WO2006032199A1 - A pearl pigment used for external outside - Google Patents

A pearl pigment used for external outside Download PDF

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Publication number
WO2006032199A1
WO2006032199A1 PCT/CN2005/001517 CN2005001517W WO2006032199A1 WO 2006032199 A1 WO2006032199 A1 WO 2006032199A1 CN 2005001517 W CN2005001517 W CN 2005001517W WO 2006032199 A1 WO2006032199 A1 WO 2006032199A1
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WIPO (PCT)
Prior art keywords
pearlescent pigment
layer
basic
coupling agent
phosphite
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PCT/CN2005/001517
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English (en)
French (fr)
Inventor
Yizhong Lin
Wensong Jin
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Priority to EP05792181A priority Critical patent/EP1808465A4/en
Priority to US11/575,924 priority patent/US20080295736A1/en
Publication of WO2006032199A1 publication Critical patent/WO2006032199A1/zh
Anticipated expiration legal-status Critical
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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
    • C09C1/0015—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
    • 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
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C09C2200/40—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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/407—Organosilicon materials, e.g. silanes, silicones
    • 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

Definitions

  • the present invention relates to a post-coated pearlescent pigment, and a process for preparing same.
  • This post-coating treated pearlescent pigment has excellent stability and significantly improves its anti-glare and anti-tarnishing anti-aging properties in external applications. It can be used in various occasions exposed to the outdoors.
  • Pearlescent pigments are formed by coating a metal oxide on a sheet-like substrate.
  • the most widely used metal oxides are titanium dioxide and iron oxide (111). Due to the refraction and reflection of light and the absorption of light and the interference of light, pearlescent pigments can exhibit pearlescent light from silvery white to various colors.
  • U.S. Patent No. 4,134,776 first discloses a post-coating treated topical pearlescent pigment.
  • the pigment is formed by coating a metal oxide on a sheet substrate and then coating a trivalent chromium hydrated oxide (or hydroxide).
  • This pigment has good stability when used externally and is still used in countries until today.
  • this pigment has been discontinued in some countries in recent years.
  • JP1-292067 discloses a post-coating-treated exterior-type pearl pigment.
  • the post-coating layer consists of a hydrated zirconia in the presence of hypophosphite, plus a hydrated oxide of manganese, cobalt, ruthenium, and finally treated with a hydrolyzed silane coupling agent.
  • the test data listed in this patent shows that the stability of pearlescent pigments is greatly improved after treatment with a hydrolyzed silane coupling agent.
  • European Patent (EP0632109B1) discloses a method of post-coating pearlescent pigments to enhance their stability.
  • the post-coating layer consists of hydrated silica, plus hydrated alumina and hydrated zirconia and/or hydrated cerium oxide. Finally, it is treated with a hydrolyzed silane coupling agent or a zirconium aluminate coupling agent. Made.
  • a newly developed post-coating treated topical pearlescent pigment is also disclosed in U.S. Patent No. 5,759,255.
  • the post-coating layer consists of a combination of hydrated alumina or hydrated alumina and hydrated cerium oxide. Finally, it is also treated by hydrolysis of a silane coupling agent.
  • the invention has been experimentally found that a metal oxide-coated pearlescent pigment is coated with a metal phosphite (aluminum phosphite or zinc phosphite) and a hydrated cerium oxide (or cerium hydroxide) compound, followed by hydrolysis.
  • a metal phosphite aluminum phosphite or zinc phosphite
  • cerium oxide or cerium hydroxide
  • the post-coating treated external-type pearl pigment of the present invention has the following structure:
  • the first layer is a sheet substrate.
  • the second layer one or more metal oxides coated on the sheet substrate.
  • the third layer is further coated with a metal phosphite and hydrazine hydrated oxide (or hydroxide) on the surface of the metal oxide coating.
  • the fourth layer is a hydrolyzed silicon germanium coupling agent.
  • the first layer and the second layer are calcined to form a basic pearlescent pigment.
  • the third and fourth layers are the back coating layers of the basic pearlescent pigment.
  • a sheet-like substrate of the first layer is applied, preferably mica.
  • the metal oxides suitable for the second layer are mainly titanium dioxide and iron oxide (111), as well as tin dioxide, zinc oxide, aluminum oxide, silicon oxide and other metal oxides.
  • One metal phosphite suitable for the third layer is aluminum phosphite or zinc phosphite.
  • the silicon germanium coupling agent to which the fourth layer is applied should have a structure of YR-SiX 3 .
  • Y is an organic functional group.
  • X is an alkoxy group and R is a hydrocarbon group.
  • the organic functional group and the oxirane group are directly or indirectly bonded to the silicon.
  • the silane coupling agent acts as an interface between the organic medium and the pearlescent pigments, enhancing the affinity between the two.
  • the silane coupling agent to be selected is a silicon-germanium coupling agent having an amino group, such as Y-aminopropyltrimethoxysilane, hydrazine-aminopropyltriethoxysilane, hydrazine-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ --( ⁇ -aminoethyl)-anthracene-aminopropylmethyldimethoxysilane, and the like.
  • a silane coupling agent such as Y-glycidoxypropyltrimethoxysilane, Y-methacryloxypropyltrimethoxysilane, Y-methacryloxypropylmethyltrimethoxy Silane, Y-mercaptopropyltrimethoxysilane, and the like.
  • the detailed preparation method of the external-type pearlescent pigment of the present invention consists of the following five steps.
  • a basic type pearlescent pigment coated with one or more metal oxides is added to deionized water, stirred to form a suspension, and heated to a temperature of 20 to 100 ° C, preferably 50 to 80 ° (.
  • phosphorous acid or phosphite is added. If phosphite is used, the pH of the suspension will increase and dilute hydrochloric acid will be added to reduce the pH of the suspension to 3.0 or below. Further, a water-soluble aluminum salt or a water-soluble zinc salt is added. After stirring uniformly, a dilute alkali solution is gradually added to slowly increase the pH of the suspension to 5.0 to 7.0, preferably 5.5 to 6.5, and stirring is continued for a quarter of an hour.
  • the added phosphorous acid or phosphite is hydrolyzed with a water-soluble aluminum salt or a water-soluble zinc salt, and is coated on the surface of the pigment particles in the form of aluminum phosphite or zinc phosphite.
  • the coated aluminum phosphite has a weight ratio of the basic pearlescent pigment of from 0.01 to 1.0%, preferably from 0.05 to 0.5%, based on the aluminum element.
  • the coated zinc phosphite has a weight ratio of the basic pearlescent pigment of 0.05 to 1.5%, preferably 0.1 to 0.6%.
  • a water-soluble cerium salt is added, and a dilute lye is added to maintain the pH of the suspension at 5.5-6.5. Stirring was continued for 20 minutes after the addition.
  • the added onium salt is coated on the surface of the pigment particles in the form of hydrated cerium oxide (or cerium hydroxide).
  • the coated hydrated cerium oxide (or cerium hydroxide) is 0.05 to 1.5% by weight, preferably 0.1 to 0.6% by weight based on the cerium element.
  • the weight ratio of the added silicon germanium coupling agent to the basic type pearlescent pigment is from 0.5 to 10%, preferably from 1.0 to 5.0%.
  • the resulting suspension was filtered, and the coated pigment particles were taken out, washed with water to remove soluble salts, and continuously dried at 140 ° C for 16 hours.
  • water-soluble compounds such as phosphorous acid and phosphite such as phosphorous acid, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, and potassium hydrogen phosphite are suitable.
  • Suitable water-soluble aluminum or zinc salts such as water-soluble chlorides, water-soluble nitrates, water-soluble sulfur An acid salt, a hydrate of these salts, and the like.
  • Suitable cerium salts are water-soluble salts such as cerium chloride and cerium nitrate.
  • Suitable silane coupling agents are selected from the various silane coupling agents previously described.
  • the post-coated pearlescent pigment of the present invention can be used in various applications exposed to the outdoors.
  • automotive paint motorcycle paint, bicycle paint, building exterior paint, etc. It can also be used in other applications such as inks, leather, plastics and cosmetics.
  • an epoxy functional silane coupling agent (Y-glycidoxypropyltrimethoxysilane) was added over 10 minutes, followed by continuous stirring at 75 ° C for 2 hours.
  • the pigment particles are then separated from the suspension by filtration and washed with deionized water to remove soluble salts.
  • the pigment was then dried at 140 ° C for 16 hours.
  • iron bronze mica pearlescent pigment (Taizhu4001 type, containing 38% Fe 2 0 3 and 62% mica) was suspended with stirring, heating to 75 ° C, and dimension Hold this temperature unchanged.
  • the pigment particles were separated from the suspension by filtration and washed with deionized water to remove soluble salts, and then the pigment was dried at 140 ° C for 16 hours.
  • Example 1 The procedure of Example 1 was repeated except that the basic pearlescent pigment used was changed to blue interference mica titanium pearlescent pigment (Taizhu 2004 type, containing 52% rutile titanium dioxide and 48% mica).
  • Dilute hydrochloric acid was added dropwise to the suspension to reduce the pH to 6.0. Then, 32 ml of a 5% solution (3 ⁇ 4 aqueous solution diluted with 100 ml of deionized water) was added dropwise. At the same time, a 10% NaOH solution was added dropwise to maintain the pH of the suspension unchanged, which took about 30 minutes to complete.
  • the pearlescent pigment was then removed from the suspension by filtration, washed, and dried at 120 ° C for 1 hour.
  • a topical silver-white pearlescent pigment prepared by hydration of chromium oxide (or chromium hydroxide) prepared by the method described in U.S. Patent 4,134,776 is obtained.
  • the pearlescent pigment and the basic pearlescent pigment obtained in the examples and the comparative examples were added to an acrylic acid/amino coating system (in which the ratio of the pearlescent pigment to the resin was 0.2) to form a pearlescent coating, and as a whole coating system. Part of it was sprayed onto a steel plate with a size of 0.8 X 70X 150mm after electrophoresis and intermediate coating.
  • the coating system consists of a white Base (thickness 15 ⁇ 20 ⁇ ⁇ ) with a pearlescent coating and a clear varnish.
  • the pearlescent coating has a thickness of about 15 to 20 4 111, and the entire coating thickness is about 60 to 8 ( ⁇ 111, and is baked at 140 ° C for 30 minutes after spraying. Thus, a test coating plate containing a pearl coating is prepared.
  • test plate was exposed to a QUV tester, subjected to an artificial accelerated aging test, irradiated with ultraviolet light at 70 Torr for 8 hours (UV-313 lamp), and then condensed at 50 ° C for 4 hours, and thus reciprocated.
  • the combined effect of the accelerated aging test is to allow the test slab to enhance the illuminating of the coating at elevated temperatures and to accelerate the destruction of the coating in a hot, humid, condensed water atmosphere.
  • US patent US 4,134,776
  • the comparison of the QUV aging test for 672 hours with the results of two years of exposure in southern Florida is relatively close.
  • test plate was taken out and then measured and rated according to "GB/T1766-1995 Paint and varnish coating aging rating method".
  • Comparative sample TZ1004 is anatase pearlescent pigment
  • TZ1201 is rutile pearlescent pigment.
  • the loss rate is the percentage of the lost gloss which is the original gloss.
  • the gloss is measured by a spectrophotometer.
  • the post-coating treated pearlescent pigment of the present invention has better stability than other various pearlescent pigments, and has better anti-glare and anti-tarnishing anti-aging properties when used externally.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Description

供外部使用的珠光颜料
本发明涉及一种经后涂覆的珠光颜料， 以及制备它的方法。 这种经后 涂覆处理的珠光颜料具有优异的稳定性， 明显提高了它在外部使用场合下 的抗失光和抗变色的抗老化性能。 可供暴露于室外的各种场合下使用。
珠光颜料是在片状基材上涂覆金属氧化物而构成， 目前应用最广泛的 金属氧化物为二氧化钛和氧化铁（111)。 由于光的折射和反射以及光的吸收 作用和光的干涉作用， 使珠光颜料能呈现出从银白色至各种彩色的珠光光 泽。
珠光颜料用于室外的各种场合时， 如汽车表面涂装漆、 建筑物外墙装 饰涂料等， 由于常年暴露室外， 经受高温、 潮湿等天气影响， 漆膜或涂层 将引起粉化、 起泡， 最终导致珠光光泽消失和严重退色， 这就是珠光涂层 老化现象。
为了克服珠光颜料外部使 ¾时引起的涂层老化现象， 近年来， 各国开 发了一些经后涂覆处理的外用型珠光颜料。
美国专利（US4134776)首先推出经后涂覆处理的外用型珠光颜料。该 颜料是在片状基材上涂覆金属氧化物后， 再涂覆三价铬的水合氧化物 （或 氢氧化物） 所构成。 这种颜料外部使用时有很好地稳定性， 直至今日仍在 各国使用。 但由于此颜料固有的淡绿色， 以及铬对环境的潜在影响， 近年 来， 一些国家已不再使用这种颜料。
日本专利 （JP1-292067) 公开了一种经后涂覆处理的外用型珠光颜料。 后涂覆层由在次磷酸盐存在下生成水合氧化锆、 加上锰、 钴、 铈的一种水 合氧化物所组成， 最后经水解硅烷偶联剂处理。 该专利所列的测试数据表 明， 经过水解硅烷偶联剂处理后， 珠光颜料的稳定性就有了较大的提高。
欧洲专利（EP0632109B1 )公开了对珠光颜料进行后涂覆处理， 增强其 稳定性的方法。 后涂覆层由水合二氧化硅、 加上水合氧化铝和水合氧化锆 和 /或水合氧化铈所组成。 最后， 再用水解硅烷偶联剂或铝酸锆偶联剂处理 而成。
美国专利 (US5759255 )也公开了一种新研制的经后涂覆处理的外用型 珠光颜料。 后涂覆层由水合氧化铝或水合氧化铝和水合氧化铈的组合物所 组成。 最后也同样经过水解硅烷偶联剂处理而成。
本发明经试验得出， 涂覆金属氧化物的珠光颜料， 再涂覆金属亚磷酸 盐 （亚磷酸铝或亚磷酸锌） 和水合氧化铈 （或氢氧化铈） 两种化合物后， 再经水解硅烷偶联剂处理， 就可以明显增强珠光颜料的稳定性， 明显提高 它在外部使用场合下的抗失光、 抗变色的抗老化性能。
本发明经后涂覆处理的外用型珠光颜料， 具有以下结构：
第一层， 为片状基材。
第二层， 在片状基材上涂覆的一种或多种金属氧化物。
第三层， 在金属氧化物涂层表面上再涂覆金属亚磷酸盐和铈的水合氧 化物 （或氢氧化物）。
第四层， 为一种水解硅垸偶联剂。
上述结构中， 第一层， 第二层， 经煅烧后形成基本型珠光颜料。 第三 层和第四层， 为该基本型珠光颜料的后涂覆层。
适用第一层的片状基材， 优选云母。
适用第二层的金属氧化物主要有二氧化钛和氧化铁（111)， 以及二氧化 锡、 氧化锌、 氧化铝， 氧化硅和其它金属氧化物。
适用第三层的一种金属亚磷酸盐是亚磷酸铝或亚磷酸锌。
适用第四层的硅垸偶联剂应具有 YR— SiX3的结构。 其中 Y为一个有 机官能团。 X为烷氧基团， R为烃基。有机官能团和垸氧基团直接或间接与 硅连接在一起。 珠光颜料在使用过程中， 硅烷偶联剂作为有机介质与珠光 颜料间的界面， 加强了两者间的亲合力。
可供选择的硅烷偶联剂有， 带氨基的硅垸偶联剂， 例如 Y—氨丙基三 甲氧基硅烷、 Υ—氨丙基三乙氧基硅烷、 Ν— ( β氨乙基）一 Υ—氨丙基三 甲氧基硅烷、 Ν-—（β氨乙基）一 Υ—氨丙基甲基二甲氧基硅烷等。不带氨 基的硅烷偶联剂， 例如 Y—缩水甘油氧丙基三甲氧基硅烷、 Y—甲基丙烯 酰氧基丙基三甲氧基硅烷、 Y—甲基丙烯酰氧基丙基甲基三甲氧基硅烷、 Y—巯丙基三甲氧基硅垸等。
本发明的外用型珠光颜料的详细制备方法由以下五步组成。
第一步， 将涂覆有一种或一种以上金属氧化物的基本型珠光颜料加入 去离子水中， 搅拌制成悬浮液， 并加热升温至 20〜100°C， 优选为 50〜80° ( 。
第二步， 加入亚磷酸或亚磷酸盐。 如果使用亚磷酸盐， 则悬浮液的 PH 值会升高， 再加入稀盐酸， 使悬浮液 PH值降至 3.0或以下。 再加入水溶性 铝盐或水溶性锌盐， 搅拌均匀后， 缓缓地加入稀碱液， 使悬浮液的 PH值慢 慢地升至 5.0〜7.0， 优选 5.5〜6.5,并继续搅拌一刻钟。此时， 加入的亚磷酸或 亚磷酸盐与水溶性铝盐或水溶性锌盐产生水解反应， 并以亚磷酸铝或亚磷 酸锌的形式涂覆在颜料颗粒表面上。
涂覆的亚磷酸铝以铝元素计占基本型珠光颜料的重量比例为 0.01〜1.0%,优选 0.05〜0.5%。 涂覆的亚磷酸锌以锌元素计占基本型珠光颜料 的重量比例为 0.05 1.5%,优选 0.1〜0.6%。
第三步， 加入水溶性铈盐， 同时加入稀碱液， 使悬浮液的 PH值维持在 5.5-6.5不变。加完后继续搅拌 20分钟。此时，加入的铈盐以水合氧化铈（或 氢氧化铈） 的形式涂覆在颜料颗粒表面上。 涂覆的水合氧化铈 （或氢氧化 铈） 以铈元素计占基本型珠光颜料的重量比例为 0.05〜1.5%,优选 0.1〜0.6%。
第四步， 继续加入稀碱液， 将悬浮液的 PH值升至 8.0。 然后滴加一种 硅烷偶联剂， 滴加完毕后， 继续维持搅拌 2 小时。 加入的硅垸偶联剂占基 本型珠光颜料的重量比例为 0.5〜10%,优选 1.0〜5.0%。
第五步， 过滤所得的悬浮液， 取出经涂覆处理的颜料颗粒， 经水洗涤 除去可溶性盐份， 并在 140°C下， 连续干燥 16小时。
后涂覆处理中， 适用的亚磷酸和亚磷酸盐如亚磷酸、 亚磷酸纳、 亚磷 酸氢钠、 亚磷酸钾、 亚磷酸氢钾等水溶性化合物。
适用的水溶性铝盐或锌盐如水溶性氯化物、 水溶性硝酸盐、 水溶性硫 酸盐以及这些盐类的水合物等。
适用的铈盐如氯化铈、 硝酸铈等水溶性盐。
适用的硅烷偶联剂选自前述的各种硅烷偶联剂。
本发明经后涂覆的珠光颜料， 可供暴露于室外的各种场合下使用。 例 如汽车漆、 摩托车漆、 自行车漆、 建筑外墙涂料等。 也可以用于其它场合， 例如油墨、 皮革、 塑料和化妆品等。
为进一步说明， 列举以下实施例。 实施例 ΐ
在一升去离子水中加入 100g银白色云母钛珠光颜料（Taizhul202型， 含 30%金红石型二氧化钛和 70%的云母）， 搅拌制成悬浮液， 加热升温至 75°C , 并维持此温度不变。
加入 0.36g亚磷酸，再加入 9ml浓度为 80g/l的 A1C13.6H20水溶液，并 搅拌 20分钟，然后加入 3.5%的氢氧化钠水溶液，将悬浮液的 PH值慢慢地 提高到 6.0， 再继续搅拌一刻钟。
加入 18ml浓度为 25g/l的 CeCl3.6H20的 水溶液， 同时加入 3.5%氢氧 化钠水溶液， 维持悬浮液的 PH值为 6.0不变。
继续搅拌 20分钟后，加入 3.5%氢氧化钠水溶液，使悬浮液的 PH值升 高至为 8.0。接着在 10分钟内加入 4g环氧官能硅烷偶联剂（ Y—缩水甘油 氧丙基三甲氧基硅烷）， 再在 75°C下连续搅拌 2小时。
然后， 经过滤将颜料颗粒从悬浮液中分离出来， 并用去离子水洗涤， 以除去可溶性盐份。 随后将颜料在 140°C下干燥 16小时。
这样， 就得到一种可以供外部使用的银白色珠光颜料。 实施例 2
在一升去离子水中加入 100g古铜色云母铁珠光颜料（Taizhu4001型， 含 38%的 Fe203和 62%的云母）搅拌制成悬浮液， 加热升温至 75°C， 并维 持此温度不变。
加入 0.12g亚磷酸， 再加入 5ml浓度为 40g/l的 ZnCl2水溶液， 并搅拌 20分钟。 然后缓缓地加入 3.5%氢氧化钠水溶液， 将悬浮液的 PH值慢慢地 提高到 6.0， 再继续搅拌一刻钟。
加入 20ml浓度为 25g/l的 CeCl3.6H20水溶液，同时加入 3.5%氢氧化钠 水溶液， 维持悬浮液的 PH值为 6.0不变。
继续搅拌 20分钟后， 加入 3.5%氢氧化钠水溶液， 使悬浮液的 PH值升 高至 8.0。接着在十分钟内加入 3g双氨基硅烷偶联剂（N— ( β氨乙基）― Υ—氨丙基三甲氧基硅烷）， 并 75°C下继续搅拌 2小时。
然后， 经过滤将颜料颗粒从悬浮液中分离出来， 并用去离子水洗涤， 以除去可溶性盐份， 随后将颜料在 140°C下干澡 16小时。
这样得到了一种可供外部使用的古铜色珠光颜料。 实施例 3
重复实施例 1 的步骤， 不同的是所用的基本型珠光颜料改为兰色干涉 色云母钛珠光颜料（Taizhu2004型，含 52%金红石型二氧化钛和 48%云母）。
最终得到可供外部使用的兰色干涉色珠光颜料。 对比实施例 1
在一升去离子水中，加入 100g银白色云母钛珠光颜料（Taizhul202型， 含 30%金红石型二氧化钛和 70%的云母）， 搅拌制成悬浮液， 加热升温至 75°C， 并维持此温度不变。
向悬浮液中滴加稀盐酸， 使 PH值降至 6.0。 然后滴加由 32ml浓度为 5%的 (¾水溶液经 100ml去离子水稀释后的溶液。 同时滴加 10%NaOH 溶液， 以维持悬浮液的 PH值不变， 大约需 30分钟加完。
接着经过滤将珠光颜料从悬浮液中取出，并经洗涤，再在 120 °C下烘干 1小时。 这样就得到了一种按 US4134776所述的方法制备的，经水合氧化铬（或 氢氧化铬）涂覆的外用型银白色珠光颜料。 老化试验
对实施例和对比实施例所得的珠光颜料， 以及基本型珠光颜料经人工 加速老化试验， 评价它们的抗老化性能。
1、 试验涂板制作
将实施例及对比实施例中得到的珠光颜料和基本型珠光颜料， 加入到 丙稀酸 /氨基涂料体系中 （其中珠光颜料与树脂的比例为 0.2)， 组成珠光涂 料， 并作为整个涂层体系的一部分， 喷涂到尺寸为 0.8 X 70X 150mm经电 泳和中涂后的钢板上。 该涂层体系由一道白色 Base (厚度 15〜20 μ πι)， 加 上一道珠光涂层再加上一道罩光清漆组成。 其中珠光涂层的厚度约 15〜20 4 111，整个涂层厚度约60〜8(^ 111， 喷涂后经 140°C X 30min烘烤。 这样就制 成了含珠光涂层的试验涂板。
2、 涂板的老化试验
将试验涂板暴露于 QUV试验机中， 经受人工加速老化试验， 在 70Ό 下紫外光照射 8小时 （UV— 313灯管）， 接着在 50°C下凝露 4小时， 如此 往复循环。
加速老化试验的综合效应， 是让试验涂板在高温下增强紫外光的照射 和在湿热的凝露水气气氛中加速对涂层的破坏作用。 按美国专利 (US4134776)对 QUV老化试验 672小时与佛罗里达州南部暴晒两年的试 验结果相比较， 两者是比较接近的。
本试验经 840 小时和 1440 小时的试验后， 取出试验涂板， 然后按 "GB/T1766— 1995色漆和清漆涂层老化的评级方法"进行测定和评级 。
3、 老化试验结果
老化试验结果如表 1。 涂板人工加速 QUV老化试验结果
Figure imgf000008_0001
备注： 1、 对比样 TZ1004为锐钛型珠光颜料； TZ1201为金红石型珠光颜料。
2、 失光率为丢失光泽占原始光泽的百分比， 光泽度由分光光度计测定。
3、 色相变化 ΔΕ， 由分光光度计测定。
由表 1 可见， 本发明经后涂覆处理的珠光颜料， 与其它各种珠光颜料 相比较， 具有更好的稳定性， 外部使用时具有更好的抗失光和抗变色的抗 老化性能。

Claims

权 利 要 求
1、 供外部使用的珠光颜料， 它的结构包括- 第一层， 为片状基材。
第二层， 该片状基材上涂覆的一种或多种金属氧化物。
第三层， 在金属氧化物涂层上再涂覆的金属亚磷酸盐和铈的水合氧化 物 (或氢氧化物)。
第四层， 为一种水解硅烷偶联剂。
其中， 第一层和第二层经煅烧后形成基本型珠光颜料。 第三层和第四 层为后涂覆层。
2、 权利要求 1的珠光颜料， 其特征在于片状基材为云母。
3、 权利要求 1、 2的珠光颜料， 第二层所述的金属氧化物的种类由二 氧化钛、 三氧化二铁、 二氧化锡、 氧化锌、 三氧化二铝和二氧化硅中的至 少一种组成。
4、 权利要求 3的珠光颜料， 金属氧化物为二氧化钛和 /或氧化铁（ΠΙ)。
5、 权利要求 1的珠光颜料， 第三层所述的金属亚磷酸盐为亚磷酸铝。
6、 权利要求 1的珠光颜料， 第三层所述的金属亚磷酸盐为亚磷酸锌。
7、权利要求 1的珠光颜料， 第四层所述的硅烷偶联剂为含有烷氧基团 的硅烷偶联剂。
8、权利要求 5中的珠光颜料， 亚磷酸铝的量， 以铝元素计占基本型珠 光颜料的重量比例为 0.01〜1.0%。
9、权利要求 8中的珠光颜料， 其中铝元素占基本型珠光颜料的重量比 例为 0.05〜0.5%。
10、 权利要求 6中的珠光颜料， 亚磷酸锌的量， 以锌元素计占基本型 珠光颜料的重量比例为 0.05〜1.5%。
11、 权利要求 10中的珠光颜料， 其中锌元素占基本型珠光颜料的重量 比例为 0.1〜0.6%。
12、 权利要求 1 中的珠光颜料， 构成第三层的铈的水合氧化物 （或氢氧 第 ¾页 化物） 的量， 以铈元素计占基本型珠光颜料的重量比例为 0·05〜1·5%。
13、 权利要求 12中的珠光颜料， 其中铈元素占基本型珠光颜料的重量比例 为 0·1〜0·6%。
14、 权利要求 1 的珠光颜料， 构成第四层的硅烷偶联剂的量， 占基本型珠 光颜料的重量比例为 0.5〜10.0%。
15、 权利要求 14中的珠光颜料， 其中硅烷偶联剂的量， 占基本型珠光颜料 的重量比例为 1.0〜5.0%。
16、 一种制备权利要求 1的珠光颜料的方法,它包括- 第一步， 将基本型珠光颜料悬浮于水中， 并加热升温至 20〜100° (：。
第二步， 加入亚磷酸或亚磷酸盐， 必要时加入稀盐酸， 使悬浮液 ΡΗ值调至
3.0或以下。再加入水溶性铝盐或锌盐，搅拌均匀后， 加入稀碱液，使悬浮液 ΡΗ 值慢慢地升至 5.0 7.0。
第三步， 加入水溶性铈盐， 同时维持悬浮液 ΡΗ值不变。
第四步， 加入稀碱液， 使悬浮液 ΡΗ值升至 8.0， 再滴加一种硅烷偶联剂， 并维持搅拌 2小时。
第五步， 过滤所得的悬浮液取出颜料， 并经洗涤， 然后在 140°C连续干燥
16小时。
17、权利要求 16的方法， 其中基本型珠光颜料为二氧化钛涂覆云母的珠光
18、扠利要求 16的方法， 其中基本型珠光颜料为氧化铁（ΠΙ)涂覆云母的珠 光颜料。
19、 权利要求 16的方法， 其中第一步加热升温至 50~80°C。
20、 权利要求 16的方法， 其中第二步使悬浮液的 PH值升至 5.5〜6.5。
21、权利要求 16的方法， 其中第四步滴加的硅烷偶联剂为含有烷氧基团的 硅烷偶联剂。
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