CN1237603A - 颜料混合物 - Google Patents

颜料混合物 Download PDF

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CN1237603A
CN1237603A CN99107079A CN99107079A CN1237603A CN 1237603 A CN1237603 A CN 1237603A CN 99107079 A CN99107079 A CN 99107079A CN 99107079 A CN99107079 A CN 99107079A CN 1237603 A CN1237603 A CN 1237603A
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S·舒恩
R·沃特
N·舒勒
K·奥斯特里德
U·默里尔
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Merck Patent GmbH
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Abstract

本发明涉及含有至少两种组分的颜料混合物，组分A是涂敷有一种或多种金属氧化物和/或金属的SiO2薄片，组分B是片状、针状或球状的着色剂或填料，还涉及它们在清漆、油漆、印刷油墨、塑料、粉末涂敷材料和化妆品制剂中的用途。

Description

颜料混合物
本发明涉及颜料混合物，它们含有至少两种组分，组分A是涂敷有一种或多种金属氧化物和/或金属的SiO2薄片，组分B是片状、针状或球状的着色剂或填料，还涉及它们在清漆、油漆、印刷油墨、塑料、粉末涂敷材料和化妆品制剂中的用途。
使用片状颜料很难同时满意地实现遮盖力和光泽度。例如，涂敷有二种或多种金属氧化物薄层的二氧化硅薄片或云母薄片的特点是具有干涉色和高光泽，但同时因其透明基质，还具有高度透明的特点，因而其遮盖力较差。
DE-A-4240511公开了一种由光干涉颜料和片状彩色颜料组成的颜料混合物。该光干涉颜料包含涂敷金属氧化物的云母薄片或二氧化硅薄片，该彩色颜料可为着色的二氧化硅薄片。该颜料混合物可引入到涂布材料、印刷油墨或塑料中。
本发明的目的是提供一种颜料混合物，其特点是具有较高遮盖力，并很有助于混入其所应用的相应体系中，并同时基本消除了体系中颜料/着色剂的分离。
令人惊奇地发现了一种克服了上述缺陷的颜料混合物。本发明的颜料混合物由至少两种组分组成，组分A是涂敷有一种或多种金属氧化物和/或金属的SiO2薄片，组分B是片状、针状或球状的着色剂或填料。通过将着色剂混入涂敷的二氧化硅薄片中，有可能使采用它们的体系具有多重随角异色，彩色效果得以加强，并获得新彩色效果。
因此，本发明提供的颜料混合物由至少两种组分组成，组分A是涂敷有一种或多种金属氧化物和/或金属的SiO2薄片，组分B是片状、针状或球状的着色剂或填料。
本发明还提供包含本发明颜料混合物的制剂，例如油漆、清漆、印刷油墨、塑料、粉末涂敷材料和化妆品制剂。
涂敷的二氧化硅薄片可与着色剂以任何比例混合。组分A与组分B之比优选在1∶10～10∶1，尤其是1∶2～2∶1。
按照WO93/08237，在连续传送带上生产的SiO2薄片基于片状、透明的着色或未着色的基体，其厚度一般为0.1-5微米，优选0.2-2.0微米。两个其它方向的尺寸一般为1-250微米，优选2-100微米，更优选地为5-40微米。所述SiO2薄片上涂敷有一层或多层金属氧化物层和/或金属层。合适的金属氧化物或金属氧化物的混合物的实例是二氧化钛、氧化锆、氧化锌、氧化铁和/或氧化铬，优选使用二氧化钛和/或氧化铁。涂敷SiO2薄片的方法例如可按WO93/08237(湿化学涂敷法)或DE-A19614637(CVD法)等上述方法进行。
可使用半透明的金属层代替金属氧化物外层。这种金属的合适实例是如Cr、Ti、Mo、W、Al、Cu、Ag、Au和Ni。优选的颜料具有下列的层结构：SiO2薄片+金属+SiO2+金属氧化物。
为了产生特殊的着色效果，可另外向高折射率或低折射率的金属氧化物层中掺入纳米级的细颗粒。合适颗粒的实例是极细的TiO2或极细的碳(炭黑)，具有的颗粒大小为10-250纳米。借助于这类颗粒的光散射性，可对光泽和遮盖力施加可控的作用。优选地，SiO2薄片涂敷有一种或多种金属氧化物。
适于用作本发明颜料混合物的组分B的着色剂均为熟练技术人员熟知的针状和球状着色剂，其颗粒尺寸为0.001～10微米，优选0.01～1微米。本发明的颜料混合物优选包含作为着色剂的吸收材料和填料。
球状着色剂尤其包括二氧化钛、着色二氧化硅、硫酸钙、各种氧化铁、氧化铬、炭黑、有机彩色颜料例如，蒽醌、喹吖啶酮、二酮吡咯并吡咯、酞菁、偶氮和异二氢吲哚(isoindoline)颜料。针状颜料优选包含BiOCl、着色玻璃纤维、α-Fe3O4、有机彩色颜料例如偶氮颜料，β-酞菁CI Blue 15.3、Cromophtal Yellow 8GN(Ciba-Geigy)、Irgalith Blue PD56(Ciba-Geigy)、亚甲胺碱铜配合物CI Yellow129、Iegazine Yellow 5GT(Ciba-Geigy)。
化妆品制剂(尤其是修饰性制剂)优选不仅仅包括着色剂和二氧化硅薄片，而且包含另一重要组分的填料(一种或多种)或其混合物，其用量为1-50％，尤其是1-30％，并且特别优选为1-15％。
合适的填料为例如，云母、滑石、二氧化钛和云母、二氧化钛+硫酸钡+云母、云母+氧化硅、氧化硅、氧化硅+二氧化钛+氧化铁、氯氧化铋、氯氧化铋+云母、氯氧化铋+滑石。这些产品可从以下Merck KGaA的商标名获得：Ronasphere、RonasphereLDP、MicronasphereM、Silk Mica、Satin Mica、Naturaleaf Powder、Low LustrePigment、Extender W、Talkum feinst gepulvert(细滑石粉)、Biron、Bital和Mibiron，和尼龙-12(来自Elf Atochem)、尼龙-6(来自Elf Atochem)、氮化硼、Nylon Powder(来自ElfAtochem)、聚酰胺12(来自Kobo)、聚乙烯(来自Kobo)、PTFE(来自presperse)、十二烷酰赖氨酸(lauroyl lysine)(来自Ikeda)、聚甲基丙烯酸甲酯(来自Ikeda)和钙铝硼硅酸盐(来自presperse)。
本发明的颜料混合物简单，易于操作。可通过简单的搅拌将该颜料混合物掺入到使用该颜料的体系中。无需对颜料进行繁琐的研磨和分散。
本发明的颜料混合物可用于着色涂敷材料、印刷油墨、塑料、农用膜、涂敷种子、着色食品、钮状膏剂(button paste)、药剂包衣或化妆品制剂。用于着色的体系中颜料混合物的含量按体系中总固相含量计一般为0.1-70％(重量)，优选0.1-50％(重量)，更优选1.0-10％(重量)。这种含量通常由特定的用途来决定。
塑料中本发明颜料混合物的含量为0.01-50％(重量)，尤其是0.1-7％(重量)时，常常以特定的闪烁效果而引人注目。
用作涂料，尤其是用于汽车罩面漆时，颜料混合物的用量-对3-涂层体系也同样-为0.1-10％(重量)，优选1-3％(重量)。与组分B混合的涂敷SiO2薄片的比例取决于要求的效果。SiO2薄片的用量与组分B之比优选地为1∶4，更优选地为1∶3。
在涂布材料中，本发明的颜料混合物的优点是可采用单层涂布(单涂层体系或双涂层体系中的底层)获得满意的随角异色效果。即使在散射光下该随角异色性也极为显著。与包含云母基光干涉颜料(而不是涂敷的SiO2薄片)的涂层体系相比，含本发明颜料混合物的涂层呈现出更明显的深度效果和闪光效应。
本发明的颜料混合物也可用于装饰和美容修饰。SiO2薄片与组分B尤其是有机和无机的彩色颜料和染料，天然或合成原料例如氧化铬、群青、球状二氧化硅或二氧化钛颜料，其用量和混合比例取决于使用它们的介质和要获得的效果。SiO2薄片可以以任何比例与其它组分混合，优选的比例为1∶10～10∶1。使用浓度的范围从香波的0.01％(重量)到压实粉的70％(重量)。在SiO2薄片与球状填料如SiO2的混合物的情况下，其在配方中的浓度可为0.01～70％(重量)。化妆品，例如指甲油、唇膏、压实粉、香波、松散粉和凝胶在特殊的光泽效果和/或彩色效果方面是很著名的。采用本发明的颜料混合物，与常规的指甲油相比，可以显著提高指甲油的闪烁效果。此外，本发明的颜料混合物可用于洗浴产品、牙膏中，并用于改良食品，例如作为原料着色剂或用作涂层。
在对用于例如油漆和凹版印刷、胶印或丝网印刷的油墨的粘合剂进行着色时，或用作印刷油墨的前体时，已经发现，具有例如高度着色的膏剂、颗粒、小球等形状，尤其是由球状着色剂涂敷的SiO2薄片组成的颜料混合物特别适合，其中所述球状着色剂例如是二氧化钛、炭黑、氧化铬、氧化铁和有机彩色颜料。该颜料混合物混入印刷油墨的量通常为2-35％(重量)、优选5-25％(重量)、尤其是8-20％(重量)。胶印油墨可包含高达40％(重量)或更多的该颜料混合物。除粘合剂和添加剂之外，例如是颗粒、小球、团块等形状的印刷油墨前体包含最多为95％的本发明的颜料混合物。组分A与组分B的混合比例优选为1∶10～10∶1。含本发明颜料混合物的印刷油墨由于其具有良好的粘度值而呈现出更纯的色彩并且其印刷适应性得以改善。
本发明也提供了含本发明颜料混合物的配方。
下面的实施例旨在用于说明本发明，而不是对其进行限制。
                        实施例实施例1印刷油墨在600rpm的搅拌下，将颜料混入含溶剂的粘合剂中，随后将印刷油墨刮涂在黑白卡片上。油墨1：88.0克Gebr.Schmidt 95MB 011TW10.0克粒径5～40微米的氧化铁涂敷的二氧化硅薄片。2.0克Gebr.Schmidt 95MB 022-TW(Green)油墨2：对照88.0克Gebr.Schmidt 95MB 011TW10.0克粒径10～60微米的氧化铁涂敷的云母。2.0克Gebr.Schmidt 95MB 022-TW(Green)就视觉效果而言，采用油墨1的彩色卡比采用对照油墨2的彩色卡呈现显著优越的随角异色性。实施例2-汽车罩面漆2.0克    涂敷Fe2O3的SiO2薄片，颗粒大小为5-40微米1.5克    Heliogen Blue L 69300.2克    Hostaperm Green 8G0.05克   颜料等级炭黑FW20066.6克   MP体系(FK=19％)底涂层(A4)29.65克  稀释混合物获得的色调具有非常显著的从蓝至绿随角异色性和金色明亮部分，并具有甚至向暗紫色转变的能力。实施例3-塑料聚乙烯塑料PP Stamylan PPH10(来自DSM)和聚苯乙烯143E(来自BASF)的颗粒以如下比例分别混合：a)1％颗粒大小为5-40微米的涂敷Fe2O3的SiO2薄片b)1％颗粒大小为5-40微米的涂敷Fe2O3的SiO2薄片和0.1％PV
Fast Blue B2G01(来自Clariant的Pigment Blue 15.3)
的混合物c)1％颗粒大小为10-60微米的涂敷Fe2O3的云母d)1％颗粒大小为10-60微米的涂敷Fe2O3的云母和0.1％PV
Fast Blue B2G01(来自Clariant的Pigment Blue 15.3)
的混合物随后在注模机上处理着色的颗粒，以形成小的阶形板。这两种塑料的差别很小，因此下表中只给出对两种材料有效的一个定性的说明值：
实验3a 实验3b 实验3c 实验3d
近0°镜面角的颜色 红相的 红相-灰 黄相的 绿相的
近80°镜面角的颜色 黄相的棕相的 黄-绿 红相的 蓝-绿
每种情况中，蓝颜料与一种光泽颜料(SiO2或云母基的)的组合很好地突出了两种光泽颜料的随角异色性的差别之处。实施例4：-眼影A相5.00％   Ronasphere(来自Merck KGaA的二氧化硅)25.00％  二氧化钛涂敷的二氧化硅薄片，颗粒大小为5-40微米
     (来自Merck KGaA的二氧化硅)5.00％   CI Pigment Green 18(CI77289)47.42％  滑石7.18％   马铃薯(Solanum Tuberosum)(马铃薯淀粉)2.40％   硬脂酸镁B相6.96％   硬脂酸异丙酯0.40％   鲸蜡油十六酸酯(Cetyl palmitate)0.40％   矿脂(Petrolatum)0.08％   防腐剂A相的组分混合形成预混物。然后融化的B相在搅拌条件下滴加到粉末混合物中。在40-50巴压力下压制粉末。实施例5：-唇膏A相8.25％   白蜂蜡(Cera alba)4.95％   纯地蜡(Ceresin),Copernica Cerifera3.30％   精制羊毛脂油(Lanolin oil)5.28％   肉豆蔻酸异丙酯1.98％   矿物油0.03％   生育酚，抗坏血酸棕榈酸酯，抗坏血酸，柠檬酸，聚乙
     二醇-80.06％   防腐剂0.50％   香剂(Aroma)1.00％   利索尔玉红(Lithol rubine)BK，C.I.Pigment Red
     57∶1(CI15850)添加至   蓖麻(Ricinus Communis)(在蓖麻油中为20％)100.00％B相2.00％   Ronasphere(来自Merck KGaA的二氧化硅)15.00％  氧化铁涂敷的二氧化硅薄片，颗粒大小为5-40微米
     (来自Merck KGaA的二氧化硅)A相的组分加热至75℃并融化。然后添加B相的颜料，并使整个配料充分搅拌。然后在已预热到65℃的浇铸装置中搅拌唇膏组合物15分钟。然后将均匀的熔体注入已预热到65℃的铸模中。然后冷却铸模并取出冷的模制品。

Claims (6)

1．颜料混合物，至少由两种组分组成，组分A是涂敷有一种或多种金属氧化物和/或金属的SiO2薄片，组分B是片状、针状或球状的着色剂或填料。
2．根据权利要求1的颜料混合物，其特征在于：组分A含有涂敷TiO2和/或Fe2O3的SiO2薄片。
3．根据权利要求1或2的颜料混合物，其特征在于：组分B包括着色玻璃颗粒，炭黑，二氧化硅，有机彩色颜料，和/或无机彩色颜料。
4．根据权利要求1-3任一项的颜料混合物，其特征在于：组分A与组分B的混合比为10∶1-1∶10。
5．权利要求1颜料混合物的用途，用于清漆、油漆、尤其是汽车罩面漆、印刷油墨、塑料、粉末涂敷材料、用于着色种子、化妆品制剂和用于改良食品。
6．配方，含有权利要求1的颜料混合物。
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