CN1826387A - A process for the preparation of a pigment comprising a core material and at least one dielectric layer - Google Patents

A process for the preparation of a pigment comprising a core material and at least one dielectric layer Download PDF

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CN1826387A
CN1826387A CN 200480016767 CN200480016767A CN1826387A CN 1826387 A CN1826387 A CN 1826387A CN 200480016767 CN200480016767 CN 200480016767 CN 200480016767 A CN200480016767 A CN 200480016767A CN 1826387 A CN1826387 A CN 1826387A
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sio
oxide
pigment
metal
core
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CN100528975C (en
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R·熊
S·D·帕斯托尔
P·布亚德
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba Spezialitaetenchemie Holding AG
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Abstract

The present invention relates to a process for the preparation of a pigment comprising a core material and at least one dielectric layer using microwave deposition of a metal oxide from an aqueous solution of fluorine scavenger onto a core material.

Description

Comprise the core and the preparation method of the pigment of one dielectric layer at least
The present invention relates to a kind of preparation method who comprises the pigment of core and at least one dielectric layer, this method adopts the microwave deposition method to deposit on the core from the metal oxide in the precursor aqueous solution.
Effect pigment (effect pigment) can be prepared by one of two kinds of methods traditionally.In first method, as U.S. Patent No. 3,438,796 is described, the preparation method of angle heterochromia effect pigment is as follows, is used alternatingly silicon-dioxide and aluminum vapor coated base plasma membrane earlier under condition of high vacuum degree, scrapes or remove the multilayered structure of generation so that granules of pigments to be provided from matrix then; This angle heterochromia effect pigment demonstrates color change with the angle variation, and is made up of the opaque aluminium film in a center, applies thicker silicon dioxide layer, a transparent aluminium film and a thick silicon dioxide film on this aluminium film symmetrically.
For example in U.S. Patent No. 5,135, in 812, set forth the improvement technology of preceding method.This patent has been illustrated following method, form multiple layer by vacuum moulding machine on the solubility reticulation, then its dissolving is obtained the multilayered structure sheet material, this sheet material is broken into fragment and obtains granules of pigments when reticulation is dissolved, perhaps vacuum moulding machine forms multiple layer on the peel ply that provides on the flexible mesh.For latter event, multilayered structure is peeled off along with the deflection of reticulation, the broken particle that forms, and reaches ideal dimensions through pulverizing then.In order to prepare suitable effect pigment, these two kinds of technologies all need the multiple coating step and/or the vacuum deposition steps of accurately control.Because this technology relates to a lot of steps, specific equipment and accurate technology controlling and process are essential, and the therefore final pigment that generates is extremely expensive.
Relate to and decompose (hydrolytic action) by the liquid phase of corresponding salt (as vitriol or halogenide) to carry out the sedimentary method of metal oxide itself be technique known, and be used to prepare spangles or the pearly pigment that comprises translucent mica core.But, these methods, for example in U.S. Patent No. 3,087,827 and No.5,733,371 is described, is considered to not to be suitable for the effect pigment that under the needed strongly-acid of these technology (the pH value is less than 4) aqueous conditions preparation has the reflecting metal kernel.
Is known with micro-wave energy depositing metal oxide film on the sheet glass of glass or coating tin indium oxide as the LED device, and it is open in a large amount of periodical literatures, E.Vigil.L.Saadoun for example, Thin Solid Films 2000,365,12-18 and E.Vigil.L.Saadoun, J.Materials Science Letters1999,181067-1069.But only obtained good binding property applying on the sheet glass of tin indium oxide, the author think since certain electron donation of indium-tin oxide coatings cause (referring to Vigil.E.; Ayll ó n, J.A; Peir ó, A.M.; Rodr í guez-Clemente, R.; Domenech, X.; Peral, J.Langmuir 2001,17, and 891).
The technology that precipitates metal oxide particle by microwave radiation has in a large number been illustrated in the literature, for example (1) Lerner.E.; Sarig, S.; Azoury, R.Journa1 of Materials Science; Materials in Medicine1991,2,138, (2) Daichuan, D; Pinjie, H.; Shushan, D.Materials Research Bulletin, 1995,30,537, (3) Leonelli, people such as C, Michrowaves:Theory and Applications inMaterials Processing 2001,111,321, (4) Girnus, people such as I., Zeolites 1995,15, and 33, (5) Rodriguez-Clemente, people such as R., Journal of Crystal Growth 1996,169,339 and (6) Daichuan, D.; Pinjie, H.; Shushan, D.Materials Research Bulletin, 1995,30,531.
Be surprisingly, the applicant finds, the use of microwave deposition technology of the present invention can create conditions for the method about uniform, the translucent or transparent metal oxide film layer of sediment-filled phase stack pile on core, this thickness can be that the basis is regulated with the mass ratio of core and metal oxide (quality of metal oxide precursor material), so that under the non-setting situation of metal oxide, prepare the metal oxide film of different thickness according to required effect.When metal oxide layer is that energy is sent to whole mixture from the surface, finally arrive base material when making and adopting conventional heating with liquid-phase precipitation method.And when carrying out microwave treatment, because base material has better microwave energy absorption than whole mixture, so energy focusing is on base material.Make matrix become the center of reaction like this, the surface that is reflected at base material is taken place with higher possibility.The reaction on surface causes that coat has better binding property and significantly reduced a large amount of precipitations simultaneously.The surface of good binding property, easily the conditioned reaction condition changes coat-thickness or composition, and the deposition that enters the main body medium minimizes and all given the present invention and compare with prior art and have significant superior part.
Therefore, the present invention relates to a kind of core and preparation method of the pigment of one dielectric layer at least of comprising, described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family.Described preparation method may further comprise the steps:
(a) core is suspended in the fluorine scavenging agent aqueous solution;
(b) add the aqueous solution of one or more fluorine-containing metal complexs, this complex compound is the precursor of required coating of metal oxides; With
(c) to described suspension carry out microwave radiation with depositing metal oxide to described core.
In order to generate one or more metal oxide layers or generation, can adopt different fluorine-containing metal complexs optionally repeating step (b) and step (c) along the concentration gradients of two kinds of different metal oxides of bed thickness direction.
These layers can change the heterochromatic performance in optics angle because of it has different specific refractory poweres, perhaps influence other performance, and for example catalysis forms certain form or suppresses photosensitivity.
In first preferred embodiment, the present invention relates to a kind of granules of pigments and coating pigment particulate preparation method of one dielectric layer at least of comprising, described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family, and described preparation method may further comprise the steps:
(a) granules of pigments is suspended in the fluorine scavenging agent aqueous solution;
(b) add the aqueous solution of one or more fluorine-containing metal complexs, this complex compound is the precursor of required coating of metal oxides; With
(c) described suspension is carried out microwave radiation with depositing metal oxide to described granules of pigments;
Wherein, in order to generate one or more metal oxide layers, can adopt different fluorine-containing metal complexs optionally repeating step (b) and step (c).
Step (b) and step (c) also can add second kind of different fluorine-containing metal complex and carry out, to form a metal oxide layer that is made of two kinds of different oxide compounds then continuously randomly by bringing into use first kind of fluorine-containing metal complex.
Coating with granules of pigments of metal oxide layer is improved the required physicals of granules of pigments, luminous reflectance factor for example, wetting ability (rheological improvement), weathering resistance, electric conductivity (requiring a conductive layer, for example stannic oxide), photosensitivity etc.Preferably, fluorine-containing metal complex is added continuously in the suspension of granules of pigments in fluorine scavenging agent solution.
In described embodiment, inorganic or pigment dyestuff all is used as core.For example at W.Herbst and K.Hunger, VCH Verlagsgesellschaft mbH, Weinheim/NewYork, 2nd, full revised edition, described in 1995, the pigment dyestuff that is fit to for example can be selected from: azo, azomethine, methyne, anthraquinone, phthalocyanine, purple cyclic ketones (perinone), perylene, diketopyrrolopyrrolecocrystals, thioindigo, imino-isoindoline, dioxazine, imino-isoindolinone, quinacridone, flavanthrone, indanthrone, anthrapyrimidine and Kui phthalein ketone pigment or their mixture or sosoloid; Especially azo, dioxazine, perylene, diketopyrrolopyrrolecocrystals, quinacridone, phthalocyanine, indanthrone or imino-isoindolinone pigment or its mixture or its sosoloid.
Used noticeable pigment is those pigment illustrated in Colour Index among the present invention, comprises C.I. Pigment red 202, C.I. pigment red 122, C.I. Pigment red 179, C.I. Pigment red 170, C.I. Pigment red 144, C.I. Pigment red 177, C.I. Pigment red 254, C.I. Pigment red 255, C.I. Pigment red 264, C.I. pigment brown 23, C.I. Pigment Yellow 73 109, C.I. Pigment Yellow 73 110, C.I. pigment yellow 147, C.I. Pigment Yellow 73 191.1, C.I. Pigment Yellow 73 74, C.I. pigment yellow 83, C.I. pigment yellow 13, C.I. pigment orange 61, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment orange 48, C.I. pigment orange 49, C.I. pigment blue 15, C.I. pigment blue 60, the C.I pigment Violet 23, C.I pigment violet 37, C.I pigment violet 19, the C.I pigment Green 7, C.I pigment green 36 or its mixture or its sosoloid.
Another kind of preferred pigments is the condensation product of following two kinds of structures
With
Wherein, R 101And R 102All be hydrogen or C independently 1-C 18Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, tert-pentyl, hexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.Preferably, R 101And R 102It is methyl.Described condensation product has following (I) and/or structure (II):
And/or
The mineral dye that is fit among the present invention use is selected from carbon black, merimee's yellow, lead chromate, chromium sulphate lead plumbate, lead molybdate, ultramarine blue, cobalt blue, manganese indigo plant, chromoxide green, transparent vert emeraude, cobalt green, metallic sulfide, cadmium sulfoselenide, zinc ferrite and pucherite and their mixture.
Particularly preferred granules of pigments, especially platy shaped particle, comprise that (flurorubine), Hong perylene, diketopyrrolopyrrolecocrystals, carbon black and graphite, it is particularly preferred wherein using the graphite flake of coated by titanium dioxide such as Graphitan  (Ciba Specialty Chemicals) for moly-sulfide, β-phthalocyanine, fluorine ruby.
Particulate size itself is unimportant, can be fit to concrete the application and get final product.Granules of pigments can stir form suspended dispersed in the fluorine scavenging agent aqueous solution by stirring or other.Described fluorine scavenging agent preferably can be removed any compound of fluorion in the aqueous solution, such as the monoxide of boric acid, Sodium Tetraborate, ammonium borate, boron trioxide, boron, preferred boric acid.Adopt boric acid in one embodiment of the invention.The concentration of boric acid solution can satisfy at least at coating of metal oxides and deposits to the requirement of eliminating fluorion in the process on the granules of pigments.Because boric acid can wash with water and remove, therefore adopted excessive boric acid in one embodiment.Based on the total amount of the aqueous solution, typically, boric acid working concentration scope is at about 0.01～1.5M, preferred about 0.08～0.8M.Under the situation of not exerting pressure, the temperature of boric acid solution is between the zero pour and boiling point of circulatory mediator.This method is easily to implement about 15 ℃-Yue 95 ℃ temperature.When the back pressure regulator that adopts assembling, when correctly configuring the pressure of reactor, this temperature also can be set in more than the boiling point of circulatory mediator.
In the inventive method, the oxide compound of the 3rd family to the 15 family's elements in the periodic table of elements, be to be deposited on the granules of pigments by the mode that adds the fluorine-containing metal complex aqueous solution and apply microwave energy, described fluorine-containing metal complex is the precursor of required metal oxide.Usually, described solution is joined in the granules of pigments of suspension continuously, with the precipitation of restriction metal oxide, rather than deposits on the granules of pigments.The metal oxide layer that is fit to be coated to the metal oxide on the base material and forms subsequently is being known in the art, and comprises TiO 2, ZrO 2, CoO, SiO 2, SnO 2, GeO 2, ZnO, Al 2O 3, V 2O 5, Fe 2O 3, Cr 2O 3, PbTiO 3, CuO or its mixture.Particularly preferably be titanium dioxide, ferric oxide and silicon-dioxide.Form a kind of aqueous solution of or its combination of the preferred following material of precursor solution of required metal oxide:
(a) soluble metal fluoride salt,
(b) soluble metal fluoro complex,
(c) any mixture of described salt of formation or complex compound.
The example includes ammonium hexa-fluorotitanate; Hexafluoro stannic acid ammonium; Ammonium hexafluorosilicate; Iron(ic) chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Aluminum chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Hexafluoro germanic acid ammonium; Three hydration indium (III) and hexafluoro stannic acid ammonium mixture.In the end in example, the metal oxide layer of formation comprises more than one metal oxides, i.e. indium tin oxide layer.For this method, the concentration of fluorine-containing metal complex is not very strict, can stipulate according to its ease for operation because can the radiation mixture up to reaching desired thickness.Therefore, this concentration range can be from about 0.01M up to saturated solution.In one embodiment of the invention, based on aqueous solution total amount, used the concentration range of about 0.2M to about 0.4M.
The thickness of layer itself is not strict yet, arrives between the 500nm scope 1 usually.
Any obtainable microwave source can adopt.And if microwave source can be regulated, microwave frequency can be adjusted to and promote that metal oxide deposits on the surface so.An at present preferred microwave oven is the NN-S542 of the Panasonic type microwave oven with laboratory repacking of 2450MHz operating frequency and 1300W output rating.
In case finish the interpolation of fluorine-containing metal complex and obtain after the required oxide compound bed thickness, suspension can be filtered and use washed with de-ionized water, drying, and optionally at about 100 ℃ to 900 ℃ temperature lower calcination.When related metal is metastable valence state, preferably adopts nonoxidizing atmosphere or be lower than under the vacuum of 1Pa.Calcining temperature must be lower than the decomposition temperature of matrix.
Optionally, can provide other on the granules of pigments, be positioned at outermost translucent extinction metal oxide layer, this layer is for example by Fe 2O 3, CoO, CoTiO 3, Cr 2O 3, Fe 2TiO 5, the perhaps suboxide SiO of silicon xForm, at this, x is less than 1 and preferred about 0.2.Described extinction metal oxide layer absorbs at least a portion of the whole light except that certain wavelength light, so that a kind of reinforced effects of selected color to be provided.SiO xLayer can form by known method, for example passes through, and in fluidized-bed reactor, carries out SiH in the presence of the core that coats 4Thermo-cracking forms.The existence of additional light-absorption layer can increase the colourity and the aberration optical dispersion (color shift optical variance) of pigment.Additional light-absorption layer should have the thickness of 5-50nm, preferred 5-30nm.Pigment prepared in accordance with the present invention can further adopt any conventional technique to carry out aftertreatment (surface modification) to improve its weathering resistance, dispersiveness and/or water-resistant stability.Pigment of the present invention is suitable for to high molecular (10 3-10 8G/mol) organic materials (plastics), glass, ceramic product, make-up composition, ink composite and particularly coating composition and paint provide color.
Pigment of the present invention also can be used with the form of using with following pigment, to help described purpose, promptly, transparent and lid end white (hiding white) pigment, colour and black pigment, carbon black and transparent, colour and black glossy pigment (promptly based on metal oxide coat micaceous those) and metallic pigment, comprise angle heterochromia coated interference pigment based on metal and nonmetal core, flake ferric oxide, graphite, moly-sulfide, and sheet pigment dyestuff.By in hydrogen, carbon monoxide, ammonia or its mixture, making described pigment react the upper layer that forms reducing metal (for example Fe or Ti) oxide compound or nitride, also can change the coloristic properties of pigment of the present invention, this upper layer will cause the deepening of paint color.
In another embodiment scheme of the present invention, relate to a kind of preparation method who shows the optically variable pigments of optics angle heterochromia effect (effect pigment), this method adopts microwave, will deposit on the core from the metal oxide in the aqeous suspension of precursor material.
A kind of core and preparation method of the effect pigment of one dielectric layer at least of comprising, described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family, and this method may further comprise the steps:
(a) core is suspended in the fluorine scavenging agent aqueous solution;
(b) add the aqueous solution of one or more fluorine-containing metal complexs, this complex compound is the precursor of required coating of metal oxides; With
(c) to described suspension carry out microwave radiation with depositing metal oxide to described core.
In order to generate one or more metal oxide layers or generation, can adopt different fluorine-containing metal complexs optionally repeating step (b) and step (c) along the concentration gradients of two kinds of different metal oxides of bed thickness direction.
These layers can change the heterochromatic performance in optics angle because of it has different specific refractory poweres, perhaps influence other performance, and for example catalysis forms certain form or suppresses photosensitivity.
Preferably, fluorine-containing metal complex is joined in the suspension of core in the fluorine scavenging agent aqueous solution continuously.
Effect pigment is inorganic platelet particles metal or nonmetallic or pigment (especially metallic effect pigments or coated interference pigment); that is to say; be that those provide the pigment of also giving other performance the color, the quality of the angle dependency of described performance such as color (geometric condition isochrome), gloss (not being meant surface luster) or pigment except giving the application media.Concerning metallic effect pigments, on the granules of pigments of certain orientation orientation directed basically reflection can take place.And under the situation of coated interference pigment, colouring effect is because the light interference phenomena in the high refractive index thin layer forms.
Say that in principle those all metals of stable existence under employed reaction conditions can be used as metal matrix.The example of Metal Flake core is titanium, silver, aluminium, copper, chromium, iron, germanium, molybdenum, tantalum or nickel.Before employing technology of the present invention applied, these metals such as aluminium can randomly apply a protective layer such as silicon-dioxide (EP-A-708155), wherein, for example, can obtain the effect pigment with understructure: aluminium (luminous reflectance core), SiO 2(thickness: 250-700nm), Fe 2O 3(thickness: 10-40nm).
Metal matrix can be used for preparing metallic effect pigments, and wherein medium thickness can be selected so that make them not influence the color characteristics in reflecting layer basically.
The preferred coated interference pigment based on metal matrix according to the inventive method preparation has with understructure: half thin opaque metal layer (chromium, nickel)/dielectric layer (SiO 2, MgF 2, Al 2O 3)/reflective metal layer (aluminium)/dielectric layer/thin half opaque metal layer, especially chromium/SiO 2/ aluminium/SiO 2/ chromium and chromium/MgF 2/ aluminium/MgF 2/ chromium (US-A-5,059,245); TM ' TMTM ' T or TM ' TM ' T, wherein, M ' is a semi-transparent metal layer, aluminium or based on the metal level of aluminium, T is the transparent low refractive index dielectric layer especially, M are the opaque aluminium of high-reflectivity or based on the layer, particularly SiO of aluminium 2/ Al/SiO 2/ Al/SiO 2And SiO 2/ Al/SiO 2/ Al/SiO 2/ Al/SiO 2(US-A-3,438,796).
Metal level can apply or chemical vapor deposition such as metal carbonyl vapour deposition prepare by wet chemistry.Under the situation that metallic compound exists, matrix is suspended in the medium that contains water and/or organic solvent, by adding reductive agent it is deposited on the matrix then.Metallic compound for example is Silver Nitrate or acetylacetonate nickel (WO03/37993).
According to US-B-3,536,520 record, nickelous chloride can be used as metallic compound, and hypophosphite can be used as reductive agent.According to the record of EP-A-353544, following compound can be used as the reductive agent that wet chemistry applies: aldehyde (formaldehyde, acetaldehyde, phenyl aldehyde), ketone (acetone), carbonic acid and salt (tartrate, xitix) thereof, reductone (saccharosonic acid, triose reductone, reductinic acid) and reducing sugar (glucose).
Translucent if desired metal level, metal layer thickness is generally 5-25nm so, especially is 5-15nm.
The example of nonmetal inorganic sheet core is at Chem.Rev.1999,99, illustrate among the 1963-1981, for example mica, another kind of layered silicate, aluminum oxide (EP-A-763573), ferric oxide, titanium dioxide (consult PCT/EP04/..., submit and require the files of US60/479011 and US60/515015 right of priority on the same day to the application), pure aluminium silicate are (by heating SiO in oxygen-free atmosphere z/ Al/SiO zObtain, the scope of z is 0.70≤z≤2.0; PCT/EP03/50777 and US-A-6013370), based on the material of Si oxide, for example silicon-dioxide (SiO 2WO93/08237, WO03/068868), SiO 2/ SiO x/ SiO 2, SiO 1.40-2.0/ SiO 0.70-0.99/ SiO 1.40-2.0(0.03≤x≤0.95; WO03/076520), Si/SiO z(0.70≤z≤2.0, WO03/106569), SiO z(0.70≤z≤2.0; Especially 1.40≤z≤2.0; PCT/EP03/11077), the wherein optional porous of selecting of these materials, for example porous silica.
Term " the SiO of 0.70≤z≤2.0 z" mean value of oxygen and silicon mol ratio is 0.7-2.0 in the expression silicon oxide layer.The composition of silicon oxide layer can be determined by ESCA (electron spectroscopy for chemical analysis).SiO yAnd SiO xAlso all definition in view of the above.
Among the present invention with the SiO of 1.4≤z≤2.0 zThin slice is the basis as core, be explained in more detail, but the present invention is not limited to this.
SiO zSlug particle has the length from 2 μ m to 5mm usually, width from 2 μ m to 2mm, thickness from 20nm to 2 μ m and the ratio of length and thickness be at least 2: 1, and have two substantially parallel faces, its spacing is minor axis, wherein 1.4≤y≤2.0 of core.
In described embodiment, the effect pigment of producing according to method of the present invention comprises core SiO zAt least one dielectric layer, this dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family.
Preferred coated interference pigment comprises the metal oxide of (a) high refractive index, for example Fe 2O 3Or TiO 2(b) metal oxide of low-refraction, for example SiO 2, wherein the difference of specific refractory power is at least 0.1; TiO 2(matrix: silicon oxide; Layer: TiO 2), (SnO 2) TiO 2, Fe 2O 3, Sn (Sb) O 2, Fe 2O 3TiO 2(matrix: silicon oxide; Fe 2O 3And TiO 2Mixolimnion), TiO 2/ Fe 2O 3(matrix: silicon oxide; The first layer: TiO 2The second layer: Fe 2O 3).Usually, the thickness range of layer is 1nm-1000nm, is preferably 1nm-300nm.
Another particularly preferred embodiment has related to a kind of coated interference pigment, comprises the layer that at least three high refractive index and low-refraction are alternately arranged, as TiO 2/ SiO 2/ TiO 2, (SnO 2) TiO 2/ SiO 2/ TiO 2, TiO 2/ SiO 2/ TiO 2/ SiO 2/ TiO 2Perhaps TiO 2/ SiO 2/ Fe 2O 3
Preferred layer structure is as follows:
(A) coating of specific refractory power＞1.65,
(B) coating of specific refractory power≤1.65,
(C) coating of specific refractory power＞1.65 and
(D) Ren Xuan external protection.
Have " height " specific refractory power, that is to say specific refractory power greater than about 1.65, be preferably greater than approximately 2.0, most preferably the example greater than about 2.2 dielectric materials has zinc sulphide (ZnS), zinc oxide (ZnO), zirconium white (ZrO 2), titanium dioxide (TiO 2), carbon, Indium sesquioxide (In 2O 3), tin indium oxide (ITO), tantalum pentoxide (Ta 2O 5), chromic oxide (Cr 2O 3), cerium oxide (CeO 2), yttrium oxide (Y 2O 3), europium sesquioxide (Eu 2O 3), ferriferous oxide such as iron (II)/iron (III) oxide compound (Fe 3O 4) and iron (III) oxide compound (Fe 2O 3), hafnium nitride (HfN), hafnium carbide (HfC), hafnia (HfO 2), lanthanum trioxide (La 2O 3), magnesium oxide (MgO), Neodymium trioxide (Nd 2O 3), Praseodymium trioxide (Pr 6O 11), Samarium trioxide (Sm 2O 3), antimonous oxide (Sb 2O 3), silicon monoxide (SiO), three oxidations, two selenium (Se 2O 3), stannic oxide (SnO 2), tungstic oxide (WO 3) or its combination.Dielectric materials is metal oxide preferably.Concerning metal oxide, can be single oxide compound or the oxide mixture that has or do not have absorptive character, for example, TiO 2, ZrO 2, Fe 2O 3, Fe 3O 4, Cr 2O 3Or ZnO etc., wherein TiO 2Be particularly preferred.
The limiting examples of the suitable low-refraction dielectric materials that can use comprises silicon-dioxide (SiO 2), aluminum oxide (Al 2O 3) and metal fluoride such as magnesium fluoride (MgF 2), aluminum fluoride (AlF 3), cerium fluoride (CeF 3), lanthanum fluoride (LaF 3), sodium aluminum fluoride is (as Na 3AlF 6Or Na 5Al 3F 14), neodymium fluoride (NdF 3), samaric fluoride (SmF 3), barium fluoride (BaF 2), Calcium Fluoride (Fluorspan) (CaF 2), lithium fluoride (LiF) and combination thereof, perhaps specific refractory power about 1.65 or less than any other low-index material of 1.65.For example, organic monomer and polymkeric substance can be used as low-index material, comprise dienes or olefines for example esters of acrylic acid (as methacrylic ester), perfluoro alkene polymkeric substance, tetrafluoroethylene (TEFLON), fluorinated ethylene-propylene polymer (FEP), perylene, p-Xylol and its combination etc.
In addition, previous materials comprises evaporation, transparent acrylate layer condensation and crosslinked, and this layer can deposit by the method for setting forth in the U.S. Pat 5,877,895, is incorporated herein its disclosure as a reference.
The high refractive index on matrix and the thickness in monolayer of low-refraction are extremely important for the optical property of pigment.Thickness in monolayer, especially metal oxide layer depend on its use field, and general thickness is 10-1000nm, preferred 15-800nm, particularly 20-600nm.
The thickness of layer (A) is 10-550nm, preferred 15-400nm, particularly 20-350nm.The thickness of layer (B) is 10-1000nm, preferred 20-800nm, particularly 30-600nm.The thickness of layer (C) is 10-550nm, preferred 15-400nm, particularly 20-350nm.
The material that is particularly suitable for layer (A) has metal oxide or metal oxide mixture, as TiO 2, Fe 2O 3, Sn (Sb) O 2, SnO 2, titanium suboxide (oxidation state from 2 to less than 4 reductive titanium class), also can be these compounds each other or with the mixture or the mixed phase of other metal oxide.
The material that is particularly suitable for layer (B) has metal oxide or its corresponding hydrous oxide, for example SiO 2
The material that is particularly suitable for layer (C) has colourless or colored metal oxide, such as TiO 2, Fe 2O 3, Sn (Sb) O 2, SnO 2, titanium suboxide (having from 2) to reductive titanium class less than 4 oxidation state, also can be these compounds each other or with the mixture or the mixed phase of other metal oxide.TiO 2Layer can comprise a kind of absorbing material in addition, and for example carbon can selectivity absorb colorant, and selectivity absorbs metallic cation, and this titanium dioxide layer can adopt absorbing material to apply or carry out partial reduction.
Absorb or non-absorbing material middle layer can be positioned at layer (A), (B), (C) and (D) between.Intermediate layer thickness is 1-50nm, preferred 1-40nm, particularly 1-30nm.
In this embodiment, preferred coated interference pigment has following layer structure:
SiO z TiO 2 SiO 2 TiO 2
SiO z TiO 2 SiO 2 Fe 2O 3
SiO z TiO 2 SiO 2 TiO 2/Fe 2O 3
SiO z TiO 2 SiO 2 (Sn，Sb)O 2
SiO z (Sn，Sb)O 2 SiO 2 TiO 2
SiO z Fe 2O 3 SiO 2 (Sn，Sb)O 2
SiO z TiO 2/Fe 2O 3 SiO 2 TiO 2/Fe 2O 3
SiO z Cr 2O 3 SiO 2 TiO 2
SiO z Fe 2O 3 SiO 2 TiO 2
SiO z The TiO suboxide SiO 2 The TiO suboxide
SiO z TiO 2 SiO 2 TiO 2+SiO 2+TiO 2
SiO z TiO 2+SiO 2+TiO 2 SiO 2 TiO 2+SiO 2+TiO 2
In described embodiment, all layers of coated interference pigment all preferably adopt microwave deposition to deposit, and still, part layer also can adopt CVD (chemical vapour deposition) or wet chemistry to apply:
SiO z TiO 2 Al 2O 3 TiO 2
SiO z Fe 2TiO 5 SiO 2 TiO 2
SiO z TiO 2 SiO 2 Fe 2TiO 5/TiO 2
SiO z TiO 2 SiO 2 MoS 2
SiO z TiO 2 SiO 2 Cr 2O 3
SiO z TiO 2 SiO 2 TiO 2+SiO 2+TiO 2+ Prussian blue
Metal oxide layer can apply by following method: adopt metal carbonyl (as pentacarbonyl iron, Chromium hexacarbonyl; EP4585lA) oxic gas phase decomposition adopts metal alcoholate (as four n-propyl alcohols and titanium isopropylate and zirconium; DE4140900A) or metal halide (titanium tetrachloride for example; EP338428A) hydrolysis gas-phase decomposition adopts organo-tin compound (especially Alkyzin compound such as tetrabutyl tin and tin tetramethide; DE4403678A) oxygenolysis, perhaps adopt the vapor phase hydrolysis of the silicoorganic compound (especially two tert.-butoxy acetoxysilanes) of being set forth among the patent EP668329A, apply operation and can in fluidized-bed reactor, carry out (EP045851A and EP106235A).The suboxide of the oxide compound of metal zirconium, titanium, iron and zinc and the hydrous oxide of these metals, iron titanate, titanium or their mixture layer can both apply by the wet chemistry precipitator method, if this method is suitable, can be used for the metal oxide that will be reduced.Under the situation that adopts wet chemistry to apply, can use to producing the wet chemistry coating method that pearly pigment is developed; For example, these methods are described in DE1467468A, DE1959988A, DE2009566A, DE2214545A, DE2215191A, DE2244298A, DE2313331A, DE2522572A, DE3137808A, DE3137809A, DE3151343A, DE3151354A, DE3151355A, DE3211602A and DE3235017A, DE1959988A, EP892832A, EP753545A, EP1213330A, WO93/08237, WO98/53001, WO98/12266, WO98/38254, WO99/20695, WO00/42111 and WO03/6558.
The preferred TiO of the metal oxide of high refractive index 2And/or ferric oxide, the preferred SiO of the metal oxide of low-refraction 2TiO 2Layer can be rutile variant or anatase octahedrite variant, at this preferred rutile variant.TiO 2Layer also can adopt known method reduction, for example ammonia, hydrogen, hydrocarbon vapour or their mixture, perhaps metal-powder, as patent EP735114A, DE3433657A, DE4125134A, EP332071A is set forth among EP707050A or the WO93/19131.
PCT/EP03/50690 is described as patent, coats TiO 2SiO ySheet (wherein 0.03≤y≤1.95) can be at first calcined being higher than under 600 ℃ the nonoxidizing atmosphere, then can be randomly with handling in air or another oxygen-containing gas, if suitable, temperature is higher than 200 ℃, preferably be higher than 400 ℃, especially 500-1000 ℃.
In a particularly preferred embodiment, the present invention relates to the SiO of 1.40≤z that thickness is 70-130nm＜2.0 zPerhaps SiO 2Thin slice, it comprises that thickness is the titanium dioxide layer of 60-120nm.
1.40 the SiO of≤z＜2.0 zPerhaps SiO 2Thin slice is not a uniform shape.Yet for simplicity, thin slice is considered to have one " diameter ".Silicon oxide flakes have high plane parallelism and limit its thickness mean thickness ± change in 10% scope, especially in ± 5% scope.1.40 the SiO of≤z＜2.0 zPerhaps SiO 2The thickness of thin slice is 70-100nm, especially 90-110nm, very preferably about 100nm.Preferred at present, the thin slice diameter is in the preferable range of about 1-60 μ m, and preferred scope is about 5-40 μ m.Therefore, the preferable range of the thin slice aspect ratio among the present invention is about 7-860, and preferred scope is about 38-572.
Titanium dioxide layer preferably adopts the microwave deposition method to deposit, and still, also can adopt aforesaid CVD (chemical vapour deposition) or wet chemistry to apply in principle.
Therefore, the present invention relates to the SiO of 1.40≤z＜2.0 2Perhaps SiO 2Thin slice, its thickness are 70-130nm, especially 90-110nm, very preferably about 100nm, and it comprises that the thickness that adopts the inventive method to apply is the titanium dioxide layer of 60-120nm.
Titanium dioxide layer has the thickness of 60nm-120nm, 80-100nm especially, especially preferably about 90nm.
By at TiO 2Apply " low " specific refractory power on the layer, that is to say that specific refractory power is less than about 1.65 metal oxide, such as SiO 2, Al 2O 3, AlOOH, B 2O 3Perhaps its mixture, preferred SiO 2, then, on the gained layer, further apply Fe 2O 3And/or TiO 2Layer can obtain the stronger and more transparent pigment of color.Height and low-refraction metal oxide layer that the coated interference pigment of this multiple coating comprises silicon/oxidative silicon matrix and alternately applies, this pigment can adopt with patent WO98/53011 and the illustrated similarity method of WO99/20695 and be prepared, perhaps preferred employing preparation method of the present invention.
So the layer structure in the described embodiment is as follows:
(A) coating of specific refractory power＞1.65,
(B) coating of specific refractory power≤1.65,
(C) randomly, the coating of specific refractory power＞1.65 and
(D) randomly, external protection.
The thickness range of layer (B) is 70-130nm, especially 90-110nm, very preferably about 100nm.The thickness range of layer (A) and layer (C) is 60-120nm, especially 80-100nm, very preferably about 90nm.
If the SiO of 1.40≤z＜2.0 zPerhaps SiO 2Thin slice comprises specific refractory power greater than 1.65 coating (A), and the coating of specific refractory power≤1.65 (B), and layer (B) is when being used as protective layer, and this protective layer has 2-250nm thick thickness, especially 10-100nm..
Particularly preferred embodiment relates to coated interference pigment, and it comprises at least two alternative height and low-index layer, as TiO 2/ SiO 2, TiO 2/ SiO 2/ TiO 2, (SnO 2) TiO 2/ SiO 2/ TiO 2, TiO 2/ SiO 2/ TiO 2/ SiO 2/ TiO 2Or TiO 2/ SiO 2/ Fe 2O 3
In addition, the pigment of finishing can also be carried out follow-up coating or follow-up processing, this has further increased brightness, resistance to weather and chemical stability, has perhaps increased the operability of pigment, especially when it sneaks in the multiple medium.For example, illustrated method is suitable for subsequent disposal or subsequent coated among patent DE2215191A, DE3151354A, DE3235017A or the DE3334598A.
If suitable, can on titanium dioxide layer, apply SiO 2Protective layer can use following method: the soda water glass solution is quantitatively joined in the suspension of coated material, heat this suspension to about 50-100 ℃, especially 70-80 ℃ for this reason.Add 10% spirit of salt simultaneously so that the pH value of solution remains on 4-10, preferred 6.5-8.5.After adding water glass solution, began to stir 30 minutes.
SiO based on 1.40≤z＜2.0 zPerhaps SiO 2The effect pigment of thin slice can be used to all common purposes (as seeing WO03/068868 and PCT/EP03/11077), the for example dyeing of block polymer, coating (comprises effect finish paint (effect finisher), comprise those that are used for automotive field) and marking ink (comprise offset printing, intaglio printing, gold stamping and flexography) and some other application examples such as makeup (as seeing PCT/EP03/09296), ink jet printing (as seeing PCT/EP03/50690), textile dyeing (as seeing PCT/EP03/11188), pottery and the glazing of glass and the laser-marking of paper and plastics.These application can be known from reference, for example " Industrielle Organische Pigmente " (W.Herbst and K.Hugner, VCH Verlagsgesellschaft mbH, Weinheim/New York, 2nd, complete revised edition, 1995).
SiO based on 1.40≤z＜2.0 zPerhaps SiO 2The effect pigment of thin slice can be used in macromolecule organic material paintedly has a good effect.
Can adopt pigment of the present invention or color compositions carry out painted macromolecule organic material can from natural also can be by synthetic.Usually, macromolecule organic material has about 10 3-10 8G/mol or higher molecular weight.For example, they can be natural resins, siccative oil, rubber or casein food grade are perhaps from the derivative of crude substance, such as chlorinated rubber, oil-modified alkyd resin, viscose glue, ether of cellulose or ester, for example ethyl cellulose, rhodia, cellulose propionate, cellulose acetate butyrate or soluble cotton, but the whole synthetic organic polymers (thermoset(ting)plastic and thermoplastics) of preference as obtaining by polymerization, polycondensation or addition polymerization.For polymer resin, that can mention has, especially polyolefins, for example polyethylene, polypropylene or polyisobutene, it also can be the polyolefins that replaces, for example the polymerisate of vinylchlorid, vinyl-acetic ester, vinylbenzene, vinyl cyanide, acrylate, methacrylic ester or divinyl also can be described monomeric copolymerization product, for example especially ABS or EVA.
SiO based on 1.40≤z＜2.0 zPerhaps SiO 2The effect pigment of thin slice adds in the macromolecule organic material of wanting painted with any painted significant quantity.Comprise macromolecule organic material and in based on macromolecule organic material 0.01-80wt%, the coloring material composition of the pigment of the present invention of preferred 0.1-30wt% is favourable.In fact, often use 1-20wt%, the content of especially about 10wt%.
In the plastics, contain the SiO of 1.40≤z＜2.0 zPerhaps SiO 2The effect pigment of thin slice, its content are 0.1-50wt%, especially 0.5-7wt%.In the coating part, pigment usage quantity of the present invention is 0.1-10wt%.In base-material system painted, for example paint and be used in the printing ink of intaglio printing, offset printing or silk screen printing, the pigment that adds in the printing-ink is 0.1-50wt%, preferred 5-30wt%, especially 8-15wt%.
SiO based on 1.40≤z＜2.0 zPerhaps SiO 2The effect pigment of thin slice also is suitable for the cosmetic of lip or skin and the dyeing of hair or nail.Therefore, the invention still further relates to cosmetic formulations or prescription, in the gross weight of cosmetic formulations or prescription, it comprises pigment of the present invention, the especially effect pigment of 0.0001-90wt% and the solid support material that 10-99.9999wt% is fit to makeup.
For example in plastics, coating or printing-ink, especially in coating or printing-ink, the painted performance that more particularly in coating, obtains with excellence, especially high saturation ratio, outstanding stability, the heterochromatic performance of high purity of color and high angle is a feature.
Can be used to substitute SiO zThin slice be extremely thin sheet glass with following performance:
(1) glass flake thickness≤1.0 μ m
(2) high-temperature stability and mechanical stability
(3) smooth finish surface (WO02/090448).
Preferably the suitable glasses thin slice according to patent EP0289240A preparation is characterised in that, the mean particle size that they have within 1000 mu m ranges, preferred 5-150 mu m range.Preferred glass flake has the mean particle size of 5-150 mu m range and the thickness of 0.1-0.5 μ m, the thickness of preferred 0.1-0.3 μ m.The aspect ratio of glass flake within the 10-300 scope, the scope of preferred 50-200.
SiO zThin slice is (WO03/68868) with the method preparation that comprises the steps:
A) with the separating agent vapour deposition to (removable) carrier forming the separating agent layer,
B) vapour deposition SiO on the separating agent layer yLayer, 0.70≤y≤1.8 wherein,
C) the separating agent layer is dissolved in the solvent and
D) from above-mentioned dose, separate SiO y
The SiO of y＞1.0 yCan obtain by evaporation SiO in the presence of oxygen.If adopt the SiO of ultraviolet radiation growth in the evaporative process yLayer (DE1621214A) can obtain not have basically the layer of absorption so.Can obtain not absorb and specific refractory power is 1.55 SiO under 550nm by so-called in pure oxygen atmosphere " reactive evaporation " SiO at visible region 15Layer (E.Ritter, J.Vac.Sci.Technol.3 (1966) 225).
SiO in the step b) yLayer is vapour deposition from the vaporizer that contains raw material, and this raw material comprises Si and SiO 2Mixture, SiO y(0.70≤y＜1.0) or their mixture, wherein Si and SiO 2Weight ratio preferably 0.15: 1 to 0.75: 1 scope, especially contain the Si and the SiO of stoichiometric ratio 2Mixture, perhaps the raw material that contains of vaporizer comprises that silicone content reaches the silicon monoxide of 20wt%.Step c) is at the pressure that is higher than step a) and step b) and be lower than that to implement under the situation of barometric point be favourable.The SiO that this method is prepared yThin slice, its thickness is preferably 20-2000nm, 20-500nm especially, 50-350nm most preferably, the ratio of the thickness of plane parallel organization and surface-area is preferably less than 0.01 μ m -1So this plane parallel organization that obtains is in the high uniformity of thickness, and (surface microstructure) is very outstanding on the good planarity and slickness.
Silicon oxide layer in the step b) preferably adopts in vaporizer by Si and SiO 2The mixture silicon monoxide steam that reaction is generated under being higher than 1300 ℃ is made.
If several 10 -2The industrial vacuum of pa evaporation silicon down (replaces Si/SiO 2Or SiO/Si), the Si oxide of Huo Deing has the oxygen level less than 0.70 so, that is to say to obtain SiO x, wherein 0.03≤x≤0.69, especially 0.05≤x≤0.50, more particularly 0.10≤x≤0.30 (PCT/EP03/02196).
By being higher than the silicon monoxide that evaporation under 1300 ℃ the temperature contains the silicon that reaches 20 weight %, just form SiO 0.7-0.99Layer.
The vapour deposition of step a) and step b) is preferably implemented under less than 0.5 vacuum.The dissolving of separating agent layer is preferably in 1-5 * 10 in the step c) 4Implement under the pa pressure range, especially 600-10 4Pa, more particularly 10 3-5 * 10 3Pa.
Vapour deposition can be a lacquer (coating) to the separating agent on the carrier in the step a), polymkeric substance, for example, as in patent US-B-6398999, setting forth, (thermoplasticity) polymkeric substance, particularly acrylic acid series or styrene polymer or their mixture, dissolve in organic solvent or water and transpirable organic substance under vacuum, such as anthracene, anthraquinone, acetoamidophenol, acetylsalicylic acid, camphoric anhydride, benzoglyoxaline, benzene-1,2, the 4-tricarboxylic acid, biphenyl-2, the 2-dioctyl phthalate, two (4-hydroxyphenyl) sulfone, dihydroxyanthraquinone, glycolylurea, the 3-hydroxy-benzoic acid, oxine-5 sulfonic acid monohydrate, 4 hydroxy coumarin, umbelliferone, 3-hydroxyl naphthalene-2 formic acid, m-phthalic acid, 4,4-methylene radical-two-3-hydroxyl-naphthalene-2-formic acid, naphthalene-1, the 8-dicarboxylic acid anhydride, phthalic imidine and sylvite thereof, phenolphthalein, thiodiphenylamine, saccharin and its salt, tetraphenyl methane, benzophenanthrene, at least two kinds mixture in triphenylcarbinol or these materials.Separating agent is transpirable inorganic salt (as seeing DE19844357), for example sodium-chlor, Repone K, lithium chloride, Sodium Fluoride, Potassium monofluoride, lithium fluoride, Calcium Fluoride (Fluorspan), sodium aluminum fluoride, disodium tetraborate or its mixture under water soluble and the vacuum preferably.
Removable carrier can constitute by one or more disks, cylinder (post) or other rotationally symmetric body that pivots (referring to, WO01/25500), the continous metal strip that is preferably had or do not have polymeric coating by one or more is formed, perhaps preferably form (US-B-6 by a kind of and multiple polyimide or polyethylene terephthalate band, 270,840).
Step d) can comprise flushing and subsequently filtration, sedimentation, centrifugation, decantation and/or evaporation.Yet, in the step d), SiO yThe plane parallel organization also can freeze with solvent, carry out freeze-drying process subsequently, at this solvent is come out by sublimation separation below triple point, and the SiO that does yForm with one plane parallel organization remains.
Except situation, several 10 at ultrahigh vacuum(HHV) -2Under the industrial vacuum condition of pa, the SiO of evaporation always can be condensed into SiO y, 1≤y≤1.8, especially 1.1≤y≤1.8 wherein, this is because the gas on surface distributes the water vapour that causes high-vacuum apparatus always to contain trace, and under vaporization temperature, water vapour very easily with active SiO reaction.
In its further step, the strip-like carrier of airtight formation ring passes the power vacuum latch well (referring to US-B-6,270,840) of known construction type, enters into 1-5 * 10 4In the pa pressure span, preferred 600-10 4Pa, especially preferred 10 3-5 * 10 3Pa, here carrier is immersed in the dissolving bath.The temperature of solvent should select so that its evaporating pressure within the indicator pressure scope.By mechanical assist device, the separating agent layer dissolves fast, and product layer is fragmented into small thin slices, and it is present in the solvent with the suspensoid form then.In further step, these bands are dried, and have eliminated any pollutent that adheres on it.It passes second group of power vacuum latch well and gets back to evaporation cavity, at the coating processes of this repeated isolation agent and SiO product layer.
Then, the suspension that occurs under two kinds of situations, it comprises product structure and solvent and is dissolved in wherein separating agent, separates in subsequent operations according to prior art.In order to reach this purpose, product structure at first concentrates in liquid, uses new solvent cleaning several times with flush away dissolved separating agent then.Remain wet solid product subsequently after filtration, sedimentation, centrifugation, decantation or evaporation separate.
Then, product can be made desired particle size by following method, by ultrasonic method or pass through mechanical means, this mechanical means adopts high speed agitator in liquid phase medium, perhaps having behind the dry fragment in the airflow pulverizer that rotates particle sizer, or adopting in grinding or the air screening plant and carry out.
SiO yThin slice can adopt oxygen-containing gas, preferably with the form of loose material, carries out oxidation in fluidized-bed, for example at least 200 ℃ air especially more than 400 ℃, perhaps is incorporated in the oxydizing flame, preferred range is 500-1000 ℃, forms the SiO of plane parallel organization z(WO03/068868).
The SiO that obtains zThin slice does not have uniform shape.Yet for simplicity, thin slice is considered to have " diameter ".SiO yThin slice have high plane parallelism and limit its thickness mean thickness ± change in 10% scope, especially in ± 5% scope.SiO zThe thickness range of thin slice is 20-2000nm, especially 20-500nm, most preferably 50-350nm.Preferred at present, the thin slice diameter is in the preferable range of about 1-60 μ m, and preferred scope is at about 5-40 μ m.Therefore, the aspect ratio preferable range of these thin slices is at about 2-3000, and preferred scope is at about 14-800.If TiO 2When layer was deposited as high-index material, its thickness should be 20-200nm so, especially 20-100nm, more preferably 20-50nm.The SiO that can purchase with market 2Thin slice is compared, SiO zThin slice has narrower thickness distribution, therefore can prepare have very good brightness, transparent positive color, intensive angle heterochromia effect has improved the effect pigment of tinctorial strength and purity of color.
On the other hand, the present invention relates to strong glossy and contain titanium dioxide nacreous pigment.This pearly pigment has multilayered structure, wherein on the plate-like titanium dioxide core, adheres to other metal oxide of one deck or hydrated metal oxide.Be coated to other metal oxide on the titanium dioxide or the example of hydrated metal oxide Fe is arranged 2O 3, Fe 3O 4, FeOOH, Cr 2O 3, CuO, Ce 2O 3, Al 2O 3, SiO 2, BiVO 4, NiTiO 3, CoTiO 3, and mix antimony, mix fluorine or mix the stannic oxide of indium.In the particular of new pigment, on the first layer of another metal oxide or hydrated metal oxide, there are second layer additional metals oxide compound or hydrated metal oxide in addition.This additional metals oxide compound or hydrated metal oxide are aluminum oxide or hydrated aluminum oxide, silicon-dioxide or hydrated SiO 2, Fe 2O 3, Fe 3O 4, FeOOH, TiO 2, ZrO 2, Cr 2O 3And mix antimony, mix fluorine or mix the stannic oxide of indium, wherein, the oxide compound of the first layer is different with the oxide compound of the second layer.
The thickness of these titanium dioxide thin slices at 10nm between the 500nm, between preferred 40 to 150nm.Size on other bidimensional is between 2 to 200 μ m, particularly between 5 to 50 μ m.
The thickness that is coated to another metal oxide layer on the titanium dioxide thin slice is 5-300nm, preferred 5-150nm.
Apply on the same day according to WO98/53010 with the present invention, and require illustrated method among the PCT/EP04/... of right of priority of U.S. Pat 60/479011 and US60/515015, can obtain the titanium dioxide thin slice.
In addition, dry or therebetween, the coating of plate-like titanium dioxide also can be carried out with metal oxide or hydrated metal oxide, for example applies by gas phase in fluidized-bed reactor, for example can adopt the method for mentioning among EP0045851 and the EP0106235 about the manufacturing pearly pigment.
Though preferably adopt microwave radiation to carry out the deposition of all metal oxide layers, the part metals oxide compound also can adopt conventional wet chemistry methods to deposit.
When applying rhombohedral iron ore layer (Fe 2O 3) time, starting raw material can be as patent US-B-3,987, the trivalent iron salt of being set forth in 828 and US-B-3,087,829 or as patent US-B-3, the divalent iron salt of setting forth in 874,890, the ironic hydroxide that begins to form (II) coating also can be oxidized to ferric oxide (III) hydrate.Preferred trivalent iron salt is as initial raw material.
Apply magnetite layer (Fe 3O 4) can in the presence of the saltpetre and the pH value be under 8.0 the condition, by divalent iron salt solution for example the hydrolysis of copperas solution carry out.Preferred precipitation embodiment is described among the EP0659843A.
In order to make iron oxide layer and titanium dioxide thin slice have better bounding force, makeshift is at first to be coated with stannic oxide layer.
The preferable alloy oxide compound that another kind is deposited on the titanium dioxide thin slice is a chromic oxide.The thermal hydrolysis that takes place in the volatilization process by ammonia from six ammonia chromium (III) the derivative aqueous solution or by the thermal hydrolysis of borax buffered chromium salt solution can realize at an easy rate the deposition.The coating of chromic oxide is described in US-B-3, in 087,828 and US-B-3,087,829.
Be not all will carry out the calcining of pigment in any situation.For specific application, dry just enough under 110 ℃ of temperature.If calcined pigment, temperature should be set at 400 ℃ to 1000 ℃ so, and preferable range is 400 ℃ to 700 ℃.
In addition, can carry out subsequent coated or subsequent disposal with further increase light stability, weather resisteant and chemical stability or improve the operability of pigment to pigment, especially when pigment adds in the various different medias.In patent such as DE2215191C, DE3151354A, DE3235017A or DE3334598A, set forth the example of the subsequent coated technology that is fit to.Very excellent and do not need this fact of additional technique means in view of new pigment performance, these additional materials that can select to apply only account for about 0-5wt% of whole pigment weight, especially about 0-3wt%.
According to applying on the same day, and require illustrated method among the patent PCT/EP04/... of right of priority of U.S. Pat 60/479011 and US60/515015, can obtain flaky ferric oxide with the present invention.Specifically, polymethylmethacrylate (PMMA) thin slice can prepare in the following manner, toluene/the acetone soln of polymethylmethacrylate is joined in the end sealed glass pipe, this Glass tubing the other end is connected under 20 vacuum of holding in the palm and horizontally rotates, the PMMA coating just forms on inwall like this, wash PMMA with deionized water, collect the PMMA thin slice by filtering then.Then, adopt FeCl 34NH 4F and boric acid are coated to the ferric oxide microwave deposition on the PMMA thin slice.The PMMA thin slice of the coated iron oxide that obtains can be collected and in vacuum oven by filtering.By heating PMMA is dissolved in the toluene then, after sedimentation is filtered, cleaning and drying can prepare the ferric oxide thin slice, and this ferric oxide thin slice just can be used to produce effect pigment.
At least comprise a layer group (pocket) based on the angle heterochromia effect colour lustre pigments that coats multiwalled ferric oxide thin slice, this layer group comprise:
A) colourless coating of refractive index n≤1.8 and
B) colourless coating of refractive index n 〉=2.0.
The size of ferric oxide thin slice itself is not very crucial, as long as can satisfy the requirement of application-specific purpose.Usually, the maximum average diameter of thin slice is about 1-50 μ m, preferred 5-20 μ m.The thickness of thin slice is generally within the scope of 10-500nm.
Colourless low refractive index coating (A) has the specific refractory power of n≤1.8, preferred n≤1.6.The example of this material is following listed.Particularly suitable material comprises, as metal oxide and hydrated metal oxide, and such as silicon oxide, hydration Si oxide, aluminum oxide, hydrated aluminum oxide and composition thereof, preferred silicon oxide (hydrate).
How much bed thickness of coating (A) are usually in the scope of 50-800nm, preferably in the scope of 100-600nm.Therefore and preferred colour lustre pigments because the interference color of layer (A) major decision pigment, so for a layer group (A)+(B) only being arranged and having significant especially color effect and, it has the minimum bed thickness of about 200nm.If layer group (A)+(B) is the situation of a plurality of (as 2,3 or 4), so the scope of the preferred 50-200nm of thickness of layer (A).
Colourless high refractive index coating (B) has the specific refractory power of n 〉=2.0, preferred n 〉=2.4.The example of this material is following listed.Particularly suitable layer (B) material not only comprises for example zinc sulphide of metallic sulfide, and particularly including the hydrate of metal oxide and metal oxide, for example titanium dioxide, hydrous titanium oxide, zirconium dioxide, hydrous zirconium oxide, tindioxide, aqua oxidation tin, zinc oxide, aqua oxidation zinc and their mixture, preferred titanium dioxide and hydrous titanium oxide and they and up to other metal oxide of about 5wt% mixture of tindioxide particularly.
Coating (B) preferably has littler bed thickness than coating (A).How much bed thickness preferable range of coating (B) are about 5-50nm, especially 10-40nm.
According to the present invention, preferred coating (B) mainly is made up of titanium dioxide.
In described embodiment, whole coatings of coated interference pigment preferably adopt the microwave deposition method to deposit, but partial coating also can adopt CVD method (chemical vapour deposition) or wet chemistry to apply.
The core of effect pigment can stir form suspended dispersed in the fluorine scavenging agent aqueous solution by stirring or other.Described fluorine scavenging agent preferably can be removed any compound of fluorion in the aqueous solution, such as boric acid, Sodium Tetraborate, ammonium borate, boron trioxide, a boron oxide, and special preferred boric acid.Just adopted boric acid in one embodiment of the invention.The concentration of boric acid solution is to deposit at coating of metal oxides and remove the needed concentration of fluorion in the process that is coated on the core at least.Eliminate because boric acid can water washes, therefore adopted excessive boric acid in one embodiment.Typically used boric acid is about 0.01～0.5M, preferred about 0.04～0.1M.Under the situation that does not adopt pressure, the temperature of boric acid solution is between the freezing point and boiling point of circulatory mediator.This method is carried out easily in about 15 ℃ and about 95 ℃ temperature usually.When the pressure of reactor was suitably set, temperature can also adopt the back pressure regulator of installation to be set in more than the boiling point of circulatory mediator.
In the inventive method, by adding the fluorine-containing metal complex aqueous solution and apply microwave energy, to core, described fluorine-containing metal complex is the precursor of required metal oxide with the oxidate of the 3rd family to the 15 family's elements in the periodic table of elements.Usually, the aqueous solution is joined in the core of suspension continuously, with restriction metal oxide precipitation, rather than deposits on the granules of pigments.The metal oxide layer that is fit to the metal oxide of coated substrate and forms subsequently is known in the art, comprises TiO 2, ZrO 2, CoO, SiO 2, SnO 2, GeO 2, ZnO 2, AlO 3, V 2O 5, Fe 2O 3, Cr 2O 3, PbTiO 3, or CuO or its mixture.Particularly preferably be titanium dioxide.
Form a kind of or its bonded aqueous solution of the preferred following material of precursor solution of required metal oxide:
(a) soluble metal fluoride salt,
(b) soluble metal fluoro complex, or
(c) any mixture of described salt of formation or complex compound.
Example includes ammonium hexa-fluorotitanate; Hexafluoro stannic acid ammonium; Ammonium hexafluorosilicate; Iron(ic) chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Aluminum chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Hexafluoro germanic acid ammonium; The combination of three hydration indium (III) and hexafluoro stannic acid ammonium.In the end in example, metal oxide layer is by more than one metal oxides, and promptly indium tin oxide layer forms.For this method, the concentration of fluorine-containing metal complex is not very strict, can stipulate according to its easy operability, because mixture can shine until reaching desired thickness.Therefore, this concentration range can be from about 0.01M up to saturated solution.In one embodiment of the invention, based on aqueous solution total amount, scope arrives about 0.2M for about 0.1M.
Interfere and absorption effect pigment in order to prepare blended, the metal oxide layer of dielectric materials is coloured (selectivity absorbs, and is not grey or black) oxide compound or coloured mixed oxide of the 5th family to the 12 family's elements preferably.Most preferred metal oxide layer comprises Fe 2O 3
In order to prepare pure coated interference pigment, metal oxide layer preferably mainly is the colourless oxide compound of the 3rd family or the 4th family's element.Most preferred metal oxide layer comprises TiO 2
The thickness of coating of metal oxides is wanted can be at SiO zProduce translucent or transparent coating on the core, described core will demonstrate optics angle heterochromia effect.The thickness of film will depend on pigment matrix to be changed with the optics angle heterochromia effect that will reach.
The thickness of layer itself is not very strict, usually should be in the scope of 1-500nm, and preferred 10-300nm.Depend on the specific refractory power of oxide compound, the different oxide compounds of different thickness will produce distinct colors.
Any obtainable microwave source can adopt.And if microwave source can be regulated, microwave frequency can be adjusted to and promote that metal oxide deposits on the surface so.At present preferred microwave oven is the laboratory repacking NN-S542 of the Panasonic type microwave oven with 2450MHz operating frequency and 1300W output rating.
In case after finishing the interpolation of metal precursor material and obtaining ideal metal oxide bed thickness, metal-cored suspension can be filtered and with washed with de-ionized water, drying and at about 100 ℃ to 900 ℃, preferred about 400 ℃ to about 600 ℃, more preferably from about calcined about 15 to 30 minutes down for 450 ℃ to about 500 ℃, most preferably under nonoxidizing atmosphere.
Optionally, that effect pigment can have is additional, be positioned at outermost translucent extinction metal oxide layer, and this layer is for example by Fe 2O 3, CoO, CoTiO 3, Cr 2O 3, Fe 2TiO 5, or the suboxide SiO of silicon xForm, wherein, x is less than 1 and preferred about 0.2.The metal oxide layer of described extinction absorbs at least a portion of the whole light except that certain wavelength light, so that the reinforced effects of selected color to be provided.SiO xLayer can form by known method, for example in fluidized-bed reactor, carries out SiH in the presence of the clad metal core 4Thermo-cracking.Additional light-absorption layer can increase the colourity and the aberration optical dispersion of pigment.Additional light-absorption layer should have the thickness of 5-50nm, preferred 5-30nm.
Effect pigment prepared in accordance with the present invention can further adopt any routine techniques to carry out subsequent disposal (surface modification) to improve its weathering resistance, dispersiveness and/or water stability.Effect pigment among the present invention is suitable for to high molecular (10 3-10 8G/mol) organic materials (plastics), glass, ceramic, make-up composition, ink composite and particularly coating composition and paint provide color.Effect pigment of the present invention also can be used for and transparent and lid end white, colour and black pigment, carbon black and transparent, colour and black glossy pigment the mica person of metal oxide-coated (promptly based on) and metallic pigment mix mutually so that their advantage is more outstanding, these pigment comprise look heterochromia coated interference pigment, flake ferric oxide, graphite, moly-sulfide and the sheet pigment dyestuff based on metal and nonmetal core.By described pigment is reacted to form the upper layer of reducing metal (as iron or titanium) oxide compound or nitride, also can also change the coloristic properties of this effect pigment, this upper layer will cause the deepening of paint color.
Can comprise the membrane carrier that becomes with above-mentioned effect pigment compounding according to paint of the present invention or coating composition.One-tenth membrane carrier to coating composition of the present invention does not have particular restriction, according to the application purpose of coating composition of the present invention, can adopt the resin of any routine.The example of suitable film forming vector resin comprises resin compound, CAB grafted acrylic resin, Synolac, urethane resin, Resins, epoxy, silicone resin, polyamide resin, epoxy alkyd resin and the resol etc. of synthetic resins such as acrylic resin, vibrin, acrylic resin and cellulose acetate butyrate (CAB), and various natural resin and derivatived cellulose.As required, these film forming vector resins can also can two or more be used in combination in single use.If necessary, the above-mentioned film forming vector resin of listing also can mix use mutually with solidifying agent such as melamine resin, isocyanate compound, the isocyanate compound with block structure and polyamine compounds etc.
Except above-mentioned film forming vector resin, randomly the coloured pigment with chromatic metallic lamellar pigment and other type adds in the said composition, as required, coating composition of the present invention can mix mutually with general various additives in the coating composition, for example comprises surface conditioner, filler, softening agent, stablizer and antioxidant etc.
The form of coating composition of the present invention does not have particular restriction, comprises dispersion in organic solvent, aqueous dispersions, powder and milk sap.The film of coating composition of the present invention does not have particular restriction yet, can be by drying at room temperature, baking-curing, UV-light or electron beam radiation cured finishing.
When coating composition of the present invention was dispersion in the organic solvent, its solvent that is fit to did not have particular restriction, comprises the organic solvent that adopts usually in those solution-based paint compositions.The appropriate organic solvent example comprises aromatic solvent such as toluene and dimethylbenzene etc., olefin(e) compound, cyclic olefins, naphthas, alcohols such as methyl alcohol, ethanol, Virahol and propyl carbinol, ketone such as methylethylketone and methyl iso-butyl ketone (MIBK), ester class such as ethyl acetate and butylacetate, hydrochloric ether compound such as methylene dichloride and trieline, gylcol ether such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, ethylene glycol ester monoether class such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate or the like.
Coating composition of the present invention can adopt any means of the various conventional coating compositions of preparation to be prepared.Coating composition of the present invention can be applied to any base material, does not have particular restriction ground to comprise as metal, timber, plastics, glass and pottery etc.Coating method does not have special restriction yet, can adopt the coating method of any routine, for example comprises aerial spraying, no air coating, electrostatic coating and roller coat etc.According to the application purpose of coated products, can adopt one coating, methods such as twice coating method apply.
Ink composite of the present invention contains film forming material and comprises the tinting material of above-mentioned metallic effect pigments.All film forming materials that are used to form conventional ink composite can be used for forming ink composite of the present invention and not have special restriction.The film forming material example that is fit to this purpose comprises, synthetic resins such as resol, Synolac, polyamide resin, acrylic resin, urea-formaldehyde resin, melamine resin and polyvinyl chloride (PVC) RESINS, natural resin such as stellar coal, derivatived cellulose and vegetables oil such as Toenol 1140, tung oil and soya-bean oil.According to the application purpose of ink composite, also can select to adopt the combination of two or more these film forming materials.
Except above-mentioned film forming material, randomly add chromatic metallic core pigment and coloured pigment as required, ink composite of the present invention also can be as required with ink composite in normally used various additive mix use, as wax, softening agent and dispersion agent etc.In addition, the form of ink composite of the present invention does not have special restriction, comprises organic solvent solution, the aqueous solution and water miscible liquid.
When ink composite of the present invention was the dispersion in organic solvent form, various organic solvents that for this reason can adopt and do not have particular restriction comprised those that adopt in the conventional solvent-based ink composition.The appropriate organic solvent example comprises, for example aromatic solvent such as toluene and dimethylbenzene, olefin(e) compound, cyclic olefins, naphthas, alcohols such as methyl alcohol, ethanol, Virahol and propyl carbinol, ketone such as methylethylketone and methyl iso-butyl ketone (MIBK), ester class such as ethyl acetate and butylacetate, hydrochloric ether compound such as methylene dichloride and trieline, gylcol ether such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, ethylene glycol ester monoether class such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate or the like.
Ink composite of the present invention can adopt in any prior art the used method of the various conventional ink composites of preparation to be prepared.Ink composite of the present invention can be applied to any conventional mode of printing, as silk screen printing, intaglio printing, gold stamping printing and flexography.
Colored moulding material according to the present invention comprises plastics with resin with as the above-mentioned metallic effect pigments of tinting material.The plastics that constitute molding of the present invention batching (molding compound) main component have no particular limits with resin, can adopt to be used for any plastics resin of common employing of molding definite shape goods in the prior art.This plastics include polyvinyl chloride (PVC) RESINS, plasticized polyvinyl chloride resin, polyvinyl resin, acrylic resin, ABS resin, resol, polyamide resin, Synolac, urethane resin and melamine resin etc. with the example of resin.
Plastics in the molding of the present invention batching with resin can be optionally with the coloured pigment of other chromatic metallic flaky pigment and/or other class mutually compounding with the aesthetic feeling effect of further its color of enhancing.Plastics of the present invention also can optionally include other additive that adopt usually various types of fillers and this area with the molding batching of resin in based on the molding batching of plastics with resin.By currently known methods, as extrusion molding and injection moulding, molding batching of the present invention can be prepared the goods of various forms definite shape.
Therefore, composition and the application of effect pigment of the present invention in macromolecule organic material is painted, the especially application in car paint of the effect pigment of the present invention that comprises macromolecule organic material and painted significant quantity have been the invention still further relates to.Based on the weight of wanting painted macromolecule organic material, pigment optimization of the present invention uses with the amount of 0.01-30wt%.
Following examples are just to illustrating the present invention, and must not be interpreted as limiting the scope of the invention by any way.
Embodiment 1
Aspect main, be similar in the vacuum system of patent US6270840 structure or in as alternative batch system, from vaporizer, evaporate following material successively:, and under 1350 ℃ to 1550 ℃, evaporate as Si and SiO at about 900 ℃ of sodium-chlor (NaCl) that evaporate down as separating agent 2The silicon monoxide of reaction product (SiO).The thickness of NaCl layer typically is 30-40nm, and the thickness of SiO layer depends on the specific end use of final product, do not wait from 20 to 2000nm, and in the present embodiment 200nm.According to known technology, the resistance heating evaporation device is designed, make and on working width, obtain good homogeneous.Under the about 0.02Pa of pressure, evaporate, the about 11g of per minute sodium-chlor steam output, the SiO steam output is approximately 72g.For the layer that is undertaken by the separated and dissolved agent subsequently separates, the carrier that vapour deposition takes place is to spend deionized water injection under about 3000Pa pressure, and by scraper with ultrasonicly handle with mechanical assist device.NaCl enters solution, and insoluble SiO yLayer is fragmented into fragment.Constantly from lysing chamber, shift out suspension and under atmospheric pressure by filter collecting, and with washed with de-ionized water several times to remove the Na that exists +And Cl -Ion.After drying step (purpose is with SiO yBe oxidized to SiO z) and under 700 ℃, by in the stove of 700 ℃ of warm airs, heat the parallel SiO in plane of loose material form yStructure, 2 hours time.After the cooling, pulverize and adopt the air sieve classification.Product is in order to follow-up use.
Embodiment 2
(0.8M 21.2mmol) stirs the formation slurry together with 0.5g silicon oxide flakes, 150g deionized water and 26.5ml boric acid aqueous solution.Its pump in continuous loop is crossed microwave oven.(0.1M 0.2mmol) joins in the slurry with 2ml hexafluoro stannic acid ammonium with the speed of per minute 0.4ml with syringe pump.Add after 30 minutes, again with identical speed add the 50ml ammonium hexa-fluorotitanate (0.2M, 10.0mmol).Finished this reaction again through 30 minutes.Power by adjusting microwave and operating time make temperature maintenance in the whole process at 50 ℃.From bulk solution, isolate solid by sedimentation and decantation.This solid is made slurry with deionized water, repeats sedimentation and decantation.Solid is placed on the filter funnel the most at last, with washed with de-ionized water and dry.Further dry under 110 ℃ in vacuum drying oven.
Embodiment 3
With 1g silicon-dioxide thin slice, 375g deionized water and 8ml boric acid solution 0.8M, 6.4mmol) stir the formation slurry together.Its pump in continuous loop is crossed microwave oven.(0.1M 0.2mmol) joins in the slurry with 2ml hexafluoro stannic acid ammonium with the speed of per minute 0.4ml with syringe pump.Add after 30 minutes, again with identical speed add the 15ml ammonium hexa-fluorotitanate (0.2M, 3.0mmol).Continue to react other 30 minutes until finishing reaction.Power by adjusting microwave oven and operating time make temperature maintenance in the whole process at 50 ℃.From bulk solution, isolate solid by sedimentation and decantation.This solid is made slurry with deionized water, repeats sedimentation and decantation.Solid is placed on the filter funnel, uses washed with de-ionized water, drying and dry under 110 ℃ in vacuum drying oven at last.
Embodiment 4
(0.8M 11.2mmol) stirs the formation slurry together with 1g silicon-dioxide thin slice, 300g deionized water and 14ml boric acid solution.Its pump in continuous loop is crossed microwave oven.(0.1M 0.5mmol) joins in the slurry with 5ml hexafluoro stannic acid ammonium with the speed of per minute 0.4ml with syringe pump.Add after 30 minutes, again with identical speed add the 25ml ammonium hexa-fluorotitanate (0.2M, 5.0mmol).Continue to react other 30 minutes up to finishing this reaction.Power by adjusting microwave and operating time make temperature maintenance in the whole process at 50 ℃.From bulk solution, isolate solid by sedimentation and decantation.This solid is made slurry with deionized water, repeats sedimentation and decantation.Solid is placed on the filter funnel, uses washed with de-ionized water, drying, finally dry under 110 ℃ in vacuum drying oven.
Embodiment 5
(0.8M 36mmol) stirs the formation slurry together with 1g silicon-dioxide thin slice, 300g deionized water and 45ml boric acid solution.Its pump in continuous loop is crossed microwave oven.(0.1M 0.5mmol) joins in the slurry with 5ml hexafluoro stannic acid ammonium with the speed of per minute 0.4ml with syringe pump.Add after 30 minutes, (0.2M 16mmol), continues to react other 30 minutes until finishing this reaction to add the 80ml ammonium hexa-fluorotitanate with identical speed again.Power by adjusting microwave and operating time make temperature maintenance in the whole process at 50 ℃.From bulk solution, isolate solid by sedimentation and decantation.This solid is made slurry with deionized water, and repeats sedimentation and decantation.Solid is placed on the filter funnel, uses washed with de-ionized water, drying, finally dry under 110 ℃ in vacuum drying oven.
Embodiment 6
With 0.4g Graphitan 7525 (graphite flake) and 75ml boric acid aqueous solution 0.8M, 60mmol) stir the formation slurry together.Slurry is pumped into and one encloses in the PTFE tube, and this pipe passes microwave oven.(0.4M, 10mmol) speed with 0.3ml/min joins in the gained mixture, and then proceeds microwave treatment and reacted other 30 minutes with the 25ml ammonium hexa-fluorotitanate aqueous solution under microwave radiation.Power by adjusting microwave and operating time make temperature maintenance in the process at 55-65 ℃.Collect solid by filtration, then with washed with de-ionized water and air-dry.Further dry under 110 ℃ in vacuum drying oven.Pigment demonstrates dark blue color.
Embodiment 7
(0.8M 60mmol) stirs together and forms slurry with 0.3g silicon oxide flakes (thickness 300nm) and 75ml boric acid aqueous solution.Slurry is pumped into and one encloses in the PTFE tube, and this pipe passes microwave oven.(0.4M, 10mmol) speed with 0.2ml/min joins in the gained mixture, and then proceeds microwave treatment other 30 minutes with the 25ml ammonium hexa-fluorotitanate aqueous solution under microwave radiation.Power by adjusting microwave and operating time make temperature maintenance in the process at 50-60 ℃.Collect solid by filtration, then with washed with de-ionized water and air-dry.Further dry under 110 ℃ in vacuum drying oven.The pigment that obtains demonstrates green.
Embodiment 8
(0.8M 36mmol) stirs together and forms slurry with 0.2g silicon oxide flakes (thickness 150nm) and 45ml boric acid aqueous solution.Slurry is pumped into and one encloses in the PTFE tube, and this pipe passes microwave oven.(0.4M, 6mmol) speed with 0.8ml/min joins in the gained mixture with the 15ml ammonium hexa-fluorotitanate aqueous solution at ambient temperature.Adopt microwave radiation with temperature maintenance 3040 ℃ 90 minutes, 50-65 ℃ 30 minutes.Collect solid by filtration, then with washed with de-ionized water and air-dry.Further dry under 110 ℃ in vacuum drying oven.The pigment that obtains demonstrates redness.
Embodiment 9
(0.8M 60mmol) stirs together and forms slurry with 0.3g silicon oxide flakes (thickness 150nm) and 75ml boric acid aqueous solution.Slurry is pumped into and one encloses in the PTFE tube, and this pipe passes microwave oven.(0.4M, 10mmol) speed with 0.3ml/min joins in the gained mixture, and then proceeds microwave treatment other 30 minutes with the 25ml ammonium hexa-fluorotitanate aqueous solution under microwave radiation.Power by adjusting microwave and operating time make temperature maintenance in the process at 55-65 ℃.Collect solid by filtration, then with washed with de-ionized water and air-dry.Further dry under 110 ℃ in vacuum drying oven.The pigment that obtains demonstrates green.
Embodiment 10
0.24g silicon oxide flakes (thickness 150nm) and 20ml deionized water are stirred the formation slurry together.Slurry is pumped into and one encloses in the PTFE tube, and this pipe passes microwave oven.At ambient temperature with 18mlFeCl 3NH 4The F aqueous solution (0.4M, 7.2mmol) and the 18ml boric acid aqueous solution (0.8M 14.4mmol) joins in the gained mixture with the speed of 0.2ml/min simultaneously, is reflected under the 40-50 ℃ of temperature microwave radiation processing then 30 minutes.Collect solid by filtration, then with washed with de-ionized water and air-dry.Further dry under 110 ℃ in vacuum drying oven.The pigment that obtains demonstrates green/yellow.
Embodiment 11
Except adopting the silicon-dioxide thin slice of the about 100nm of thickness, and reach outside the deposition that about 90nm stops titanium dioxide later on repetition embodiment 4 at the thickness of titanium dioxide layer.The thin slice that is obtained shows red.
Embodiment 12
Except adopting SiOz (about 1.6≤z≤1.8) thin slice of the about 100nm of thickness, and reach outside the deposition that about 90nm stops titanium dioxide later on repetition embodiment 7 at the thickness of titanium dioxide layer.The thin slice that is obtained shows red.

Claims (14)

1. one kind comprises the core and the preparation method of the pigment of one dielectric layer at least, and described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family.This method may further comprise the steps:
(a) core is suspended in the fluorine scavenging agent aqueous solution;
(b) add the aqueous solution of one or more fluorine-containing metal complexs, this complex compound is the precursor of required coating of metal oxides; With
(c) to described suspension carry out microwave radiation with depositing metal oxide to described core.
2. the method for claim 1, wherein said pigment are a kind of core and effect pigments of one dielectric layer at least of comprising, described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family.
3. method as claimed in claim 2, wherein said core are the flaky material with low-refraction, especially mica, another kind of layered silicate, Al 2O 3, SiO z, SiO especially 2, SiO 2/ SiO x/ SiO 2(0.03≤x≤0.95), SiO 1.40-2.0/ SiO 0.70-0.99/ SiO 1.40-2.0Or Si/SiO z, 0.70≤z≤2.0, especially 1.40≤z≤2.0 wherein,
4. method as claimed in claim 2, wherein said core are the flaky material with high refractive index, especially TiO 2Or Fe 2O 3
5. method as claimed in claim 2, wherein said core are flaky metallic substance, especially titanium, silver, aluminium, copper, chromium, iron, germanium, molybdenum, tantalum or nickel.
6. the method for claim 1, wherein said pigment are a kind of granules of pigments and pigment of coating of the metal oxide of one dielectric layer at least of comprising, described dielectric layer is made of the oxide compound that one or more are selected from the metal of the periodic table of elements the 3rd to 15 family.
7. method as claimed in claim 3, wherein said core are organic or inorganic pigment.
8. as each described method among the claim 1-7, wherein said fluorine scavenging agent is selected from boric acid, alkali metal borate such as Sodium Tetraborate, ammonium borate, boron trioxide and a boron oxide.
9. as each described method among the claim 1-8, wherein fluorine-containing metal complex is selected from: ammonium hexa-fluorotitanate; Hexafluoro stannic acid ammonium; Ammonium hexafluorosilicate; Iron(ic) chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Aluminum chloride (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Hexafluoro germanic acid ammonium; Indium (III), hydrofluoric acid and Neutral ammonium fluoride mixture; Comprise the combination of the metal-salt of the metal oxide film of more than one elements and indium tin oxides film with formation.
10. as each described method among claim 1-3 and the 5-9, wherein metal oxide is a titanium dioxide, and fluorine-containing metal complex is an ammonium hexa-fluorotitanate, and is a kind of by Neutral ammonium fluoride and titanium chloride, or by the complex compound of titanium chloride, Neutral ammonium fluoride and hydrogen fluoride preparation; Perhaps this metal oxide is a silicon-dioxide, and fluorine-containing metal complex is ammonium hexafluorosilicate or five ammonium silicofluorides.
11., further comprising the steps of as each described method among claim 1-3 and the 5-10:
(d) add the aqueous solution that one or more are fluorine-containing metal complexs of required coating of metal oxides precursor, this coating of metal oxides is different with the oxide coating of step (b); With
(e) to described suspension carry out microwave radiation with depositing metal oxide to the core of described coating.
12. method as claimed in claim 11, wherein the fluorine-containing metal complex of step (b) is an ammonium hexa-fluorotitanate, and the fluorine-containing metal complex of step (d) is the silicofluoric acid ammonium salt.
13. the method for claim 1, wherein said core are the SiO of 1.40≤z＜2.0 zOr SiO 2, first dielectric layer is a high refractive index metal oxide, as Fe 2O 3Or TiO 2, optional second dielectric layer that exists is the metal oxide of low-refraction, as SiO 2, or Al 2O 3, refractive index difference at least 0.1 wherein; Perhaps core is flaky graphite, and dielectric layer is a titanium dioxide; Perhaps core is a titanium dioxide, and first dielectric layer is selected from Fe 2O 3, Fe 3O 4, FeOOH, Cr 2O 3, CuO, Ce 2O 3, Al 2O 3, SiO 2, BiVO 4, NiTiO 3, CoTiO 3With mix antimony, mix fluorine or mix the stannic oxide ferric oxide of indium and optional second dielectric layer that exists is selected from aluminum oxide or hydrated aluminum oxide, silicon-dioxide or hydrated SiO 2, Fe 2O 3, Fe 3O 4, FeOOH, TiO 2, ZrO 2, Cr 2O 3And mix antimony, mix fluorine or mix the stannic oxide of indium; Perhaps core is a ferric oxide, first dielectric layer is the colourless coating of refractive index n≤1.8, for example silicon oxide, hydrated silica, aluminum oxide, hydrated aluminum oxide and composition thereof, optional second dielectric layer that exists is the colourless coating of specific refractory power 〉=2.0, for example titanium dioxide, hydrous titanium oxide, zirconium dioxide, hydrous zirconium oxide, tindioxide, aqua oxidation tin, zinc oxide, aqua oxidation zinc and its mixture.
14.1.40 the SiO of≤z＜2.0 zOr SiO 2Thin slice, thickness is 70-130nm, comprises the titanium dioxide layer that thickness is 60-120nm.
CNB2004800167678A 2003-06-17 2004-06-07 A process for the preparation of a pigment comprising a core material and at least one dielectric layer Expired - Fee Related CN100528975C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101889060A (en) * 2007-12-19 2010-11-17 默克专利股份有限公司 Optically variable pigments of high electrical conductivity
CN107474588A (en) * 2012-10-05 2017-12-15 巴斯夫公司 Effect pigment containing iron oxide, its preparation and application thereof
CN110669360A (en) * 2019-08-30 2020-01-10 惠州市华阳光学技术有限公司 Composite color pigment flake and preparation method thereof
CN110951282A (en) * 2019-12-18 2020-04-03 龙蟒佰利联集团股份有限公司 Preparation method for improving weather resistance of titanium dioxide
CN111534129A (en) * 2020-04-07 2020-08-14 惠州市华阳光学技术有限公司 Composite color pigment flake and preparation method thereof
CN112426881A (en) * 2020-11-30 2021-03-02 桂林理工大学 Bionic nano deodorant, preparation method and application thereof
CN112442287A (en) * 2020-11-20 2021-03-05 惠州市华阳光学技术有限公司 Pigment flakes and inks
CN112656958A (en) * 2020-12-29 2021-04-16 中国人民解放军陆军军医大学第二附属医院 Fluorine-doped iron oxide nanoparticle contrast agent and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101889060A (en) * 2007-12-19 2010-11-17 默克专利股份有限公司 Optically variable pigments of high electrical conductivity
CN101889060B (en) * 2007-12-19 2014-04-16 默克专利股份有限公司 Optically variable pigments of high electrical conductivity
CN107474588A (en) * 2012-10-05 2017-12-15 巴斯夫公司 Effect pigment containing iron oxide, its preparation and application thereof
CN110669360A (en) * 2019-08-30 2020-01-10 惠州市华阳光学技术有限公司 Composite color pigment flake and preparation method thereof
CN110951282A (en) * 2019-12-18 2020-04-03 龙蟒佰利联集团股份有限公司 Preparation method for improving weather resistance of titanium dioxide
CN111534129A (en) * 2020-04-07 2020-08-14 惠州市华阳光学技术有限公司 Composite color pigment flake and preparation method thereof
CN112442287A (en) * 2020-11-20 2021-03-05 惠州市华阳光学技术有限公司 Pigment flakes and inks
CN112426881A (en) * 2020-11-30 2021-03-02 桂林理工大学 Bionic nano deodorant, preparation method and application thereof
CN112656958A (en) * 2020-12-29 2021-04-16 中国人民解放军陆军军医大学第二附属医院 Fluorine-doped iron oxide nanoparticle contrast agent and preparation method thereof

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