - Fee Related
- 2002-04-23 KR KR20020022192A patent/KR100864456B1/ko not_active IP Right Cessation
- 2002-04-24 US US10/128,521 patent/US6884289B2/en not_active Expired - Fee Related
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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 |
CN1637079B (zh) * | 2003-10-01 | 2010-05-12 | 默克专利股份有限公司 | 闪光黑色干涉颜料 |
CN101463194A (zh) * | 2007-12-17 | 2009-06-24 | 默克专利股份有限公司 | 填充颜料 |
CN105462296A (zh) * | 2007-12-17 | 2016-04-06 | 默克专利股份有限公司 | 填充颜料 |
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 |
JP2013209511A (ja) * | 2012-03-30 | 2013-10-10 | Dainichiseika Color & Chem Mfg Co Ltd | 紺青組成物 |
CN105813629A (zh) * | 2013-12-13 | 2016-07-27 | Cqv株式会社 | 化妆品用组合物 |
CN108338931A (zh) * | 2018-01-23 | 2018-07-31 | 信利光电股份有限公司 | 一种光学美白活性颗粒及含有该颗粒的化妆品组合物 |
CN113174145A (zh) * | 2020-01-27 | 2021-07-27 | 唯亚威解决方案股份有限公司 | 具有纳米颗粒涂层的薄膜干涉颜料 |
Also Published As
Publication number | Publication date |
---|---|
CN1230473C (zh) | 2005-12-07 |
KR100864456B1 (ko) | 2008-10-22 |
EP1254928A1 (de) | 2002-11-06 |
KR20020082776A (ko) | 2002-10-31 |
US6884289B2 (en) | 2005-04-26 |
US20020192448A1 (en) | 2002-12-19 |
TWI303263B (en) | 2008-11-21 |
JP2003055575A (ja) | 2003-02-26 |
DE10120179A1 (de) | 2002-10-31 |
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