CN1225659A - Metal oxide coated titanium dioxide lamellas - Google Patents
Metal oxide coated titanium dioxide lamellas Download PDFInfo
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- CN1225659A CN1225659A CN 97196621 CN97196621A CN1225659A CN 1225659 A CN1225659 A CN 1225659A CN 97196621 CN97196621 CN 97196621 CN 97196621 A CN97196621 A CN 97196621A CN 1225659 A CN1225659 A CN 1225659A
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- pigment
- metal oxide
- titanium dioxide
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- lamellas
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Abstract
The invention relates to a pearly lustre pigment, consisting of a titanium oxide lamella-shaped core and one or several coatings of different metal oxides or metal oxide hydrates, which can be obtained by hardening an aqueous solution of a titanium compound that can be thermally hydrolyzed on a continuous strip, by separating the layer thus arising, by coating the titanium dioxide lamellas thus obtained with one or several metal oxide or metal oxide hydrates, e. g. Fe2O3, Fe3O4, FeOOH or Cr2O3 after or without intermediate drying in a wet process and by separating, drying and optionally calcinating the material thus obtained.
Description
The present invention relates to extremely thin pearlescent pigment based on the plate-like titanium dioxide of coated metal oxide or coated metal oxide hydrate.
Based on the micaceous pearlescent pigment is known, and said pearlescent pigment also has the additional metals oxide skin on titanium dioxide layer.United States Patent (USP) 3087828 and 3087829 proposes aluminum oxide, and zirconium white, zinc oxide and stannic oxide propose ferric oxide as the colourless oxide compound of second kind of metal oxide layer, nickel oxide, and cobalt oxide, cupric oxide and chromic oxide are as the oxide compound with intrinsic color.The deposition of second kind of metal oxide on the titanium dioxide hydrates layer causes the obvious stabilization of the photosensitivity of this layer.Especially the TiO 2 pigment that contains ferric oxide successfully used many years.
United States Patent (USP) 3087828 has been described and has been passed through at TiO
2Deposition Fe on the layer
2O
3-layer can obtain the golden pigments, mica, and said golden pigment presents a kind of pink tone when calcining.
United States Patent (USP) 3874890 has been described a kind of method for preparing golden pearlescent pigment, wherein, scribbles TiO
2And/or ZrO
2Pigments, mica at first apply ironic hydroxide (II), be oxidized to Fe then
2O
3
United States Patent (USP) 4744832 has been described based on the flake substrate of coated metal oxide micaceous pearlescent pigment particularly, and said metal oxide layer contains titanium and iron, and said pigment has multilayered structure, has the first layer TiO of rutile-type
2Last coating one deck pseudobrookite and one deck ferric oxide.
Pigments, mica is widely used in printing and coatings industry and cosmetic industry and polymer processing industry.They can be differentiated by interference color and high glossiness.Yet in order to form coating as thin as a wafer, pigments, mica is inappropriate, because be 200～1200nm as the thickness of mica of the matrix of the metal oxide layer of said pigment own.The another one shortcoming is that the mica sheet particulate thickness in a certain grade scope of being determined by said platy shaped particle size changes near mean value in some cases significantly.In addition, mica is naturally occurring mineral substance, and it mixes external ion.And, need high complexity and step consuming time technically, specifically comprise and pulverizing and classification.
Because the thickness at edge, have the obvious scattering rate based on the pearlescent pigment of spissatus master slice shape particle and metallizing oxide compound, especially be lower than under the thinner particle size distribution situation of 20 μ m.
As the micaceous surrogate, proposed to use the thin glass sheet sprills, said thin glass sheet sprills can grind acquisition then by the rolling glass melt.Coated interference pigment based on such material shows the color effect that is better than those traditional mica-based pigment.Yet shortcoming is that said sheet glass sprills have very large mean thickness, i.e. the thickness distribution of 10-15 μ m and non-constant width (being generally 4～20 μ m), and the thickness of coated interference pigment generally is not more than 3 μ m.
EP0,384,596 have described a kind of method, and wherein, hydrated alkali metal silicate forms the bubble of thin-walled 480～500 ℃ of effects that are subjected to air spray; Then said bubble is pulverized and obtained the flaky alkali metal silicate base status that thickness is 3 μ m.Yet said method is a thickness distribution broad complicated and platy shaped particle gained.
DE1136042 describes a kind of prepare IV and the sheet of V family and iron group or the continuous band method of flicker oxide compound or hydrated metal oxide in the periodic table of elements.In the method, in order to promote the separation of metal oxide layer subsequently, if desired, at first be with continuously to one and apply a separating layer, said separating layer for example comprises, a kind of polysiloxane coating materials.Apply one deck liquid film then, this liquid film comprises a kind of hydrolyzable solution of metal compound, and said hydrolyzable metallic compound can change into required oxide compound, and dry said liquid film utilizes a shaking device to separate subsequently.Though do not quote the specific embodiment of this method, the bed thickness of the platy shaped particle of gained is 0.2-2 μ m.
EP0,240,952 and EP0,236,952 propose a kind of continuous band method for preparing different flaky materials, comprise silicon-dioxide, aluminum oxide and titanium dioxide.In this method,, a kind of thin liquid film of said flaky material presoma of definite thickness is coated on slick being with by a roller system; Said liquid film drying and from said separation, the formation platy shaped particle be with.If desired, with said particle calcining, grind classification subsequently.
The thickness of the platy shaped particle that the method for having determined preferably to describe according to EP0240952 obtains saidly is with continuously because said liquid film is coated to very equably by a roller system.The bed thickness that has provided said platy shaped particle in said embodiment is 0.3～3.0 μ m.According to embodiment 1, by the part dipping of first cylinder in a material container that is full of said presoma, with wetting this cylinder of used presoma.Said film is delivered on the cylinder of second common rotation from this cylinder, and second cylinder very closely contacts with first cylinder.At last, said film slips away from second cylinder and saidly is with continuously.
Yet shortcoming is to use very expensive persursor material, particularly when using organometallic compound, must satisfy the raising aspect the factory building security requirement.The coated material that the complete chemical transformation of said presoma becomes to require generally needs said film of intense heating and said carrying material.Except this can produce the very big thermal stresses on the material of said band, the limitation of high energy consumption and process velocity is very disadvantageous to the economy of said method.
WO93/08237 has described the platy shaped particle pigment of being made up of the flaky matrix that comprises silicon-dioxide, and this platy shaped particle pigment can contain tinting material solubility or insoluble, and covers the reflecting layer of one or more metal oxides or metal.By being with the said platy shaped particle matrix of sodified water glass preparation continuously.
DE1273098 describes by being with vapour deposition ZnS, MgF continuously
2, ZnO, CaF
2And TiO
2A kind of nacre pigment of film preparation.Yet this method is similar to United States Patent (USP) 4,879, and the method for describing in 140 has very high cost of equipment, wherein, and by from SiH
4And SiCl
4Plasma deposition obtain to have Si and SiO
2The platy shaped particle pigment of layer.
Although carried out multiple trial, up to now, also can not develop the method for the extremely thin bed thickness of any preparation less than the economy of the platy shaped particle TiO 2 pigment of 500nm.
The purpose of this invention is to provide bed thickness less than 500nm, bed thickness tolerance the nacreous pigment that contains titanium dioxide less than 10% high glossiness.
According to the present invention, reached this purpose by a kind of pearlescent pigment with multilayered structure, promptly on the platy shaped particle titanium dioxide core, apply another kind of metal oxide of one deck or metal oxide hydrate, the pearlescent pigment of said multilayered structure can obtain by following steps: by one continuously with on solidify a kind of aqueous solution of titanium compound that can thermal hydrolysis, separating obtained layer, under the centre does not have dry situation, by the titanium dioxide lamellas of wet method with another kind of metal oxide-coated gained, separate, the material of dry gained, if desired, can be with the calcined material of gained.
Other metal oxide or the metal oxide hydrate that are coated on the said titanium dioxide are Fe
2O
3, Fe
3O
4, FeOOH, Cr
2O
3, CuO, Ce
2O
3, Al
2O
3, SiO
2, BiVO
4, NiTiO
3, CoTiO
3And antimony dopant, stannic oxide doped with fluorine or doping iodine.
In one of said novel pigment specific embodiment, on the second layer of another kind of metal oxide or metal oxide hydrate, also there are the 3rd layer of additional metals oxide compound or metal oxide hydrate.This additional metals oxide compound or metal oxide hydrate are aluminum oxide or hydrated alumina, silicon-dioxide or Silicon dioxide, hydrate, Fe
2O
3, Fe
3O
4, FeOOH, ZrO
2, Cr
2O
3And antimony dopant, stannic oxide doped with fluorine or doping iodine.
Be used for continuously with on the preparation titanium dioxide lamellas can thermal hydrolysis preferably a kind of titanium tetrachloride aqueous solution of the aqueous solution of titanium compound.
The concentration of titanium salt is 7～30wt% in these solution, preferably 8～15wt%.
Can reach this purpose according to the present invention in addition by a kind of method for preparing said novel pigment, wherein,
-but a kind of aqueous solution of titanium compound of thermal hydrolysis is coated to one with the form of film be with continuously,
-said liquid film is by dry solidification, and in this solidification process, titanium dioxide produces from said presoma by chemical reaction,
-layer with gained separates and washing from said being with subsequently,
-under middle dry or moist condition, be suspended in the titanium dioxide lamellas of gained in the water and apply another kind of metal oxide, if desired, apply another metal oxide again,
-coated titanium dioxide lamellas to be separated from said water base suspension, drying if desired, is calcined.
In addition, the coating of said titanium dioxide lamellas, after middle drying, also can in a fluidized-bed reactor, be undertaken, for example, can utilize EP0 with metal oxide or metal oxide hydrate by the gas phase coating, 045, the method for preparing pearlescent pigment that proposes in 851 and EP0,106,235.
In addition, the invention still further relates to pigment according to the present invention and be used for colo(u)r-in-oil, printing-ink, plastics, makeup and the application that is used for the glaze of pottery and glass.
For this reason, can adopt pigment of the present invention and commercial available pigment such as mixture inorganic and organic light absorbing pigment, metal effect pigments and LCP pigment.
Said novel pigment is based on the titanium dioxide of platy shaped particle.The thickness of these platy shaped particles is between 10～500nm, preferably between 40～150nm.The scope of two other sizes is between 2～200 μ m, particularly between 5～50 μ m.
The thickness that is coated to the another kind of metal oxide layer on the said titanium dioxide lamellas is between 5～300 μ m, preferably between 5～150 μ m.
Prepare said novel pigment with a kind of three stage methods.In first stage, prepare titanium dioxide lamellas by continuous band.
At first, will explain said continuous band method with reference to figure 1.
By a roller system 2 control be with 1 continuously by an applicator unit 3, wherein, said continuously with the film of the said presoma of 1 coating one deck.Suitable applicator unit can be the drum-type applicator, also can be the unit of flow model.Said belt speed is 2～400m/min, preferably 5～200m/min.
In order to make said plastic tape reach wetting uniformly, best bet is to add the commercial wetting agent that gets in said coating liquid, or activates said belt surface by flame treating, Corona discharge Treatment or ionization.
Coated subsequently band is by a dry workshop section 4, and the temperature in this workshop section between 30～200 ℃ is with said coating drying.As drying machine, can use for example commercial infrared, the recirculated air that gets to spray and the ultraviolet drying machine.
After said dry workshop section, said band is by containing suitable separating medium, the separator tank 5 of deionized water for example, and in this groove, said drying layer is with separation from said.Said sepn process is auxiliary by other device, for example air jet system, brush and Vltrasonic device.
In moisture eliminator 6 subsequently, before applying said band once more that said band is dry.
In order to guarantee enough work-ing life and high drying temperature, said continuous band should be by chemically stable and heat-staple plastics manufacturing.The material that is suitable for said band comprises polyethylene terephthalate (PET) or other polyester and polyacrylic ester.
The width of said film is generally several centimetres and two meters or between greater than two meters.Said thickness is between 10 μ m are to several millimeters, and these two parameters are to optimize according to special needs.
From US3138475, can recognize the further detailed content of continuous band method among EP0240952 and the WO93/08237.
In second operational phase,, be with the isolating exsiccant titanium dioxide lamellas that do not have in advance from said with another kind of metal oxide-coated according to a kind of known method.
When using rhombohedral iron ore (Fe
2O
3) when applying, parent material can be iron (III) salt described in US3087828 and the US3087829 for example, also can be iron (II) salt of describing among the US3874890, initial ironic hydroxide (II) coating that forms can be oxidized to ferric oxide (III) hydrate.Molysite (III) is preferably as parent material., a kind of iron(ic) chloride (III) solution is quantitatively joined under 60～90 ℃ temperature, the pH value is the water base suspension of 2.5～4.5 titanium dioxide lamellas for this reason.By adding 32% sodium hydroxide solution simultaneously the pH value is kept constant.After finishing, and after 110 ℃ of dryings, obtain a kind of red pigment.
In the presence of saltpetre, be 8.0 o'clock in the pH value, by the hydrolysis of a kind of iron (II) salts solution, carry out magnetite (Fe as the hydrolysis of ferric sulfate (II)
3O
4) coating.At EP0, specific precipitation example has been described in 659,843.After finishing, and after 100 ℃ of dryings, obtain a kind of black pigment.
The said titanium dioxide lamellas of yellow FeO (OH) coating that is used in the pyrrhosiderite modification also is preferred.In this case, a kind of FeSO
4The aqueous solution under nitrogen atmosphere in 70 ℃ of suspension that quantitatively join said titanium dioxide lamellas.Use 10% Na then
2CO
3Solution is adjusted to 4 to the pH value, and in said suspension aerating oxygen.After finishing, and after 110 ℃ of dryings, obtain a kind of yellow ultramarine.About accurate deposition condition, with reference to EP0,659,843.
In conjunction with said iron oxide layer and said titanium dioxide lamellas, the best way is to apply a doped tin oxide coatings earlier for better.In this way, SnCl with the salt acid treatment
4Solution quantitatively adds in the suspension of titanium dioxide lamellas, and the pH value is adjusted to 1.8, adds 32% sodium hydroxide solution simultaneously and makes this pH value keep constant.At tin dioxide hydrate layer post precipitation, can apply iron oxide hydrate immediately.
The another kind of metal oxide that preferably is deposited on the titanium dioxide lamellas is a chromic oxide.
Said precipitation can easily be carried out by the thermal hydrolysis of generation when ammonia volatilizees from the aqueous solution of six ammino chromium (III) derivatives or by the thermal hydrolysis with borax buffered chromium salt solution.The method of coating chromic oxide has been described in US3087828 and 3087829.
Said novel pigment not necessarily in each case all must calcining.For some purposes, just enough 110 ℃ of dryings.If calcine said pigment, temperature determines that preferred range is between 400 ℃ and 700 ℃ between 400 ℃～1000 ℃.
In addition, said novel pigment can apply the inorganic or organic colorant of the low solubility of combining closely.Preferably use colored precipitated pigment, concrete is the aluminum precipitation colorant.For this reason, by a kind of aluminium hydroxide coating of precipitation coating, and in second step, paint with colored colour lake.This process has been described in DE2429762 and DE2928287 in more detail.
Described in EP0141173 and DE2313332, equally preferably another applies pigment, especially the iron cyano complex of complexing salt, as Prussian blue and Turnbull indigo plant.
According to DE4009567, said novel pigment also can be coated with organic dye, especially applies phthalocyanine or metal phthalocyanine and/or indanthrene dye.In order to reach this purpose, prepare a kind of pigment suspension in dye solution, then this suspension and a kind of solvent, said dyestuff solubleness in said solvent is very low or be zero.
For a kind of other coating, also can use the chalkogenide of metal or the chalkogenide hydrate and the carbon black of metal.
In addition, can make said pigment through coating or aftertreatment later, with further increase light stability, weathering resistance and chemical stability or promote the processing treatment of said pigment, especially it sneaks into the processing treatment in the different media.Suitable back coating technology is those technology described in DE-C2215191, DE-A3151354, DE-A3235017 or DE-A3334598.Because the performance of said novel pigment is very good when not having these additional measures, so the material of the other coating that these are optional only accounts for about 0～5wt% of whole pigment, especially is about 0～3wt%.
With regard to thickness, the representative of said novel pigment is with the available optimal state of nacreous pigment because they only are made up of optical functional layer, do not have other to optical effect less than traditional solid support material of contributing, as mica or glass fragment.Because micaceous thickness, for the functional layer of given thickness, the thickness of pigments, mica is up to 25 times.Aspect technological use, this has produced the intrinsic advantage that can not obtain with other traditional pearlescent pigment.For example, can make dope layer thinner, and can reduce required amount of pigment, because there is not said solid support material " filler ", said pigment optical activity is higher.
Embodiment given below is used to illustrate the present invention but does not limit the present invention.
The endless belt of a polyethylene terephthalate (wide 0.3m, speed 20m/min) application roll by a retrograde rotation applied a kind of 20% titanium tetrachloride solution.Said coating liquid contains tensio-active agent (DISPERSE-AYD W-28, the manufacturers: DANIEL PRODUCTS COMPANY) of 0.3wt%.Dry workshop section by make its through 70 ℃ hot-air dry said with on moisture film, formed layer is with separation from said in being full of the separator tank of deionized water.Filter said plate-like titanium dioxide particle and use deionized water wash.Said platy shaped particle has silvering, and bed thickness is 100 ± 10nm.For the another kind of metal oxide of coating, they can be dispersed in the deionized water again.2 liters of said suspension (TiO of solids content: 15g
2) be heated to 75 ℃ and to be adjusted to the pH value with dilute hydrochloric acid be 1.8.
The SnCl of 4.3g
45H
2O is dissolved among the HCl of 29ml, said solution is diluted to 290ml with deionized water and stirred 10 minutes.
To said TiO
2Speed with 3ml/min in the suspension adds said SnCl
4Solution, in this process, keeping the pH value constant with 32%NaOH solution is 1.8.Using SnO
2After the coating, stirred 15 minutes at following said suspension of the condition of constant temperature and permanent pH value.
With 32% NaOH solution the pH value is adjusted to 3.0 then, quantitatively adds a kind of 8% iron(ic) chloride (III) aqueous solution, add said NaOH solution simultaneously and keep pH constant with the speed of 3ml/min.Add said FeCl continuously
3Until the interference color that obtain requiring.Filter out the pigment of gained, with deionized water wash and 110 ℃ of dryings 12 hours.Said pigment has the interference color of requirement and has red integral color.
Claims (11)
1, colored pearl colour lustre pigments, nuclear by a kind of platy shaped particle titanium dioxide is formed with one or more layers other metal oxide or metal oxide hydrate, can obtain by following process: but one continuously with on solidify the aqueous solution of the titanium compound of thermal hydrolysis, separating obtained layer, in the centre drying is arranged or do not have under the dry situation, apply the titanium dioxide lamellas of gained by wet method with one or more other metal oxides or metal oxide hydrate, separate, the material of dry gained, if necessary, can calcine the material of gained.
2,, be characterised in that said other metal oxide is Fe according to the pearlescent pigment of claim 1
2O
3, Fe
3O
4, FeOOH or Cr
2O
3
3, according to the preparation method of the pearlescent pigment of claim 1～2, characteristics are:
-but a kind of aqueous solution of titanium compound of thermal hydrolysis is coated to one with the form of film be with continuously,
-by the said liquid film of dry solidification, in this process, from solution, produce titanium dioxide by chemical reaction,
-subsequently the layer of gained is separated and washing from said being with,
-under the centre is with or without dry situation, is suspended in the titanium dioxide lamellas of gained in the water and applies one or more metal oxides,
-coated titanium dioxide lamellas to be separated from said aqeous suspension, drying if necessary, is calcined.
4, according to the method for claim 3, characteristics are that the said titanium compound aqueous solution that can thermal hydrolysis is titanium tetrachloride aqueous solution.
5, according to the method for claim 3 and 4, characteristics are that other used metal oxide is Fe
2O
3, Fe
3O
4, FeOOH and Cr
2O
3
6, according at least one method of claim 3～5, characteristics are that said pigment is at 110～150 ℃ temperature drying.
7, according at least one method of claim 3～6, characteristics are that said pigment is 400～700 ℃ temperature calcining.
8, according at least one method of claim 3～7, characteristics are described other metal oxide or additional metals oxide compound to be coated on the said titanium dioxide lamellas by the CVD method at a fluidized-bed.
9, the purposes that is used for the glaze of pigment coating, printing-ink, plastics, makeup and pottery and glass according to the pigment of claim 1 and 2.
10, according to the purposes of claim 9, characteristics are that said pigment is to use with the form of the mixture of commercial available pigment.
11, use coating, printing-ink, plastics and makeup according to the pigment coloring of claim 1 and 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97196621A CN1095863C (en) | 1997-05-23 | 1997-05-23 | Metal oxide coated titanium dioxide lamellas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97196621A CN1095863C (en) | 1997-05-23 | 1997-05-23 | Metal oxide coated titanium dioxide lamellas |
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| Publication Number | Publication Date |
|---|---|
| CN1225659A true CN1225659A (en) | 1999-08-11 |
| CN1095863C CN1095863C (en) | 2002-12-11 |
Family
ID=5179765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97196621A Expired - Fee Related CN1095863C (en) | 1997-05-23 | 1997-05-23 | Metal oxide coated titanium dioxide lamellas |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947450A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Nanometer titanium dioxide-coated iron oxide yellow composite material and preparation method thereof |
| CN102952418A (en) * | 2011-08-16 | 2013-03-06 | Jds尤尼弗思公司 | Manufacturing of diffractive pigments by fluidized bed chemical vapor deposition |
| CN103249782A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Brilliant black pigments |
| CN103249783A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Magnetic pigments |
| CN104893366A (en) * | 2015-06-18 | 2015-09-09 | 广西七色珠光材料股份有限公司 | Magnetic pearlescent pigment with 3D (three-dimensional) effect and preparation method of magnetic pearlescent pigment |
| CN108727877A (en) * | 2018-07-12 | 2018-11-02 | 福建坤彩材料科技股份有限公司 | Pearlescent pigment, preparation method and its colored nacreous pigment used for cosmetic of preparation |
| CN110028812A (en) * | 2019-04-30 | 2019-07-19 | 河南佰利联新材料有限公司 | A kind of preparation method of special raising titanium dioxide weatherability |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61295234A (en) * | 1985-06-11 | 1986-12-26 | Sumitomo Chem Co Ltd | Metal oxide-coated flakelike titanium oxide |
-
1997
- 1997-05-23 CN CN97196621A patent/CN1095863C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947450B (en) * | 2010-08-30 | 2012-12-12 | 浙江工业大学 | Nanometer titanium dioxide-coated iron oxide yellow composite material and preparation method thereof |
| CN101947450A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Nanometer titanium dioxide-coated iron oxide yellow composite material and preparation method thereof |
| CN103249782B (en) * | 2010-12-09 | 2015-05-20 | 默克专利股份有限公司 | Brilliant black pigments |
| CN103249782A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Brilliant black pigments |
| CN103249783A (en) * | 2010-12-09 | 2013-08-14 | 默克专利股份有限公司 | Magnetic pigments |
| CN103249783B (en) * | 2010-12-09 | 2015-04-15 | 默克专利股份有限公司 | Magnetic pigments |
| CN102952418B (en) * | 2011-08-16 | 2015-12-16 | Jds尤尼弗思公司 | The diffractive pigment manufactured by fluidized-bed chemical vapor deposition method |
| CN102952418A (en) * | 2011-08-16 | 2013-03-06 | Jds尤尼弗思公司 | Manufacturing of diffractive pigments by fluidized bed chemical vapor deposition |
| CN105419392A (en) * | 2011-08-16 | 2016-03-23 | Jds尤尼弗思公司 | Manufacturing of diffractive pigments by fluidized bed chemical vapor deposition |
| US9732228B2 (en) | 2011-08-16 | 2017-08-15 | Viavi Solutions Inc. | Manufacturing of diffractive pigments by fluidized bed chemical vapor deposition |
| CN105419392B (en) * | 2011-08-16 | 2018-05-18 | Viavi科技有限公司 | The diffractive pigment manufactured by fluidized-bed chemical vapor deposition method |
| CN104893366A (en) * | 2015-06-18 | 2015-09-09 | 广西七色珠光材料股份有限公司 | Magnetic pearlescent pigment with 3D (three-dimensional) effect and preparation method of magnetic pearlescent pigment |
| CN108727877A (en) * | 2018-07-12 | 2018-11-02 | 福建坤彩材料科技股份有限公司 | Pearlescent pigment, preparation method and its colored nacreous pigment used for cosmetic of preparation |
| CN108727877B (en) * | 2018-07-12 | 2020-04-10 | 福建坤彩材料科技股份有限公司 | Pearlescent pigment, preparation method and coloring pearlescent pigment for cosmetics prepared from pearlescent pigment |
| CN110028812A (en) * | 2019-04-30 | 2019-07-19 | 河南佰利联新材料有限公司 | A kind of preparation method of special raising titanium dioxide weatherability |
| CN110028812B (en) * | 2019-04-30 | 2020-11-24 | 河南佰利联新材料有限公司 | Special preparation method for improving weather resistance of titanium dioxide |
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|---|---|
| CN1095863C (en) | 2002-12-11 |
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