CN1282766A - 薄片颜料及其生产方法 - Google Patents
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Abstract
本发明提供一种同时具有高的软焦点效果、铺展效果、紫外线遮蔽效果和合适白度的薄片颜料。本发明涉及一种薄片颜料,其中将平均粒径20—400纳米的球状硅石颗粒粘附到平均粒径0.5—10μm的片状基材的表面上,然后将粘附有球状硅石的片状基材的所述粘附有球状硅石颗粒的表面进一步涂以二氧化钛的超细颗粒。
Description
本发明涉及一种用于化妆品、树脂等的薄片颜料。更具体地说,本发明涉及一种具有化妆品所需的高软焦点效果(这是一种针对皮肤的遮皱效果)、良好的皮肤铺展效果、紫外线遮蔽效果和合适白度的薄片颜料,并涉及一种生产它的方法。
迄今已经使用薄片物质如天然云母、合成云母、涂有二氧化钛的云母、滑石、绢云母和氮化硼作为用于化妆品的增量剂或用于树脂等的填料等。但它们在用于化妆品时,它们不能同时满足各种所需特性,如遮皱效果、紫外线遮蔽效果和白度、以及皮肤粘附性和在皮肤上的铺展性能。
对于具有良好皮肤铺展性的颜料,增量剂如没有光泽的滑石、和氮化硼已可以商业供应,但某些滑石已证实包含石棉,因此目前其作为化妆品颜料的应用已受到限制。由氮化硼组成的颜料并不适用于化妆品应用,因为氮化硼昂贵,而且未反应的硼酸有时包含在其原料中。此外,薄片氯氧化铋、涂有二氧化钛的云母、等已在某些化妆品中用作具有良好铺展性的颜料,因为它们的触觉和在皮肤上的铺展性良好。但氯氧化铋光泽太强因此对皮肤不自然,结果其在粉底等中的应用受到限制。
对于具有改进铺展性的颜料,已经提出将0.05-50μm的硅石颗粒粘附到云母或云母钛的表面上(GP3922178/1989;日本专利公开Hei-03/45660)。该颜料是想通过硅石颗粒的球轴承效应(ball bearingeffect)来提高铺展性,但缺点在于与皮肤的粘附性弱,而且硅石颗粒与云母表面的粘附性也不足。因此,在生产之后和使用之前往往会出现剥落,这样就难以实现足够的铺展效果。此外,粘附硅石颗粒的直径高至0.05-50μm,因此难以预期对应于遮皱效果的软焦点效果(参考NaokiNakamura等人:the ⅩⅣth I.F.S.C.C.Congress,Barcelona,1986,第1卷,51-63页)。
关于其中改进了涂有硅石颗粒的上述薄片颜料的颜料,已经提出其中使用有机硅石如4-乙基硅酸盐或硅酸钠来提高球状硅石颗粒粘附性能的颜料(W0 92/03119)。据说这种颜料具有改进的皮肤粘附性能和铺展效果,而且还具有软焦点效果。在此公开的硅石颗粒的直径据说为约5μm或更低,优选0.05-3μm。但即便粒径如此,该硅石颗粒仍然太大,因此需要一种特定的粘附性能处理条件(分散体溶液的介电常数和离子浓度要根据粘附性能而规定)。这不便于生产。此外,由于颜料的白度低,另一问题在于,如果用于化妆品,还要加入二氧化钛或类似物以提高白度。
此外,在上述两种涂有硅石颗粒的颜料中,分别使用了粒径高至1-500μm以及约30μm(指实施例)的片状基材,它们太大,尤其是对于粉底,而且它们在皮肤上的滑动性不好。
本发明人为了改进尤其用于化妆品的颜料进行了深入研究,目的是解决上述问题,结果成功地开发出一种具有遮皱效果(软焦点效果)、铺展效果(产品的摩擦系数或MIU低)、紫外线遮蔽效果和合适白度的薄片颜料。
因此,本发明提供了一种薄片颜料、其生产方法及其作为化妆品和填料的应用,正如以下[1]-[6]所述。
[1]一种薄片颜料,其中将平均粒径20-400纳米的球状硅石颗粒粘附到平均粒径0.5-10μm的片状基材的表面上,然后将粘附有球状硅石的片状基材的所述表面进一步涂以二氧化钛的超细颗粒。
[2]根据[1]的薄片颜料,其中所述球状硅石颗粒的量为基于粘附有球状硅石的片状基材的30%重量或更低。
[3]根据[1]或[2]的薄片颜料,其中所述二氧化钛细颗粒的量为基于薄片颜料的1-50%重量且所述二氧化钛细颗粒的粒径为30纳米或更低。
[4]一种生产根据任何[1]-[3]的薄片颜料的方法,其特征在于,该方法包括将碱的水溶液加入片状基材的水悬浮液中以形成碱性,将球状硅石细颗粒的悬浮液在加热和搅拌下加入所述碱性悬浮液中,将一部分预定量的钛盐水溶液滴加其中以使pH值为1.5-2.5,这样可将球状硅石颗粒粘附到所述片状基材的表面上,将剩余的钛盐水溶液加入其中并保持pH值为1.5-2.5,然后将pH值升至5并过滤出所得固体,水洗、干燥并煅烧。
[5]一种包含根据任何[1]-[3]的薄片颜料的化妆剂。
[6]根据任何[1]-[3]的薄片颜料作为填料的应用。
基本上任何天然和合成物质都可用作本发明所用片状基材的材质,但考虑到作为颜料的应用,优选安全性高且耐久性如耐热性良好的物质。更具体地说,可以列举薄片状的天然云母、合成云母、云母钛(涂有二氧化钛的薄片云母;该术语在本说明书中具有相同的含义)、滑石、绢云母、高岭土和矾土(包括涂有二氧化钛的那些),其中优选天然云母、合成云母、云母钛、滑石和绢云母。其中,天然云母、合成云母和云母钛更为优选。
至于这些片状基材的形状,建议平均粒径为0.5-10μm或优选2-8μm,这样这些颗粒的粒径可保持适用作化妆品的低摩擦系数(MIU),同时几乎不造成粉末的聚集。如果使用小于0.5μm的颗粒,那么通过本发明得到的产品就容易聚集,不能实现作为原始颗粒的功能,因此不优选。结果,毋庸置疑,不能预期在铺展性和软焦点效果上的改进。另一方面,如果使用大于10μm的颗粒,难以得到在皮肤上具有良好滑动性的颜料。具有这种优选粒径的颗粒容易通过结合利用本领域熟练技术人员常用的粉碎和分级法,由天然或合成物质制成。某些合成物质可在合成过程中,如水热工艺和熔融盐工艺中通过控制晶体的生长速率而制成上述范围内的预定粒径。也可简单地使用具有上述粒径的市售品。在这些薄片状基材中,天然云母或涂有二氧化钛的天然云母(云母钛)由于成本低且易得而特别适用作基材。
用于本发明的球状硅石颗粒在市场上容易得到。粒径是根据上述片状基材尺寸(0.5-10μm)的限制、目标低摩擦系数、等来确定的,因此平均粒径20-400纳米,优选40-300纳米的颗粒是合适的。如果球状硅石的粒径大于该值,球状硅石在片状基材上的粘附性就下降,因此不能实现铺展性。这样就不能实现软焦点效果。另一方面,如果粒径大于该值,虽然球状硅石颗粒在片状基材表面上的粘附性良好,但铺展性没有改进,因此不能得到具有低摩擦系数(MIU)的产品。存在这样一种倾向:如果使用具有上述范围内大粒径的薄片基材颗粒,优选使用具有上述范围内大粒径的球状硅石颗粒,而如果片状基材本身的粒径变小,那么就相应使用具有小粒径的球状硅石颗粒。结果,球状硅石的粒径越大,那么片状基材的摩擦系数就越低,因此效果越好。如果使用具有大粒径的球状硅石,那么由于少量涂覆可实现降低摩擦系数(MIU)的效果,而如果球状硅石颗粒变小,那么就难以实现降低摩擦系数的效果。
因此,随着球状硅石颗粒的粘附量的增加,摩擦系数(MIU)的降低作用可在起始阶段观察到但随后变为最低,而且在此之后,摩擦系数逐渐增加。这种倾向在所用球状硅石粒径大时是显著的,但如果球状硅石粒径小,那么所述最低值往往难以实现。这估计是因为,如果使用具有小粒径的球状硅石颗粒,那么其单位表面积大,因此与片状基材的表观接触面积变大,导致高摩擦系数。此外,在摩擦系数变为最低值之后摩擦系数逐渐增加的原因估计是因为,粘附球状硅石颗粒相互聚集,导致硅石颗粒间的接触面积变大。在本发明中,考虑到这种现象,平均粒径20-400纳米的球状硅石颗粒要根据软焦点效果和铺展性并结合考虑粘附量为30%重量或更低来进行适当选择。在此,MIU值通过“KES-SE-DC型摩擦感觉测试仪”(由Katoteeh K.K.生产),按照所指示的条件来测定,该值越小,摩擦系数就越低或铺展效果越高。
例如,如果使用平均粒径约5μm的云母作为片状基材,那么当球状硅石的粒径分别为70-400纳米和40-50纳米时,该合适量分别为5-30%重量和5-20%重量。
这种球状硅石颗粒在市场上有售,因此商业上容易得到。(例如,由Nissan Chemical生产的Snowtex系列、和由Merck生产的用于柱色谱的硅石。)
按照本发明的薄片颜料是这样一种颜料,其中二氧化钛被涂覆到粘附有上述球状硅石颗粒的片状基材的表面上。结果,球状硅石颗粒与片状基材的粘附性能可得到提高,此外,紫外线遮蔽效果和白度也得到提高。
至于用于本发明二氧化钛的起始原料,可以使用任何物质,只要它是一种钛盐化合物。其中,为了在生产阶段降低pH值,优选使用酸性盐如四氯化钛、硫酸氧钛或硝酸氧钛。在本发明中,这种钛盐的一部分水溶液可替换成锌盐或铯盐的溶液,这样可合适地改变紫外线遮蔽能力或紫外线遮蔽波长。
以下方法用于生产本发明的薄片颜料。
首先,制备出片状基材的水悬浮液,然后在加热(约70℃)和搅拌下加入碱的水溶液,直到该悬浮液的pH值变为碱性,pH值为10或更高,或优选12或更高。将pH值变为碱性的原因是为了避免片状基材的等电点(即,表面电荷变为0且倾向发生聚集时的pH值)并将薄片基材相互排斥以形成一种分散态。因此,需要根据片状基材的等电点来适当改变能够导致这种分散态的pH值。例如,如果使用天然云母作为片状基材,那么合适的pH值通常为12。毋庸置疑,如果使用具有高等电点的片状基材,那么pH值要变得更高才能保持这种分散性,而如果等电点低于天然云母,那么pH值变低,通常采用10左右的pH值。
然后,将球状硅石颗粒在这种碱性范围下加入片状基材的悬浮液中。在片状基材和球状硅石颗粒分散良好的状态下,将上述钛盐的水溶液在搅拌下加入,将pH值降至1.5-2.5。使片状基材和球状硅石颗粒的表面电荷接近它们的等电点(即,降低排斥力),这样片状基材和球状硅石颗粒就相互粘附。该pH值将片状基材与球状硅石颗粒在接近它们等电点的pH值点上(在表面电荷的绝对值相互较小的状态下)进行粘附,这也是考虑到随后钛盐水解反应时pH值的结果。在这种情况下,也可加入锡盐或类似物的溶液并用作能够产生金红石型的试剂,这样二氧化钛在最终产品时的结晶形态不是常见的锐钛矿型而是金红石型。然后加入剩余的预定量的钛盐水溶液,同时加入碱的水溶液以保持pH值恒定,这样水解的钛产物或所谓的水合钛(氢氧化物、氧化物与结晶水的加成物、水合物和氧化物的混合态)被涂覆。还可采用这样一种生产方法,其中将一部分预定量的钛盐水溶液事先加热水解成金红石型,然后涂覆,这样最终二氧化钛的结晶形态就成为金红石型。
以二氧化钛计,所用钛盐的量(包括用于降低pH值至1.5-2.5的量)为最终产品的1-50%重量。这是因为,钛盐水解并粘附到片状基材和球状硅石的表面上,从而抑制球状硅石颗粒的剥落作用,同时,可提高紫外线遮蔽效果和白度。这些效果在该量低于1%时不能实现,但如果该量超过50%,球状硅石颗粒的相对量下降,因此,本发明的主要目的,即通过球状硅石颗粒来实现用于遮皱的软焦点效果下降。在钛盐的水解反应中,生产条件要选择使得最终产品二氧化钛的粒径为30纳米或更低。所述条件容易通过合适选择常规的颜料生产条件,如加料速度、搅拌叶片的转速和温度来确定。在所述预定pH值下,在将预定量的钛盐水溶液滴加之后,使用碱的水溶液将pH值调节至约5,然后过滤出反应溶液中的涂覆颜料,水洗脱盐,在常温下干燥,最后在约600-900℃下煅烧。
通过上述方法生产的薄片颜料具有软焦点效果、铺展性(较低的MIU)和紫外线遮蔽效果,具有合适的白度,而且表现出作为化妆品颜料的优异特性。此外,按照本发明的薄片颜料可用作树脂填料,而且可用作印刷油墨或油漆,这些都是常规颜料的用途。
本发明现通过以下实施例更详细说明。但,本发明不限于以下实施例。
实施例1
将平均粒径5μm的云母(145克)悬浮在1400毫升水中,然后在搅拌下加热至70℃。将32%重量氢氧化钠的溶液(约3.0毫升)加入所得水悬浮液中,将pH值调节至12。在搅拌下,在5毫升/分钟的定量速率下,向所述悬浮液中加入40克40%重量的胶态硅石颗粒(商品名:“SnowtexZL”,平均粒径:70纳米;由Nissan Chemical生产)的悬浮液。然后,制备出约100毫升的浓度为436克/升的四氯化钛水溶液,然后以2.5毫升/分钟的定量速率加入其中,将所述水悬浮液的pH值由12降至2。通过加入作为酸性组分的四氯化钛,球状硅石颗粒粘附到所述云母的表面上。类似地将剩余的四氯化钛水溶液加入所述悬浮液中,同时使用32%重量氢氧化钠的水溶液保持pH值为2。加入所有的四氯化钛水溶液之后,使用32%重量氢氧化钠的水溶液将pH值升至5。然后,过滤出产物,用去离子水洗涤,在110℃下干燥,最后在700℃下煅烧,得到所需的薄片颜料。所得薄片颜料包含9.4%重量的球状硅石颗粒和11.9%重量的二氧化钛,且通过SEM(扫描电子显微镜)测得的涂覆二氧化钛的粒径不超过30纳米。
1)色调的测定:
[1]测试纸的制备
分别将1克的实施例1制备的本发明薄片颜料和下表所示样品加入包含20%重量固体的9克氯乙烯介质中,然后混合搅拌,使用刮条涂机№20将所得分散体施用到黑白测试纸上,然后使用该测试纸如下测定色调。
[2]软焦点的测定
使用三维光谱弯曲色差仪(GC-2000型,由Nippon Denshoku Kogyo生产),测定在以上[1]制成的测试纸的白色漫反射比率(Y),其中标准板在光入射角45度和反射角45度进行白色漫反射时的值定义为100,然后使用光入射角45度且反射角以5度间隔变化的入射光束进行测量。结果在图1中给出,其中横坐标表示光的反射角,而纵座标表示反射强度。
Y(-45°/30°)表示当入射光与法线成45°角时,与法线成相反的30°角的反射光束的反射强度。
从图1可以看出,与云母相比,实施例1中制成的颜料在45°/45°常规反射时具有低光反射性,因此所述颜料具有强的软焦点效果。
顺便指出,表格中给出了在Y(-45°/30°)、Y(-45°/45°)和Y(-45°/60°)时的值。
[3]白度
该值由关系式100-[(100-L)2+a2+b2]1/2计算,其中L、a和b是使用三维色差仪(GC-3000A型,由Nippon Denshoku Kogyo生产)测得的。
[4]遮盖力
该值由关系式{Y(-45°/45°)(在黑纸上)/Y(-45°/45°)(在白纸上)}×100计算。
2)紫外线遮蔽性能的测量
将样品(0.5克)加入包含20%重量固体的9.5克氯乙烯型介质,随后搅拌混合,然后使用涂布器将所得分散体施用到玻璃板上,厚度为120μm。干燥之后,使用光谱仪(由Hitachi生产的228型)测定所得膜在300纳米(UVB)紫外线波长下的透光度。因此,数字越低,UV遮蔽性能越高。
通过上述方法测得的样品的物理性能在下表中给出。
表1.样品的物理性能
所用样品 | Y(-45°/30°)* | Y(-45°/45°)* | Y(-45°/60°)* | 白度 | 遮盖力 | MIU | UV遮蔽** |
实施例1 | 60.7 | 85.2 | 85.2 | 89.2 | 6.8 | 0.42 | 15.0 |
对比例1(云母) | 66.9 | 123.0 | 91.6 | 84.5 | 5.7 | 0.77 | 62.5 |
对比例2(滑石) | 61.6 | 86.3 | 84.5 | 92.5 | 5.0 | 0.57 | |
对比例3(BLF) | 70.8 | 166.0 | 111.6 | 88.4 | 9.4 | 0.43 |
*:在白纸上;
**:在300纳米的透过率
在该表中,样品分别如下。
云母:平均粒径为5μm(与实施例1所用云母材料相同)
滑石:由Asada seifun生产的Talc-L;平均粒径为6μm。
BLF:氯氧化铋(商品名:Biron LF 2000,由Rona生产)
MIU表示摩擦系数(由Katotech KK生产的KES-SE-DC型摩擦感觉测试仪”测量)
在表1所示样品的物理性能以及图1可以看出,如果测量角(反射角)在45°入射角时变为30°、45°和60°,那么按照本发明的薄片颜料具有较小的反射强度变化,因此具有良好的所谓软焦点效果。此外,所述颜料具有良好的遮盖力和白度,而且根据MIU的结果,所述颜料具有低滑动摩擦系数、良好的铺展性和良好的紫外线遮蔽效果。
应用实施例。
应用实施例1.作为化妆品的应用
使用实施例1中得到的薄片粉末,制备出具有以下组成的化妆剂(压型粉末)。
组合物:实施例1中得到的薄片颜料 25重量份着色颜料 5重量份羊毛脂 3重量份肉豆蔻酸异丙酯 适量硬脂酸镁 2重量份滑石 50重量份
应用实施例2.作为塑料填料的应用
组合物:高密度聚乙烯树脂(粒料) 100重量份实施例1中得到的薄片颜料 1重量份硬脂酸镁 0.1重量份硬脂酸锌 0.1重量份
将按照上述配混比率的粒料进行干混,然后注塑。
按照实施例1,另外生产出9个颜料样品。测定所有样品的摩擦系数(MIU)以及实施例1和9样品的UV遮蔽效果(在300纳米波长时的百分透明度)。实施例9得到最佳结果。颜料的摩擦系数(MIU)和透明度具有最佳值。
表2.MIU和uV遮蔽效果的评估结果
试验序号 | 硅石(平均粒径纳米,和%重量) | TiO2(%重量) | MIU×10-1 | 透明度(%),在300纳米 |
1 | 70纳米,9.4%重量 | 11.9%重量 | 4.2 | 15.0 |
2 | 50纳米,9.7%重量 | 2.2%重量 | 4.93 | - |
3 | 70纳米,9.7%重量 | 2.2%重量 | 3.76 | - |
4 | 100纳米,9.7%重量 | 2.2%重量 | 3.73 | - |
5 | 300纳米,9.7%重量 | 2.2%重量 | 3.41 | - |
6 | 70纳米,9.3%重量 | 6.3%重量 | 4.08 | - |
7 | 70纳米,8.7%重量 | 11.9%重量 | 4.75 | - |
8 | 70纳米,5.1%重量 | 2.3%重量 | 3.93 | - |
9 | 300纳米,9.7%重量 | 5.0%重量 | 2.87 | 12.4 |
10 | 300纳米,5.0%重量 | 2.2%重量 | 3.37 | - |
图1是测定本发明薄片颜料以及测定云母时的反射光的分布图。
如上所述,按照本发明的薄片颜料具有软焦点效果、具有低摩擦系数(MIU)、同时具有合适的白度和紫外线遮蔽性能,而且具有优异的作为尤其用于化妆品的颜料的特性。
Claims (6)
1.一种薄片颜料,其中将平均粒径20-400纳米的球状硅石颗粒粘附到平均粒径0.5-10μm的片状基材的表面上,然后将粘附有球状硅石的片状基材的所述粘附有球状硅石颗粒的表面进一步涂以二氧化钛的超细颗粒。
2.根据权利要求1的薄片颜料,其中所述球状硅石颗粒的量为基于粘附有球状硅石的片状基材的30%重量或更低。
3.根据权利要求1或2的薄片颜料,其中所述二氧化钛细颗粒的量为基于薄片颜料的1-50%重量且所述二氧化钛细颗粒的粒径为30纳米或更低。
4.一种生产根据权利要求1-3中任一项的薄片颜料的方法,其特征在于,将碱的水溶液加入片状基材的水悬浮液中以形成碱性,将球状硅石细颗粒的悬浮液在加热和搅拌下加入所述碱性悬浮液中,将一部分预定量的钛盐水溶液滴加其中以使pH值为1.5-2.5,这样可将球状硅石颗粒粘附到所述片状基材的表面上,将剩余的钛盐水溶液加入其中并保持pH值为1.5-2.5,然后将pH值升至5并过滤出所得固体,水洗、干燥并煅烧。
5.一种包含根据权利要求1-3中任一项的薄片颜料的化妆剂。
6.根据权利要求1-3中任一项的薄片颜料作为填料的应用。
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CN102391693A (zh) * | 2011-09-01 | 2012-03-28 | 江苏双乐化工颜料有限公司 | 一种有金属光泽的颜料及其制备方法 |
CN102573764A (zh) * | 2009-09-29 | 2012-07-11 | 东洋纺织株式会社 | 化妆品用颜料及其制造方法以及含有该化妆品用颜料的化妆品 |
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EP2123721B1 (de) | 2008-04-15 | 2013-11-27 | Eckart GmbH | Perlglanzpigmente auf Basis von feinen und dünnen Substraten |
FR2932384B1 (fr) * | 2008-06-17 | 2010-11-26 | Chanel Parfums Beaute | Poudre compacte pour le soin ou le maquillage de la peau |
US8206730B2 (en) * | 2008-06-30 | 2012-06-26 | Conopco, Inc. | Sunscreen composite particles and porous particles in cosmetic compostions |
JP4562791B2 (ja) * | 2008-10-30 | 2010-10-13 | 株式会社資生堂 | 油性固形化粧料 |
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JPH0683781B2 (ja) * | 1986-03-14 | 1994-10-26 | 住友化学工業株式会社 | 薄片状物質の製造方法 |
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EP0803550B1 (en) * | 1996-04-22 | 2003-07-09 | MERCK PATENT GmbH | Coated SiO2 particles |
KR100283124B1 (ko) * | 1998-06-09 | 2001-04-02 | 서경배 | 색조화장료용복합분체의제조방법및이것에의해제조된복합분체를함유하는색조화장료 |
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2000
- 2000-07-11 EP EP20000114131 patent/EP1072651B1/en not_active Expired - Lifetime
- 2000-07-11 DE DE2000614273 patent/DE60014273T2/de not_active Expired - Fee Related
- 2000-07-25 TW TW89114840A patent/TWI225084B/zh not_active IP Right Cessation
- 2000-07-27 KR KR20000043432A patent/KR100678806B1/ko not_active IP Right Cessation
- 2000-07-28 CN CNB001217682A patent/CN1198883C/zh not_active Expired - Fee Related
- 2000-07-31 US US09/629,150 patent/US6432535B1/en not_active Expired - Fee Related
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CN102076315B (zh) * | 2008-06-30 | 2013-03-06 | 荷兰联合利华有限公司 | 分散在油包水化妆用组合物中的遮光复合颗粒 |
CN102573764A (zh) * | 2009-09-29 | 2012-07-11 | 东洋纺织株式会社 | 化妆品用颜料及其制造方法以及含有该化妆品用颜料的化妆品 |
CN104323924A (zh) * | 2009-09-29 | 2015-02-04 | 东洋纺织株式会社 | 化妆品用颜料及其制造方法以及含有该化妆品用颜料的化妆品 |
US9181436B2 (en) | 2009-09-29 | 2015-11-10 | Toyobo Co., Ltd. | Cosmetic pigments, their production method, and cosmetics containing the cosmetic pigments |
JP2014511397A (ja) * | 2011-02-04 | 2014-05-15 | ロレアル | 複合顔料及びその調製方法 |
CN102391693A (zh) * | 2011-09-01 | 2012-03-28 | 江苏双乐化工颜料有限公司 | 一种有金属光泽的颜料及其制备方法 |
CN102391693B (zh) * | 2011-09-01 | 2013-12-04 | 江苏双乐化工颜料有限公司 | 一种有金属光泽的颜料及其制备方法 |
CN106189373A (zh) * | 2016-07-21 | 2016-12-07 | 四川省川宏精细化工有限公司 | 一种有助于植物生长的珠光颜料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60014273T2 (de) | 2005-10-06 |
EP1072651A1 (en) | 2001-01-31 |
DE60014273D1 (de) | 2004-11-04 |
US6432535B1 (en) | 2002-08-13 |
KR20010030021A (ko) | 2001-04-16 |
CN1198883C (zh) | 2005-04-27 |
EP1072651B1 (en) | 2004-09-29 |
TWI225084B (en) | 2004-12-11 |
KR100678806B1 (ko) | 2007-02-05 |
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