CN1046301C - 表面改善的片层状颜料及其制备方法和应用 - Google Patents

表面改善的片层状颜料及其制备方法和应用 Download PDF

Info

Publication number
CN1046301C
CN1046301C CN92105147A CN92105147A CN1046301C CN 1046301 C CN1046301 C CN 1046301C CN 92105147 A CN92105147 A CN 92105147A CN 92105147 A CN92105147 A CN 92105147A CN 1046301 C CN1046301 C CN 1046301C
Authority
CN
China
Prior art keywords
alkaline earth
titanium dioxide
earth metal
titanium
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN92105147A
Other languages
English (en)
Other versions
CN1068129A (zh
Inventor
K-D·弗朗兹
J·迪茨
M·基艾萨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of CN1068129A publication Critical patent/CN1068129A/zh
Application granted granted Critical
Publication of CN1046301C publication Critical patent/CN1046301C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/401—Inorganic protective coating
    • 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
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Cosmetics (AREA)
  • Paints Or Removers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及基于涂敷二氧化钛层并在其顶面有一碱土金属钛酸盐薄膜之片层状基质的表面改善的片层状颜料，其中为了提高光稳定性并降低对有机化合物的表面反应性，该颜料在至少800℃的温度下点火。

Description

表面改善的片层状颜料及其制备方法和应用
本发明涉及基于片层状基质的表面改善的片层状颜料，所说的片层状基质涂有二氧化钛层并且在其顶面有一薄层碱土金属钛酸盐膜。
涂敷二氧化钛的片层状基质，如云母片晶常常被用来着色塑料、化妆品或涂料组合物，如油漆或油墨。然而，其缺点是二氧化钛的光稳定性低，例如在用于白色颜料的情况下可导致颜色逐渐变灰。在聚合物基质中掺入涂有二氧化钛的片层状基质后，许多情况可观察到发生在二氧化钛表面和外周聚合物基质间的表面相互作用，从而损害了添加颜料之聚合物的外观美感。因此，例如含羟基二氧化钛表面与酚类稳定剂添加剂的反应常常导致聚合物发黄，此外还可进一步损害表面相互作用。
以前提出的一些避免这些问题的办法大多没有收到令人满意的效果，或者只适于解决一部分问题。例如，西德专利DE4,041,663中提出的颜料表面硅烷化方法虽可在许多情况下有效地抑制表面反应，但最终还是不能提高光稳定性。进一步应用金属氧化物层也是不适宜的，因为例如当使用着色的氧化物层，如氧化铁时，下面涂有二氧化钛的颜料的着色性质会完全改变，然后使顶面上的金属氧化物层常常仍具有提高的表面反应性。
本发明的目的是提供一种基于涂有二氧化钛之片层状基质的表面改善的颜料，其不同之处在于具有高度光稳定性，并且对有机化合物有低的表面反应性。
业已发现，这一目的是通过提供根据本发明的颜料而实现的。
因此，本发明涉及一种基于表面涂有二氧化钛层及在其顶面有一薄层碱土金属钛酸盐之片层样基质的表面改善的颜料，特征在于为了提高光稳定性和降低对有机化合物的表面反应性，该颜料在至少800℃的温度下着火。
本发明还涉及制备根据本发明之颜料的方法以及本发明颜料在涂料、聚合物材料及化妆品等中的应用。
本发明的颜料是基于片层状，且最好是由例如层迭硅酸盐，如云母、滑石、高岭土或玻璃或其他类似材料组成的透明或半透明基质。此外，还可以是金属片如铝片或片层状金属氧化物，如片层状氧化铁或氯氧化钛等材料。这些片层状基质的厚度一般是0.1至0.5μm，特别是0.2至4.5μm。另外两个径向的延伸范围一般是1至250μm，更好是2至200μm。
为了沉积二氧化钛，可将片层状基质分散在硫酸氧钛水溶液中，然后加热所得悬浮液(参见西德专利DE1,467,468)。在西德专利DE2,009,566所述的方法中，是将钛盐和碱的水溶液同时定量加到有适于沉积二氧化钛之PH的待涂敷之片状基质的悬浮液中，并在此期间经加入碱来维持基本上恒定的PH值。
因为用金红石改善的二氧化钛比锐锥石改善者有更高的折光指数，而且用金红石型二氧化钛(钛白粉)涂敷的云母基质比锐锥石型二氧化钛云母颜料有更好的光泽度，所以常常优选金红石改良之。西德专利DE2,214,545中描述了在云母上以金红石形式沉积二氧化钛的方法。本文只是以实施例的方式给出用已到的用二氧化钛涂敷基质的方法，并且只是为了举例说明本发明。但显然也可以使用文中没有提到的其他方法，用二氧化钛涂敷后，通常要分离掉基质，清洗，必要时进行干燥或点火。
最初可用例如包括氧化铬、氧化铁、氧化锆、氧化铝、氧化锡和/或其他金属氧化物的一种或多种其他金属氧化物层涂敷片层状基质，然后再涂敷二氧化钛层。西德专利DE1,959,998、DE2,215,191、DE2,244,298、DE2,313,331、DE2,522,572、DE3,137,808、DE3,151,343、DE3,151,354、DE3,151,355、DE3,211,602或DE3,235,017中都描述了沉积其他金属氧化物的方法。本发明的颜料是特别可取的，该颜料在二氧化钛层下面包含不超过两种，特别是只有一种或没有其他金属氧化物层。
为了产生碱土金属钛酸盐膜，可将水溶性碱土金属盐或水溶性碱土金属盐的混合物及水溶性二醇化合物及水溶性钛盐加到用二氧化钛涂敷之片层样基质的含水悬浮液中，有些情况下，也可使用低级醇如甲醇、乙醇、丙醇或异丁醇作为溶剂，以代替水或其他含水溶剂。这种类型的溶剂以定名的含水溶剂形式总结在本申请的上下文中。
适用的碱土金属盐包括碱土金属氯化物、还包括碱土金属硝酸盐及其他水溶性化合物。所用的钛盐通常是氯化钛(Ⅳ)、硫酸氧钛、硝酸氧钛或可溶于水溶液中的其他钛盐。
有确定名称的水溶性二醇化合物是指短链且最好有不超过5个碳原子的脂族二醇，还可以是其中两个OH基被不超过1个CH2基团彼此分开的芳族二醇，特别是H2O2。特别适用的二醇是1,2-亚乙基二醇、丙二醇、丁基-1,2-二醇、乙醇酸、乳酸、草酸、丙二酸、以及邻苯二酚和间苯二酚，特别是H2O2。
反应溶液的温度并不是很严格的，一般可在20至80℃之间。
沉积反应一般是在PH为6-12，特别是在PH≥7的条件下完成。
通常是在涂敷二氧化钛之片层状基质的含水悬浮液中加入二醇的水溶液和一种或多种碱土金属盐以进行反应。然后缓慢逐滴加入钛盐的水溶液并在此期间通过加入碱来恒定PH值。
较好以基本上相等的量加入钛盐和碱土金属盐。但已证明在某些情况下，最好以过量或少于化学计算的量加入碱土金属盐，碱土金属盐对钛盐的相对比较例好在0.8至1.2之间，更好在0.95至1.05之间。相对于钛盐或一种或多种碱土金属盐的量，二醇较好为两倍摩尔量，在这种情况下也可能偏离化学计算量。给出的这一相对量只是为了举例说明本发明而不是限制本发明。
当使用碱土金属氯化物，氯化钛和草酸时，可得到下列等式(G.Pfaff,Z.Chem,30(1990)379),但应明确的是它只是作一个例子用于举例说明而不是限制本发明：
M=Ba,Sr,Ca
对这种类型钛复合物的沉淀是已知的，并且在例如G.Pfaff,Z.Chem,28(1988)76、Z.Chem.29(1989)295及上述引文中描述过。在沉淀的复合物中，钛氧基离子被2个草酸根离子和4个水分子环绕，而在使用H2O2的情况下可见有组分MTiO2(O2)的复合物(G.Pfaff,Z.Chem,28(1988)76)。上述二醇对本发明方法的特殊适用性可能是由于这些小的或相对小的二醇分子能利于这些复合物的形成，而不会造成空间位阻。
西德专利DE3,824,809中已描述了草酸氧钛一钙复合物在涂敷二氧化钛之云母基质上的沉积(见实施例14)。但当分离掉涂敷的基质并在低气流中点火时，可形成一个青铜色氧化物层。
相反，本发明的基本特征是，涂甫物基质在被分离掉、清洗并根据情况干燥后，要在至少800℃的温度下点火。在上述高温度下，随着以钙钛矿结构存在之碱土金属钛酸盐的形成，沉淀的复合物被分解。点火温度较好为至少850℃，更好为至少900℃。最大点火温度较好为1,200℃，更好不超过1,000℃。
已发现，涂有二氧化钛并包括由化学计算量碱土金属钛酸盐组成之这种类型表面膜的片层状基质，比只涂敷二氧化钛的基质有高得多的光稳定性，而且对有机化合物特别是对含羟基的有机化合物有低得多的表面反应性。
沉淀反应最好以这样一种方式进行，即在点火后得到少于40nm的相当薄的碱土金属钛酸盐膜，因为涂敷二氧化钛之片层状基质的光学性质不会受或很少受这种薄表面膜的影响，而这在许多情况下正如人们所期望的。但为了得到特定的光学效果也有可能使用厚度大于40nm的较厚碱土金属钛酸盐膜；最大膜厚度为大约400nm，但一般最好不超过250nm，相对于本发明的颜料，碱土金属钛酸盐膜的重量比例较好在0.1至20％(重量)之间，更好在0.2至10％(重量)之间。
下面的实施例旨在进一步说明而不是限制本发明。
实施例
将100gIriodin199(涂有TiO2的云母，由Merck KGaA,Darmstadt生产)悬浮在去离子水中，加入10％NaOH水溶液使悬浮液PH达到9，于75℃在30分钟时间内定量加入50mlCaCl2和H2O2的水溶液(7.2gCaCl2·2H2O和6ml30％H2O2溶液，加水使总体积达到50ml)，此期间使PH基本上保持不变。
滤出反应产物，干燥并在900℃点火。结果得到一种稳定的不会发黄的带白色珍珠光泽的颜料。

Claims (4)

1．基于涂有二氧化钛层且其顶面上有一薄层碱土金属钛酸盐膜的片层状基质的表面改善的片层状颜料，该基层选自层状硅酸盐、玻璃、金属薄层或薄层状金属氧化物，所述颜料可通过包括如下步骤的方法获得：于20℃-80℃将二元醇、碱土金属盐和钛盐的水溶液同时加到涂有二氧化钛的薄层状基质的水悬浮液中，或者先将二元醇和碱土金属盐的水溶液同时加入，然后再加入钛盐的水溶液，并且在此期间通过加碱维持pH在6-12，分离产物，洗涤，并将颜料在800℃至1200℃的温度下点火。
2．根据权利要求1所述颜料的制备方法，其特征在于：于20-80℃将水溶性碱土金属盐或水溶性碱土金属盐的混合物与水溶性二元醇化合物以及水溶性钛盐加到涂有二氧化钛的薄层状基质的水悬浮液中，并通过加碱维持pH为6-12，然后分离反应产物，洗涤，干燥以及在800-1200℃的温度下点火。
3．根据权利要求1所述颜料的制备方法，其特征在于：于20-80℃将二元醇和碱土金属盐的水溶液加到涂有二氧化钛的薄层状基质的水悬浮液中，然后缓慢滴加钛盐水溶液，在此期间最好通过加碱维持pH在6-12的范围内，然后分离反应产物、洗涤、干燥并于800℃-1200℃的温度下点火。
4．根据权利要求1的颜料在涂料、塑料和化装品等制剂中的应用。
CN92105147A 1991-06-28 1992-06-27 表面改善的片层状颜料及其制备方法和应用 Expired - Fee Related CN1046301C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4121352.1 1991-06-28
DE4121352A DE4121352A1 (de) 1991-06-28 1991-06-28 Oberflaechenmodifizierte plaettchenfoermige pigmente

Publications (2)

Publication Number Publication Date
CN1068129A CN1068129A (zh) 1993-01-20
CN1046301C true CN1046301C (zh) 1999-11-10

Family

ID=6434939

Family Applications (1)

Application Number Title Priority Date Filing Date
CN92105147A Expired - Fee Related CN1046301C (zh) 1991-06-28 1992-06-27 表面改善的片层状颜料及其制备方法和应用

Country Status (12)

Country Link
US (1) US5221341A (zh)
EP (1) EP0520313B1 (zh)
JP (1) JP3258708B2 (zh)
KR (1) KR100240527B1 (zh)
CN (1) CN1046301C (zh)
CZ (1) CZ282439B6 (zh)
DE (2) DE4121352A1 (zh)
ES (1) ES2071383T3 (zh)
FI (1) FI102385B (zh)
MX (1) MX9203617A (zh)
RU (1) RU2101311C1 (zh)
TW (1) TW213481B (zh)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0641842B1 (de) * 1993-09-02 1998-05-06 MERCK PATENT GmbH Oberflächenmodifizierte Pigmente und deren Verwendung zur Vergilbungsinhibierung von pigmentierten Kunststoffen
US5588996A (en) * 1994-04-01 1996-12-31 Argus International Apparatus for spray coating flat surfaces
US5733376A (en) * 1994-04-01 1998-03-31 Argus International Apparatus for spray coating opposing major surfaces of a workpiece
DE4443048A1 (de) * 1994-12-05 1996-06-13 Merck Patent Gmbh Effektpulverlacke
JP2741499B2 (ja) * 1996-02-15 1998-04-15 工業技術院長 耐熱性無機顔料粉末及びその製造方法
US6369147B1 (en) * 1999-01-25 2002-04-09 Ciba Specialty Chemicals Corporation Color effect pigments and method of forming the same
JP4103293B2 (ja) * 1999-05-14 2008-06-18 日本板硝子株式会社 ルチル型二酸化チタンの製造方法
US6379804B1 (en) * 2000-01-24 2002-04-30 General Electric Company Coating system containing surface-protected metallic flake particles, and its preparation
AUPQ619400A0 (en) 2000-03-10 2000-04-06 Depco-Trh Pty Ltd Titanium dioxide coated product
TWI292773B (en) * 2001-05-09 2008-01-21 Merck Patent Gmbh Effect pigments based on coated glass flakes
AU2002328827A1 (en) * 2001-07-12 2003-01-29 Merck Patent Gmbh Multilayer pigments based on glass flakes
WO2004042785A2 (en) * 2002-08-16 2004-05-21 The Regents Of The University Of California Functional bimorph composite nanotapes and methods of fabrication
EP1813575A1 (en) * 2004-09-29 2007-08-01 Kansai Paint Co., Ltd. Clay composite material
DE102006014095A1 (de) * 2006-03-24 2007-09-27 Merck Patent Gmbh Glasplättchen und deren Verwendung als transparenter Füllstoff
DE102006027025A1 (de) * 2006-06-08 2007-12-13 Merck Patent Gmbh Silberweiße-Effektpigmente
JP5535637B2 (ja) * 2006-10-18 2014-07-02 ビーエーエスエフ コーポレーション 色移動を示す多層顔料
JP5717343B2 (ja) * 2007-02-27 2015-05-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ （ルチル形）二酸化チタンで被覆された小板状顔料の形成方法
ATE432964T1 (de) 2007-04-05 2009-06-15 Eckart Gmbh Effektpigmente mit einem substrat aus glasplättchen
JP4995212B2 (ja) * 2009-02-27 2012-08-08 ダンロップスポーツ株式会社 ゴルフボール
JP6608813B2 (ja) * 2013-06-17 2019-11-20 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 高い色濃度を有する透明な電気的半導体性干渉顔料
JP6553372B2 (ja) * 2015-02-17 2019-07-31 ジェイオーコスメティックス株式会社 化粧料
JP7394788B2 (ja) * 2018-05-16 2023-12-08 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリマー材料におけるレーザー添加剤およびその使用
EP3967491A1 (en) 2020-09-15 2022-03-16 Röhm GmbH Heat reflective foils with improved mechanical properties and a high weathering resistance

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3649171A (en) * 1970-02-18 1972-03-14 Du Pont Preparation of alkali metal tetratitanate
JPS5876461A (ja) * 1981-10-26 1983-05-09 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング 透明性着色顔料およびその製造法
DE3824809A1 (de) * 1988-07-21 1990-03-15 Merck Patent Gmbh Plaettchenfoermige farbglanzpigmente

Also Published As

Publication number Publication date
DE59201881D1 (de) 1995-05-18
KR930000623A (ko) 1993-01-15
EP0520313A2 (de) 1992-12-30
TW213481B (zh) 1993-09-21
JPH05186705A (ja) 1993-07-27
ES2071383T3 (es) 1995-06-16
FI922985A0 (fi) 1992-06-26
CZ198492A3 (en) 1993-01-13
DE4121352A1 (de) 1993-01-07
FI922985A (fi) 1992-12-29
KR100240527B1 (ko) 2000-02-01
CZ282439B6 (cs) 1997-07-16
FI102385B1 (fi) 1998-11-30
FI102385B (fi) 1998-11-30
MX9203617A (es) 1993-11-01
US5221341A (en) 1993-06-22
EP0520313B1 (de) 1995-04-12
JP3258708B2 (ja) 2002-02-18
RU2101311C1 (ru) 1998-01-10
EP0520313A3 (en) 1993-01-27
CN1068129A (zh) 1993-01-20

Similar Documents

Publication Publication Date Title
CN1046301C (zh) 表面改善的片层状颜料及其制备方法和应用
JP6268179B2 (ja) 耐候性真珠光沢顔料、それを製造するためのプロセス、およびそれの使用
KR101906625B1 (ko) 내후성 진주광택 안료, 그 제조 방법 및 용도
KR100876775B1 (ko) 고도로 내식성인 금속 안료
US11479681B2 (en) Effect pigments
US4828623A (en) Water resistant nacreous pigment and process for producing the same
KR100266106B1 (ko) 도전성안료
JP5717343B2 (ja) （ルチル形）二酸化チタンで被覆された小板状顔料の形成方法
EP2052035B1 (en) Synthetic mica based pearlescent pigments containing ferrites
JP2000044834A (ja) 還元雰囲気中で加熱された、二酸化チタン被覆された珪酸塩小板状物を基礎とするゴニオクロマチックラスタ―顔料
EP0446986B1 (en) Process for producing light and moisture resistant metal oxide-coated mica pigments
JP5030946B2 (ja) 金色調を有する光輝性顔料、これを含有する化粧料、塗料、インク、または樹脂組成物
KR20120130330A (ko) 효과 안료
US5565025A (en) Surface-modified pigments and use thereof as yellowness inhibitors in pigmented plastics
KR20010070125A (ko) 고배향성 박편상 안료 및 그의 제조방법
WO2001030920A1 (de) Farbstarke interferenzpigmente
US6984682B2 (en) Color effect pigments and method of forming the same
JP2007505987A (ja) 光安定化効果顔料
JP2016519638A (ja) 熱水製造を介した合成メガカルシライト
US5501731A (en) Carbon-containing luster pigments
EP1153088B1 (en) Colour effect pigments and method of forming the same
US5228911A (en) Oxidized graphite flaky particles and pigments based thereon
JP3961082B2 (ja) 着色金属粉末顔料および塗料組成物
JPH11310737A (ja) 樹脂コンパウンド

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 19991110

Termination date: 20110627