CN101460572A - 颜料混合物及其在化妆品中以及在食品和药物方面的用途 - Google Patents
颜料混合物及其在化妆品中以及在食品和药物方面的用途 Download PDFInfo
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- CN101460572A CN101460572A CNA2007800204261A CN200780020426A CN101460572A CN 101460572 A CN101460572 A CN 101460572A CN A2007800204261 A CNA2007800204261 A CN A2007800204261A CN 200780020426 A CN200780020426 A CN 200780020426A CN 101460572 A CN101460572 A CN 101460572A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
本发明涉及包含至少两种组分A和B的颜料混合物,本发明的颜料组合物的特征在于组分A作为效果颜料具体化而组分B作为着色剂具体化。还公开了所述颜料混合物在化妆品配制剂中的用途和用于对食品和药物产品着色的用途。
Description
本发明涉及基于薄片状底物的效果颜料,而且涉及它们在化妆品配制剂中以及食品和药物方面在与其它着色剂和/或填料的混合物中的用途。
基于薄片状底物的金色颜料是重要的,尤其是在印刷应用和化妆品中。然而,现有技术已知的金色颜料经常显示出它们没有足够的浓色和亮度以及因此无法在各种应用介质中产生真正金色的影像的缺点。
本发明的目的是寻找用于化妆品的金色颜料(gold pigment),其突出之处在于更浓的金色光泽而且没有上述缺点。本发明的另一目的是寻找其中以特别有利的方式维持或者以光学上有吸引力的方式改进金色光泽的配制剂。
令人惊讶地,现已发现包含与其它着色剂和/或赋予非常柔软的皮肤触感的填料组合的、基于多层涂布的薄片状底物的效果颜料、优选金色颜料的颜料混合物是光稳定的,不会渗出/迁移,无毒而且具有高遮盖力。所述颜料的突出之处在于它们具有交替的高折射率和低折射率层而且包含至少一个由摩尔比为1:0.5-1:2.0的TiO2和Fe2O3的混合物组成的高折射率涂层。
基于多层涂布的薄片状底物的金色颜料例如公开在WO 01/30921中。
与有机和无机填料和/或与薄片状、针形、球形或结晶着色剂组合的具有金色主色的多层颜料的应用使得能够提高彩色效果而且实现新的彩色效果。此外,颜料混合物的突出之处在于它们的高光泽和很好的皮肤触感。
本发明因此涉及由至少两种组分A和B组成的颜料混合物,其中
组分A包含基于多层涂布的薄片状底物的效果颜料,其具有包含如下的层序列
(A)由摩尔比为1:0.5-1:2.0的TiO2和Fe2O3的混合物以及任选的基于层(A)<20wt%量的一种或多种金属氧化物组成的高折射率涂层,
(B)折射率n<1.8的无色涂层,
(C)折射率n>1.8的无色涂层,
(D)折射率n>1.8的吸收性涂层
和任选地
(E)外保护层,
且
组分B包含选自由片状、针形、球形或不规则形状的颗粒组成的无机颜料、有机颜料、染料、着色天然果实和/或植物提取物的着色剂和/或填料。
颜料混合物的突出的色彩参数是浓的、优选纯金色的具有最佳的光泽效果和/或丝质效果(silk effect)的颜色。组分A的颜料优选具有的Lab值为L=60至85;a=-15至25;b=22至45(测量方法:Phyma,黑色背景的22.5°/22.5°)。
本发明同样涉及化妆品配制剂,例如包含根据本发明的颜料混合物的化装品、粉饼、散粉(loose powder)、唇膏、化妆水、乳液等。该颜料混合物另外适合对食品和包括OTC制剂在内的药物产品进行着色,以及适合对食品和包括OTC制剂在内的药物产品的涂层、例如片剂、糖衣剂、明胶胶囊等的医用涂层的着色。
组分A的效果颜料可以以任何比率与着色剂或填料混合。组分A与组分B的混合比率优选为99:1-50:50,特别是95:5-70:30,特别优选70:30-50:50。如果组分B包含填料,组分A:B的比率还可以是99:1-1:99。
优选的组分A的效果颜料具有下列结构:
底物+Fe2O3/TiO2+SiO2+TiO2+Fe2O3/TiO2
底物+Fe2O3/TiO2+SiO2+TiO2+Fe2O3
底物+Fe2O3/TiO2+SiO2+TiO2+SiO2+Fe2O3/TiO2
层(A)至(D)或(A)至(E)优选直接施涂至底物表面上,即层(A)直接位于底物表面上。
为了改善颜料性能,例如光泽和亮度,可以任选地施涂中间层(ILs),例如,可以将优选具有层厚度为1-100nm、特别是1-80nm和特别优选1-50nm的TiO2层,或者优选具有层厚度为5-100nm的SiO2层施涂至底物上。在该情况下,特别优选包含以下的层结构
底物+(IL)TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3/TiO2
底物+(IL)TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3
本发明同样涉及这些具有中间层的效果颜料以及它们在油漆、涂料、印刷油墨、塑料、在化妆品配制剂和用于对食品和药物产品着色的用途。
适合于组分A的效果颜料的底部底物一方面是不透明的薄片状底物而另一方面是透明的薄片状底物。优选的底物是层状硅酸盐和玻璃薄片。特别合适的是天然和/或合成云母,滑石,高岭土,薄片状氧化铁或氧化铝,玻璃薄片,SiO2薄片,SiOx薄片(0.70≤x≤2.0)、优选SiO2薄片,TiO2薄片,石墨薄片,合成无载体薄片,液晶聚合物(LCPs),全息颜料(holographic pigment),BiOCl薄片,金属薄片、任选钝化的,例如铝薄片、铝青铜、黄铜青铜、锌青铜、钛青铜或其它类似材料的薄片。
底部底物的尺寸本身不是关键的而且可以与具体的应用匹配。通常,薄片状底物的厚度为0.02-5μm,特别是0.05-4.5μm。在另外两个维度上的尺寸通常是1-250μm,优选2-200μm和特别是5-150μm。玻璃薄片优选层厚度为≤1.0μm,特别是≤0.8μm和特别优选≤0.5μm。
效果颜料具有在底物上交替地与无色低折射率涂层(B)组合的高折射率涂层(A),该涂层(A)由TiO2和Fe2O3的混合物、优选以摩尔比为1:1组成。层(A)可以通过本领域技术人员已知的合适措施、例如在温度>800℃下煅烧颜料而转化成假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物。
层(C)优选由TiO2、ZrO2、SnO2、Ce2O3、BiOCl或其混合物或组合组成。在层(C)由TiO2组成的情况下,TiO2优选是金红石型。
适合于层(D)的材料是吸收性材料,例如金属,例如铁、钨、铬、钴、镍、铜、银、金、铝及其合金,金属氧化物,例如CoO、Co3O4、Fe2O3、Fe3O4、假板钛矿、TiO2/Fe2O3混合物、VO2、V2O3,金属硫化物,例如硫化钼、硫化铁、硫化钨、硫化铬、硫化钴、硫化镍和这些硫化物的混合物。吸收层(D)优选是TiO2和Fe2O3的混合物,其中混合比率如同层(A)的情况下可以在宽范围内变化。TiO2与Fe2O3摩尔比优选是1:1。层(D)可以类似于层(A)通过合适措施、例如在温度>800℃下煅烧颜料而转化成假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物。该层(D)的折射率n>1.8,特别是n≥2.0。
可以在层(C)和(D)之间设置另一无色低折射率层(B*),它可以与层(B)相同或不同。
高折射率层(A)优选折射率n>1.8,特别是n≥2.0,而且是TiO2和Fe2O3的混合物,其中混合比率是1:0.5-1:2.0,优选1:0.7-1:1.5,特别是1:1。层(A)优选是浓着色的假板钛矿。层(A)的厚度优选为10-300nm,优选15-250nm和特别是20-200nm。
为了提高层(A)的着色强度,另外可取的是混合一种或多种来自Al2O3、Ce2O3、B2O3、ZrO2、SnO2的氧化物。除了Fe2O3/TiO2混合物之外其它金属氧化物的wt%比例应当不大于20wt%,优选不大于10wt%。
在其中层(D)同样是TiO2/Fe2O3混合物层的情况下,同样可取的是以基于层(D)的不大于20wt%的量添加一种或多种金属氧化物,例如Al2O3、Ce2O3、B2O3、ZrO2、SnO2,以便提高着色强度。
适合于涂层(B)的合适的无色低折射率材料优选是金属氧化物或相应的氧化物水合物,例如SiO2、Al2O3、AlO(OH)、B2O3、MgF2、MgSiO3或所述金属氧化物的混合物。层(B)的厚度是10-600nm,优选20-500nm和特别是20-400nm。
如果层(C)是TiO2层,这优选是金红石型。用于金红石型制备的方法在现有技术中得到描述,例如US 5,433,779、US 4,038,099、US 6,626,989、DE 25 22 572 C2、EP 0 271 767 B1。在TiO2沉淀至层(B)上以前,优选施涂氧化锡薄层(层B*),其充当用于TiO2转化成金红石型的添加剂。
效果颜料可以例如像WO 01/30921中所述那样制备。
用层(A)-(D)涂布底物薄片可以通过湿化学方法和/或通过CVD法进行。在施涂层(A)前,还可以任选地沉积n<1.8的薄介电层。例如在玻璃上的这类涂层可以例如由厚度为5-100nm的SiO2层组成。
优选使用湿化学方法制备效果颜料,可以使用已知的湿化学涂布技术,这些已知的湿化学涂布技术是为了生产珠光颜料而开发的并且例如在下列出版物中得到描述:DE 14 67 648、DE 19 59 988、DE 2009 566、DE 22 14 545、DE 22 15 191、DE 22 44 298、DE 23 13 331、DE 25 22 572、DE 31 37 808、DE 31 37 809、DE 31 51 343、DE 3151 354、DE 31 51 355、DE 32 11 602、DE 32 35 017。
在湿涂布的情况下,底物颗粒悬浮在水中,并且在适于水解的pH下加入一种或多种可水解的金属盐,选择该盐以使得金属氧化物或金属氧化物水合物直接沉淀至薄片上而没有明显的二次沉淀发生。在涂布操作期间,使底物颗粒保持运动以便确保底物颗粒的均匀涂布和将底物完全包封没有留下未遮盖的边缘。通常通过同时计量加入碱和/或酸来使pH保持不变。随后分离出颜料,洗涤并优选在50-180℃干燥以及任选地煅烧,其中必须相对于每种情况下存在的涂层和所用的底物对煅烧温度优化。通常煅烧温度为250-1000℃,优选350-900℃。如果需要,可以在单个涂层的施涂之后分离出颜料,干燥和任选地煅烧,然后再悬浮以便其它层沉淀。
此外,也可以在流化床反应器中通过气相涂布进行涂布,其中例如可以相应地采用EP 0 045 851 A1和EP 0 106 235 A1中为了生产珠光颜料而提出的方法。这里底物必需在涂布操作期间均匀地保持运动以便确保所有颗粒表面的均匀涂布且将底物完全包封没有留下未遮盖的边缘。
组分A的效果颜料还可以具备有机或无机保护层(层E)以便提高光、气候和化学稳定性或者以便提高在各种介质中的相容性。合适的后涂布或后处理为例如硅烷、有机硅、吸附性有机硅、金属皂、氨基酸、卵磷脂、氟组分、聚乙烯、胶原或者在DE 22 15 191、DE 31 51354、DE 32 35 017或DE 33 34 598、EP 06 32 109、US 5,759,255、DE 43 17 019、DE 39 29 423、EP 04 92 223、EP 03 42 533、EP 0268 918、EP 0 141 174、EP 0 764 191、WO 98/13426或EP 0 465 805中所述的方法。该后涂层进一步提高金色颜料的化学和光化学稳定性或简化其处理,特别是掺入各种介质中。为了改善与使用者介质的润湿性、分散性和/或相容性,可以将Al2O3或ZrO2或其混合物或混合相的功能性涂层施涂至颜料表面。此外可能的是有机或利于与硅烷组合的有机/无机后涂层,如描述在下列文献中:EP 0090259、EP 0 634 459、WO 99/57204、WO 96/32446、WO 99/57204、US 5,759,255、US 5,571,851、WO 01/92425或J.J.Ponje é,Philips Technical Review,卷44,第3期,第81页及其后以及P.H.Harding,J.C.Berg,J.AdhesionSci.Technol.,卷11,第4期,第471-493页。另外施涂的物质仅仅构成整个颜料的约0.1-5wt%,优选0.5-3.0wt%。
可以用一锅法直接进行效果颜料在层(D)上的后涂布。然而,也可以首先分离,任选地干燥和煅烧多层颜料,随后施涂后涂层。
除了效果颜料、优选金色颜料(组分A)以外,根据本发明的颜料混合物包含组分B的填料和/或着色剂。
适合作为根据本发明颜料混合物的组分B的是本领域技术人员所有已知的片状、针形、球形和结晶着色剂或填料,特别是颗粒尺寸为0.001-10μm、优选0.01-1μm的那些。着色剂用来指按照DIN标准55944的无机和有机着色剂。在本申请中,着色剂还用来指着色天然果实和植物提取物。
根据本发明的颜料混合物优选包含无机染料和无机颜料作为着色剂,例如无机白色颜料、无机彩色颜料、无机黑色颜料、无机效果颜料。后者当然与组分A的颜料不同。除了无机着色剂以外,有机着色剂,例如有机颜料,例如彩色颜料、黑色颜料、效果颜料,以及无机染料,例如彩色染料、黑色染料也是适合的。合适的填料优选是薄片状或球形材料。
组分B优选包含涂布或未涂布的SiO2珠粒。涂布有一种或多种金属氧化物的SiO2珠粒例如在EP 0 803 550 A2中得到公开。
组分B的着色剂进一步优选是与组分(A)不同的无机效果颜料,例如珠光颜料,包括多层颜料或干涉颜料。所用的珠光颜料是基于薄片状的透明或半透明底物的颜料,所述底物包含例如多层硅酸盐如天然或合成云母、滑石、绢云母、高岭土或其他硅酸盐材料,它们涂布有彩色或无色的金属氧化物,所述金属氧化物例如TiO2、钛的低价氧化物、钛的氮氧化物、Fe2O3、Fe3O4、FeOOH、SnO2、Cr2O3、ZnO、CuO、NiO和其他金属氧化物,它们单独或以混合物形式在单一层或在连续层中。
珠光颜料例如公开于在德国专利和专利申请14 67 468、19 59998、20 09 566、22 14 454、22 15 191、22 44 298、23 13 331、25 22 572、31 37 808、31 37 809、31 51 343、31 51 354、31 51355、32 11 602、32 35 017和P 38 42 330中,以及例如可作为从Merck KGaA,Darmstadt,Germany和/或Rona,USA的商标、、而商购。特别优选的颜料组合物包含TiO2/云母、Fe2O3/云母和/或TiO2/Fe2O3/云母颜料。珠光颜料可以另外在表面上具有柏林蓝或胭脂红(Carmine Red)的层。
进一步优选涂布或未涂布的BiOCl颜料、TiO2-和/或Fe2O3-涂布的SiO2、玻璃或Al2O3薄片。用一种或多种金属氧化物涂布SiO2薄片可以例如像WO 93/08237(湿化学涂布)或DE-A 196 14 637(CVD法)中所述的那样进行。
例如在DE-A 196 18 563、DE-A 196 18 566、DE-A 196 18 569、DE-A 197 07 805、DE-A 197 07 806、DE-A 197 46 067中公开的多层颜料是基于片状、透明、彩色或无色的基质,该基质由云母(合成的或天然的)、SiO2薄片、玻璃薄片、Al2O3薄片、聚合物薄片组成,而且其厚度通常为0.3-5μm,特别是0.4-2.0μm。在另外两个维度上的尺寸通常是1-250μm,优选2-100μm和特别是5-40μm。该多层颜料由涂布有金属氧化物(至少两种)的基质(底物)组成。底物薄片云母、SiO2薄片、玻璃薄片、Al2O3薄片的多层涂布是使得如下进行:即使得形成优选由交替的高折射率和低折射率层组成的层结构。该多层颜料优选含有2、3、4、5、6或7层,特别是3、4或5层。合适的高折射率金属氧化物例如是二氧化钛、氧化锆、氧化锌、铁氧化物、铁/钛氧化物(钛酸铁)和/或铬氧化物,特别是TiO2和/或Fe2O3。所用的低折射率氧化物是SiO2和Al2O3。然而,也可以为此使用MgF2或有机聚合物(例如丙烯酸酯)。底物薄片的涂布可以例如像WO 93/08237(湿化学涂布)或DE-A-196 14 637(CVD法)中所述的那样进行。特别优选的基于云母(天然的或合成的)、玻璃薄片、Al2O3薄片、Fe2O3薄片、SiO2薄片的多层颜料包含层序列TiO2-SiO2-TiO2。TiO2可以是锐钛矿型或金红石型。它优选是金红石的形式。
干涉颜料优选为涂布有彩色或无色金属氧化物的基于云母、玻璃薄片或SiO2薄片的颜料,所述金属氧化物例如TiO2、钛的低价氧化物、钛的氮氧化物、Fe2O3、Fe3O4、SnO2、Cr2O3、ZnO、CuO、NiO和其他金属氧化物,它们单独或以混合物形式在单一层或在连续层中。
合适的薄片状着色剂特别是珠光颜料,尤其是基于只覆盖有一种金属氧化物层的云母、SiO2薄片或Al2O3薄片的珠光颜料,金属-效果颜料(Al薄片、青铜),光学可变颜料(OVPs),液晶聚合物颜料(LCPs)或全息颜料。
球形着色剂特别包括TiO2、彩色SiO2、CaSO4、铁氧化物、铬氧化物、炭黑、有机彩色颜料如蒽醌颜料、喹吖啶酮颜料、二酮吡咯并吡咯颜料、酞菁颜料、偶氮颜料、异吲哚啉颜料。针形颜料优选是BiOCl、彩色玻璃纤维、α-FeOOH、有机彩色颜料如偶氮颜料、β-酞菁CI蓝15.3、Cromophtal黄8GN(Ciba)、Irgalith蓝PD56(Ciba)、偶氮甲碱铜配合物CI黄129、Irgazine黄5GT(Ciba)。
同样可以混合纳米级电介质以便改善皮肤触感。这种混合物的实例为Al2O3、SiO2、ZnO或TiO2,它们通常以0.01-15%的量添加到配制剂中。
根据本发明的颜料混合物简单而易于处理。可以通过简单的拌入将该颜料混合物掺入应用体系中。可以将组分A和B同时、相继或作为混合物添加到应用体系中。颜料的复杂的研磨和分散不是必需的。
根据本发明的颜料混合物可以优选用于着色食品上色,用于食品的涂饰(finishing),例如罩色或作为涂层,用于药物涂层,例如用于糖衣剂和片剂中,或者用于化妆品配制剂,例如唇膏、唇彩、眼线膏、眼影、胭脂、防晒品、晒前和晒后组合物、化妆品、体用化妆水、沐浴凝胶、皂、浴盐、牙膏、发胶、(浓密(volume))睫毛膏、指甲油、粉饼、香波、散粉和凝胶等。
颜料混合物在待着色的应用体系中的浓度基于该体系的全部固体含量计一般是0.01-70wt%,优选0.1-50wt%和特别是1.0-10wt%。它一般取决于具体的应用以及在散粉的情况下可以最高100%。根据本发明的颜料混合物的使用浓度从香波中的0.01wt%延伸到粉饼中的70wt%。在组分A的多层颜料与球形填料例如SiO2的混合物中,在配制剂中浓度可以是0.01-70wt%。化妆品、例如指甲油、唇膏、粉饼、香波、散粉和凝胶的突出之处在于特别引人注意的光泽效果。
根据本发明的颜料混合物可以有利地用于装饰性和护理性化妆品中。组分A的多层颜料的使用浓度以及与组分B、特别是天然或合成来源的有机和无机彩色颜料和染料例如铬氧化物、群青、球形SiO2或TiO2颜料的混合比率取决于应用介质和待达到的效果。
组分A的效果颜料可以进一步与可商购填料混合。可以提及的填料例如是天然和合成云母、玻璃珠粒或玻璃粉末、尼龙粉末、纯的或填充的三聚氰胺树脂、滑石、玻璃、高岭土、铝、镁、钙或锌的氧化物或氢氧化物、BiOCl、硫酸钡、硫酸钙、碳酸钙、碳酸镁、碳、以及这些物质的物理或化学组合。
关于填料的颗粒形状没有限制。根据需要,它可以是例如片状、球形、针形、结晶或无定形。
根据本发明的颜料混合物当然也可以在配制剂中与任意种类的化妆品原料和辅料组合。这些物质尤其包括油、脂肪、蜡、成膜剂、表面活性剂、抗氧化剂例如维生素C或维生素E、稳定剂、气味增强剂、硅油、乳化剂、溶剂例如乙醇或乙酸乙酯或乙酸丁酯、防腐剂和通常决定施涂性能的助剂,例如增稠剂和流变学添加剂,例如膨润土、水辉石、二氧化硅、硅酸钙、明胶、高分子量碳水化合物和/或表面活性助剂等。
包含根据本发明的颜料混合物的配制剂可以属于亲脂性、亲水性或疏水性类型。在具有不连续的水相和非水相的多相配制剂的情况下,根据本发明的颜料混合物在各自情况下可以只存在于两相之一中,或者分布在两相中。
配制剂的pH可以是1-14,优选2-11和特别优选5-8。
根据本发明的颜料混合物在配制剂中的浓度没有限制。它们取决于应用,可以是0.001(洗去型产品,例如沐浴凝胶)-100%(例如特定应用的光泽效果制品)。
根据本发明的颜料混合物还可以另外与化妆品活性化合物组合。合适的活性化合物例如是驱虫剂,无机UV过滤剂(filter)例如TiO2、UV A/BC保护过滤剂(例如OMC、B3、MBC),以及胶囊形式的抗老化活性化合物、维生素及其衍生物(例如维生素A、C、E等)、自晒黑剂(例如DHA、赤藓酮糖及其他)和其它化妆品活性化合物例如红没药醇、LPO、VTA、ectoine、emblica、尿囊素、生物类黄酮及其衍生物。有机UV过滤剂在化妆品配制剂中的掺入量基于整个配制剂通常为0.5-10wt%,优选1-8wt%,无机填料为0.1-30wt%。
根据本发明的组合物可以另外包含其它常用的皮肤保护或皮肤护理活性化合物。这些化合物原则上可以是本领域技术人员已知的任何活性化合物。
特别优选的活性化合物是嘧啶羧酸和/或芳基肟。
在化妆品应用中,特别应当提及将ectoine和ectoine衍生物用于护理老化的、干燥的或受刺激的皮肤的应用。因而,EP-A-0 671 161特别描述将ectoine和hydroxyectoine用于化妆品组合物中,如粉剂、皂、含表面活性剂的清洁产品、唇膏、胭脂、化妆品、护理霜和防晒制剂。根据本发明的化妆品配制剂优选包含基于制剂的0.05-5wt%、特别是0.1-3wt%的ectoine或ectoine衍生物。
可以提及的化妆品配制剂的应用形式例如为:溶液、悬浮液、乳液、PIT乳液、糊剂、软膏、凝胶、霜剂、化妆水、粉剂、皂、含表面活性剂的清洁制剂、油剂、气溶胶和喷雾剂。其它的应用形式的实例为棒、香波和沐浴制剂。可以将任何期望的常规载体、辅料以及需要的话其它活性化合物加入到组合物中。
软膏、糊剂、霜剂和凝胶可以包含常用的载体,例如动物和植物脂肪、蜡、石蜡、淀粉、黄芪胶、纤维素衍生物、聚乙二醇、有机硅、膨润土、二氧化硅、滑石和氧化锌,或这些物质的混合物。
粉剂和喷雾剂可以包含常用的载体例如乳糖、滑石、二氧化硅、氢氧化铝、硅酸钙和聚酰胺粉末或这些物质的混合物。喷雾剂可以另外包含常用推进剂例如氯氟烃、丙烷/丁烷或二甲醚。
溶液和乳液可以包含常用的载体,例如溶剂、增溶剂和乳化剂,例如水、乙醇、异丙醇、碳酸乙酯、乙酸乙酯、苄醇、苯甲酸苄酯、丙二醇、1,3-丁二醇、油、特别是棉籽油、花生油、麦胚芽油、橄榄油、蓖麻油和芝麻油、脂肪酸甘油酯、聚乙二醇和脱水山梨糖醇的脂肪酸酯或这些物质的混合物。
悬浮液可以包含常用的载体,例如液体稀释剂如水、乙醇或丙二醇,悬浮介质例如乙氧基化异硬脂醇、聚氧乙烯山梨糖醇酯和聚氧乙烯脱水山梨糖醇酯、微晶纤维素、偏氢氧化铝、膨润土、琼脂-琼脂和黄芪胶,或这些物质的混合物。
皂可以包含常用的载体,例如脂肪酸的碱金属盐、脂肪酸单酯的盐、脂肪酸蛋白质水解产物、异硫代硫酸盐、羊毛脂、脂肪醇、植物油、植物提取物、甘油、糖,或这些物质的混合物。
含表面活性剂的清洁产品可以包含常用的载体,例如脂肪醇硫酸酯的盐、脂肪醇醚硫酸酯、磺基丁二酸单酯、脂肪酸蛋白质水解产物、异硫代硫酸盐、咪唑啉鎓衍生物、甲基牛磺酸酯、肌氨酸酯、脂肪酸酰胺醚硫酸盐、烷基酰氨基甜菜碱、脂肪醇、脂肪酸甘油酯、脂肪酸二乙醇酰胺、植物和合成油、羊毛脂衍生物、乙氧基化甘油脂肪酸酯或这些物质的混合物。
面部和身体用油可以包含常用的载体,例如合成油如脂肪酸酯、脂肪醇、硅油,天然油例如植物油和油性的植物提取物、石蜡油、羊毛脂油,或这些物质的混合物。
化妆品组合物可以以各种形式存在。因而,它们可以例如是溶液、无水组合物、油包水(W/O)型或水包油(O/W)型的乳液或微乳液、多重乳液例如水包油包水(W/O/W)型的多重乳液、凝胶、固体棒、软膏或气溶胶。还有利的是将ectoine以胶囊形式给予,例如在胶原基质和其它常规的包囊材料例如纤维素胶囊中,包入明胶、蜡基质或酯质体胶囊中。特别是如在DE-A 43 08 282中所述的蜡基质已经证实是有利的。优选乳液。特别优选O/W乳液。乳液、W/O乳液和O/W乳液可用常规方法得到。
其它实施方案是基于天然或合成油以及蜡、羊毛脂、脂肪酸酯、特别是脂肪酸甘油三酸酯的油性化妆水,或者是基于低级醇例如乙醇、或甘油、例如丙二醇和/或多元醇例如甘油以及油、蜡和脂肪酸酯例如脂肪酸甘油三酸酯的油性/醇化妆水。
固体棒由天然或合成的蜡以及油、脂肪醇、脂肪酸、脂肪酸酯、羊毛脂和其它脂族物质组成。
如果将组合物配制成气溶胶,则一般使用通常的推进剂,例如链烷、氟代烷烃和氯氟烃。
化妆品组合物还可以用于保护头发免受光化学损伤以便防止变色、脱色或机械性损害。在这种情况下,合适的配制剂是洗去型香波、化妆水、凝胶或乳液形式,所述组合物在洗发之前或之后、染色或脱色之前或之后或烫发前后应用。也可以选择用于对头发进行定型和处理的化妆水或凝胶形式的组合物,用于染发(brushing)或吹烫的化妆水或凝胶形式的组合物,亮发剂、永久烫发组合物、头发着色剂或脱色剂形式的组合物。具有光保护性能的组合物可以包含助剂,例如表面活性剂、增稠剂、聚合物、软化剂、防腐剂、泡沫稳定剂、电解质、有机溶剂、有机硅衍生物、油、蜡、防油脂剂(antigrease)、使组合物自身或头发着色的染料和/或颜料、或用于头发护理其它常用成分。
通过向有待着色的产品中以0.005-15wt%、优选0.01-100wt%的量添加根据本发明的颜料混合物而着色药物和食物产品,所述根据本发明的混合物优选以期望混合比率包含至少一种金色颜料(组分(A))和来自天然或等同于天然的染料的领域的着色剂(组分(B))。
食品方面认可的天然或等同于天然的染料、有机或无机彩色颜料(组分(B))或着色天然果实和植物提取物的混合使得能够影响产品中的金色颜料的颜色效果而且同时使得能够实现新的虹彩颜色效果。
适合于根据本发明的颜料混合物的天然或等同于天然的染料特别是E 101、E 104、E 110、E 124、E 131、E 132、E 140、E 141、E 151、E 160a。适合于根据本发明的颜料混合物的彩色颜料例如是E 171、E172、E 153。
基于食品或药物产品的除了金色颜料以外的染料比例优选是0.5-25wt%。所用染料同样可以是果实和植物提取物,例如胡萝卜汁、甜菜根汁、接骨木果汁、木槿汁、红辣椒提取物、aronia提取物。
待着色的产品中的所有颜料的总浓度基于该产品应当不超过50wt%。它一般取决于具体应用。
还可以向食品和药物产品中添加各种活性化合物添加剂,例如维生素、酶、痕量元素、蛋白质、碳水化合物、必要的脂肪和/或矿物质,其中活性化合物的总量按该食品或药物产品计应当不超过25wt%。活性化合物或活性化合物混合物的总量基于产品优选为0.01-20wt%。
通过在生产期间或之后、在成形之前或之后(例如在挤出、成丸、膨胀、粒化等期间)直接或者在水和/或有机溶剂的存在下、以期望的混合比率同时地或者连续地将单独或者与辅料、化妆品活性化合物、成分等组合的根据本发明颜料混合物加入到待着色的产品中,从而将产品着色。效果颜料与粉状或松散粉末的混合同样是可以的。
也可以在成形后将根据本发明的颜料混合物涂布到表面上以便着色食品和药物产品。在这种情况下,根据本发明的颜料混合物一般与施涂介质混合且随后用合适的施涂和喷射装置施涂到制品上。该施涂或涂布介质则确保颜料混合物相应附着于制品表面上。或者则相应地得以着色。
在掺入产品基质本身时,根据本发明颜料混合物的用量优选是0.5-40wt%,特别是1-30wt%。在食品和药物产品的表面着色的情况下,在所用着色或涂布溶液的用量范围是0.1-25wt%,特别是1-15wt%。在粉状产品中使用根据本发明的颜料混合物时,用量范围是0.05-50wt%,特别是2-10wt%。
涂布溶液优选包含水或有机溶剂例如乙醇或异丙醇。用于涂布溶液中的成膜剂优选是纤维素衍生物,例如羟丙基甲基纤维素。特别优选包含5-80wt%的合适的有机溶剂而不是水的包含纤维素衍生物的施涂溶液。
与涂布水溶液相比,醇的或者醇-水性的含纤维素施涂溶液具有显著的施涂优点:
-在喷涂过程使用较冷的干燥空气
-用金色颜料将热敏产品、例如含维生素的食品着色很容易进行。
可以提及的适合着色的制品特别是各种食品上的涂层,尤其是着色的糖和紫胶涂层(醇或水性的)、具有油和蜡的涂层、具有阿拉伯树胶的涂层、纤维素物质(例如HPMC=羟丙基甲基纤维素)涂层、具有淀粉和白蛋白衍生物、角叉菜胶和其它适合于涂层的本领域技术人员已知的物质的涂层。这里一般将根据本发明的颜料混合物与施涂介质混合随后用合适的施涂和喷射装置或者手工施涂到食品或药物产品上。该施涂或涂布介质则确保颜料相应附着于该食品或药物产品表面上。
后者则相应地得以着色。施涂和涂布溶液优选包含0.1-20wt%、特别是2-15wt%的颜料混合物。
用于涂层的优选的干粉混合物包含纤维素衍生物例如羟丙基甲基纤维素、羧甲基纤维素钠,脱模剂例如卵磷脂或硬脂酸,光泽提高剂例如麦芽糖糊精和/或右旋糖,以及根据本发明的颜料混合物。这类干粉混合物优选包含基于粉末混合物的0.01-50wt%、特别是0.5-40wt%的颜料混合物。如果需要,还可以向这些干粉混合物中加入染料、调味料、维生素、甜味剂等。
适合着色或涂布的产品是例如,糖产品、糕点装饰、压制品(compress)、糖衣剂、口香糖、胶产品、软糖产品、杏仁糖产品、填充组合物、可可和脂肪糖浆(glaze)、巧克力和含巧克力的产品、冰激凌、谷物、小吃产品、涂布组合物、糕点糖浆、分散的糖装饰品、彩色糖粒、果冻和明胶产品、甜食、甘草、糖衣、棉花糖、脂肪、糖和乳脂组合物、牛奶冻、甜点、果馅饼、冰镇水果甜汤、软饮料和碳酸饮料、含稳定化添加剂,例如羧甲基纤维素的饮料、酸化和未酸化乳产品,例如quark、酸奶、奶酪、干酪外皮、肠衣等。
在涂布的食品和药物产品的情况下,可以将根据本发明的颜料混合物与芳香物质(粉末或液体香料(aromas))、酸和/或与甜味剂例如阿斯巴甜糖组合,以便在风味方面另外地增强视觉效果。
本发明因此涉及食品和药物方面的所有配制剂,其包含组分A的效果颜料和作为组分B的着色剂的其它颜料、填料或染料(天然或等同于天然的)、着色天然果实和植物提取物。
另一主要应用领域是药物和OTC方面,用于着色或作为片剂、明胶胶囊、糖衣剂、软膏、止咳剂等的涂层。在与常规涂层如聚甲基丙烯酸酯和纤维素物质例如HPMC组合,根据本发明的颜料混合物或金色颜料可以以各种方式用于着色和涂饰。
本发明因此还涉及包含根据本发明的颜料混合物的配制剂。
本发明同样涉及包含根据本发明的颜料混合物的配制剂,所述颜料混合物包含与如下物质组合的组分A和B:水、多元醇、极性和非极性油、脂肪、蜡、成膜剂、聚合物、共聚物、表面活性剂、自由基清除剂、抗氧化剂、稳定剂、气味增强剂、硅油、乳化剂、溶剂、防腐剂、增稠剂、流变学添加剂、香料、UV吸收剂、表面活性助剂和/或化妆品活性化合物。
下列实施例意图说明本发明,但是不限制本发明。
实施例
实施例1
将100g颗粒尺寸为10-60μm的云母在2升软化水中加热至75℃。当达到该温度时,将157.5g TiCl4(30wt% TiCl4)、236.6g FeCl3溶液(11.7% Fe)、5.9g AlCl3×6H2O和60g软化水的混合溶液在剧烈搅拌下缓慢计量加入。用32%氢氧化钠溶液将pH保持在pH2.6不变。当添加过该溶液时,将混合物再搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=7.5,在该pH下缓慢计量加入431g钠水玻璃溶液(13.5% SiO2)。接着用10%盐酸使pH降低至2.0,将混合物又搅拌15分钟,且计量加入393g TiCl4溶液(370g TiCl4/l)。该添加过程中,用32%氢氧化钠溶液保持pH不变。随后用32%氢氧化钠溶液使pH升到2.9,且缓慢计量加入由34g FeCl3×6H2O和49g软化水组成的溶液。用32%氢氧化钠溶液将pH保持在pH=2.9不变。当添加过该溶液时,将混合物再搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=5.0,且再将混合物搅拌15分钟。
滤出颜料,用软化水洗涤并在110℃干燥16小时。最后在850℃煅烧颜料30分钟,产生具有浓色、高遮盖力和强烈光泽的金色颜料。
该浓光泽的金色颜料具有下列L、a、b值:
(Phyma 22.5°/22.5°,黑色背景):
L=77.7;a=1.4;b=32.2
实施例2
将100g颗粒尺寸为10-60μm的云母在2升软化水中加热至75℃。当达到该温度时,将215g FeCl3×6H2O(11.7% Fe)、144g TiCl4溶液(30wt% TiCl4)和5.4g AlCl3×6H2O以及50g软化水的混合溶液在剧烈搅拌下缓慢计量加入。用32%氢氧化钠溶液将pH保持在pH2.6不变。当添加过该溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=7.5,在该pH下缓慢计量加入394g钠水玻璃溶液(13.5% SiO2)。接着用10%盐酸使pH降低至2.0,将混合物又搅拌15分钟,接着计量加入314g TiCl4溶液(370g TiCl4/l)。该添加过程中,用32%氢氧化钠溶液保持pH不变。随后用32%氢氧化钠溶液使pH升到2.9,缓慢计量加入由86g FeCl3×6H2O溶液(11.7%Fe)和50g软化水组成的溶液。用32%氢氧化钠溶液将pH保持在2.9不变。当添加过该溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=5.0,且再将混合物搅拌15分钟。
滤出颜料,用软化水洗涤并在110℃干燥16小时。最后在850℃煅烧颜料30分钟,产生具有浓色、高遮盖力和强烈光泽的金色颜料。
该强烈光泽的金色颜料具有下列L、a、b值:
(Phyma 22.5°/22.5°,黑色背景):
L=80.0;a=-0.9;b=34.0
实施例3
将100g颗粒尺寸为10-60μm的云母在2升软化水中加热至75℃。当达到该温度时,将215g FeCl3×6H2O溶液(11.7%Fe)、144g TiCl4溶液(30wt% TiCl4)和5.4g AlCl3×6H2O以及50g软化水的混合溶液在剧烈搅拌下缓慢计量加入。用32%氢氧化钠溶液将pH保持在pH2.6不变。当添加过该溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=7.5,在该pH下缓慢计量加入394g钠水玻璃溶液(13.5% SiO2)。接着用10%盐酸使pH降低至2.0,将混合物又搅拌15分钟,计量加入235g TiCl4溶液(370g TiCl4/l)。该添加过程中,用32%氢氧化钠溶液保持pH不变。随后在pH=2.0缓慢计量加入22g钠水玻璃溶液(13.5% SiO2),将混合物又搅拌15分钟。接着用32%氢氧化钠溶液使pH升到2.6,将混合物又搅拌15分钟,缓慢计量加入由116g FeCl3×6H2O(11.7% Fe)、78g TiCl4溶液(30wt% TiCl4)和2.5g AlCl3×6H2O以及30g软化水组成的混合溶液。用32%氢氧化钠溶液将pH保持在pH=2.6不变。当添加过该溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=5.0,再将混合物搅拌15分钟。
滤出颜料,用软化水洗涤并在110℃干燥16小时。最后在850℃煅烧颜料30分钟,产生具有浓色、高遮盖力和强烈光泽的金色颜料。
该强烈光泽的金色颜料具有下列L、a、b值:
(Phyma 22.5/22.5°,黑色背景):
L=75.0;a=-1.2;b=28.3
实施例4
将100g颗粒尺寸为10-60μm的云母在2升软化水中加热至75℃。当达到该温度时,将215g FeCl3×6H2O溶液(11.7% Fe)、144g TiCl4溶液(30wt% TiCl4)和5.4g AlCl3×6H2O以及50g软化水的混合溶液在剧烈搅拌下缓慢计量加入。用32%氢氧化钠溶液将pH保持在pH2.6不变。当添加过该溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=7.5,在该pH下缓慢计量加入394g钠水玻璃溶液(13.5% SiO2)。接着用10%盐酸使pH降低至2.0,将混合物又搅拌15分钟,在该pH下加入3.0g SnCl4×5H2O和10ml盐酸(37% HCl)在100ml去离子水中的溶液。接着用10%盐酸使pH降低至1.8,将混合物又搅拌15分钟,且计量加入235g TiCl4溶液(370g TiCl4/l)。该添加过程中,用32%氢氧化钠溶液保持pH不变。随后用32%氢氧化钠溶液使pH升到2.6,将混合物又搅拌15分钟,且缓慢计量加入116gFeCl3×6H2O溶液(11.7%Fe)、78g TiCl4溶液(30wt% TiCl4)和2.5gAlCl3×6H2O以及30g软化水的混合溶液。用32%氢氧化钠溶液将pH保持在pH=2.6不变。当添加过该金属盐溶液时,再将混合物搅拌约15分钟。随后用32%氢氧化钠溶液使pH升到pH=5.0,且再将混合物搅拌15分钟。
滤出颜料,用软化水洗涤并在110℃干燥16小时。最后在850℃煅烧颜料30分钟,产生具有下列L、a、b值的强烈光泽的金色颜料:
(Phyma 22.5°/22.5°,黑色背景):
L=79.0;a=-0.9;b=31.7。
应用实施例
实施例1A:沐浴凝胶
原料 INCI [%]
A
化钛),氧化锡
根据实施例4的多层金色颜料 (1) 云母,CI 77891(二氧化钛),二氧化硅, 0.10
CI 77491(铁氧化物),氧化铝,氧化锡
Keltrol CG-SFT (2) 黄原胶 1.10
软化水 水,水剂(水) 54.90
B
Plantacare 2000 UP (3) 癸基葡糖苷 20.00
Texapon ASV 50 (3) 月桂基聚氧乙烯醚硫酸钠,月桂基聚氧乙 3.60
烯(8)醚硫酸钠,月桂基聚氧乙烯醚硫酸
镁,月桂基聚氧乙烯(8)醚硫酸镁,油基
聚氧乙烯醚硫酸钠,油基聚氧乙烯醚硫酸
镁
Bronidox L (3) 丙二醇,5-溴-5-硝基-1,3-二噁烷 0.30
Frag 280851 Fruit Cocktail (4) 香精(parfum) 0.20
在水中0.1%的Sicovit Quinol ine (5) 水剂(水),水,CI 47005(酸性黄3), 8.30
Yellow 70 E1 04 酸性黄3
在水中0.1%的Dragocolor True Blue (6) 水剂(水),水,CI 42090(FD&C BLUE No.1), 1.30
FD&C BLUE No.1
C
柠檬酸一水合物 (1) 柠檬酸 0.15
软化水 水,水剂(水) 10.00
制备:
相A:将水引入反应器中并搅拌入颜料。在搅拌下缓慢撒入Keltrol CG-SFT并且搅拌直至它完全溶解为止(没有均化)。将相B的成分单独加入到相A中。在水中溶解柠檬酸一水合物并加入到批料中,缓慢搅拌直至所有成分均匀分布为止。添加柠檬酸(如果需要)调节pH至6.0-6.5。
供货来源:
(1)Merck
(2)C.P.Kelco
(3)Cognis GmbH
(4)Drom
(5)BASF AG
(6)Symrise
实施例2A:眼影
原料 INCI [%]
A
根据实施例4的多层金色颜料 (1) 云母,CI 77891(二氧化钛)二氧化硅,CI 25.00
77491(铁氧化物),氧化铝,氧化锡
滑石 (1) 滑石 49.50
马铃薯淀粉 (2) 马铃薯淀粉,马铃薯 7.50
(马铃薯淀粉)
硬脂酸镁 (1) 硬脂酸镁 2.50
B
硬脂酸异丙酯 (3) 硬脂酸异丙酯 9.34
棕榈酸鲸蜡酯 (1) 棕榈酸鲸蜡酯 0.53
Ewalin1751 (4) 矿脂 0.53
芳香油Elegance+79228 D MF (5) 香精 0.20
4-羟基苯甲酸丙酯 (1) 对羟基苯甲酸丙酯 0.10
制备:
将相A的成分合并且预混。随后在搅拌下向粉末混合物中滴加熔融的相B。将粉末引入大直径的粉末盘中并在80巴下压制。
供货来源:
(2)Suedstaerke GmbH
(3)Cognis GmbH
(4)H.Erhard Wagner GmbH
(5)Symrise
实施例3A:日霜(O/W)
原料 INCI [%]
A
(铁氧化物)
根据实施例4的多层金色颜 (1) 云母,CI77891(二氧化钛)二氧化硅,CI 0.10
料 77491(铁氧化物),氧化铝,氧化锡
Veegum HV (2) 硅酸铝镁 1.00
Karion F liquid (1) 山梨糖醇 3.00
4-羟基苯甲酸甲酯 (1) 对羟基苯甲酸甲酯 0.18
软化水 水剂(水) 56.34
B
Arlacel 165 VP (3) 硬脂酸甘油酯,PEG-100硬脂酸酯 5.00
Lanette 0 (4) 鲸蜡基/硬脂基醇(cetearyl alcohol) 1.50
Miglyol 812 N (5) 辛酸/癸酸甘油三酸酯 7.00
牛油树脂固体 (6) BUTYROSPERMUM PARKII(牛油树脂) 2.00
Cetiol SN (4) 异壬酸鲸蜡基/硬脂基酯 7.00
Eutanol G (4) 辛基十二烷醇 7.50
Emulgade PL 68/50 (4) 鲸蜡基/硬脂基醇,鲸蜡基/硬脂基葡糖苷 2.00
4-羟基苯甲酸丙酯 (1) 对羟基苯甲酸丙酯 0.08
C
芳香油200 530 (7) 香精 0.20
Dow Corning 345 (8) 环状聚二甲基硅氧烷(cyclomethicomne) 2.00
Euxyl K 400 (9) 苯氧基乙醇,甲基二溴戊二腈 0.10
柠檬酸一水合物 (1) 柠檬酸 0.00
制备:
加温相B直至溶液澄清为止。在相A的水中分散Veegum,加剩余的原料,加热至80℃,并加入相B。均化相A/B。在搅拌下冷却至40℃并加入相C。冷却至室温并调节至pH 6.0。
供货来源:
(2)Vanderbilt
(3)Uniqema
(4)Cognis GmbH
(5)Sasol Germany GmbH
(6)H.Erhard Wagner GmbH
(7)Fragrance Resources
(8)Dow Corning
(9)Sch ü lke & Mayr GmbH
实施例4A:闪光身体霜(sparkling body cream)(O/W)
原料 INCI [%]
A
Golden Sparks (1) 硼硅酸铝钙,二氧化硅,CI77891(二氧化钛), 1.00
氧化锡
根据实施例4的多层金色颜 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI77491 1.00
料 (铁氧化物),氧化铝,氧化锡
软化水 水,水剂(水) 40.60
Carbopol Ultrez 21 (2) 丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物 0.60
柠檬酸一水合物 (1) 柠檬酸 0.00
B
软化水水,水剂(水) 26.35
1,2-丙二醇 (1) 丙二醇 3.00
尿囊素 (1) 尿囊素 0.20
C
液体石蜡 (1) 液体石蜡(矿物油) 10.00
矿物油
Cetiol V (3) 油酸癸酯 6.00
Hostaphat KL 340 D (4) 三月桂基聚氧乙烯(4)醚磷酸酯 3.00
鲸蜡醇 (1) 鲸蜡醇2.00
Phenonip (5) 苯氧基乙醇,对羟基苯甲酸丁酯,对羟基苯甲 0.50
酸乙酯,对羟基苯甲酸丙酯,对羟基苯甲酸甲
酯
D
软化水 水,水剂(水) 3.50
三乙醇胺 三乙醇胺 0.35
E
Germall 115 (6) 咪唑烷基脲 0.30
芳香油Vogue (7) 香精 0.10
软化水 水,水剂(水) 1.50
制备:
将珠光颜料分散在相A的水中。如果需要,用几滴柠檬酸酸化以便降低粘度。在搅拌下撒入Carbopol。当完全溶解时,缓慢搅拌入预先溶解的相B。将相A/B和相C加热至80℃,将相C搅拌入相A/B中,与相D均化,中和,再次均化并在搅拌下冷却。40℃下将Germall 115溶解在相E的水中,在搅拌下加入。然后添加芳香油并在搅拌下冷却至室温。
供货来源:
(2)Noveon
(3)Cognis GmbH
(4)Clariant GmbH
(5)Nipa Laboratorien GmbH
(6)ISP Global Technologies
(7)Drom
实施例5A:膏状眼影
原料 INCI [%]
A
根据实施例4的多层金色颜 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 77491 20.00
料 (铁氧化物),氧化铝,氧化锡
Unipure Green LC 789 CF (2) CI 77289(氢氧化铬绿) 4.00
B
Crodamol PMP (3) PPG-2肉豆蔻基醚丙酸酯 37.80
Syncrowax HGLC (3) C18-36酸甘油三酸酯 10.00
Syncrowax HRC (3) 山嵛酸甘油三酯 3.00
Miglyol 812 N (4) 辛酸/癸酸甘油三酸酯 14.00
硬脂酸 (1) 硬脂酸 3.00
Antaron V-216 (5) PVP/十六碳烯共聚物 2.00
柠檬酸
4-羟基苯甲酸丙酯 (1) 对羟基苯甲酸丙酯 0.10
制备:
将相B加热到约80℃直至所有成分熔融为止并冷却到65℃。然后在搅拌下添加相A的珠光颜料,Micronasphere和研磨的铬氧化物。65℃下将眼影转移到容器中。
供货来源:
(2)Les Colorants Wackherr
(3)Croda GmbH
(4)Sasol Germany GmbH
(5)ISP Global Technologies
实施例6A:发用定型凝胶
原料 INCI [%]
A
硅,氧化锡
根据实施例4的多层金色颜 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 7749 10.10
料 (铁氧化物),氧化铝,氧化锡
Carbopol Ultrez 21 (2) 丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物 0.90
软化水 水,水剂(水) 50.35
B
Luviskol K 30粉末 (3) PVP 2.00
Germaben II (4) 丙二醇,二偶氮利定脲,对羟基苯甲酸甲酯, 1.00
对羟基苯甲酸丙酯
三乙醇胺,超纯 (1) 三乙醇胺 2.16
软化水 水,水剂(水) 40.94
制备:
在相A的水中分散珠光颜料,并在搅拌下撒入Carbopol。当完全溶解时,缓慢搅拌入预先溶解的相B。
供货来源:
(2)Noveon
(3)BASF AG
(4)ISP Global Technologies
实施例7A:香波
原料 INCI [%]
A
根据实施例4的多层金色颜 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 77491 0.20
料 (铁氧化物),氧化铝,氧化锡
Carbopol ETD 2020 (2) 丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物 0.90
软化水 水,水剂(水) 63.40
B
三乙醇胺,超纯 (1) 三乙醇胺 0.90
软化水 水,水剂(水) 10.00
C
Plantacare 2000 UP (3) 癸基葡糖苷 20.00
Texapon ASV 50 (3) 月桂基聚氧乙烯醚硫酸钠,月桂基聚氧乙烯(8) 4.35
醚硫酸钠,月桂基聚氧乙烯醚硫酸镁,月桂基
聚氧乙烯(8)醚硫酸镁,油基聚氧乙烯醚硫酸
钠,油基聚氧乙烯醚硫酸镁
Bronidox L (3) 丙二醇,5-溴-5-硝基-1,3-二噁烷 0.20
芳香油200 524 (4) 香精 0.05
染料溶液(适量) 0.00
制备:
对于相A,将颜料搅拌入水中。用几滴柠檬酸(10%)酸化以便降低粘度,并在搅拌下缓慢撒入Carbopol。当完全溶解时,缓慢加入相B。然后连续加入相C的成分。调节pH至6.0-6.5。
供货来源:
(2)Noveon
(3)Cognis GmbH
(4)Fragrance Resources
实施例8A:闪亮体粉(shimmering body powder)
原料 INCI [%]
A
根据实施例4的多层金色颜 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 1 0.00
料 77491(铁氧化物),氧化铝,氧化锡
B
(铁氧化物)
滑石 (1) 滑石 25.00
玻璃薄片 (1) 硼硅酸铝钙 15.00
白粘土 (1) 高岭土 14.70
云母M (1) 云母 15.00
丝云母(silk mica) (1) 云母 9.50
4-羟基苯甲酸丙酯 (1) 对羟基苯甲酸丙酯 0.30
C
Cetiol SQ (2)角鲨烷 2.00
Miglyol 812 N (3)辛酸/癸酸甘油三酸酯 2.00
香精 (4)香精 0.30
制备:
将相B的所有成分一起称量出并在混合器中均匀研磨。随后加入相C并继续混合,然后加入相A并简短地研磨直至珠光颜料均匀分布为止。
供货来源:
(2)Cognis GmbH
(3)Sasol Germany GmbH
(4)Symrise
实施例9A:长效唇彩
原料 INCI [%]
A
根据实施例4的多层金色颜料 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 4.00
77491(铁氧化物),氧化铝,氧化锡
氧化锡
B
Indopol H 100 (2) 聚丁烯 30.00
Jojoba Glaze LV (3) 希蒙得木(霍霍巴)种子油(SIMMONDSIA 20.00
CHINENSIS(JOJOBA)SEED OIL),乙烯/丙烯
/苯乙烯共聚物,丁烯/乙烯/苯乙烯共聚物
Jojoba Glaze HV (3) 希蒙得木(霍霍巴)种子油,乙烯/丙烯/苯乙 10.00
烯共聚物,丁烯/乙烯/苯乙烯共聚物
蓖麻油 (4) 蓖麻油,蓖麻(蓖麻油) 23.15
蜂蜡,白色 (1) 蜂蜡,白蜂蜡(蜂蜡) 4.00
4-羟基苯基酸丙酯 (1) 对羟基苯甲酸丙酯 0.10
酸,柠檬酸
Jaune Covapate W 1761 (5) 蓖麻(蓖麻油),CI 19140(FD&C YELLOW No. 1.00
5铝色淀)
C
Neosil CT 11 (6) 二氧化硅 1.50
Fragrance Tendresse 75418C (7) 香精 0.20
制备:
将相B的所有成分一起称量出,加热至80℃并充分搅拌。搅拌入相A的颜料,在搅拌下撒入Neosil,且最后加入香精(perfume)。将均匀的混合物转移至容器中。
供货来源:
(2)BP Lavera Sud
(3)Desert Whale
(4)Henry Lamotte GmbH
(5)Les Colorants Wackherr
(6)Ineos Silicas Limited
(7)Symrise
实施例10A:指甲油
原料 INCI [%]
根据实施例4的多层金色颜料 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 77491 1.75
(铁氧化物),氧化铝,氧化锡
Golden Sparks (1) 硼硅酸铝钙,二氧化硅,CI 77891(二氧化钛), 0.25
氧化锡
触变指甲油基料155 (2) 乙酸丁酯,乙酸乙酯,硝化纤维素,乙酰基三 98.00
丁基柠檬酸酯,邻苯二甲酸酐/苯偏三酸酐/二
醇共聚物,异丙醇,硬脂基二甲基苄基铵锂蒙
脱石,己二酸/富马酸/邻苯二甲酸/三环癸烷二
甲醇共聚物,柠檬酸
制备:
一起称量出颜料和指甲油基料,用抹刀手工充分混合并随后以1000rpm搅拌10分钟。
供货来源:
(2)Durlin/Bergerac NC
实施例11A:浓密睫毛膏(O/W)
原料 INCI [%]
A
Mica Black (1) CI 77499(铁氧化物),云母,CI 77891(二 5.00
氧化钛)
氧化钛)
实施例4的多层金色颜料 (1) 云母,CI 77891(二氧化钛),二氧化硅,CI 77491 2.00
(铁氧化物),氧化铝,氧化锡
Satin mica (1) 云母 2.00
B
Dermacryl 79 (2) 丙烯酸酯/辛基丙烯酰胺共聚物 3.50
蜂蜡,白色 (1) 蜂蜡,白蜂蜡(蜂蜡) 3.00
Syncrowax HRC (3) 山嵛酸甘油三酯 3.50
硬脂酸 (1) 硬脂酸 5.00
Tegin M (4) 硬脂酸甘油酯 3.50
Tegosoft CT (4) 辛酸/癸酸甘油三酸酯 2.50
Dow Corning 556 (5) 聚苯基三甲基硅氧烷 2.00
Phenonip (6) 苯氧基乙醇,对羟基苯甲酸丁酯,对羟基苯甲 0.80
酸乙酯,对羟基苯甲酸丙酯,对羟基苯甲酸甲
酯
C
软化水 水,水剂(水) 59.15
AMP Ultra PC 1000 (7) 氨基甲基丙醇 1.25
1,3-丁二醇 (1) 丁二醇 1.00
D
Germall 115 (8) 咪唑烷基脲 0.30
软化水 水,水剂(水) 1.50
制备:
在约85℃将除了Dermacryl 79以外的相B的所有成分一起熔融,在搅拌下加入Dermacryl 79,并且搅拌20分钟直至所有成分均匀分散为止。加热相C的成分到约85℃。将相A的珠光颜料搅拌入相C中。将相C加入相B中,继续搅拌,并用Ultra-Turrax T25以8000rpm均化1分钟。在搅拌下冷却,并在40℃加入相D。
供货来源:
(2)National Starch & Chemical
(3)Croda GmbH
(4)Degussa-Goldschmidt AG
(5)Dow Corning
(6)Nipa Laboratorien GmbH
(7)Angus Chemie GmbH
(8)ISP Global Technologies
实施例12A:具有UV保护的浅色日霜(O/W)
原料 INCI [%]
A
Arlacel 165 VP (2) 硬脂酸甘油酯,PEG-100硬脂酸酯 5.00
Arlacel 165 VP (2) 硬脂酸甘油酯,PEG-100硬脂酸酯 3.00
Montanov 68 (3) 鲸蜡基/硬脂基醇,鲸蜡基/硬脂基葡糖苷 3.00
Dow Corning 345 (4) 环状聚二甲基硅氧烷 0.50
Eutanol G (5) 辛基十二烷醇 2.00
4-羟基苯甲酸丙酯 (1) 对羟基苯甲酸丙酯 0.05
B
Extender W (1) 云母,CI77891(二氧化钛) 4.00
Matte Red (1) CI77491(铁氧化物),云母 0.20
实施例4的多层金色颜料 (1) 云母,CI77891(二氧化钛),二氧化硅, 2.00
CI77491(铁氧化物),氧化铝,氧化锡
Karion FP,liquid (1) 山梨糖醇 5.00
KeltrolT (6) 黄原胶 0.20
Chemag 2000 (7) 咪唑烷基脲 0.30
Euxyl K 400 (8) 苯氧基乙醇,甲基二溴戊二腈 0.10
4-羟基苯甲酸甲酯 (1) 对羟基苯甲酸甲酯 0.15
软化水 水剂(水) 57.60
制备:
将相B中除了Keltrol T以外的所有成分都分散在水中。在搅拌下将Keltrol撒入相B中并在15分钟后加热至80℃。将相A加热至75℃。将相B缓慢搅入到相A中并均化。在搅拌下冷却。
供货来源:
(1)Merck
(2)Uniqema
(3)Seppic
(4)Dow Corning
(5)Cognis GmbH
(6)C.P.Kelco
(7)Chemag AG
(8)Schülke & Mayr GmbH
实施例13A:霜膏调理剂
相 原料 INCI [%]
A 水 水剂(水) 79.7
实施例4的多层金色颜料 (1) 云母,CI77891(二氧化钛),二氧化硅, 0.50
CI 77491(铁氧化物),氧化铝,氧化锡
Luviquat Hold (2)聚季铵盐-46 5.00
Luviquat PQ11 (2)聚季铵盐-11 2.00
1,3-丁二醇 (1)丁二醇 3.00
B Cremophor A 6 (2)鲸蜡基聚氧乙烯(6)醚和硬脂醇 3.00
Ammonyx 4 (2)硬脂基二甲基苄基氯化铵 3.00
Lanette Wax0 (3)鲸蜡基/硬脂基醇 2.00
Eusolex 2292 (1)甲氧基肉桂酸辛酯 0.10
香精 香精 0.10
Germaben II (4)丙二醇,二偶氮利定脲,对羟基苯甲酸甲 1.00
酯,对羟基苯甲酸丙酯
制备:
将颜料分散在相A的水中并加入剩余的原料。在每次加入后搅拌并随后加热至75℃。混合相B的原料,加热至75-80℃并加入到相A中。混合直至存在均匀的分布为止。在45℃下加入相C。
供货来源:
(2)BASF AG
(3)Cognis GmbH
(4)ISP Global Technologies
实施例1A-13A的化妆品配制剂的突出之处在于它们的强的金色光泽及其它们很好的皮肤触感。
实施例14A:硬焦糖(hard caramel)的生产
原料 | % | 供货来源 |
糖 | 41% | Südzucker |
水 | 17.118% | |
葡萄糖浆 | 41%C*甜 | Cerestar,Krefeld |
根据实施例1的多层金色颜料 | 0.082%(基于浇注材料0.1%) | Merck KGaA,Darmstadt |
E 104 1:100稀释 | Sikovit的0.4% | BASF,Ludwigshafen |
香料 | 0.4%(香蕉9/030388) | Dragaco,Holzminden |
将糖与水一起加热到100℃,然后加入葡萄糖浆。随后将溶液加热到145℃。在添加金色颜料之后,用浇注漏斗将着色溶液和香料、焦糖溶液注入涂上油脂了的模具中。最后,使焦糖冷却2小时。金色颜料可以与糖混合或与葡萄糖浆混合而添加。该变型不含酸,因为这会使焦糖化过度。
实施例15A:片剂涂布
a)初始重量1kg的白色片剂d=8mm,G=200mg
总施涂量:200g
这对应于1.2mg聚合物/cm2片剂表面
膜涂布溶液的制备:
将金色颜料搅拌入水中。随后加入另外的染料。最后,将成膜剂(HPMC)撒入悬浮液中。由于增加的粘度,搅拌速度还必须相应提高。在约40-60分钟后,HPMC已经完全溶解且然后将溶液喷涂至片剂上。
借助于标准涂布方法进行喷涂。
Claims (21)
1.由至少两种组分A和B组成的颜料混合物,其特征在于
组分A包含基于多层涂布的薄片状底物的效果颜料,所述效果颜料具有包含如下的层序列
(A)由摩尔比为1:0.5-1:2.0的TiO2和Fe2O3的混合物以及任选地基于层(A)<20wt%量的一种或多种金属氧化物组成的高折射率涂层,
(B)折射率n<1.8的无色涂层,
(C)折射率n>1.8的无色涂层,
(D)折射率n>1.8的吸收性涂层
和任选地
(E)外保护层,
且
组分B包含选自由片状、针形、球形或不规则形状的颗粒组成的无机颜料、有机颜料、染料、着色天然果实和/或植物提取物的着色剂和/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的效果颜料具有下列层结构:
底物+Fe2O3/TiO2+SiO2+TiO2+Fe2O3/TiO2
底物+Fe2O3/TiO2+SiO2+TiO2+Fe2O3
底物+Fe2O3/TiO2+SiO2+TiO2+SiO2+Fe2O3/TiO2。
3.根据权利要求1或2的颜料混合物,其特征在于组分A的薄片状底物覆盖有TiO2或SiO2层。
4.根据权利要求1-3中一项或多项的颜料混合物,其特征在于组分A的效果颜料具有下列层结构:
底物+TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3/TiO2
底物+TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3。
5.根据权利要求1-4中一项或多项的颜料混合物,其特征在于组分A的效果颜料的层(A)的TiO2和Fe2O3的摩尔比为1:1。
6.根据权利要求1-5中一项或多项的颜料混合物,其特征在于组分A的效果颜料的层(D)的TiO2和Fe2O3的摩尔比为1:1。
7.根据权利要求1-6中一项或多项的颜料混合物,其特征在于组分A的效果颜料的层(A)是假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物的层。
8.权利要求1-7中一项或多项的颜料混合物,其特征在于所述组分A的效果颜料的层(D)是假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物的层。
9.根据权利要求1-8中一项或多项的颜料混合物,其特征在于组分A的效果颜料的层(A)和(D)各自是假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物的层。
10.根据权利要求1-9中一项或多项的颜料混合物,其特征在于所述组分B的着色剂是与组分A不同的珠光颜料、多层颜料和/或干涉颜料或其混合物。
11.根据权利要求1-10中一项或多项的颜料混合物,其特征在于组分A和组分B以99:1-50:50的混合比率混合。
12.根据权利要求1-10中一项或多项的颜料混合物,其特征在于组分A和组分B以99:1-1:99的混合比率混合,其中组分B是填料。
13.基于多层涂布的薄片状底物的效果颜料,其特征在于它们具有层序列(IL)、(A)-(D)或(IL)(A)-(E):
(IL)高折射率TiO2涂层,
(A)由摩尔比为1:0.5-1:2.0的TiO2和Fe2O3的混合物以及任选地基于层(A)的<20wt%量的一种或多种金属氧化物组成的高折射率涂层,
(B)折射率n<1.8的无色涂层,
(C)折射率n>1.8的无色涂层,
(D)折射率n>1.8的吸收性涂层
和任选地
(E)外保护层。
14.根据权利要求13的效果颜料,其特征在于它们具有下列层结构:
底物+TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3/TiO2
底物+TiO2+Fe2O3/TiO2+SiO2+TiO2+Fe2O3。
15.根据权利要求13或14的效果颜料,其特征在于TiO2和Fe2O3的混合物是假板钛矿或者假板钛矿与TiO2或假板钛矿与Fe2O3的混合物。
16.根据权利要求13-15中一项或多项的效果颜料在油漆、涂料、印刷油墨、塑料、化妆品配制剂中以及在食品和药物产品中的用途。
17.根据权利要求1-12中一项或多项的颜料混合物在化妆品配制剂中以及在食品和药物产品中的用途。
18.根据权利要求1-12中一项或多项的颜料混合物在食品和药物产品中的用途,其特征在于它与芳香物质和/或甜味剂组合使用。
19.包含根据权利要求1-12中一项或多项的颜料混合物的配制剂。
20.基于整个配制剂以0.01-99wt%的量包含权利要求1-12中一项或多项的颜料混合物的配制剂。
21.根据权利要求19或20的包含权利要求1-12中一项或多项的颜料混合物的配制剂,其特征在于它另外包含水、多元醇、极性和非极性油、脂肪、蜡、成膜剂、聚合物、共聚物、表面活性剂、自由基清除剂、抗氧化剂、稳定剂、气味增强剂、硅油、乳化剂、溶剂、防腐剂、增稠剂、流变学添加剂、香料、UV吸收剂、表面活性助剂和/或化妆品活性化合物。
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DE102006021784A DE102006021784A1 (de) | 2006-05-09 | 2006-05-09 | Effektpigmente und deren Verwendung in der Kosmetik und im Lebensmittel- und Pharmabereich |
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EP (1) | EP2016136A2 (zh) |
JP (2) | JP2009536231A (zh) |
KR (2) | KR20090009961A (zh) |
CN (1) | CN101460572A (zh) |
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CN107286706A (zh) * | 2016-04-11 | 2017-10-24 | 默克专利股份有限公司 | 颜料混合物 |
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CN109749485A (zh) * | 2013-08-02 | 2019-05-14 | 舒伦克金属颜料公司 | 厚度为1-50nm的基于基底片的金属光泽颜料 |
CN110358327A (zh) * | 2019-07-25 | 2019-10-22 | 汕头市镇发珠光颜料有限公司 | 一种高纯度红色珠光效果颜料及其制备方法 |
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EP2675423B1 (en) | 2011-02-15 | 2020-02-12 | BASF Corporation | Mixture of effect pigments showing a hue comparable to carmine for cosmetics |
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US9320687B2 (en) | 2013-03-13 | 2016-04-26 | Johnson & Johnson Consumer Inc. | Pigmented skin-care compositions |
JP6309834B2 (ja) * | 2013-12-11 | 2018-04-11 | 株式会社Adeka | 着色性組成物 |
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KR20210041539A (ko) * | 2018-07-27 | 2021-04-15 | 마테리온 코포레이션 | 인광체 조명 시스템에 대한 반사 컬러 보정 |
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JP2021080235A (ja) * | 2019-11-22 | 2021-05-27 | 株式会社ノエビア | 皮膚外用剤 |
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2006
- 2006-05-09 DE DE102006021784A patent/DE102006021784A1/de not_active Withdrawn
-
2007
- 2007-05-09 JP JP2009508248A patent/JP2009536231A/ja active Pending
- 2007-05-09 WO PCT/EP2007/004097 patent/WO2007128576A2/de active Application Filing
- 2007-05-09 DE DE112007001008T patent/DE112007001008A5/de not_active Withdrawn
- 2007-05-09 US US12/300,012 patent/US20090246294A1/en not_active Abandoned
- 2007-05-09 KR KR1020087029950A patent/KR20090009961A/ko not_active Application Discontinuation
- 2007-05-09 CN CNA2007800204261A patent/CN101460572A/zh active Pending
- 2007-05-09 KR KR1020147006123A patent/KR20140051400A/ko not_active Application Discontinuation
- 2007-05-09 EP EP07725020A patent/EP2016136A2/de not_active Withdrawn
-
2012
- 2012-12-18 US US13/718,439 patent/US20130108569A1/en not_active Abandoned
-
2013
- 2013-11-21 JP JP2013240893A patent/JP2014077137A/ja active Pending
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- 2016-04-19 US US15/132,842 patent/US20160230012A1/en not_active Abandoned
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CN113767151A (zh) * | 2019-04-30 | 2021-12-07 | 默克专利股份有限公司 | 效果颜料 |
CN113767151B (zh) * | 2019-04-30 | 2023-07-04 | 默克专利股份有限公司 | 效果颜料 |
CN110358327A (zh) * | 2019-07-25 | 2019-10-22 | 汕头市镇发珠光颜料有限公司 | 一种高纯度红色珠光效果颜料及其制备方法 |
Also Published As
Publication number | Publication date |
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US20090246294A1 (en) | 2009-10-01 |
KR20090009961A (ko) | 2009-01-23 |
KR20140051400A (ko) | 2014-04-30 |
EP2016136A2 (de) | 2009-01-21 |
JP2014077137A (ja) | 2014-05-01 |
US20130108569A1 (en) | 2013-05-02 |
US20160230012A1 (en) | 2016-08-11 |
DE102006021784A1 (de) | 2007-11-15 |
WO2007128576A2 (de) | 2007-11-15 |
WO2007128576A3 (de) | 2008-11-20 |
DE112007001008A5 (de) | 2009-04-23 |
JP2009536231A (ja) | 2009-10-08 |
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