CN101121832A - 粒子 - Google Patents
粒子 Download PDFInfo
- Publication number
- CN101121832A CN101121832A CNA2007101051528A CN200710105152A CN101121832A CN 101121832 A CN101121832 A CN 101121832A CN A2007101051528 A CNA2007101051528 A CN A2007101051528A CN 200710105152 A CN200710105152 A CN 200710105152A CN 101121832 A CN101121832 A CN 101121832A
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- China
- Prior art keywords
- negatively charged
- charged ion
- particle
- active compound
- base material
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
本发明涉及包含基材和阴离子结合层的粒子,该阴离子结合层包含一种或多种阴离子形成性有机活性化合物或活性化合物/着色剂混合物。本发明另外涉及粒子的制备方法和涉及其用于化妆品、药物、配制剂、油漆、涂料、塑料、薄膜中,用于安全印刷中,用于文件和身份证件中的安全特征中,用于种子着色,用于食品着色或用于药剂包衣中和用于制备颜料组合物和干制剂的用途。
Description
技术领域
本发明涉及包含基材和阴离子结合层的粒子,其中该阴离子结合层包含一种或多种阴离子形成性有机活性化合物。本发明另外涉及粒子的制备方法,和涉及其用于化妆品、药物、配制剂、油漆、涂料、塑料、薄膜中,用于安全印刷中,用于文件和身份证件中的安全特征中,用于种子着色,用于食品着色或用于药剂包衣中和用于制备颜料组合物和干制剂的用途。
背景技术
活性化合物在化妆品中和在药物产品中起杰出的作用。化妆品活性化合物的例子是UV过滤剂、炎症抑制物质等。通常,该活性化合物是有机官能活性化合物。将这些有机官能活性化合物通常以配制剂的形式施加或给用。在化妆品方面这样的配制剂的例子是,例如霜膏剂、软膏或凝胶,在药物活性化合物的情况下是例如片剂、糖锭剂、溶液,但也是软膏。
然而,该活性化合物经常在配制剂中不足够稳定或可以与配制剂的其它成分反应。此外,活性化合物在配制剂使用时的剂量经常不能受到控制,例如在施加软膏的情况下皮肤与整个浓度的活性化合物接触,即使这是初始不希望的。存在用于改进或调节活性化合物的释放或稳定的许多方案。在许多情况下这通过在载体中将所述活性化合物包囊而进行,该载体然后预计以特定的方式释放活性化合物。
发明内容
本发明的目的因此是提供能够稳定活性化合物和/或采用受控方式释放它们的粒子。本发明的目的此外还有通过基材和阴离子结合层的合适选择而达到协同作用分布型(profiles)。
令人惊奇地,由本发明的粒子达到了上述目的。
因此,本发明首先涉及包含基材和阴离子结合层的粒子,该阴离子结合层包含一种或多种阴离子形成性有机活性化合物。根据本发明的粒子可达到两个在关于结合的阴离子活性化合物方面基本不同的功能:在低pH(<6)下,固定层相继溶解,导致粒子的受控释放功能。相反在更高pH(>6)下,固定层稳定和因此对结合的阴离子活性化合物施加保护和稳定功能。根据本发明的粒子因此特别是多功能混杂粒子。
由于有利的性能,根据本发明的粒子普遍适于许多种广泛不同的应用。本发明因此也涉及这些粒子用于化妆品、药物、配制剂、油漆、涂料、塑料、薄膜中,用于安全印刷中,用于文件和身份证件中的安全特征中,用于种子着色、用于食品着色或用于药剂包衣中和用于制备颜料组合物和干制剂的用途。
根据本发明的粒子基于基材,该基材可基本上具有任何形状。适当成形的基材的例子是薄片状、球形或针形基材,但也可以采用不规则成形的基材。对于本发明的目的,球形用于表示成球状的,但也表示成不对称球状的,例如椭圆形。
合适的薄片状基材是,例如玻璃薄片、SiO2薄片、Al2O3薄片、BiOCl薄片、石墨薄片、合成或天然薄片状氧化铁或薄片状金属。合适的金属薄片可尤其由铝、钛、青铜、钢或银组成,优选由铝和/或钛组成。金属薄片在此可以由适当的处理而钝化。
薄片状基材的尺寸自身不是关键的和可以匹配于特定的应用。薄片状基材的直径平均通常为1-500μm,优选5-200μm和特别地10-200μm。优选的较小粒度此外是1-100μm,特别地5-60μm和1-15μm的那些。它们的平均厚度为0.05-10μm和优选0.1-1.0μm。薄片状基材的平均纵横比,即在此对应于平均直径的平均长度测量值,与平均厚度测量值之间的比,通常为5-750,优选10-300和特别优选20-200。
薄片状基材优选是玻璃薄片、SiO2薄片或Al2O3薄片,和由于它们的特别平滑的表面和非常高的反射能力,非常特别优选玻璃薄片。
优选采用的SiO2薄片是具有均一层厚度和优选根据国际申请WO93/08237在连续带上由水玻璃溶液的凝固和水解而制备的合成SiO2薄片。均一层厚度在此用于表示层厚度容差为粒子总干层厚度的3-10%,优选3-5%。薄片状二氧化硅粒子通常为无定形形式。此类型的合成薄片具有相对于天然材料,例如云母的优点,该优点是,可以关于所需的效果而调节层厚度和层厚度容差有限。
原则上,本领域技术人员已知的所有玻璃类型和形式(例如薄片,珠粒,纤维等)可用于根据本发明的粒子。非常特别优选是玻璃薄片,它可以由本领域技术人员已知的所有玻璃类型,特别地Ca-Al-硼硅酸盐玻璃,例如窗玻璃、C玻璃、E玻璃、ECR玻璃、Duran玻璃、实验室设备玻璃或光学玻璃组成。特别优选E玻璃或ECR玻璃,但也是含铁、含铋、含铌、含锡和/或含钛的玻璃。薄片的折射率优选为1.20-2.20,特别地1.50-1.70。
合适的薄片状基材因此是基于如下物质的基材:Ca-A1-硼硅酸盐(例如购自Merck KGaA的RONASTAR)、SiO2(例如购自Merck KGaA的COLORSTREAM)、Al2O3(例如购自Merck KGaA的XIRALLIC)、天然叶状氧化铁(例如购自krntner Montan Industrie的MIOX)、合成或天然石墨、合成叶状氧化铁(例如购自Titan Kogyo的TAROX)或金属铝。
球形基材特别基于Ca-Al-硼硅酸盐、SiO2、TiO2、Al2O3、GeO2、ZrO2、ZnO、B2O3、Ga2O3、In2O3、SnO2,但也基于(Ca/Mg)2(OH)(PO4)、高岭土、BaSO4、白垩、MgCO3、BiOCl(例如BironESQ)。合适的基材此外也是球形有色颜料,例如天然或合成氧化铁、群青蓝、炭黑、氧化铬绿、钴蓝、柏林蓝和锰紫。特别地,ZnO或TiO2构成的球形基材用作UV过滤剂。基于这些基材的粒子特别适于制备多功能粒子。基材在此显示功能作用,该作用由阴离子结合层中结合的活性化合物和它们的作用补充。
将有机和/或无机化合物和材料包囊的上述材料构成的球形胶囊同样适于作为球形基材。包囊的化合物可以例如选自UV过滤剂。优选的胶囊具有例如由WO 00/09652,WO 00/72806和WO 00/71084中描述的方法获得的胶囊壁。胶囊壁优选是基于SiO2或TiO2的包覆层。此类型胶囊的例子是EusolexUV-PearlsTM(Merck KGaA,Darmstadt)。
基于球形基材的粒子对于化妆品和药物应用是特别有利的。依赖于材料而定,本发明的球形粒子显示良好的皱纹遮盖效果,良好的皮肤触感,并且既可以用作填料,也可用作活性剂。此外,降低了皮肤的光泽和给予皮肤更柔软的外观。球形粒子的滚动和滑动效果显著改进皮肤触感。
球形基材的尺寸自身同样不是关键的和可以匹配于特定的应用。球形粒子的直径通常为1nm-2000μm,优选5nm-1000μm和特别优选10nm-500μm。球形金属氧化物,特别地具有UV过滤活性的金属氧化物优选具有平均直径为5-1000μm,特别地8-500nm和非常特别优选8-300nm。
此外,针形基材也适于本发明的目的。其例子是玻璃纤维、塑料纤维和具有针形晶体结构的颜料,例如黄色氧化铁(针铁矿)。
上述基材也可以为混合物(例如二元或三元混合物)形式,即例如将薄片状基材粒子与球形和/或针形基材粒子混合。在球形和非球形粒子之间,例如在薄片状和针形粒子之间的混合比,不是关键的和可以匹配于应用;例如它可以选自1∶99-99∶1重量份,特别地10∶90-90∶10重量份和特别是1∶9-9∶1重量份。此类型的混合物使得可以采用特定的方式设定最终产物的某些物理性能,例如光泽、遮盖力或皮肤触感。
上述基材可以用导致基材着色的离子或元素掺杂。此外,基材也可以用离子或元素掺杂,该离子或元素除颜色以外还引起基材的某些物理性能,例如电导率,增加的折射率,荧光,磷光,磁性,NLO性能,IR或UV反射/吸收等。所提及的由离子或元素掺杂诱导的物理性能仅希望解释本发明,而不限制本发明。
在本发明的进一步实施方案中,可将由金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物构成的一个或多个透明、半透明和/或不透明层施加到上述基材上和在阴离子结合层下方。金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层或其混合物可具有低折射率(折射率<1.8)或高折射率(折射率≥1.8)。合适的金属氧化物和金属氧化物水合物是本领域技术人员已知的所有金属氧化物和金属氧化物水合物,例如氧化铝、氧化铝水合物、氧化硅、氧化硅水合物、氧化铁、氧化锡、氧化铈、氧化锌、氧化锆、氧化铬、氧化钛,特别是二氧化钛、氧化钛水合物,及其混合物,例如钛铁矿或铁板钛矿。可以采用的金属低氧化物是,例如钛的低氧化物。合适的金属是,例如铬、铝、镍、银、金、钛、铜或合金,和合适的金属氟化物是,例如氟化镁。可以采用的金属氮化物或金属氧氮化物是,例如金属钛、锆和/或钽的氮化物或氧氮化物。将金属氧化物、金属、金属氟化物和/或金属氧化物水合物层和非常特别优选金属氧化物和/或金属氧化物水合物层优选施加到载体上。此外,也可以存在包含高-和低-折射率金属氧化物、金属氧化物水合物、金属或金属氟化物层的多层结构,其中高-和低-折射率层优选交替。特别优选包含高折射率层和低折射率层的层组(package),其中这些层组中的一个或多个可以施加到载体上。高-和低-折射率层的序列在此可以匹配于基材,以便在多层结构中包括基材。在进一步的实施方案中,金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层可以与着色剂或其它元素混合或用其掺杂。合适的着色剂或其它元素是,例如有机或无机有色颜料,如有色金属氧化物,例如磁铁矿、氧化铬,或有色颜料,例如柏林蓝、群青、钒酸铋、特纳德(Thénard)蓝,或有机有色颜料,例如靛、偶氮颜料、酞菁或还有胭脂红,或元素,例如钇或锑。在优选的实施方案中,基材上的外层是高折射率金属氧化物。此外层可额外在上述层组的顶部上,或在高折射率载体的情况下,是层组的一部分和可例如由TiO2、钛的低氧化物、Fe2O3、SnO2、ZnO、ZrO2、Ce2O3、CoO、Co3O4、V2O5、Cr2O3和/或其混合物,例如钛铁矿或铁板钛矿组成。特别优选TiO2。该涂覆的基材可显示一种或多种角度依赖性的干涉色。然而,它们也可以恰好产生基材的一种吸收色或除一种或多种角度依赖性的干涉色以外的一种吸收色。
金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层或其混合物的厚度通常为3-500nm,和在金属氧化物、金属氧化物水合物、金属低氧化物、金属氟化物、金属氮化物或金属氧氮化物层或其混合物的情况下优选是5-600nm。金属层的厚度优选为4-100nm。
在玻璃薄片作为薄片状基材的情况下,这些非常特别优选由SiO2层涂覆。SiO2涂层保护玻璃表面以抗化学变化,如玻璃成分的溶胀、浸出,或在侵蚀性酸性涂料溶液中的溶解。在这些基材制备中的煅烧过程中,化学相关材料的紧密结合在玻璃薄片的情况下在玻璃体和沉淀SiO2之间的界面处发生。由于高的软化温度,沉淀SiO2包覆层向基材提供必要的机械稳定性,甚至在700℃以上煅烧时也如此。在SiO2层之后所述一个或多个涂层的粘合也非常好。依赖于所需的效果而定,玻璃薄片上SiO2层的厚度可以在宽范围内变化。层的厚度为5-350nm,优选5-150nm。对于光泽和颜色强度的控制,优选是30-100nm的层厚度。SiO2层也可以用炭黑粒子、无机有色颜料和/或金属粒子掺杂,只要此掺杂在空气中或在惰性气体下在>700℃的温度下是稳定的。SiO2基体中掺杂剂的比例则是1-50wt%,优选2-30wt%,特别地5-20wt%。在特别优选的实施方案中,将高折射率金属氧化物的层,特别地TiO2层,施加到SiO2层上。
在基于SiO2(例如Monosphere或Ronasphere)的球形基材的情况下,这些优选具有金属氧化物,特别地TiO2(例如RonasphereLDP)的涂层。
除上述薄片状、球形或针形的涂覆或未涂覆基材或基材混合物以外,根据本发明的粒子还具有阴离子结合层;特别地,基材由阴离子结合层涂覆。阴离子结合层优选包含层状双氢氧化物。此类型的层也称为LDH层。
层状双氢氧化物(LDH)优选是如下通式的双氢氧化物:
M2+ 1-xM3+ x(OH)2(Zn-)x/n·mH2O
其中0.2<x<0.33,其中
M3+选自Al3+、Cr3+、Fe3+、Ga3+、In3+、Y3+、La3+和/或Ce3+和
M2+选自Ba2+、Ca2+、Cu2+、Mg2+、Sr2+和/或Zn2+,
Zn-表示金属盐的反荷离子和/或阴离子形成性有机官能活性化合物的阴离子或阴离子混合物,其中n表示阴离子的电荷数目。
m是化学计量因子和指示LDH中结晶水的含量。对于本发明的目的,m可以是例如1-12,但此外也可以是其它数值,它们可以是整数或非整数。
该双氢氧化物的例子是:
Mg0.67Al0.33(OH)2(Zn-)0.33/n·mH2O和Mg0.67Fe0.33(OH)2(Zn-)0.33/n·mH2O,
Zn0.67Al0.33(OH)2(Zn-)0.33/n·mH2O和Zn0.67Fe0.33(OH)2(Zn-)0.33/n·mH2O,
Ca0.67Al0.33(OH)2(Zn-)0.33/n·mH2O和Ca0.67Fe0.33(OH)2(Zn-)0.33/n·mH2O。
Ca0.67Al0.33(OH)2(Zn-)0.33/n·mH2O,Mg0.67Al0.33(OH)2(Zn-)0.33/n·mH2O和Zn0.67Al0.33(OH)2(Zn-)0.33/N·mH2O,尤其经证明是特别有利的。
优选M3+=Al3+或Fe3+,和M2+=Mg2+、Ca2+或Zn2+。非常特别优选,M3+=-Al3+。阴离子结合层的层厚度为0.5-500nm,特别地1-300nm。
该阴离子结合层包含一种或多种阴离子形成性有机活性化合物。有机活性化合物特别地是阴离子或阴离子形成性药物活性化合物、食品增补剂、诊断用物质和化合物和/或化妆品活性化合物,即也可以存在该活性化合物的混合物。原则上,关于包囊的活性化合物的功能活性没有限制,只要它们仅是阴离子的或可以转化成阴离子。就此程度,可以在基材上固定在药理学和/或皮肤保护和/或皮肤护理和/或皮肤再生和/或抗菌和/或抗真菌和/或化妆品效力的意义上起活性化合物作用的有机物质或物质混合物。在优选的实施方案中,这些活性化合物是至少双阴离子地带电的形式或可以转化成至少双阴离子地带电的分子。这样的分子包含至少两个阴离子官能团或可以转化成阴离子的官能团。这些可以选自,例如磺酸(磺酸酯)和/或羧酸(羧酸酯)和/或硫酸单酯(硫酸酯)和/或酚(酚盐)和/或磷酸单酯或二酯(单或二磷酸酯)和/或膦酸酯和/或烯醇(烯醇化物)和/或亚氨酸的阴离子和/或二硫羟酸的阴离子。有机活性化合物因此包含一种或多种,特别地至少两种阴离子形成性酚盐、烯醇化物、羧酸酯、硫酸酯、磺酸酯、亚磺酸酯、二硫羟酸酯、磷酸酯和/或亚磷酸酯结构单元。在这些活性化合物的情况下,可能是不希望的皮肤接触/皮肤渗透(例如在UV过滤剂的情况下)因此基本被避免。活性化合物,防腐剂或染料的固定的此效果,特别地在使用至少可双电离物质时,加强了在pH>6下在稳定功能的情况下阴离子的固定,和通过采用此方式增加的产物安全而抑制不希望的渗透。因此可以在pH>6下实现几乎完全的固定。然而,也可以在pH<6下建立活性化合物的受控释放,它导致活性化合物的更好剂量。
合适的阴离子形成性药物活性化合物是例如:
1)镇静药物:例如巴比土酸衍生物的那些,例如异戊巴比妥钠(CAS:64-43-7)
2)炎症抑制性抗风湿药:例如乙酸衍生物的那些,例如吲哚美辛(CAS:53-86-1),阿西美辛(CAS:53164-05-9),托美丁(CAS:26171-23-3),双氯芬酸(CAS:15307-86-5),Ionozolac(CAS:53808-88-1),和/或丙酸衍生物的那些,例如布洛芬(CAS:15687-27-1),非诺洛芬(CAS:31879-05-7),萘普生钠(CAS:26159-34-2),酮洛芬(CAS:22071-15-4)
3)抗动脉硬化B维生物:例如卡尼汀(CAS:461-06-3),烟酸铝(CAS:1976-28-9),生物素(CAS:58-85-5),泛酸钙(CAS:137-08-6),氨基苯甲酸(CAS:150-13-0)
4)抗心律失常,抗惊厥非类固醇,例如扶他林/双氯芬酸(CAS:15307-86-5)
5)选自类别I,II,III和IV的抗心律失常,β-抗交感神经物质,例如波美洛尔(CAS:65008-93-7)和BW-A-575-C(CAS:103221-88-1)
6)β-内酰胺抗生素:例如青霉烷,crabapenem,氧青霉烷,头孢烯,氧头孢烯和单环β-内酰胺,例如羧苄西林(CAS:4697-36-3),阿莫西林(CAS:26787-78-0),头孢西丁(CAS:35607-66-0)和氨苄西林(CAS:69-53-4)
7)选自青霉素,氨基青霉素,酰氨基青霉素,羧基青霉素和头孢菌素类别的抗生素,例如三唑巴坦(CAS:89786-04-9),氯唑西林砜(CAS:76788-83-5),舒巴坦(CAS:68373-14-8)
8)选自四环素类别的抗生素,例如甘氨酸甲基四环素(CAS:751-98-4),赖甲环素(CAS:992-21-2),氯四环素钙(CAS:57122-99-3),阿哌环素(CAS:15599-51-6)
9)选自香豆素衍生物类别的抗凝剂和凝固因子合成抑制剂,例如华法林(CAS:5543-58-8),醋硝香豆素(CAS:152-72-7),6-羟基华法林(CAS:17834-02-5),3-羟基华法林(CAS:30992-81-5),coumachlorine(CAS:81-82-3),4-羟基华法林(CAS:63740-78-3)
10)二苯基胺衍生物的炎症抑制性前列腺素拮抗剂,例如氯芬那酸(CAS:4295-55-0),氟来酸铝(CAS:16449-54-0),氯苯扎利钠(CAS:64808-48-6),氟替阿嗪(CAS:7220-56-6),阿拉洛芬(CAS:15250-13-2)
11)选自苯基磺酰胺的防腐剂和抗糖尿病药,例如aristoplomb(CAS:60662-80-8),acrotiazol(CAS:60595-59-7),BA-32641(CAS:92569-06-7),alfasol(CAS:38114-83-9),羧基甲苯磺丁脲(CAS:2224-10-4)
12)炎症抑制剂,镇痛剂,胶原酶抑制剂和角质溶解性物质,例如水杨酸(CAS:69-72-7)
13)抗惊厥药,例如丙戊酸盐的那些,例如丙戊酸钙(CAS:33433-82-8),丙戊酸钠(CAS:1069-66-5),丙戊酸半钠(CAS:76584-70-8)
14)平喘药和抗过敏药,例如花黄素衍生物的那些,例如克醋茶碱(CAS:652-37-9),阿鲁斯特钠(CAS:96565-55-8),氨来呫诺(CAS:68302-57-8),AH-7725(CAS:68302-57-8),萘多罗米钙(CAS:101626-68-0)
15)抑制细胞剂和免疫抑制剂,例如硫唑嘌呤衍生物的那些,例如硫唑嘌呤钠(CAS:55774-33-9),硫米嘌呤(CAS:5581-52-2),间硫唑嘌呤(CAS:97746-12-8)
16)皮质类固醇和孕激素,例如前列腺素衍生物的那些,例如甲泼尼龙琥珀酸钠(CAS:2375-03-3),倍他米松磷酸钠(CAS:151-73-5)
17)杀病毒剂,例如鸟苷衍生物的那些,例如2’-单磷酸鸟核苷(CAS:130-50-7),3’-单磷酸鸟核苷(CAS:82570-66-9),磷酸阿昔洛韦(CAS:66341-16-0),2’-环单磷酸鸟核苷NOR(CAS:91516-85-7)
18)甲状腺激素和抗动脉粥样硬化剂,例如二苯基醚衍生物的那些,例如右旋三碘甲状腺氨酸(CAS:5714-08-9),左甲状腺素钠(CAS:55-03-8),右旋甲状腺素钠(CAS:137-53-1)
19)镇痛剂,炎症抑制剂,退热剂,例如昔康衍生物的那些,例如美洛昔康(CAS:71125-38-7),伊索昔康(CAS:34552-84-6),吡罗昔康乙醇胺(CAS:85056-47-9),磷酸吡罗昔康(CAS:82801-42-1),和/或吡唑衍生物的那些,例如安乃近镁(CAS:6150-97-6)和地布匹隆(CAS:1046-17-9),和/或吡唑烷衍生物的那些,例如anthradione(CAS:19854-90-1)和sulfodethamedione(CAS:53039-87-5)
20)螯合剂,例如HBED(CAS:35998-29-9),钙立醇(CAS:132722-73-7),cadystin-A(CAS:86220-45-3),ditiocarb钠(CAS:148-18-5),mugineic acid(CAS:69199-37-7),CDTA(CAS:13291-61-7),三胺五乙酸钙(CAS:2531-75-1)
21)杀原生动物剂,例如对羧基苯甲醚酯衍生物的那些,例如青蒿酯(CAS:88495-63-0)
22)用于溃疡治疗的前列腺素,例如carbacyclin(CAS:69552-46-1),阿前列素(CAS:83997-19-7),阿法前列醇(CAS:74176-31-1),贝前列素钠(CAS:88475-69-8),AY-16809(CAS:21269-28-3),α-PGFl(CAS:745-62-0)。
这些例子意于通过例子解释可能方案,而不限制选择。
合适的阴离子形成性食品增补剂或化妆品活性化合物或诊断用活性化合物是,例如以下列举的生物类黄酮。此外,所有的氨基酸,例如谷氨酸和天冬氨酸,此外还有具有甜菜碱结构的氨基酸,例如依克多因(ectoin)、羟基依克多因或三甲基甘氨酸,也适于此目的。阴离子形成性维生素和维生素衍生物,特别地磷酸酯,根据本发明同样是合适的。在此可以通过例子提及维生素C和维生素C磷酸酯。另外可以使用:硫辛酸、饱和或不饱和脂肪酸的阴离子、视黄酸、生育酚(α,β,γ,δ)、维生素B1(例如硫胺焦磷酸素)、维生素B2、维生素B6(吡哆素,吡哆醛)、烟酸、泛酸、生物素、叶酸、维生素B12(氰钴胺素)、核苷酸和核苷或其衍生物,例如烟酰胺腺嘌呤二核苷酸(NAD或NADH2)、腺嘌呤三磷酸酯(ATP)、腺嘌呤单磷酸酯(AMP)、腺嘌呤二磷酸酯(ADP)、5’-次黄苷单磷酸酯(IMP)、5’-鸟苷单磷酸酯(GMP)、和肌酸、肌酸磷酸酯和肌酸酐。此外,DNA和/或RNA结构单元和DNA和/或RNA片段或结构部分也是合适的。
特别具有抗氧化性能的有机活性化合物尤其是二羧酸(草酸,琥珀酸)和羟基羧酸(乳酸,苹果酸,酒石酸和柠檬酸)。
合适的阴离子形成性诊断用物质和化合物是,例如:
X射线造影剂,例如iocetaminic acid(CAS:16034-77-8),碘软脂酸(CAS:54510-20-2),meglumin acetrizoate(CAS:22154-43-4),碘代马尿酸(iodohippurinic acid)(CAS:147-58-0),sodium bunamiodate(CAS:1923-76-8),醋碘苯酸(CAS:85-36-9),但也是用于其它应用的诊断剂,例如二硝基氯苯(CAS:97-00-7),gluceptinic acid(CAS:87-74-1),靛青二磺酸钠(CAS:860-22-0),碘苯十五酸(CAS:74855-17-7),布替膦酸(CAS:51395-42-7),wofazurin(CAS:7488-76-8),upenazim(CAS:95268-62-5),Vert-Sulfo-J(CAS:519-76-6),荧光素银(CAS:25931-86-6),pankensan(CAS:38219-60-2),琥巯酸(CAS:304-55-2)。
这些例子仅意于举例解释用于结合阴离子食品增补剂或化妆品活性化合物或诊断用物质的可能方案,而不限制选择。
化妆品活性化合物特别地是护理和保护性活性化合物。保护性活性化合物的例子是UV过滤剂,具有抗菌或抗真菌作用的物质或也是防腐剂。
功能性活性化合物优选选自UV过滤剂类别。在UV过滤剂作为功能性活性化合物的情况下,优选UV过滤剂的完全固定。采用此方式,避免UV过滤剂的可能皮肤接触,该接触经常是不希望的。此外,具有对应选择的基材(例如ZnO)的对应UV过滤剂作为活性化合物的选择使得能够提供宽谱带UV过滤剂,它提供宽吸收光谱和因此由于活性化合物和基材的不同吸收性能而提供改进的保护。
吸收紫外光辐射的合适阴离子形成性或阴离子UV过滤剂可以选自对氨基苯并咪唑-5-磺酸酯、丙烯酸3-咪唑-4-基酯、水杨酸酯、对甲氧基肉桂酸酯、2-乙基己基-2-氰基-3,3-二苯基丙烯酸酯、3,3,5-三甲基环己基-2-乙酰氨基苯甲酸酯、对氨基苯甲酸酯、肉桂酸酯、3,4-二甲氧基苯基乙醛酸酯、(2-氧代冰片-3-亚基)-对二甲苯-2-磺酸酯、(2-氧代冰片-3-亚基)甲苯-4-磺酸酯、氰基-4-甲氧基肉桂酸酯和2-苯基苯并咪唑-5-磺酸酯。
这些阴离子,如果它们处于游离状态,已知用于在290-400nm的波长范围中吸收。所有的代表性例子被视为是防晒物质的相容性材料。在LDH层中的固定使得已知UV过滤剂的吸收情况能够保持或另选采用特定的方式移动。因此最终也可以将阴离子的UV过滤剂性能具体匹配于基材的那些。它是特别令人感兴趣的和因此根据本发明优选的本发明的实施方案是在此方面采用稳定的方式在单一产物中结合UV-A和UV-B过滤剂性能的可能性。
适于根据本发明的目的的另一类有机材料是通过在分子中包含酚质子或另一个弱酸性质子而具有弱酸性官能度的物质。已经发现作为本发明一部分的是,此质子可以脱除,形成可以引入层状双氢氧化物中的阴离子。衍生自此类型化合物的阴离子可具有显著不同于母体化合物的吸收光谱,但这些阴离子,在混入层状双氢氧化物中之后,显示290-400nm(UV-A区域)的特征光吸收。在根据本发明的优选实施方案中,优点来自如下事实:这些阴离子当混入层状双氢氧化物中时,显示这样的光谱,使得与在层状双氢氧化物不存在下使用母体化合物时获得的UV-A防护相比,得到增加的UV-A防护。一组重要的此类型酚化合物包含羟基化二苯酮衍生物。合适的二酮化合物(例如二苯甲酰基甲烷,例如Eusolex9020),它们处于它们的烯醇形式,可同样是经包囊的。用于根据本发明的优选实施方案的阴离子从其衍生的化合物的例子包括如下材料,但不限于此:
CTFA名称 化学名称
二苯酮-1 2,4-二羟基二苯酮
二苯酮-2 2,2’,4,4’-四羟基二苯酮
二苯酮-3 2-羟基-4-甲氧基二苯酮
二苯酮-4 2-羟基-4-甲氧基二苯酮-5-磺酸
二苯酮-5 2-羟基-4-甲氧基二苯酮-5-磺酸单钠盐
二苯酮-6 2,2’-二羟基-4,4’-二甲氧基二苯酮
二苯酮-7 5-氯-2-羟基二苯酮
二苯酮-8 2,2’-二羟基-4-甲氧基二苯酮
二苯酮-9 2,2’-二羟基-4,4’-二甲氧基二苯酮-3,
3’-二磺酸二钠盐
二苯酮-10 2-羟基-4-甲氧基-4’-甲基二苯酮
二苯酮-12 2-羟基-4-辛氧基二苯酮
胡莫柳酯 水杨酸三甲环己酯
水杨酸辛酯 水杨酸2-乙基己酯
能够提供层间阴离子的进一步化合物是丁基甲氧基二苯甲酰基甲烷,以PARSOL 1789从Givaudan Corp获得。同样根据本发明采用此形式包囊的是衍生自如下的阴离子物质:pongomol,取代的1,3-二酮,它的系统命名是1-(4-甲氧基-5-苯并呋喃基)-3-苯基-1,3-丙二酮。它的紫外吸收谱带为250-500nm和吸光度系数为5000-70,000。此二酮更精确地描述于US专利5 152 983,该文献的公开内容由此引入说明书中。在这些物质中,二苯酮-4和同样二苯酮-9两者具有由磺酸酯基团提供的强酸性官能度,和由酚质子提供的弱酸性官能度。对于这些材料(和对于二苯酮-5,即二苯酮-4的单钠盐),可以制备该物质的多阴离子形式和将其引入氢氧化物固定层。例如,可以将二苯酮-4在基材上固定既作为单阴离子和也作为二阴离子形式。引入层状双氢氧化物中的此材料的单阴离子和二阴离子形式两者和其任何所需组合可适用于防晒剂并被视为在本发明的保护范围内。
UV过滤剂特别优选选自;苯基苯并咪唑磺酸(CAS 27503-81-7;商品名Eusolex 232),二苯酮-4(CAS 4065-45-6;商品名Uvinul-MS-40(BASF)),亚苄基樟脑磺酸(CAS 56039-58-8;商品名Mexoryl SL(Chimex/Loreal)),对苯二亚甲基二樟脑磺酸(CAS 90457-82-2;商品名Mexoryl SX(Chimex,Loreal)),苯基二苯并咪唑四磺酸二钠(CAS 180898-37-7;商品名Neo Heliopan AP(Symrise))。
合适的阴离子形成性防腐剂是苯甲酸、水杨酸、对羟基苯甲酸、对羟基苯甲酸酯(PHB酯)、山梨酸、丙酸、乙酸、亚硫酸酯、二碳酸二乙酯、二碳酸二甲酯、亚硝酸盐、硝酸盐、阴离子形成性抗生素和邻苯基苯酚。合适的阴离子形成性活性化合物同样是生物类黄酮,它们由于它们的基本结构,可以分为如下类别:查耳酮、橙酮、黄烷酮、黄烷-3-醇(儿荼素)、黄酮、异黄酮、黄烷-3,4-二醇(leukoanthocyanidine)、黄酮醇(3-羟基-黄烷(flaven)-4-酮)或黄烷酮醇。
如下类黄酮应当举例提及:5-羟基-7,4’-二甲氧基黄酮8-硫酸酯、7,8-二羟基黄酮、藤黄菌素(黄酮);儿茶素、表儿茶素、表没食子儿荼精没食子酸酯(EGCG,TEA-VIGODSM)(黄烷-3-醇或黄烷-3-醇衍生物);山萘酚(黄酮醇);黄杉素(黄烷酮醇)。
优选的类黄酮衍生自如下物质:黄酮醇、黄酮醇O-糖苷或含黄酮醇O-糖苷的提取物。类黄酮通常作为植物细胞液中的可溶性糖苷出现。优选的类黄酮也包括糖苷配基(无糖结构)和糖苷配基共轭物。可能的糖苷配基共轭物是羟基衍生物,其中所有或一些羟基被烷基化、甲基化、甘氨酰基化、硫酸化或酯化。除羟基衍生物以外,C衍生物也合适作为糖苷配基共轭物。
对于黄酮醇类,特别优选是糖苷配基栎精。在黄酮醇o-糖苷类中,特别优选是黄酮醇3-糖苷,如芦丁、α-葡萄糖基芦丁、银椴苷、异槲皮素、芦丁硫酸酯、三羟基乙基芦丁(曲克芦丁)及其硫酸酯和磷酸酯。术语“芦丁硫酸酯”包括芦丁的单-,二-,三-,四-和多硫酸酯或这些芦丁硫酸酯的混合物。术语“曲克芦丁”包括芦丁的单-,二-,三-,四-和多乙氧基化物或这些芦丁乙氧基化物的混合物。也可以使用黄酮醇7-和8-糖苷。
描述的物质类别仅应当认为是说明性的和仅希望解释本发明而不限制本发明。各种活性化合物当然可以彼此组合,即多种官能活性化合物的混合物可以固定在基材上。
这样固定的活性化合物的数量为0.001-50wt%,基于作为整体的颜料。优选,固定0.5-20.0wt%,特别地1.0-10.0wt%。
在本发明的特别优选的实施方案中,除活性化合物以外,阴离子结合层另外包含阴离子形成性有机、无机和/或有机金属着色剂。这得到多功能粒子,该粒子除活性化合物的功能作用以外,另外显示颜色效果。采用此方式,彼此独立的两种性能彼此结合。这对于用户而言具有的优点是功能作用和颜色效果不再必须通过待单独加入的组分而引入应用体系,反而这可以通过仅加入一种组分而进行。这简化了配制剂的制备和增加对于应用领域的可变化性。由单一工序中同时向配制剂加入多个功能,可另外由消费者经由较短的配制时间而实现节省。这由如下事实论证:有机活性化合物/着色剂或其混合物由于在基材上固定而已经为预分散状态类型,这是由于未固定有机活性化合物/着色剂如已知的那样,经常难以分散。相反由于根据本发明的粒子,此耗时和高能量分散步骤是多余的或仅以非常大地缩短的形式出现。
如果采用的物质的干涉色对应于着色剂的吸收色,则达到特别强的颜色印象。如果基材的干涉色不同于着色剂的吸收色,则达到有吸引力的多色效果,它然后与功能活性化合物的活性相结合。
此类型的着色剂可以是:衍生自有机染料或颜料或衍生自染料或颜料前体的阴离子,或无机或有机阴离子或自由基阴离子或有色杂多阴离子,或上述着色剂的混合物。
可用于非化妆品应用的着色剂原则上是所有的阴离子或阴离子形成性染料。在此合适的特别是C.I.酸性染料,例如:C.I.酸性黄13、C.I.酸性黄17、C.I.酸性黄23、C.I.酸性黄25、C.I.酸性黄36、C.I.酸性黄38、C.I.酸性黄42、C.I.酸性黄44、C.I.酸性黄56、C.I.酸性黄65、C.I.酸性黄76、C.I.酸性黄127、C.I.酸性橙7、C.I.酸性橙10、C.I.酸性橙19、C.I.酸性橙65、C.I.酸性橙67、C.I.酸性红1、C.I.酸性红13、C.I.酸性红14、C.I.酸性红32、C.I.酸性红37、C.I.酸性红38、C.I.酸性红42、C.I.酸性红88、C.I.酸性红119、C.I.酸性红131、C.I.酸性红138、C.I.酸性红154、C.I.酸性红249、C.I.酸性红299、C.I.酸性紫14、C.I.酸性紫42、C.I.酸性紫43、C.I.酸性蓝25、C.I.酸性蓝40、C.I.酸性蓝43、C.I.酸性蓝62、C.I.酸性蓝92、C.I.酸性蓝113、C.I.酸性蓝117、C.I.酸性蓝129、C.I.酸性绿1、C.I.酸性绿25、C.I.酸性绿41、C.I.酸性黑1、C.I.酸性黑24、C.I.酸性黑26、C.I.酸性黑48、C.I.酸性黑210、C.I.酸性黑234、C.I.酸性棕14、C.I.酸性棕20。
此外,C.I.反应性染料也是合适的,例如:C.I.反应性黄4、C.I.反应性黄17、C.I.反应性橙1、C.I.反应性红8、C.I.反应性红12、C.I.反应性红23、C.I.反应性蓝15、C.I.反应性蓝19、C.I.反应性蓝216、C.I.反应性黑5、C.I.反应性黑8、C.I.反应性黑31。
也合适的是C.I.直接染料,例如:
C.I.直接黄12、C.I.直接黄27、C.I.直接黄29、C.I.直接黄50、C.I.直接黄86、C.I.直接橙26、C.I.直接红23、C.I.直接红75、C.I.直接红76、C.I.直接红79、C.I.直接红80、C.I.直接红81、C.I.直接红250、C.I.直接蓝78、C.I.直接蓝86、C.I.直接蓝93、C.I.直接蓝106、C.I.直接绿26、C.I.直接黑19、C.I.直接黑22、C.I.直接黑51、C.I.直接黑150、C.I.直接黑151、C.I.直接黑166、C.I.直接黑168。
最后,也可以采用C.I.媒染染料,例如:C.I.媒染黄1、C.I.媒染黄5、C.I.媒染黄30、C.I.媒染红7、C.I.媒染红19、C.I.媒染红30、C.I.媒染蓝7、C.I.媒染蓝13、C.I.媒染黑3、C.I.媒染黑9、C.I.媒染黑11、C.I.媒染棕33、C.I.媒染棕48,但也可是C.I.可溶性硫化红11,和荧光染料,例如:C.I.碱性黄40、C.I.碱性红12、C.I.溶剂黄94。
优选使用在化妆品应用中批准的有机染料和颜料或其前体和混合物的阴离子。例子是:FD&C黄5(酒石黄)、FD&C黄6(日落黄FCF)、FD&C黄10、FD&C红3(赤藓红)、FD&C红6(LitholrubinB)、FD&C红7(Litholrubin BN)、FD&C红21、FD&C红27、FD&C红28(FloxineB)、FD&C红33、C.I.天然红33、FD&C红36、FD&C红40、胭脂红、FD&C蓝1(艳蓝FCF)、C.I.天然绿3(E141)、FD&C蓝、FD&C黑1(艳黑)。
特别地,也可以在基材上的阴离子结合层上方固定至少两种着色剂阴离子的混合物。这得到无数的颜色变化方案。同样,对着色剂混合物的百分比组成一点也没有限制。
描述的着色剂仅应当认为是说明性的和仅希望解释本发明而不限制本发明。各种基材当然也可以与其它阴离子/阴离子形成性有机或无机着色剂组合。
阴离子形成性有机、无机和/或有机金属着色剂或其混合物的比例是0.01-30wt%,特别地0.5-10wt%,基于作为整体的颜料。
在本发明的特别优选和解释的实施方案中,由Ca0.67Fe0.33(OH)2(Zn-)0.33/n·mH2O组成的阴离子结合层包含UV过滤剂和/或皮肤活性物质。复合材料已经沉淀到薄片状干涉颜料上。因此获得多功能粒子,该粒子在化妆品应用中特别适于用作皮肤修正剂。基材的干涉色和阴离子结合层的皮肤着色吸收色产生着色皮肤不均匀性的直接可觉察的光学修正,和在复合材料中结合的物质保证有利的另外效果,该效果不仅仅在光学方面抑制,反而在活性方面抑制或至少精确地降低这些皮肤变色。
在本发明的进一步实施方案中,另外已经将稳定作用的无机和/或有机涂层施加到粒子上。依赖于应用领域,此后涂覆增加光、水和气候稳定性。也进一步增加产物的渗出稳定性。此类型涂料的例子,例如在DE2215191,DE3151354,DE3334598,EP0632109,US5759255,DE4317019,DE3929423,DE3235017,EP0492223,EP0342533,EP0268918,EP0141174,EP0764191,WO98/13426,EP0090259,EP0634459,WO99/57204,WO96/32446,WO99/57204,US5571851,WO01/92425或EP0465805中描述,该文献的公开内容由此通过参考引入。用于后涂覆的合适无机材料是Al、Si、Zr、Ce、Zn、Fe的氧化物和/或氧化物水合物和/或其混合物,优选Al、Ce、Zn、Zr和/或Si的氧化物和/或氧化物水合物。该层可以为各自氧化物和/或氧化物水合物的单个层形式,但也可以是混合层形式。此外,除单独沉积的氧化物以外,也可以采用氧化物与硫酸盐、磷酸盐和/或硼酸盐的混合物。硫酸盐的例子是ZnSO4和CaSO4,磷酸盐的例子是AlPO4和CePO4及硼酸盐的例子是AlBO4。
这些材料层的突出之处为高透明度,零或仅轻微的固有颜色和高光泽,意味着未改进粒子的色彩性能。总之,应当选择另外的稳定作用涂层的各自比例,使得根据本发明的粒子的光学性能不显著受影响。
任选地施加的有机涂层用作偶联剂和可由如下通式的有机硅烷、有机铝酸酯、有机钛酸酯和/或有机锆酸酯组成:
X4-n-mZ-Rn(-B-Y)m
其中X=OH、卤素、烷氧基或芳氧基
Z=Si、Al、Ti或Zr
R=烷基、苯基或氢
B=有机的至少双官能基团(亚烷基或亚烷基氧亚烷基)
Y=氨基、取代氨基、羟基、羟基烷基、硅氧烷、乙酰氧基、异氰酸酯基、乙烯基、丙烯酰基、环氧化物基团、环氧丙氧基、咪唑基团或脲基
n和m=0、1、2或3,其中n+m≤3。
偶联剂由结合到表面的固着基团(X4-n-mZ),至少一个疏水性基团(R,B)和一个或多个官能团(Y)组成。偶联剂优选是其中Z=Si的化合物。固着基团优选由烷氧基硅烷组成,它可以由水解反应条件转化成对应的羟基。后者能够结合到粒子的表面和通过氧桥完成固着。此外,也可以采用不同偶联剂的混合物,它们可以作为混合物形式或单独施加。
通过合适官能团的选择,有机涂层可以匹配于使用介质。此外,另外的键可以在颜料和介质之间经偶联剂通过官能团与应用介质中对应官能度的反应而形成。在特定的实施方案中,根据本发明的颜料的表面由匹配于使用介质的有机官能度的组合而改性。也适用于此目的的是不同偶联剂的混合物在有机涂层中的使用。颜料表面的疏水性可以由含烷基的偶联剂,例如烷基硅烷的整合入而适应性调节。除有机硅烷以外,也优选使用其水解产物和均质和非均质低聚物和/或聚合物,它们可同样单独采用或与硅烷、锆酸酯、铝酸酯、锆铝酸酯和/或羧基锆铝酸酯结合用作有机涂层。特别优选是包含不同偶联剂,特别地具有彼此不同的官能度Y的不同偶联剂的混合物的有机涂层,这保证特别宽的应用范围。
有机硅烷的例子是丙基三甲氧基硅烷、丙基三乙氧基硅烷、异丁基三甲氧基硅烷、正辛基三甲氧基硅烷、异辛基三甲氧基硅烷、正辛基三乙氧基硅烷、正癸基三甲氧基硅烷、十二烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、乙烯基三甲氧基硅烷,优选正辛基三甲氧基硅烷和正辛基三乙氧基硅烷。合适的低聚物型无醇有机硅烷水解产物尤其是由Sivento以商品名“Dynasylan”销售的产品,例如DynasylanHS 2926、Dynasylan HS 2909、Dynasylan HS 2907、Dynasylan HS 2781、Dynasylan HS 2776、Dynasylan HS 2627。此外,低聚物乙烯基硅烷和氨基硅烷水解产物合适作为有机涂层。官能化有机硅烷是,例如3-氨基丙基三甲氧基硅烷、3-甲基丙烯酰氧基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-异氰酸基丙基三甲氧基硅烷、1,3-双(3-缩水甘油氧基丙基)-1,1,3,3-四甲基二硅氧烷、脲基丙基三乙氧基硅烷,优选3-氨基丙基三甲氧基硅烷、3-甲基丙烯酰氧基三甲氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-异氰酸基丙基三甲氧基硅烷。聚合物硅烷体系的例子描述于WO98/13426和例如由Sivento以商品名Hydrosil销售。
有机涂层的数量为0.2-5wt%,优选0.5-2wt%,基于颜料。
本发明另外涉及根据本发明的粒子的制备方法,其中将由一种或多种基材、金属阳离子盐,活性化合物或着色剂盐或这些盐的混合物(下文缩写为“活性化合物盐”),和碱液和/或脲在溶剂或溶剂混合物中形成的悬浮液在50-120℃的温度下搅拌,使得基材上形成阴离子结合层在,其中阴离子结合层包含阴离子形成性有机活性化合物,和将产物随后分离出,洗涤,干燥和任选地筛分。
在最简单的情况下,将由基材,金属阳离子盐和所述一种或多种活性化合物盐与碱液和/或碱液前体一起初始引入悬浮液中,和在层状双氢氧化物的情况下,依赖于采用的LDH和活性化合物盐的类型,在10-120℃的温度下搅拌2-48小时。在反应悬浮液冷却之后,将产物吸滤出和采用合适的溶剂洗涤直到流出的滤液几乎没有活性化合物。随后将滤饼在50-180℃下干燥和任选地筛分到所需细度。
在进一步的变化方案中,可以将金属阳离子盐的溶液加入由所述一种或多种基材,活性化合物盐和碱液和/或碱液前体形成的悬浮液中。在最简单的情况下,这意味着将基材,碱液和/或碱液前体和活性化合物盐初始引入悬浮液中。随后在室温下滴加金属阳离子盐的溶液。在加料完成之后,依赖于LDH和活性化合物的类型,将反应混合物加热到50-100℃和在此温度下搅拌2-48小时。在反应悬浮液冷却之后,将产物吸滤出和采用合适的溶剂洗涤直到流出的滤液几乎没有活性化合物。随后将滤饼在50-180℃下干燥和任选地筛分到所需细度。
合适的碱液是NaOH、KOH或NH3的水溶液,但也是碱液前体,例如脲,它仅在反应介质中释放出实际碱液,例如通过水解。在反应期间的pH(它意味着在整个反应中的pH行为)通常是2-13,特别地3-11。
用于形成LDH层的合适金属阳离子从专业文献中是已知的。合适的金属阳离子盐原则上是具有Al3+、Cr3+、Fe3+、Ga3+、In3+、γ3+、La3+、Ce3+、Ba2+、Ca2+、Cu2+、Mg2+、Sr2+和/或Zn2+阳离子的所有可溶性盐,可以从其制备由层状双氢氧化物组成的阴离子结合层。特别地,该金属阳离子盐是对应的卤化物,特别地氯化物、溴化物或碘化物。然而,金属阳离子的硫酸盐和硝酸盐也是合适的。非常特别优选采用对应的氯化物和硝酸盐。
在根据本发明的多功能粒子的制备的替代性两步变化方案中,将由基材/基材混合物,金属阳离子盐和碱液和/或脲在溶剂或溶剂混合物中形成的悬浮液在10-120℃的温度下搅拌,使得由层状双氢氧化物组成的阴离子结合层在基材上形成,然后将中间体分离出,洗涤,在50-300℃下干燥和任选地筛分。随后采用搅拌将LDH涂覆的基材加入到阴离子形成性有机官能活性化合物的溶液中。在此方法变化方案中,发生离子交换,其中阴离子结合性的双氢氧化物的阴离子Zn-由阴离子形成性活性化合物替代。在反应悬浮液冷却之后,将产物吸滤出和洗涤。将滤饼在40-70℃下干燥。可以随后任选地研磨和/或筛分经干燥的混杂颜料。
在后提及的方法中,采用的金属盐应当优选是对应的氯化物或硝酸盐,这是由于这两种阴离子在随后步骤中交换最快。此两步方法也特别适于温度敏感性活性化合物,这是由于与其它方法相比,活性化合物在合成期间不经历高温达延长的时间和此外可以在显著更低的温度下干燥含活性化合物的最终产物。
此外,也证明在此两步合成变化方案中有利的是在加入到阴离子形成性有机活性化合物的溶液中之前,在300-600℃的温度下煅烧中间体,其具有在基材上形成的由层状双氢氧化物组成的阴离子结合层。在此,通过在300-600℃下煅烧将LDH涂覆的基材首先转化成LDO涂覆的基材。LDO(“层状双氧化物”)随后在水性或包含水的介质中再形成LDH结构和促进更容易和更完全的插层。
在上述两步方法的替代变化方案中,也可以首先制备LDH或LDO涂覆的基材的悬浮液,向其中然后在20-70℃下采用搅拌加入活性化合物阴离子的溶液。可通常在此温度下搅拌混合物2-48h。当活性化合物阴离子的固定完成时,将产物吸滤出和采用合适的溶剂洗涤直到流出的滤液几乎没有活性化合物。随后将滤饼在40-70℃下干燥和任选地筛分到所需细度。
上述方法适于制备包含活性化合物的粒子,也适合用于包含活性化合物和着色剂的组合的粒子的优选制备。着色剂在此可已经从开始就在含有活性化合物的混合物中存在或随后加入。特别地,也可以首先制备包含着色剂或活性化合物的粒子和随后在进一步的步骤中如上所述,通过离子交换向阴离子结合层中引入各自的其它组分。
此外,在同样根据本发明的方法中可以另外将无机和/或有机涂层施加为外层。此类型的涂覆工艺的例子尤其在EP0632109,US5759255,DE4317019,DE3929423,DE3235017,EP0492223,EP0342533,EP0268918,EP0141174,EP0764191,WO98/13426或EP0465805中给出。无机和/或有机涂料的例子和相关优点以上在根据本发明的颜料的合成部分中已经描述过。有机涂层的施加的工艺步骤可以立即在根据本发明的方法的其它步骤之后进行。将偶联剂在溶液中在高于60℃,优选高于70℃的温度下施加。合适的溶剂是有机溶剂,水或其混合物,优选水。用于有机涂层的施加所必需的反应时间是至少5分钟,它优选在超过10-90分钟的时间内进行,但如需要这也可以延长。将获得的颜料后处理和由本领域技术人员熟悉的方法,例如由过滤,干燥和筛分而分离。
根据本发明的粒子可用于各种应用。因此,本发明同样涉及根据本发明的粒子在化妆品、药物、配制剂、油漆、涂料、塑料、薄膜中,在安全印刷中,在文件和身份证件中的安全特征中,用于种子着色、用于食品着色或在药剂包衣中和用于制备颜料组合物和干制剂的用途。
在化妆品的情况下,根据本发明的混杂颜料特别适于装饰和护理化妆品方面的产品和配制剂,例如软膏、霜膏剂、糊剂、指甲油、着色粉、唇膏或眼影、肥皂、牙膏、自晒黑配制剂等。根据本发明的混杂颜料当然也可以与所有类型的化妆品原材料和助剂在配制剂中组合。这些尤其包括油、脂肪、蜡、成膜剂、防腐剂和一般性确定应用性能的助剂,例如增稠剂和流变添加剂,例如膨润土、锂蒙脱石、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。包含根据本发明的混杂颜料的配制剂可以为亲脂性、亲水性或疏水性类型。在含有离散的含水和非含水相的多相配制剂的情况下,根据本发明的粒子在每种情况下可在两相中的仅一个相中存在或在两个相中分布。
含水配制剂的pH值可以为4-14,优选5-11和特别优选6-9。如先前所述,配制剂中的pH确定LDH固定层的功能;在pH<6下,LDH的缓慢溶解得到受控释放功能。相反,如果pH>6在配制剂中占优势,则LDH是稳定的和因此用作结合阴离子的固体“容器”。使用范围或受控释放功能当然地受到已经提及的任选后涂覆的显著影响。因此,在更宽pH范围内由后涂覆的稳定化可能伴随着受控释放功能的部分或完全损失。例如,后者优选在UV过滤剂的固定期间完成。
将有机UV过滤剂通常采用0.5-10wt%,优选1-8%的数量引入化妆品配制剂中,和无机填料的数量为0.1-30%。
根据本发明的混杂颜料在配制剂中的浓度不受限制。依赖于应用,它们可以在0.001(冲洗掉型产品,例如淋浴凝胶)和99%(例如用于特定应用的光泽效应制品)之间。根据本发明的混杂颜料此外也可以与化妆品活性化合物结合。合适的活性化合物是,例如驱虫剂、UV A/BC防护过滤剂(例如OMC,B3,MBC)、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(例如尤其DHA,赤藓酮糖)和另外的化妆品活性化合物,例如没药醇、LPO、依克多因、余甘子(emblica)、尿囊素、生物类黄酮及其衍生物。通常,根据本发明的粒子也可以与通过阴离子结合层结合到基材的物质/物质混合物结合。这例如可以在延长的时间内得到配制剂,其中在施加配制剂之后的中间体作用(由非结合活性化合物)伴随着另外的延迟作用(LDH结合的活性化合物的受控释放)。
根据本发明的制剂可另外包含进一步的常规皮肤保护或皮肤护理活性化合物。这些可原则上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,应当特别提及依克多因和依克多因衍生物用于老化、干燥或受刺激皮肤的护理。因此,欧洲专利申请EP-A-0671161特别描述的是依克多因和羟基依克多因用于化妆品配制剂,如粉末、肥皂、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。
可以提及的化妆品配制剂的应用形式是,例如:溶液、悬浮液、乳液、PIT乳液、糊剂、软膏、凝胶、霜膏剂、洗剂、粉剂、肥皂、含表面活性剂的清洁制剂、油、气溶胶和喷雾剂。其它应用形式的例子是棒、香波和淋浴制剂。任何所需的常规载体,助剂和如需要,进一步的活性化合物可以加入制剂中。
软膏、糊剂、霜膏剂和凝胶可包含常规载体,例如动物和植物脂肪、蜡、石蜡、淀粉、黄蓍胶、纤维素衍生物、聚乙二醇、硅氧烷、膨润土、二氧化硅、滑石和氧化锌或这些物质的混合物。
粉末和喷雾剂可包含常规载体,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。喷雾剂可另外包含常规推进剂,例如含氯氟烃、丙烷/丁烷或二甲基醚。
溶液和乳液可包含常规载体,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-丁基乙二醇、油,特别地棉籽油、花生油、玉米胚芽油、橄榄油、蓖麻油和芝麻油、甘油脂肪酸酯、聚乙二醇和脱水山梨醇脂肪酸酯或这些物质的混合物。
悬浮液可包含常规载体,如液体稀释剂,例如水、乙醇或丙二醇,悬浮介质,例如乙氧基化异硬脂醇、聚氧乙烯山梨醇酯和聚氧乙烯脱水山梨醇酯、微晶纤维素、偏氢氧化铝、膨润土、琼脂和黄蓍胶或这些物质的混合物。
肥皂可包含常规载体,如脂肪酸碱金属盐、脂肪酸单酯盐、脂肪酸蛋白质水解产物、羟乙基磺酸盐(isothionate)、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包含常规载体,如脂肪醇硫酸酯的盐、脂肪醇醚硫酸酯、磺基琥珀酸单酯、脂肪酸蛋白质水解产物、羟乙基磺酸盐、咪唑衍生物、牛磺酸甲酯、肌氨酸盐、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。
面部和身体油可包含常规载体,如合成油,例如脂肪酸酯、脂肪醇、硅油、天然油,如植物油和油性植物提取物、石蜡油、羊毛脂油,或这些物质的混合物。
化妆品制剂可以采用各种形式存在。例如,它们可以是例如溶液、无水制剂、油包水(W/O)或水包油(O/W)类型的乳液或微乳液、例如为水包油包水(W/O/W)类型的多重乳液、凝胶、固体棒、软膏或气溶胶。也有利地采用包囊形式给用依克多因,例如在胶原基体和其它常规包囊材料中,例如作为纤维素包囊形式,在明胶、蜡基体中,或脂质体包囊的。特别地,如在DE-A-4308282中描述的蜡基体证明是有利的。优选是乳液。特别优选是O/W乳液。乳液、W/O乳液和O/W乳液可采用常规方式获得。
进一步的实施方案是基于天然或合成油和蜡、羊毛脂、脂肪酸酯,特别地脂肪酸甘油三酯的油性洗剂,或基于低级醇,如乙醇,或甘油,如丙二醇,和/或多元醇,如甘油,和油、蜡和脂肪酸酯,如脂肪酸甘油三酯的油性-含醇洗剂。
固体棒由天然或合成蜡和油、脂肪醇、脂肪酸、脂肪酸酯、羊毛脂和其它脂肪物质组成。
如果将制剂配制为气溶胶形式,则一般使用常规推进剂,如烷烃、氟烷烃和含氯氟烃。
化妆品制剂也可用于保护头发以免光化学损害,以防止颜色变化,漂白或机械性质的损害。在此情况下,合适的配制剂为冲洗掉型香波、洗剂、凝胶或乳液形式,将关注的制剂在洗发之前或之后,在着色或漂白之前或之后,或在持久卷发之前或之后施加。也可以选择用于定型或处理头发的洗剂或凝胶形式的制剂,用于刷洗或吹烫的洗剂或凝胶形式的制剂,用于头发的头蜡、持久卷发组合物、着色剂或漂白剂形式的制剂。具有光防护性能的制剂可包含佐剂,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,硅氧烷衍生物,油,蜡,防油腻剂,将组合物自身或头发着色的染料和/或颜料,或通常用于头发护理的其它成分。
在油漆和涂料中使用粒子时,本领域技术人员已知的所有应用领域是可能的,例如粉末涂料、汽车油漆、凹版印刷油墨、胶版印刷油墨、丝网印刷油墨或柔性版印刷油墨和室外应用中的涂料。油漆和涂料在此可以是,例如辐射固化、物理固化或化学固化的。多种粘结剂适于制备印刷油墨或液体表面涂料,例如基于丙烯酸酯、甲基丙烯酸酯、聚酯、聚氨酯、硝基纤维素、乙基纤维素、聚酰胺、聚丁酸乙烯酯、酚醛树脂、马来酸树脂、淀粉或聚乙烯醇、氨基树脂、醇酸树脂、环氧树脂、聚四氟乙烯、聚偏二氟乙烯、聚氯乙烯或其混合物,特别地水溶性品级。表面涂料可以是粉末涂料或水基或溶剂基涂料,其中涂料组分的选择是本领域技术人员公知常识的一部分。用于粉末涂料的通常聚合物粘结剂是,例如聚酯、环氧化物、聚氨酯、丙烯酸酯或其混合物。
此外,根据本发明的粒子可用于薄膜和塑料,例如用于农用薄膜、红外反射性膜片和片材、礼品箔、塑料容器和用于本领域技术人员已知的所有应用的模塑件。用于引入根据本发明的粒子的合适塑料是所有通用塑料,例如热固性塑料或热塑性塑料。可能应用和可以采用的塑料,加工方法和添加剂的描述例如在RD472005中或在R.Glausch,M.Kieser,R.Maisch,G.Pfaff,J.Weitzel,Perlglanzpigmente(珠光颜料),Curt R. Vincentz Verlag,1996,第83页及后几页中给出,该文献的公开内容也在此引入。
此外,根据本发明的粒子也适用于安全印刷和安全相关特征,该特征例如用于防伪卡和身份证件,例如入场票、个人身份证件、钞票、支票和支票卡,和用于其它防伪文件。在农业领域中,除在食品领域中用于食品着色以外,粒子可用于种子和其它起开始材料的着色。根据本发明的粒子可同样用于将药剂,例如片剂或糖锭剂中的包衣着色。
根据本发明的粒子在上述应用领域中同样适合与有机染料和/或颜料,例如透明和不透明白色、彩色和黑色颜料,和与薄片状氧化铁,有机颜料,全息颜料,LCP(液晶聚合物)和基于金属氧化物涂覆的薄片的常规透明的彩色和黑色光泽颜料掺混使用,所述薄片基于云母、玻璃、Al2O3、Fe2O3、SiO2等。上述材料和颜料结构的例子和实施方案也例如在研究公开RD471001和RD472005中给出,该文献的公开内容在此通过参考引入。根据本发明的粒子可以采用任何比例与市售颜料和填料混合。
可以提及的填料是,例如天然和合成云母、尼龙粉末、纯或填充的蜜胺树脂、滑石、玻璃、高岭土,铝、镁、钙、锌的氧化物或氢氧化物、BiOCl、硫酸钡、硫酸钙、碳酸钙、碳酸镁、碳,和这些物质的物理或化学组合。关于填料的粒子形状没有限制。例如,根据要求它可以是薄片状、球形或针形的。
根据本发明的粒子另外适于制备包含如下物质的可流动颜料组合物和干制剂:一种或多种根据本发明的粒子,粘结剂和任选地一种或多种添加剂。干制剂也用于表示包含0-8wt%,优选2-8wt%,特别地3-6wt%水和/或溶剂或溶剂混合物的制剂。干制剂优选为粒料、颗粒、屑片、香肠状物或压块的形式,和粒度为0.2-80mm。干制剂特别用于制备印刷油墨和用于化妆品配制剂中。
本发明此外涉及包含根据本发明的粒子的化妆品、药物、配制剂、油漆、涂料、塑料、薄膜、文件和身份证件、种子、食品或药剂包衣和颜料组合物和干制剂。
以上提及的所有专利申请,专利和公开文本的完整公开内容通过参考引入本申请。
具体实施方式
如下实施例希望更详细地解释本发明,而不限制本发明。
实施例:
实施例 1:
将50g玻璃薄片(ECR玻璃,粒度级10-100μm,基材厚度:870nm)加入300ml水和150ml NaOH(0.5M)中。在搅拌30min之后,加入作为染料的2.9g的C.I.FD&C红6“Unipure Red LC303”和作为UV-A过滤剂的2.9g的Neo Heliopan AP。将10.15g的MgCl2×6H2O,6.05g的AlCl3×6H2O和20.95g脲各自溶于约100ml水中和同样加入。将混合物在回流下搅拌24h。让悬浮液冷却,和将残余物吸滤出和采用水洗涤。将残余物在50℃下干燥,得到具有亮红色的闪光粒子,该粒子由于有机UV过滤剂的含量而在UV-A区域中具有另外的吸收谱带。
实施例2:
将50g红色干涉颜料(由约4wt%SiO2,约1wt%SnO2和约25wt%TiO2涂覆的ECR玻璃,粒度级:10-100μm,基材厚度:850nm)加入190ml水和310ml NaOH(0.5M)中。在搅拌30min之后,加入作为活性化合物的4g芦丁硫酸酯(特定的生物类黄酮)。将10.15g的MgCl2×6H2O溶于约150ml水,与包含15wt%Fe的9.3g FeCl3溶液混合和在一小时时间内采用搅拌下加入。随后采用水将混合物补足到750ml的总体积。将混合物在回流下搅拌12h。让悬浮液冷却,和将残余物吸滤出和采用水洗涤直到流出的滤液几乎没有活性化合物。将残余物在60℃下干燥,得到具有红色干涉色的闪光颜料,该颜料在pH<6下在配制剂中释放出芦丁硫酸酯的抗氧化作用。
实施例3:
a)将50g的TimironSplendid红(基于云母在10-60μm级分中的多层红色干涉颜料)加入190ml水和310ml NaOH(0.5M)中,和将混合物搅拌30min。将7.34g的CaCl2×2H2O和6.05g的AlCl3×6H2O溶于约200ml水和在一小时时间内采用搅拌下加入。随后采用水将混合物补足到750ml的总体积。将混合物在回流下搅拌12h。让悬浮液冷却,和将残余物吸滤出和采用约两升水洗涤。将残余物首先在110℃下干燥和随后在300-600℃下煅烧。
b)在pH=7.5-8下将2.9g苯基苯并咪唑磺酸(Eusolex232,UV-B过滤剂)溶于500ml水。然后加入得自步骤a)的0.25g中间体。将悬浮液搅拌12小时,和将产物吸滤出,采用水洗涤直到UV过滤剂在滤液中不再可检测出和随后在50℃下干燥,得到具有弱红色干涉色的颜料,该颜料由于UV过滤剂的含量而在UV-B区域中具有另外的吸收谱带。
Claims (22)
1.包含基材和阴离子结合层的粒子,该阴离子结合层包含一种或多种阴离子形成性有机活性化合物。
2.根据权利要求1的粒子,其特征在于基材由阴离子结合层涂覆。
3.根据权利要求1或2的粒子,其特征在于阴离子结合层包含层状双氢氧化物。
4.根据权利要求1-3中一项或多项的粒子,其特征在于基材是薄片状、球形、针形或不规则形状。
5.根据权利要求1-4中一项或多项的粒子,其特征在于有机活性化合物选自药物活性化合物、食品增补剂、诊断用物质和化合物和/或化妆品活性化合物。
6.根据权利要求1-5中一项或多项的粒子,其特征在于有机活性化合物包含一种或多种阴离子形成性酚盐、烯醇化物、羧酸酯、硫酸酯、磺酸酯、亚磺酸酯、二硫羟酸酯、磷酸酯和/或亚磷酸酯结构单元。
7.根据权利要求1-6中一项或多项的粒子,其特征在于有机活性化合物包含至少两种阴离子形成性酚盐、烯醇化物、羧酸酯、硫酸酯、磺酸酯、亚磺酸酯、二硫羟酸酯、磷酸酯和/或亚磷酸酯结构单元。
8.根据权利要求1-7中一项或多项的粒子,其特征在于由金属氧化物、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物、金属氧氮化物或这些材料的混合物构成的一个或多个透明、半透明和/或不透明层施加到基材上和在阴离子结合层下方。
9.根据权利要求1-8中一项或多项的粒子,其特征在于基材采用离子或元素掺杂。
10.根据权利要求1-9中一项或多项的粒子,其特征在于阴离子结合层包含如下通式的双氢氧化物
M2+ 1-xM3+ x(OH)2(Zn-)x/n·mH2O
其中0.2<x<0.33,其中
M3+选自Al3+、Cr3+、Fe3+、Ga3+、In3+、Y3+、La3+和/或Ce3+和
M2+选自Ba2+、Ca2+、Cu2+、Mg2+、Sr2+和/或Zn2+,
Z表示金属盐的反荷离子和/或阴离子形成性有机活性化合物的阴离子或阴离子混合物,其中n表示阴离子的电荷数目。
11.根据权利要求10的粒子,其特征在于M3+=Al3+或Fe3+,和M2+=Mg2+、Ca2+或Zn2+。
12.根据权利要求1-11中一项或多项的粒子,其特征在于阴离子结合层的层厚度为0.5-500nm。
13.根据权利要求1-12中一项或多项的粒子,其特征在于阴离子形成性活性化合物或活性化合物混合物的比例是0.001-50wt%,特别地0.5-20wt%,基于作为整体的粒子。
14.根据权利要求1-13中一项或多项的粒子,其特征在于除活性化合物以外,阴离子结合层另外包含阴离子形成性有机、无机和/或有机金属着色剂。
15.根据权利要求1-14中一项或多项的粒子,其特征在于阴离子形成性有机、无机和/或有机金属着色剂的比例是0.01-30wt%,特别地0.5-10wt%,基于作为整体的粒子。
16.根据权利要求1-15中任一项的粒子,其特征在于另外已将稳定作用的无机和/或有机涂层施加到粒子上。
17.制备根据权利要求1的粒子的方法,其中将由基材、金属阳离子盐、一种或多种活性化合物盐和非必要的一种或多种着色剂盐和碱液和/或脲在溶剂或溶剂混合物中形成的悬浮液在50-120℃的温度下搅拌,使得在基材上形成阴离子结合层,其中阴离子结合层包含阴离子形成性有机活性化合物和非必要的着色剂,和将产物随后分离出,洗涤,干燥和非必要地筛分。
18.根据权利要求17的方法,其特征在于将金属阳离子盐的溶液加入由基材、活性化合物盐和非必要的着色剂盐和碱液和/或脲形成的悬浮液中。
19.制备根据权利要求1的粒子的方法,其中将由基材、金属阳离子盐和碱液和/或脲在溶剂或溶剂混合物中形成的悬浮液在50-120℃的温度下搅拌,使得在基材上形成阴离子结合层,然后将产物分离出,洗涤,干燥和非必要地筛分,和随后采用搅拌将此产物加入到由阴离子形成性有机活性化合物和非必要的阴离子形成性着色剂形成的溶液中。
20.根据权利要求19的方法,其特征在于在加入到由阴离子形成性有机活性化合物和非必要的阴离子形成性着色剂形成的溶液中之前,将产物在300-600℃的温度下煅烧,其中在基材上形成阴离子结合层。
21.根据权利要求1的粒子用于化妆品、药物、配制剂、油漆、涂料、塑料、薄膜中,用于安全印刷中,用于文件和身份证件中的安全特征中,用于种子着色,用于食品着色或用于药剂包衣中和用于制备颜料组合物和干制剂的用途。
22.包含根据权利要求1的粒子的化妆品、药物、配制剂、油漆、涂料、塑料、薄膜、文件和身份证件、种子、食品或药剂包衣和颜料组合物和干制剂。
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| JP2860673B2 (ja) * | 1989-11-10 | 1999-02-24 | 花王株式会社 | 含色素薄片状顔料の製造法 |
| GB9203806D0 (en) * | 1992-02-21 | 1992-04-08 | Unilever Plc | Sunscreen agents |
| GB9424445D0 (en) * | 1994-12-02 | 1995-01-18 | Unilever Plc | Cosmetic composition |
| JP2001234090A (ja) * | 2000-02-22 | 2001-08-28 | Yasushi Kubo | 着色フレーク顔料とその製造法 |
| JP4288452B2 (ja) * | 2001-04-03 | 2009-07-01 | 戸田工業株式会社 | Mg−Al系ハイドロタルサイト型粒子粉末の製造法及び塩素含有樹脂安定剤並びに塩素含有樹脂組成物 |
| GB0220578D0 (en) * | 2001-12-04 | 2002-10-09 | Unilever Plc | Hair treatement composition |
| CN1243535C (zh) * | 2001-07-28 | 2006-03-01 | 株式会社纳诺喜博莱德 | 具有改进性能的化妆品原料及其制备方法 |
| JP2003213156A (ja) * | 2002-01-17 | 2003-07-30 | Yasushi Kubo | 着色真珠光沢フレーク顔料 |
| JP2004091421A (ja) * | 2002-09-03 | 2004-03-25 | Tayca Corp | アスコルビン酸を取り込んだ層状複水酸化物およびそれを含む化粧料組成物 |
| US20060225609A1 (en) * | 2002-12-17 | 2006-10-12 | Reinhold Rueger | Silvery white interference pigments having a high luster and based on transparent substrate laminae |
| JP4193044B2 (ja) * | 2003-03-28 | 2008-12-10 | 戸田工業株式会社 | Mg−Zn−Al系ハイドロタルサイト型粒子粉末及び該Mg−Zn−Al系ハイドロタルサイト型粒子粉末を用いた樹脂組成物 |
| EP1481658B1 (en) * | 2003-05-27 | 2009-08-05 | Yasushi Kubo | Coloring pearlescent flake pigment, manufacturing method of the same and cosmetic product containing the same |
| EP1847571B1 (de) * | 2006-04-21 | 2013-12-25 | Merck Patent GmbH | Pigment comprising a plate-shaped substrate |
| JP2007297621A (ja) * | 2006-04-21 | 2007-11-15 | Merck Patent Gmbh | 顔料 |
-
2006
- 2006-05-24 DE DE102006024289A patent/DE102006024289A1/de not_active Withdrawn
-
2007
- 2007-05-21 EP EP07010046.6A patent/EP1860158B1/de not_active Not-in-force
- 2007-05-21 TW TW096117979A patent/TW200815099A/zh unknown
- 2007-05-22 KR KR1020070049669A patent/KR20070113147A/ko not_active Withdrawn
- 2007-05-22 JP JP2007135024A patent/JP2008024916A/ja active Pending
- 2007-05-24 CN CNA2007101051528A patent/CN101121832A/zh active Pending
- 2007-05-24 US US11/802,715 patent/US7914893B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020889A (zh) * | 2011-01-14 | 2011-04-20 | 深圳市墨库图文技术有限公司 | 喷墨打印用的防日晒红色喷墨墨水组合物 |
| CN102020889B (zh) * | 2011-01-14 | 2013-07-17 | 深圳市墨库图文技术有限公司 | 喷墨打印用的防日晒红色喷墨墨水组合物 |
| CN116687831A (zh) * | 2023-07-03 | 2023-09-05 | 广州多多化妆品有限公司 | 一种多色眼影及其制备方法 |
| CN117731545A (zh) * | 2023-12-20 | 2024-03-22 | 北京工商大学 | 一种稳定有机防晒剂丁基甲氧基二苯甲酰基甲烷的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008024916A (ja) | 2008-02-07 |
| US20070275244A1 (en) | 2007-11-29 |
| KR20070113147A (ko) | 2007-11-28 |
| TW200815099A (en) | 2008-04-01 |
| EP1860158B1 (de) | 2013-12-04 |
| US7914893B2 (en) | 2011-03-29 |
| EP1860158A3 (de) | 2011-05-04 |
| EP1860158A2 (de) | 2007-11-28 |
| DE102006024289A1 (de) | 2007-11-29 |
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