WO2006015530A1 - Pigment ayant une dependance angulaire des couleurs d’interference et son procede de fabrication - Google Patents

Pigment ayant une dependance angulaire des couleurs d’interference et son procede de fabrication Download PDF

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Publication number
WO2006015530A1
WO2006015530A1 PCT/CN2005/000828 CN2005000828W WO2006015530A1 WO 2006015530 A1 WO2006015530 A1 WO 2006015530A1 CN 2005000828 W CN2005000828 W CN 2005000828W WO 2006015530 A1 WO2006015530 A1 WO 2006015530A1
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Prior art keywords
refractive index
color
suspension
oxide layer
metal oxide
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PCT/CN2005/000828
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English (en)
French (fr)
Inventor
Jiansheng Fu
Yiting Peng
Xiaohui Tian
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Shantou Longhua Pearl Lustre Co., Ltd.
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34665951&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006015530(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Shantou Longhua Pearl Lustre Co., Ltd. filed Critical Shantou Longhua Pearl Lustre Co., Ltd.
Priority to US11/573,447 priority Critical patent/US20090090275A1/en
Priority to JP2007525148A priority patent/JP5456252B2/ja
Priority to ES05752501T priority patent/ES2395131T3/es
Priority to AT05752501T priority patent/ATE531768T1/de
Priority to EP05752501A priority patent/EP1780245B1/en
Publication of WO2006015530A1 publication Critical patent/WO2006015530A1/zh

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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
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • 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
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic 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
    • C09C2200/30—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
    • 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 color changing pigment.
  • it relates to a color-changing pigment having different interference colors depending on the angle of observation; the present invention also relates to a method of producing such a color-changing pigment. Background technique
  • Multi-layered color-changing pigments exhibit a color change between two or more strong interference colors depending on the viewing angle.
  • such flop pigments are mostly formed by coating a metal oxide and a non-metal oxide on a surface of a substrate by a vapor phase method, a plasma sputtering method or a wet chemical method to form a multilayer structure. Due to the difference in the substrate, the production methods of the pigments are also different, but there are problems such as complicated process, high price, and small color variation range.
  • a multi-layer color-changing pigment based on an opaque metal foil or a metal oxide is a vacuum coating method, a substrate formed on a mesh or a dissolvable film, or a side of a metal foil, or two The surface is coated with a metal oxide which is alternately coated with a material having a low refractive index and a high refractive index, and different color change and discoloration ranges are obtained by controlling the optical thickness of the coating layer, and then peeled off.
  • This process requires high precision equipment, high chemical purity, high process control requirements, and low production yield, which results in high production costs, which limits its large number of applications; in addition, the color and range of the pigment are not easily controlled.
  • a multilayer color-changing pigment based on aluminum powder or synthetic iron oxide sheet (prepared by using high temperature and high pressure method), which is alternately coated with a low refractive index and a high refractive index on the surface of the substrate by vapor deposition.
  • a metal oxide which is carried into an ebullated bed by using an inert gas.
  • the organometallic compound is adsorbed on the substrate and decomposed into a metal oxide at a certain temperature to be deposited on the substrate.
  • the surface forms a coating of the desired thickness.
  • This process has the problem that the substrate is effectively dispersed in the fluidized bed, and it is difficult to measure and control.
  • the use of organometallic compounds also has environmental problems.
  • the pigment manufacturing process is complicated, the equipment requirements are high, the substrate preparation cost is high, and the process control precision is required, so that the product also has a problem of high price and limited use.
  • a color-changing pigment based on synthetic silica (this substrate is prepared by coating a certain concentration of water glass on a special equipment and dried and peeled), and hydrolyzing the soluble inorganic by a wet chemical process.
  • U.S. Patent 6,692,561 is a strong color interference color pigment based on mica.
  • the pigment is coated on the mica substrate with the first layer being a low refractive index metal oxide layer, and the second layer is a high refractive index metal oxide layer. Since the optimum thickness of the oxide layer is not given, it can be considered The invention does not solve the substantial problem. And from the data analysis of its tests, the invention test uses a fixed angle. It can be seen that its color variation range is very small, still belongs to the category of ordinary color-changing pigments, and does not solve the problem of flop.
  • the thickness of the oxide coating on the substrate is difficult to measure and is typically calculated by measuring the percentage of the coated oxide layer as a percentage of the total pigment weight, i.e., the coverage.
  • An object of the present invention is to provide a color-changing pigment which is inexpensive, has a simple manufacturing process, and exhibits different strong interference colors depending on the angle of observation.
  • Another object of the present invention is to provide a process for producing the above color changing pigment.
  • the color-changing pigment of the present invention is a synthetic silicate plate as a substrate, and the surface of the synthetic silicate plate is alternately coated with a metal oxide layer having a refractive index of more than 1.8 and a refractive index of less than 1.8.
  • the oxide layer, the cladding layer is at least three layers, and the oxide layer having a refractive index of less than 1.8 is always located between the metal oxide layers having a refractive index greater than 1.8.
  • the above synthetic silicate flakes are sodium calcium silicate flakes having a thickness of 0.1 to 10 ⁇ m and a particle diameter of 5 to 1500 ⁇ m, preferably sodium silicate having a thickness of 1 to 5 ⁇ m and a particle diameter of 30 to 150 ⁇ m. Sheet.
  • the coating ratio of the metal oxide layer having a refractive index of more than 1.8 is 1 to 50%, preferably 3 to 30%.
  • the coating ratio of the above oxide layer having a refractive index of less than 1.8 is from 5 to 80%, preferably from 10 to 60%.
  • the metal oxide having a refractive index of more than 1.8 is Ti0 2 , SnO 2 , Fe 2 0 3 , Fe 3 0 4 , CoO, Co 2 O 3 , Zr0 2 , Cr 2 0 3 or a mixture or a composite thereof.
  • the above oxide having a refractive index of less than 1.8 is Si0 2 , A1 2 0 3 , Al(OH) 3 , B 2 0 3 or a mixture thereof or a composite thereof.
  • the invention also provides a method for producing the above color changing pigment, which method comprises the following steps in sequence:
  • step (3) adjusting the pH of the step (2) suspension to 2-9, and then metering the solution of the soluble inorganic metal salt by 1-50% of the metal oxide layer to maintain a constant pH, when feeding After the completion, stir at a constant temperature for 10-30 minutes;
  • step (3) filtering the suspension of step (3), washing with deionized water, drying, calcining, and sieving;
  • hydrolyzate of the soluble inorganic metal salt has a metal oxide refractive index of more than 1.8, and the oxide of the hydrolyzate of the soluble inorganic salt has a refractive index of less than 1.8.
  • the above soluble inorganic metal salt is selected from the group consisting of TiCl 4 , TiOCl 2 , SnCl 4 , SnCl 2 , FeCl 3 , FeCl 2 , CoCl 2 , ZrOCl 2 or CrCl 3 .
  • the above soluble inorganic salt is selected from the group consisting of water glass, silicate, A1C1 3 , NaA10 2 or borax.
  • the drying temperature in the above step (4) is 100 to 150 ° C, and the calcination temperature is 250 to 1000 ° C.
  • the flop color multi-layer color-changing pigment of the present invention has the following advantages - the pigment of the present invention is made of a synthetic silicic acid 3 ⁇ 4 sheet as a substrate, which is convenient and inexpensive, compared to opaque metal foil or metal oxide, Synthetic silica and silicone liquid crystal sheets are substrates, which are much cheaper, which greatly reduces the price of pigments and broadens their application fields.
  • the pigment of the invention is coated on the surface of the synthetic silicate plate with a certain thickness of high refractive index metal oxide, so that the active groups on the surface of the silicate plate are evenly distributed, and the optical properties are consistent, and then directly
  • the low refractive index oxide layer is coated to a desired thickness, and other high refractive index metal oxides are coated to obtain an effect of exhibiting different interference colors depending on the viewing angle.
  • the substrate of the pigment of the present invention is a synthetic silicate plate, and the synthetic silicate plate is a single-layer structure, and light is irradiated thereon, and the number of times of light refraction is much less than that of a pigment using mica as a substrate, and the reflection intensity is It is much larger, so the macroscopic performance of its color is much brighter and brighter than the pigment based on mica.
  • the method of the present invention alternately coats the surface of the synthetic silicate sheet substrate by a wet chemical hydrolysis process.
  • the refractive index oxide layer and the low refractive index oxide layer, the alternating coating may be multiple times, or may be one time, and is very flexible, so that a plurality of color tones and different color changing intervals can be prepared, and the color changing interval can be two colors. , three or more color changes until all color intervals are covered; the hydrolyzing process can control the coating of the coated metal oxide by controlling the amount of the inorganic salt solution added to control its optical The thickness is controlled to control the hue change of the pigment.
  • the method of the present invention is easy to handle, easy to control product quality, and product quality is stable.
  • due to the wet chemical hydrolysis coating process large-scale industrial production can be realized, and the product after hydrolysis reaction of the soluble inorganic metal compound has almost no environmental problems and is easy to handle.
  • a pigment having a structure of Fe 2 O 3 / Si0 2 1 Fe 2 0 3 1 silicate flakes I Fe 2 0 3 1 Si0 2 1 Fe 2 0 3 is taken as a sample of 100 g and a thickness of 1-5 ⁇ m.
  • a sodium calcium silicate silicate flake having a diameter of 30-150 microns was suspended in 1000 ml of deionized water, stirred and heated to 75 °C.
  • the pH of the suspension was adjusted to 3.5 with 18% hydrochloric acid, followed by metering in 200 ml of 10% ferric chloride solution, during which the pH of the suspension was maintained by dropwise addition of 15% sodium hydroxide solution. Constant, after the addition was completed, the constant temperature was continued for 15 minutes.
  • the pH of the suspension was adjusted to 9.5 with 32% sodium hydroxide solution and stirred for another 15 minutes.
  • a 3 liter sodium silicate solution (13 g/liter of SiO 2 ) was metered in dropwise, and 15% hydrochloric acid was added dropwise thereto to make the pH constant. When the addition was completed, the mixture was stirred at a constant temperature for 30 minutes.
  • the pH of the suspension was adjusted to 3.5 with 18% hydrochloric acid, stirred at a constant temperature for 30 minutes, and 70 ml of a ferric chloride solution having a concentration of 120 g/liter was added dropwise. During the addition, the pH of the suspension was passed. Add 15% sodium hydroxide to keep it constant. After the addition is completed, stir it for 15 minutes.
  • the suspension was filtered, and the filtered product was washed with deionized water, dried at 120 ° C, calcined at 50 CTC, and passed through a 100 mesh sieve to obtain a product.
  • the total oxide coverage of the resulting product is 35.9%, with the first layer of ferric oxide coating rate of 7.6%, the second layer of silica coverage of 25.7%, and the third layer of ferric oxide package.
  • the coverage rate is 2.65%.
  • Example 2 The obtained product was mixed with a colorless transparent nitrocellulose adhesive in a certain ratio, and then scraped on a scratched paper having a black and white base, which showed that the color value was from a purple-yellow-green color flow. Viewed from a vertical to a horizontal perspective.
  • Example 2
  • the pH of the suspension was adjusted to 3.5 with 18% hydrochloric acid, and then 300 ml of 10% ferric chloride solution was metered in. During this process, the pH of the suspension was maintained by dropwise addition of 15% sodium hydroxide solution. Constant, after the addition was completed, the constant temperature was continued for 15 minutes.
  • the pH of the suspension was adjusted to 9.5 with 32% sodium hydroxide solution and stirred for another 15 minutes.
  • a 4 liter sodium silicate solution (13 g/liter of SiO 2 ) was metered in dropwise, and 15% hydrochloric acid was added dropwise thereto to make the pH constant. When the addition was completed, the mixture was stirred at a constant temperature for 30 minutes.
  • the pH of the suspension was adjusted to 3.5 with 18% hydrochloric acid, stirred at a constant temperature for 30 minutes, and 94 ml of a ferric chloride solution having a concentration of 120 g/liter was added dropwise. During the addition, the pH of the suspension was passed. Add 15% sodium hydroxide to keep it constant. After the addition is completed, stir it for 15 minutes.
  • the suspension was filtered, and the filtered product was washed with deionized water, dried at 120 ° C, calcined at 500 ° C, and passed through a 200 mesh sieve to obtain a product.
  • the total oxide coverage of the obtained product was 41.25%, wherein the first layer of ferric oxide coating ratio was 8.68%, the second layer of silica coating ratio was 30.55%, and the third layer of ferric oxide coating was coated.
  • the rate is 2.04%.
  • the obtained product was mixed with a colorless transparent nitrocellulose adhesive in a certain ratio, and then scraped on a scratched paper having a black and white base, which showed that the color value was from a purple-yellow-green color flow. Viewed from a vertical to a horizontal perspective.
  • the coating of the above-mentioned high refractive index metal oxide and low refractive index metal oxide may be alternately repeated to form a different structure such as Fe 2 O 3 /Si0 2 /Fe 2 0 3 1 Si0 2 1 Fe 2 0 3 1 Si0 2 1 Fe 2 0 3 1 silicate sheet / Fe 2 0 3 1 Si0 2 I Fe 2 0 3 / Si0 2 1 Fe 2 0 3 1 Si0 2 I Fe 2 0 3 or ⁇ 0 2 1 Fe 2 0 3 1 Si0 2 1 Fe 2 0 3 / Ti0 2 1 silicate flakes / Ti0 2 / Fe 2 O 3 / Si0 2 / Fe 2 0 3 / Ti0 2; thereby preparing pigments of various color tones and different color-changing intervals.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Description

一种随角异色的多层变色颜料及其生产方法
技术领域
本发明涉及一种变色颜料。 具体而言， 涉及一种具有随着观察角度的不同而呈现 出不同干涉色的变色颜料； 本发明还涉及这种变色颜料的生产方法。 背景技术
多层变色颜料会随观察角度不同在二种或多种强干涉色之间呈现颜色变化。目前， 这种随角异色颜料多是在基片的表面通过气相法、 等离子溅射或湿化学方法包覆金属 氧化物和非金属氧化物形成多层的结构。 由于基片的不同，其颜料的生产方法也不同， 但都存在工艺复杂、 价格昂贵、 颜色变化范围小等问题。
以不透明金属箔或金属氧化物为基片的多层变色颜料， 是采用真空镀膜的方法， 在一定目数网上， 或在可溶解膜上形成的基片， 再在金属箔的一面， 或二面包覆金属 氧化物， 此金属氧化物是低折射率和高折射率的材料交替包覆， 通过控制其包覆层光 学厚度得到不同颜色变化和变色范围，然后剥离脱落下来的。此工艺要求设备精度高， 化学品纯度髙， 工艺控制要求也高， 而且产量小， 因而生产成本高， 从而限制了它的 大量应用； 另外此颜料的颜色及变化范围不易控制。
以铝粉或人工合成的氧化铁片 (制备该氧化铁片是采用高温高压法)为基片的多层 变色颜料，采用气相沉积法在基片的表面交替包覆低折射率和高折射率的金属氧化物， 此金属氧化物通过用惰性气体将有机金属化合物带进沸腾床， 有机金属化合物吸附在 基片上， 并在一定的温度下分解为金属氧化物而沉积在基片上， 在基片表面形成所需 要厚度的包覆层。 此工艺存在基片在沸腾床内有效分散难的问题， 计量控制加入也困 难， 另外采用有机金属化合物， 也存在环保问题。此颜料制造工艺复杂， 设备要求高， 基片制备成本高， 要求工艺控制精度高等， 因此产品也同样存在价格高而限制广泛使 用的问题。
以人工合成的二氧化硅为基片的变色颜料 (此基片是通过涂覆一定浓度的水玻璃 于一个特制设备上， 并通过干燥、 剥离而制备的)， 通过湿化学工艺， 水解可溶性无机 金属化合物和可溶性非金属化合物， 生成水合金属氧化物和非金属氧化物， 沉积于基 片上，并且可以是交替在基片上包覆低折射率的金属氧化物和高折射率的金属氧化物， 此工艺由于是湿化学方法， 所以易于操作和控制所需包覆层的光学厚度， 工艺简单， 易于大规模生产， 也可以只在二氧化硅基片表面包覆一层高折射率的金属氧化物而获 得随角异色效果， 但由于基片要求的厚度小于 1微米， 一般是在 200-500nm范围， 这 就给制备基片带来了很大的困难， 制备基片的成本很高， 产量也低， 因而该颜料也存 在成本高、 应用不广泛的问题。
美国专利 US 6,692,561是以云母为基片的强色彩干涉色颜料。 该颜料是在云母基 片上包覆第一层是低折射率的金属氧化物层， 第二层是高折射率的金属氧化物层， 由 于没有给出氧化物层厚度的最佳值， 可以认为该发明没有解决实质问题。 而且从其测 试的数据分析，该发明测试是采用一个固定的角度。可见它的颜色变化范围是很小的， 仍属于普通变色颜料范畴， 没有解决随角异色的问题。
基片上氧化物包覆层的厚度是很难测量的， 一般通过测量所包覆氧化物层占总颜 料重量的百分比， 也即包覆率计算得到。 发明内容
本发明的一个目的是提供一种价格低廉、 制造工艺简单、 具有随着观察角度的不 同而呈现出不同强干涉色的变色颜料。
本发明的另一目的是提供一种上述变色颜料的生产方法。
为实现以上目的， 本发明的变色颜料是以人工合成的硅酸盐薄片为基片， 在该合 成硅酸盐薄片的表面交替包覆有折射率大于 1.8的金属氧化物层和折射率小于 1.8的氧 化物层， 这种包覆层至少为三层， 并且折射率小于 1.8 的氧化物层总是位于两折射率 大于 1.8的金属氧化物层之间。
上述的合成硅酸盐薄片是厚度为 0.1-10微米、粒径为 5-1500微米的硅酸钙钠薄片， 优选为厚度为 1-5微米， 粒径为 30-150微米的硅酸钙钠薄片。
上述折射率大于 1.8的金属氧化物层的包覆率为 1-50%, 优选为 3-30%。
上述折射率小于 1.8的氧化物层的包覆率为 5-80%， 优选为 10-60%。
上述折射率大于 1.8的金属氧化物为 Ti02、 Sn02、 Fe203、 Fe304、 CoO、 Co203、 Zr02、 Cr203或它们的混合物、 或复合物。
上述折射率小于 1.8的氧化物为 Si02、 A1203、 Al(OH)3、 B203或它.们的混合物、 或复合物。 本发明还提供一种上述变色颜料的生产方法， 该方法依次包括如下 骤：
(1)将一定规格要求的人工合成硅酸盐薄片投入到一定量的去离子永中， 搅拌分散 成含固量为 1-20%的悬浮液； 将此悬浮液升温至 60-90°C， 并将此悬浮液的 pH值调到 2-9； 按金属氧化物层的包覆率为 1-50%计量加入可溶性无机金属盐的溶液， 同时维持 其 pH值恒定， 当加料完毕后， 恒温搅拌 10-30分钟；
(2)将步骤 (1)悬浮液的 pH值调到 6-14， 再按氧化物层的包覆率为 5-80%计量加入 可溶性无机盐的溶液，同时维持此悬浮液的 pH值恒定，当加料完毕后，恒温搅拌 10-30 分钟；
(3)将步骤 (2)悬浮液的 pH值调到 2-9，再按金属氧化物层的包覆率为 1-50%计量加 入可溶性无机金属盐的溶液， 维持其 pH恒定， 当加料完毕后， 恒温搅拌 10-30分钟；
(4)将步骤 (3)的悬浮液过滤、 用去离子水洗涤、 干燥、 煅烧， 过筛；
上述的步骤 (1)、 （2)、 （3)可重复交替进行，
其中所述可溶性无机金属盐的水解产物的金属氧化物折射率大于 1.8，且所述可溶 性无机盐的水解产物的氧化物的折射率小于 1.8。
上述可溶性无机金属盐选自 TiCl4、 TiOCl2、 SnCl4、 SnCl2、 FeCl3、 FeCl2、 CoCl2、 ZrOCl2或 CrCl3等。
上述可溶性无机盐选自水玻璃、 硅酸盐、 A1C13、 NaA102或硼砂等。
上述步骤 (4)的干燥温度为 100~150°C， 煅烧温度为 250~1000°C。
本发明的随角异色的多层变色颜料具有如下的优点- 本发明的颜料由于是采用人工合成硅酸 ¾薄片为基片， 取材方便、 价格便宜， 比 起不透明金属箔或金属氧化物、 合成二氧化硅、 有机硅液晶片为基片， 价格低得多， 大大降低了颜料价格， 拓宽了其应用领域。
本发明的颜料是在合成硅酸盐薄片的表面先包覆一定厚度的高折射率的金属氧化 物， 使硅酸盐薄片表面的活性基团得以均匀分布， 并取得一致光学性质， 然后再直接 包覆低折射率的氧化物层至所需厚度， 再包覆其它的高折射率的金属氧化物， 从而获 得随着观察角度的不同而呈现出不同干涉色的效果。
本发明颜料的基片是合成硅酸盐薄片， 而合成硅酸盐薄片是单层结构， 光照射到 其上面， 光线的折射次数就远远少于以云母作为基片的颜料， 反射强度却大得多， 从 而宏观表现它的颜色的鲜艳性和亮度远远高于以云母为基片的颜料。
本发明的方法由于采用湿化学水解工艺， 在合成硅酸盐薄片基片表面交替包覆高 折射率氧化物层和低折射率氧化物层， 这种交替包覆可以是多次， 也可以是一次， 十 分灵活， 因而可以制备出多种色调和不同的变色区间， 此变色区间可以是双色、 三色 或更多的颜色的变化， 直至涵盖所有的颜色区间； 水解包覆过程可通过控制所添加无 机盐溶液的量来控制所包覆金属氧化物的包覆率， 从而控制它的光学厚度， 达到控制 颜料的色相变化。
本发明的方法易于操作， 易于控制产品质量， 而且产品质量稳定。 另外， 由于采 用了湿化学水解包覆工艺， 可以实现大规模工业化生产， 而采用可溶的无机金属化合 物水解反应后的产物， 几乎没有环保问题， 处理简单。 具体实施方式
实施例 1
以结构为 Fe203 / Si021 Fe203 1硅酸盐薄片 I Fe203 1 Si021 Fe203的颜料为例 ·' 取 100 g厚度为 1-5微米， 粒径为 30-150微米的硅酸钙钠硅酸盐薄片粉， 将其悬 浮于 1000毫升的去离子水中， 搅拌并加热到 75°C。
悬浮液的 pH值用 18%的盐酸调为 3.5，接着计量加入 200毫升的 10%的三氯化铁 溶液，在此过程中悬浮液的 pH值通过逐滴地加入 15%氢氧化钠溶液保持恒定，当加料 完毕后， 恒温继续搅拌 15分钟。
用 32%氢氧化钠溶液将悬浮液的 pH调高到 9.5， 再搅拌 15分钟。
将 3升硅酸钠溶液 (13克 /升的 Si02)逐滴计量加入， 在此过程中逐滴加入 15%的盐 酸来使其 pH恒定， 当加料完毕， 再恒温搅拌 30分钟。
用 18%的盐酸将悬浮液的 pH调到 3.5， 恒温搅拌 30分钟， 再逐滴加入 70毫升的 浓度为 120克 /升的三氯化铁溶液,在加入过程中，悬浮液的 pH值通过加入浓度为 15% 的氢氧化钠来保持恒定， 加料完毕， 再恒温搅拌 15分钟。
悬浮液被过滤， 过滤后产物经去离子水洗涤， 在 120°C下干燥， 在 50CTC下煅烧， 然后过 100目筛， 即得到产品。
• 所得产品的总氧化物包覆率为 35.9%，其中第一层三氧化二铁包覆率为 7.6%,第二层 二氧化硅包覆率为 25.7%,第三层三氧化二铁包覆率为 2.65%。
将所得产品与无色透明的硝酸纤维素制成的胶粘剂按一定比例混合， 然后在有黑 白底的刮样纸上刮样， 它示出色彩值是从***——黄绿色的色彩流动， 从垂直到水 平视角观察。 实施例 2
以结构为 Fe203 1 Si021 Fe203 1硅酸盐薄片 I Fe203 1 Si021 Fe203的颜料为例； 取 100 g厚度为 1-5微米， 粒径为 10-60微米的硅酸钙钠硅酸盐薄片粉， 将其悬 浮于 1000毫升的去离子水中， 搅拌并加热到 75°C。
悬浮液的 pH值用 18%的盐酸调为 3.5,接着计量加入 300毫升的 10%的三氯化铁 溶液，在此过程中悬浮液的 pH值通过逐滴地加入 15%氢氧化钠溶液保持恒定，当加料 完毕后， 恒温继续搅拌 15分钟。
用 32%氢氧化钠溶液将悬浮液的 pH调高到 9.5， 再搅拌 15分钟。
将 4升硅酸钠溶液 (13克 /升的 Si02)逐滴计量加入， 在此过程中逐滴加入 15%的盐 酸来使其 pH恒定， 当加料完毕， 再恒温搅拌 30分钟。
用 18%的盐酸将悬浮液的 pH调到 3.5， 恒温搅拌 30分钟， 再逐滴加入 94毫升的 浓度为 120克 /升的三氯化铁溶液，在加入过程中，悬浮液的 pH值通过加入浓度为 15% 的氢氧化钠来保持恒定， 加料完毕， 再恒温搅拌 15分钟。
悬浮液被过滤， 过滤后产物经去离子水洗涤， 在 120°C下干燥， 在 500°C下煅烧， 然后过 200目筛， 即得到产品。
所得产品的总氧化物包覆率为 41.25%， 其中第一层三氧化二铁包覆率为 8.68%,第 二层二氧化硅包覆率为 30.55%， 第三层三氧化二铁包覆率为 2.04%。
将所得产品与无色透明的硝酸纤维素制成的胶粘剂按一定比例混合， 然后在有黑 白底的刮样纸上刮样， 它示出色彩值是从***——黄绿色的色彩流动， 从垂直到水 平视角观察。
上述高折射率的金属氧化物和低折射率的金属氧化物的包覆可以交替重复进行，形 成不同的结构， 如 Fe203/Si02/Fe203 1 Si021 Fe203 1 Si021 Fe203 1硅酸盐薄片 / Fe203 1 Si02 I Fe203/ Si02 1 Fe203 1 Si02 I Fe203或 ΊΪ02 1 Fe203 1 Si02 1 Fe203 / Ti02 1硅酸盐薄 片 / Ti02 / Fe203 / Si02 / Fe203 / Ti02; 从而制备出多种色调和不同变色区间的颜料。
以上实施例只是本发明随角异色的多层变色颜料及其生产方法的举例说明， 但这 些实施例并非用以限制本发明保护范围，凡未脱离本发明技术方案的等效实施或变更， 均应包含在发明的范围中。

Claims

权 利 要 求
1、一种随角异色的多层变色颜料， 其特征在于： 所述变色颜料是以人工合成硅酸 盐薄片为基片， 在该合成硅酸盐薄片的表面交替包覆有折射率大于 1.8 的金属氧化物 层和折射率小于 1.8的氧化物层，这种包覆层至少为三层，并且折射率小于 1.8的氧化 物层总是位于两折射率大于 1.8的金属氧化物层之间。
2、根据权利要求 1所述的变色颜料， 其特征在于： 所述的合成硅酸盐薄片是厚度 为 0.1-10微米、 粒径为 5-1500微米的合成硅酸钙钠薄片。
3、 根据权利要求 1或 2所述的变色颜料， 其特征在于： 所述折射率大于 1.8的金 属氧化物层的包覆率为 1-50%。
4、 根据权利要求 1或 2所述的变色颜料， 其特征在于： 所述折射率小于 1.8的氧 化物层的包覆率为 5-80%。
5、 根据权利要求 3所述的变色颜料， 其特征在于： 所述折射率大于 1.8的金属氧 化物层的包覆率为 3.-30%。
6、 根据权利要求 4所述的变色颜料， 其特征在于： 所述折射率小于 1.8的氧化物 层的包覆率为 10-60%。
7、 根据权利要求 1或 2所述的变色颜料， 其特征在于： 所述折射率大于 1.8的金 属氧化物为 Ti02、 Sn02、 Fe203、 Fe304、 CoO、 Co203、 Zr02、 Cr203或它们的混合物、 或复合物。
8、 根据权利要求 1或 2所述的变色颜料， 其特征在于： 所述折射率小于 1.8的氧 化物为 Si02、 A1203、 Al(OH)3、 B203或它们的混合物、 或复合物。
9、 一种根据权利要求 1所述的变色颜料的生产方法， 该方法依次包括如下步骤：
(1)将一定规格的人工合成硅酸盐薄片投入到一定量的去离子水中， 搅拌分散成含 固量为 1-20%的悬浮液； 将此悬浮液升温至 60-90 °C， 并将此悬浮液的 pH值调到 2-9; 按金属氧化物层的包覆率为 1-50%计量加入可溶性无机金属盐的溶液，同时维持其 pH 值恒定， 当加料完毕后， 恒温搅拌 10-30分钟；
(2)将步骤 (1)悬浮液的 pH值调到 6-14， 再按氧化物层的包覆率为 5-80%计量加入 可溶性无机盐的溶液，同时维持此悬浮液的 pH值恒定，当加料完毕后，恒温搅拌 10-30 分钟； (3)将步骤 (2)悬浮液的 pH值调到 2-9，再按金属氧化物层的包覆率为 1-50%计量加 入折射率可溶性无机金属盐的溶液， 同时维持其 pH值恒定， 当加料完毕后， 恒温搅 拌 10-30分钟；
(4)将步骤 (3)的悬浮液过滤、 用去离子水洗涤、 干燥、 煅烧， 过筛；
上述的步骤 (1)、 （2)、 （3)可重复交替进行，
其中所述可溶性无机金属盐的水解产物的金属氧化物折射率大于 1.8，且所述可溶 性无机盐的水解产物的氧化物的折射率小于 1.8。
10、 根据权利要求 9所述的生产方法， 其特征在于： 所述的合成硅酸盐薄片是厚 度为 0.1-10微米、 粒径为 5-1500微米的合成硅酸钙钠薄片。
11、根据权利要求 9或 10所述的生产方法， 其特征在于： 所述可溶性无机金属盐 选自 TiCl4、 TiOCl2、 SnCl4、 SnCl2、 FeCl3、 FeCl2、 CoCl2、 ZrOCl2或 CrCl3。
12、根据权利要求 9或 10所述的生产方法， 其特征在于： 所述可溶性无机盐选自 水玻璃、 硅酸盐、 A1C13、 NaA102或硼砂。
13、 根据权利要求 9或 10所述的生产方法， 其特征在于： 所述步骤 (4)的干燥温 度为 100~150°C， 且煅烧温度为 250~1000°C。
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JP5456252B2 (ja) 2014-03-26
CN1597793A (zh) 2005-03-23
ES2395131T3 (es) 2013-02-08
EP1780245A4 (en) 2010-08-04
EP1780245B1 (en) 2011-11-02
ATE531768T1 (de) 2011-11-15
JP2008509068A (ja) 2008-03-27
US20090090275A1 (en) 2009-04-09
EP1780245A1 (en) 2007-05-02
CN1266229C (zh) 2006-07-26

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