CN110183875A

CN110183875A - A kind of pigment of high brightness and its preparation method and application

Info

Publication number: CN110183875A
Application number: CN201910576360.9A
Authority: CN
Inventors: 林一中; 王振兴
Original assignee: Individual
Current assignee: Shanghai Jianuova Cosmetics Co ltd
Priority date: 2018-06-29
Filing date: 2019-06-28
Publication date: 2019-08-30
Anticipated expiration: 2039-06-28
Also published as: CN108752977A; CN110183875B; WO2020001010A1

Abstract

The present invention relates to a kind of pigment of high brightness, the pigment includes core material and external coating, the core material is 1-6 layers of structure, including one layer of smooth air layer, or the combination of at least one layer of air layer and at least one layer of dielectric layer and/or at least one layer of reflecting layer, the overall thickness of the core material is 20-1000nm, the thickness in monolayer of the dielectric layer is 50-300nm, the thickness in monolayer in the reflecting layer is 20-100nm, and the thickness in monolayer deviation in the overall thickness of the core material and the dielectric layer or the reflecting layer is no more than 1% or 5nm of the average value of overall thickness and equivalent layer thickness, the external coating is 2-6 layers, the overall thickness of the external coating is 20-1000nm, every layer of clad with a thickness of 10-300nm.Pigment of the invention can be used for coating, ink, cosmetics, in color make-up.

Description

A kind of pigment of high brightness and its preparation method and application

Chinese invention patent application number 201810698484.X (the invention name submitted this application claims on June 29th, 2018 Referred to as there is the pigment and preparation method thereof of high brightness, excitation purity and covering effect simultaneously) preference, the priority document Full content is incorporated herein by quoting.

Technical field

The present invention relates to a kind of pigment, more specifically to a kind of pigment and its preparation method and application of high brightness.

Background technique

Pearlescent pigment has colourful color, can satisfy the application demand of a variety of industries.With use scope Further expanding for further expansion and use occasion, also proposes more strict requirements to pearlescent pigment.For common The general brightness of pearlescent pigment and covering power be two contradictory properties, if the covering power of powder is good, general brightness is with regard to poor, instead It is also anti-, therefore just propose at the same have it is preferable cover and the requirement of brightness, but because of for common pearlescent pigment The cladding for the flaky material of grinding is used as substrate carrying out again gas phase or liquid phase, causes two performances that cannot take into account.

For example titania/silica/titanium dioxide can for the verified three-decker with specific thicknesses of optical theory To obtain the pigment with color changeable effect；If the flaky material with uniform thickness is similarly used to serve as above-mentioned three as substrate Low-index layer such as silicon dioxide layer in layer structure, then wet chemical method cladding single layer, which can be used, can be obtained color changeable effect Pearlescent pigment.Such as Merck pearlescent pigmentThe series of products such as T10-01 are exactly uniform in smooth thickness Silicon dioxide layer on cladding single layer titanium dioxide obtain camouflage paint；And for substrate in uneven thickness, such as by grinding The flaky materials such as the mica that mill technology obtains pass through single layer packet because its base material thickness has the characteristics that wider thickness distribution The pigment with obvious color travel can not be obtained by covering, and to obtain on this material in uneven thickness has obvious become The pigment of color effect, it is necessary to which carrying out three layers, there is high refractive index/low-refraction/high-index material cladding could all obtain.

The material that physical vapour deposition (PVD) (PVD) method obtains various optical effects is widely used in many industries, makes The multilayered structure pigment that each thickness degree of acquisition that can be convenient with PVD method can be controlled accurately, is obtained using PVD method Optically Variable Pigments (OVP) effect pigment is also widely used high-level in the needs such as security, coin Anti-fake occasion, such as 100 yuan of technologies similar with being exactly in 50 yuan of optically variable anti-counterfeiting of RMB in China, structure have 5 layers of symmetrical structure: half-absorption layer/dielectric layer/reflecting layer/dielectric layer/half-absorption layer [related patents US4779898, US5059245, ZL02816899.2] because the presence of its absorbed layer makes powder have extraordinary covering power；In order to obtain The structure of more numbers of plies generally can be used in better color effects, pure in order to obtain such as Chinese patent 201510632169.3 Red optics color-changing anti-counterfeit pigment uses the structure of 7+2 (n) layer, and general structure is with central reflector, first medium The structure of layer, the first half-absorption layer, second dielectric layer, the second half-absorption layer ..., this by particular design can be into one Step eliminates variegated interference, obtains purer red.It is obtained in addition, being sequentially depositing using PVD process using high low-refraction The pigment with specific composition and thickness obtained has broader color change interval, and smooth layer and uniform thickness are to powder herein Final color effect play the role of it is vital.For the pigment for using PVD process to prepare merely, technique usually exists Object to be deposited is gasified under specific temperature and pressure, is deposited under specific sedimentary condition again later, eventually passes through demoulding, powder The programs such as broken, classification obtain final product, can carry out some surface treatments again later to improve the superficiality such as its hydrophilic and oleophilic Matter, these general surface treatments are the Nomenclature Composition and Structure of Complexes for not changing original PVD process and preparing pigment, and purpose is not to remove certain layer Or change certain layer of structure；Nor obtaining smooth air layer to handle；In coat of colo(u)r prepared by the PVD of the above structure In structure, it is the closely coupled structural stability to guarantee pigment between each layer of deposition, is that impossible deposit in this structure In independent smooth air layer；Because of air layer if it exists, it is equivalent to air layer two sides and is separated from each other, be separated from each other Layer structure be that cannot retain the original layer structure comprising air layer；And after air layer two side portions separate, Separated two parts coat of colo(u)r structure hollow gas-bearing formation just becomes to be not present again.For the pigment for using PVD process to prepare merely For, preparation process determines the presence of the rare educt of the pigment, pigment will not be caused bright powder granule is smaller Degree is decreased obviously, and each layer smooth degree of pigment is higher, excitation purity, brightness are preferable.But the pigment is using PVD process Carry out crushing etc. processing acquisition after preparation again, so that pigment can generally have exposed metal layer, for reflecting layer or semi-absorbing Layer, may be subjected to the effect of sky gas and water, acid, alkali or sulfide etc. and causes under brightness in storage or use process Drop.Its use is influenced using having phenomena such as getting angry in water-based system especially for the pigment containing aluminium layer.

According to coated interference pigment principle, the refractive index difference of adjacent layer is bigger, color effects can it is better, excitation purity is higher.It is existing Air can be considered as the minimum substance of refractive index in known material, if therefore air layer can be introduced in layer structure will Improve the effect of pigment, improves pigment brightness.But for the pigment of PVD preparation, each layer is arranged in parallel and mutual in pigment Contact, it is impossible to introduce smooth air layer in the structure to obtain special effect (probably due to preparation reason is in powder Part layer there are hollow parts with the interface zone of layer, cause the powder of two sides not contact, but the region is not Air layer with levelling blanket meaning, and the most region of layer and layer interconnects to guarantee pigment at this time The physical stability of structure, therefore can not have complete smooth air layer in the powder of PVD process preparation.And The pigment mentioned in aforementioned patent will be generally made of reflecting layer, dielectric layer and half-absorption layer, and for only reflecting Layer and/or dielectric layer carried out again as substrate wet-chemical coat without reference to.Because its surface of substrate that PVD method obtains can be with More smooth, thickness can be controlled more accurately, if with the layer structure of the PVD process particular design of the layer structure of particular design Preparation material as substrate again using specific technique carry out wet-chemical cladding, air layer is introduced into coat of colo(u)r structure, It can assign and prepare the new effect of pigment.

For mica substrate class pearlescent pigment, because the use of mica of grinding etc. being raw material, the step on surface be will cause The scattering of light, and there are apparent thickness distributions for mica thickness, even for apparent thickness distribution is also had for monolithic, carefully The substrate of partial size can be more obvious to the scattering of light.In order to obtain better covering power, the scattering for improving light is generally required, therefore It is typically chosen the lesser material of partial size, but its smaller excitation purity of partial size and flicker effect can roll over significantly because of the scattering of light Button.And it is poor for large-sized substrate, its covering meeting, in order to reach covering and brightness purpose simultaneously, generally require in material Middle addition high-absorbility or high reflection layer improve.Such as using aluminium flake as substrate, coated silica protects aluminium layer on it, then The iron oxide for coating high refractive index on it obtains pigment under conditions of biggish partial size with stronger covering power.

For the pearlescent pigment prepared with glass baseplate, because the transparency of glass baseplate is more preferable compared with mica substrate, and not Situations such as there are steps, and the thickness distribution of single substrate is more uniform, therefore the excitation purity of the pigment prepared is more compared with mica substrate Height, but because the thickness distribution of its glass baseplate is wider, this, which also results in single layer cladding and cannot generally obtain, obviously has discoloration The pigment of effect, and the substrate of PVD method preparation is used, its thickness can be strictly controlled, uses coating method than common The control of the base material thickness of preparation is more concentrated, and the general thickness distribution unobtainable color effects of substrate can be obtained.

For refractive index, vacuum or air are the smallest, if the air layer of low-refraction can be introduced in pigment, can also be obtained Obtain more excellent color effects.But for existing PVD preparation process, and there is no wherein introducing air layer structure Condition.And color effects can be improved by obtaining air layer (voided layer) by special processing.United States Patent (USP) US5611851 is disclosed Patent in pearlescent pigment is handled using phosphoric acid etc., remove part mica-based material, obtain part hollow structure pigment, It is a degree of to change color effects.But the because out-of-flatnesses such as step that the substrate that natural mica grinding obtains is inherently present Property, and the substrate of part can only be removed, this all causes that smooth air layer cannot be obtained, and can only obtain shape to a certain extent Irregular cavity structure, prevent air layer as layer structure effect from giving full play of, affect special color effect The displaying and performance of fruit.Therefore we are by the cladding under the substrate precursor progress certain condition by PVD, then change condition removing The certain layer of core material precursor is to introduce air layer, it will is further promoted to existing pigment performance.

Summary of the invention

In view of the deficiencies in the prior art, the object of the present invention is to provide can have high brightness, high color purity simultaneously With the pigment of high covering power effect, which includes core material and external coating,

The core material be 1-20 layers of structure, including air layer and/or it is three following in one:

The multilayered structure of dielectric layer, reflecting layer and dielectric layer and one layer of reflecting layer composition,

The overall thickness of the core material is 20-1000nm,

The thickness in monolayer of the dielectric layer is 50-300nm, and the thickness in monolayer in the reflecting layer is 20-100nm, and

The thickness in monolayer deviation in the overall thickness of the core material and the dielectric layer or the reflecting layer be no more than overall thickness and 1% or 5nm of the average value of equivalent layer thickness,

The external coating is 1-6 layers, and the overall thickness of the external coating is 20-1000nm, the thickness of every layer of clad For 10-300nm.

The material in heretofore described reflecting layer can be selected from metal with high reflectivity, metal oxide, nonmetallic, non- One of metal oxide is a variety of；

The material of heretofore described dielectric layer can be selected from metal oxide of the refractive index lower than 1.8, metal fluoride, gold Belong to one of sulfide, nonmetal oxide, nonmetallic fluoride and nonmetallic sulfide or a variety of.

The material of heretofore described external coating can be selected from metal oxide, metal hydroxides, nonmetal oxide, Non-metal hydroxides, metal suboxides, metal fluoride, metal oxyhalide, metal chalogenides, metal vulcanization One of object, metal nitride, metal oxynitrides and metal carbides are a variety of, and at least one layer of in the clad Material have and penetrate rate higher than 1.6.

In a more preferred embodiment of the invention, every layer of dielectric layer with a thickness of 80-250nm.

In a preferred embodiment of the invention, the material of the dielectric layer is selected from SiO₂、MgF₂、Al₂O₃、AlF₃、 Na AlF₆、BaF₂、NdF₃、CaF₂, one of LiF and ZnS or a variety of.

In a more preferred embodiment of the present invention, the material of the dielectric layer is selected from SiO₂And/or Al₂O₃。

In a preferred embodiment of the invention, the material in the reflecting layer be selected from aluminium, silver, copper, gold, titanium, tantalum, One of niobium, chromium, nickel are a variety of.

In a preferred embodiment of the invention, the material of the external coating is selected from TiO₂、Fe₂O₃、TiFe₂O₅、 Fe₃O₄、BiOCl、Cr₂O₃、ZrO₂、ZnO、SnO₂、CoO、Co₃O₄、VO₂、V₂O₃, iron titanate, Ti₂O₃, pucherite, cobalt aluminate, SiO₂、Al₂O₃、Al(OH)₃、MgF₂、B₂O₃, one of ZnS or a variety of.

In a more preferred embodiment of the present invention, the core material is 3-9 layers of structure.Of the invention another more In preferred embodiment, the core material includes 3-9 layers of dielectric layer.It is described in another more preferred of the invention Core material includes 3-9 layers of reflecting layer.In another more preferred of the invention, the core material includes one layer of air layer. In another more preferred of the invention, the core material includes one dielectric layer.Another is more excellent of the invention It selects in embodiment, the core material includes one layer of reflecting layer.

In another more preferred of the invention, the core material is 3-9 layers of structure, including air layer and dielectric Layer, and the air layer and the dielectric layer are alternately distributed.In another more preferred of the invention, the core Material is 3-tier architecture, including one layer of air layer and two layers of silica, and the air layer is between two layers of the silica.

In another more preferred of the invention, the core material be 3,5,7 or 9 layers of structure, including 2,4,6 or 8 layers of dielectric layer and one layer of reflecting layer, described 2,4,6 or 8 layers of dielectric layer are symmetrical arranged centered on the reflecting layer.

In another more preferred of the invention, the core material is 3-9 layers of structure, including air layer and reflection Layer, and the air layer and the reflecting layer are alternately distributed.

In view of the deficiencies in the prior art, of the invention also to provide a kind of pigment of high brightness, which includes core Material and external coating,

The core material is 1-6 layer structure, including one layer of smooth air layer, or the smooth air layer of at least one layer and at least The combination in one dielectric layer and/or at least one layer of reflecting layer,

The overall thickness of the core material is 20-1000nm,

The thickness in monolayer deviation in the overall thickness of the core material and the dielectric layer or the reflecting layer be no more than overall thickness and 1% or 5nm of the average value of equivalent layer thickness；

The external coating is 2-6 layers, and the overall thickness of the external coating is 20-1000nm, the thickness of every layer of clad For 10-300nm.

In a more preferred embodiment of the invention, every layer of dielectric layer with a thickness of 50-250nm.

In a preferred embodiment of the invention, the material of the dielectric layer is selected from SiO₂、MgF₂、Al₂O₃、AlF₃、 Na AlF₆、BaF₂、NdF₃、CaF₂, one of LiF and ZnS, CoS, MnS, FeS, CuS or a variety of.

In a preferred embodiment of the invention, the material in the reflecting layer be selected from silver, copper, gold, titanium, tantalum, niobium, One of chromium, nickel are a variety of.

In the present invention, in the external coating, the external coating close to the core material is the first external coating, is coated on External coating on first external coating is the second external coating, and so on, wherein the material of first external coating Material is selected from material of the refractive index less than 1.8, and further, first external coating part is selected from silica and/or three oxygen Change two aluminium；The material of second external coating and remaining an external coating at least layer choosing is greater than 1.8 material from refractive index, into One step, it each is selected from TiO₂, Fe₂O₃, TiFe₂O₅, Fe₃O₄, BiOCl, Cr₂O₃, ZrO₂, ZnO, SnO₂, CoO, Co₃O₄, VO₂, V₂O₃, iron titanate, Ti₂O₃, pucherite, one of cobalt aluminate or a variety of.

In a preferred embodiment of the invention, the core material is one layer of smooth air layer.Of the invention one In a preferred embodiment, the core material is 3-6 layers of structure, including smooth air layer and dielectric layer, and it is described smooth Air layer and the dielectric layer are alternately distributed.In another more preferred of the invention, the core material is 3 layers of knot Structure, including one layer of smooth air layer and two layers of silica, the smooth air layer be located at two layers of the silica it Between.In another more preferred of the invention, the core material is 3-tier architecture, including layer of silicon dioxide layer and 2 layers Smooth air layer, the silicon dioxide layer is between 2 layers of smooth air layer.

Another object of the present invention is to provide pigment that is a kind of while having high brightness, high color purity and high covering power effect Preparation method, the method comprising the steps of:

(1) the stainless steel bottom liner or glass for providing design are as bottom liner；

(2) one layer of peelable separation layer is deposited on the bottom liner using PVD method, then deposit 1- using PVD method The multilayered structure of 20 layers of dielectric layer, 1-20 layers of reflecting layer or 2-19 layers of dielectric layer and one layer of reflecting layer composition, redeposited one layer can Separation layer is removed, in this way, to deposit one layer of peelable separation layer and the 1-20 layers of dielectric layer, 1-20 layers of reflecting layer, or The multilayered structure of 2-19 layers of dielectric layer and one layer of reflecting layer composition is a cycle, is repeated the period 2-50 times；

(3) the peelable separation layer in step (2) resulting materials is removed using remover, it is pre- is washed out and is classified acquisition Determine the core material precursor of particle diameter distribution；

(4) the resulting core material precursor dispersion of step (3) is configured in water or ethyl alcohol slurry, coating solution is added, Wet-chemical cladding is carried out, 1-6 layers of outer cladding object are successively coated,

Wherein, after every layer of coating cladding terminates, can continue to coat next layer of coating by adjusting capsulation condition, Or be scattered in again after the treatment processes such as being filtered and being washed slurry is configured in solvent after carry out the cladding of lower layer's coating,

(5) it is filtered, washed and dried acquisition after being covered to complete while there is high brightness, high color purity and high covering power effect Pigment.

In a preferred embodiment of the invention, the material layer of the outer cladding is selected from TiO₂, Fe₂O₃, TiFe₂O₅, Fe₃O₄, BiOCl, Cr₂O₃, ZrO₂, ZnO, SnO₂, CoO, Co₃O₄, VO₂, V₂O₃, iron titanate, Ti₂O₃, pucherite, cobalt aluminate, SiO₂、Al₂O₃、Al(OH)₃、MgF₂、B₂O₃, one of ZnS or a variety of.

In a preferred embodiment of the invention, step (5) further may include the dry step calcined later Suddenly.

In a preferred embodiment of the invention, in step (1) every layer of dielectric layer with a thickness of 50-300nm, every layer Reflecting layer with a thickness of 20-100nm, the overall thickness and single layer thickness deviation of the core material are no more than overall thickness and corresponding thickness 1% or 5nm of the average value of degree.

In a preferred embodiment of the invention, step (2) is that one layer is deposited on the bottom liner using PVD method Then peelable separation layer deposits 1-20 layers of dielectric layer, redeposited one layer of peelable separation layer, in this way, with heavy using PVD method Product one layer of peelable separation layer and the 1-20 layers of dielectric layer are a cycle, are repeated the period 2-50 times.In the present invention Another preferred embodiment in, step (2) is using PVD method one layer of peelable separation layer to be deposited on the bottom liner, Then 1-20 layers of reflecting layer, redeposited one layer of peelable separation layer, in this way, can to deposit described one layer are deposited using PVD method It removes separation layer and the reflecting layer 1-20 layers of is a cycle, repeat the period 2-50 times.Of the invention another preferably In embodiment, step (2) is that one layer of peelable separation layer is deposited on the bottom liner using PVD method, then uses the side PVD Method deposits the multilayered structure of 2-19 layers of dielectric layer and one layer of reflecting layer composition, redeposited one layer of peelable separation layer, in this way, with heavy The multilayered structure of product one layer of peelable separation layer and the 2-19 layers of dielectric layer and one layer of reflecting layer composition is a cycle, It repeats the period 2-50 times.

In a preferred embodiment of the invention, the dielectric layer deposited in step (2) or reflecting layer are in step (4) Removing can be dissolved in wet-chemical cladding.

In a more preferred embodiment of the present invention, the material of the dielectric layer in step (2) is zinc sulphide, zinc sulphide Dielectric layer is dissolved during the cladding of step (5) and removes and substituted in the core material of final products by air.

In another more preferred of the invention, the material in the reflecting layer in step (2) is metallic aluminum, gold Belong to aluminium reflecting layer to be dissolved removing during the cladding of step (5) and substituted in the core material of final products by air.

The present invention also provides a kind of preparation methods of the pigment of high brightness, and the method comprising the steps of:

1) preparation of core material precursor:

1.1) the stainless steel bottom liner or glass for providing design are as bottom liner；

1.2) one layer of peelable separation layer is deposited on the bottom liner using PVD method, then using PVD method deposition one The smooth air layer precursor layer of layer, or at least one layer of smooth air layer precursor layer and at least one layer of dielectric layer and/or at least The combination in one layer of reflecting layer, redeposited one layer of peelable separation layer, in this way, with one layer of one layer of peelable separation layer of deposition and deposition Smooth air layer precursor layer, or at least one layer of smooth air layer precursor layer and at least one layer of dielectric layer precursor layer and/or The group of at least one layer of reflecting layer precursor layer is combined into a cycle, repeats the period 1-50 times；

1.3) the peelable separation layer in step 1.2) resulting materials is removed using remover, is washed out and is classified acquisition The core material precursor of predetermined particle diameter distribution；

2) the first external coating precursor layer of cladding air layer smooth with acquisition:

2.1) by the resulting core material precursor dispersion of step 1.3) in the solution for not destroying the core material front body structure with packet The first external coating precursor layer is covered, then, being filtered, washed and/or dry and/or calcining acquisition has smooth air layer precursor Layer and the powder for coating the first external coating；

2.2) powder point with smooth air layer precursor layer and the first external coating of cladding for obtaining 2.1) step It dissipates in that can dissolve to be formed in the solution of smooth air layer by the air layer precursor layer in the core material precursor, described Air layer precursor layer in core material precursor, which is dissolved, to be formed after smooth air layer, and filtering, sufficiently washing, drying are contained There is air layer and is coated with the powder of the first external coating or the first external coating precursor layer；

3) the second external coating precursor layer is coated:

2.2) powder is dispersed in solution again, to carry out the cladding of the second external coating precursor layer；

Or

2.1) powder with air layer precursor layer and the first external coating precursor of cladding that step is obtained is without step It is rapid 2.2) to be directly scattered under the reaction condition for being used to form the second external coating precursor layer and incite somebody to action under this condition Air layer precursor layer dissolution in the core material precursor is to form in the solution of smooth air layer, in second outer cladding Layer precursor layer reaches predetermined thickness and the air layer precursor layer is dissolved and is formed after smooth air layer, be filtered, washed, Dry and/or calcining；

4) cladding (if any) for carrying out remaining external coating, after all external coating precursor layers are covered to complete It is filtered, washed and dried and/or calcines and obtain pigment.

In a preferred embodiment of the invention, during second and remaining external coating precursor coat, every After layer external coating precursor cladding terminates, it can continue to coat next layer of external coating, Huo Zhejing by adjusting capsulation condition Be filtered, washed and/or dry and/or calcine etc. after processing be scattered in solvent again be configured to slurry after carry out lower layer's outer cladding The cladding of layer precursor layer；It is filtered, washed, dries and/or calcines after whole external coating precursor layers are covered to complete and obtain pigment. Powder can be post-processed as needed to improve its hydrophilic and oleophilic property, it is more preferable with specific system compatibility with it；

In a preferred embodiment of the invention, the first external coating precursor layer of cladding is not break in step 2.1) Under conditions of obtaining core material precursor, preferably carry out in organic solvent.The preferred alcohols solvent of the organic solvent；More preferable ethyl alcohol.

In a more preferred embodiment of the present invention, the first external coating precursor layer of cladding is in ethyl orthosilicate It is carried out in ethanol solution.

In a preferred embodiment of the invention, in step 2.2) after the second external coating precursor layer cladding The cladding that reaction condition carries out lower layer can be directly adjusted, can also be filtered, washed according to conventional wet-chemical cladding process With the cladding for re-starting lower layer after drying or calcining again；Such as pH can choose for the cladding of the precursor layer of titanium dioxide layer Under the conditions of=2.0, titration cladding is carried out using titanium tetrachloride；The cladding of the precursor layer of silica can choose in pH Under the conditions of=8.5, coated using sodium metasilicate；These method for coating can find in existing literature with reference to method (for example, The manufacture processing of pearlescent pigment and application-Xu Yang group-Chemical Industry Press).

In a preferred embodiment of the invention, the smooth air layer precursor layer is selected from metal simple-substance, fluorination One of object, sulfide are a variety of.

In a preferred embodiment of the invention, the metal simple-substance is selected from aluminium and/or zinc, in subsequent acid Property under the conditions of carry out wet-chemical cladding during be dissolved remove and be flattened in the core material of final products air layer substitution.

In a preferred embodiment of the invention, the fluoride is selected from magnesium fluoride and/or calcirm-fluoride, subsequent The dissolved air layer for removing and being flattened in the core material of final products replaces during carrying out wet-chemical cladding under acid condition Generation.

In a preferred embodiment of the invention, the sulfide is selected from zinc sulphide, under subsequent acid condition It carries out being dissolved the air layer substitution for removing and being flattened in the core material of final products during wet-chemical cladding.

In a preferred embodiment of the invention, the material of the dielectric layer is selected from SiO₂、MgF₂、Al₂O₃、AlF₃、 Na AlF₆、BaF₂、NdF₃、CaF₂, one of LiF, ZnS, CoS, MnS, FeS and CuS or a variety of.

In a preferred embodiment of the invention, the second external coating precursor layer and remaining clad precursor layer Material layer be selected from through subsequent drying, heating and/or calcining after be capable of forming TiO₂, Fe₂O₃, TiFe₂O₅, Fe₃O₄, BiOCl, Cr₂O₃, ZrO₂, ZnO, SnO₂, CoO, Co₃O₄, VO₂, V₂O₃, iron titanate, Ti₂O₃, pucherite, cobalt aluminate, SiO₂、Al₂O₃、Al (OH)₃、MgF₂、B₂O₃, one of ZnS or a variety of substances.

In a preferred embodiment of the invention, every layer of dielectric layer with a thickness of 50-300nm, every layer of reflecting layer With a thickness of 20-100nm, the overall thickness and single layer thickness deviation of the core material are no more than being averaged for overall thickness and equivalent layer thickness 1% or 5nm of value.

The present invention also provides simultaneously have the pigment of high brightness, high color purity and high covering power effect coating, ink, Purposes in cosmetics, color make-up.

Pigment with high brightness, high color purity and high covering power effect while of the invention can be used in coating, ink, In cosmetics, color make-up, it is particularly suitable for needing while obtaining the high occasion covered with high brightness, dosage exists according to different occasions 0.1-90%.

The present invention also provides the pigment with high brightness in the purposes in coating, ink, cosmetics, color make-up.It is used Amount is according to different occasions in 0.1-90%.

Compared with prior art, the invention has the following advantages:

The oxide skin(coating) of existing individual high refractive index also can produce interference effect, but because thickness spend it is thin, Mechanical light intensity is poor, is easily broken in use and loses pigment value.But for we it is bright for, due to using Core material in the core material precursor or final products of the preparation of PVD method also acts as the effect of substrate support, so that keeping pigment The mechanical stability that pigment is kept while effect, makes product have workable pigment property.

Pigment containing air layer core material of the invention is that cannot obtain using the pigment that PVD method obtains according to the prior art , using mica etc. as the product of substrate because the reason of substrate etc. can not obtain smooth air layer.The present invention By the smooth of PVD substrate, thickness can accurately control a little and handled by subsequent wet chemical and introduce smooth air layer, can To obtain pigment more of high brightness.

Pigment of the invention has the excellent effect of high brightness.

Detailed description of the invention

Fig. 1 be include single layer dielectric layer or reflecting layer composition core material and single layer external coating pigment structural representation Figure.Wherein, 1 core material is indicated, 2 indicate external coating.

Fig. 2 be include three-decker core material and single layer external coating pigment structural schematic diagram.Wherein, 1-1,1-2 Three layers of core material are indicated with 1-3,2 indicate external coating.

Fig. 3 be include three-decker core material and two layers of external coating pigment structural schematic diagram.Wherein, 1-1,1-2 Three layers of core material are indicated with 1-3,1-2 can be dielectric layer or reflecting layer, or air layer, 2-1 and 2-2 indicate two External coating.

Fig. 4 is the electron microscope that embodiment 8 prepares resulting product, wherein 1 indicates air layer, 2 indicate the first external coating, 3 indicate the second external coating.

Specific embodiment

For defect existing for existing pigment, the present inventor passes through in-depth study, to the preparation method of existing pigment It is improved, has obtained pigment a kind of while that there is high brightness, high color purity and high covering power effect.It is complete on this basis At the present invention.

The core material precursor of pigment with high brightness, high color purity and high covering power effect while of the invention is to pass through What PVD method obtained, it can be single layer dielectric layer or reflecting layer, be also possible to multilayer dielectric layer or reflecting layer, be also possible to more Layer dielectric layer and one layer of reflecting layer.For multilayer, odd-level can be, be also possible to even level；These layers can be symmetrically Structure is also possible to asymmetrical structure, preferably has symmetrical structure.For example, core material is multilayer dielectric layer and one layer of reflecting layer When, the number of plies of preferably dielectric layer is odd-level, and more preferable dielectric layer is symmetrical arranged centered on reflecting layer.For example, the layer of core material Number is three layers, and it includes one layer of central core and two layers of boundary layer, central core is usually reflecting layer, and boundary layer is usually dielectric layer.

The material in reflecting layer of the invention can be selected from the metal with high reflectance and low transmission rate, metal oxide, non- One of metal, nonmetal oxide are a variety of.For example, a kind of or its group in aluminium, silver, copper, gold, titanium, tantalum, niobium, chromium, nickel It closes.

The material of dielectric layer of the invention can be selected from metal oxide of the refractive index lower than 1.8, metal fluoride, metal sulphur One of compound, nonmetal oxide, nonmetallic fluoride and nonmetallic sulfide are a variety of.For example, SiO₂、MgF₂、 Al₂O₃、AlF₃、Na AlF₆、BaF₂、NdF3、CaF₂、LiF。

Stainless steel lining bottom that the present invention selects design or glass are as substrate, using physical vapour deposition (PVD) (PVD) (any combination that such as thermal resistance evaporation, electron beam evaporation, one kind of sputtering sedimentation or above-mentioned three kinds of modes can be used) Peelable separation layer is prepared on the bottom liner, then according to design deposition of reflective layer and/or dielectric layer on peelable separation layer (reflecting layer and/or dielectric layer according to design deposition, can be single layer, bilayer, be also possible to multilayer), in the reflecting layer of design And/or after dielectric layer deposition is complete, peelable separation layer is deposited again, to deposit one layer of peelable separation layer and one layer of reflection Layer and/or dielectric layer are a cycle, repeat the period 1-50 time, preferably 5-30 time, to guarantee to vacuumize once installing Under the conditions of, equipment capacity is improved to greatest extent, is reduced equipment power dissipation, is improved production efficiency.And guarantee coat it is opposed flattened, It is fine and close and complete.After completing deposition using the method, multiple peelable separation layers and multiple anti-are formd on the substrate of rigidity Penetrate the periodicity of layer and/or dielectric layer (being also possible to single peelable separation layer and single reflecting layer and/or dielectric layer) composition The rigid substrate for carrying above-mentioned periodical composite construction is carried out demoulding process using specific demoulding solvent by composite construction, can Removing separation layer will be dissolved in remover, and the composition of reflecting layer and/or dielectric layer will strip down more from rigid substrate It can also be separated between the multilayered structure unit that a reflecting layer and/or dielectric layer are formed, then rinsed their collections, Filtering crushes, classification processing, obtains core material precursor.

For the core material precursor of above method preparation, reflecting layer and/or dielectric layer between two peelable separation layers It can be single layer, such as single layer silica, aluminum oxide, calcirm-fluoride, magnesium fluoride, zinc sulphide, be also possible to multilayer, such as have There is boundary layer/middle layer/boundary layer structure, further boundary layer is silica, aluminum oxide, calcirm-fluoride, magnesium fluoride etc., in Interbed is metallic aluminium, titanium, copper, copper, zinc, gold or its codeposit or magnesium fluoride, zinc sulphide etc., for boundary layer and centre Layer requires not to be fluoride and/or sulfide simultaneously.It is also possible to more layers structure, the number of plies can be odd-level, can also To be even level.

For depositing the reflecting layer of specific structure and/or when dielectric layer, when carrying out demoulding technique, different demoulding program energy Different structural core precursors can be obtained.Therefore different processing modes is according to circumstances taken: 1) such as the sedimentary of core material precursor Middle layer is to contain zinc sulfide layer, and when boundary layer is silica or alchlor structure, as using can react with zinc sulphide Using zinc sulphide remove if dilute hydrochloric acid is as remover, then after can removing peelable separation layer and zinc sulphide, then may obtain Obtain smooth single layer silica or three dichloroxide core materials.Such as sulphur cannot be influenced with can remove peelable separation layer When changing the remover processing of zinc layers, then it can get the multilayer knot of alternatively distributed silica or aluminum oxide and zinc sulphide Structure；2) as contained fluoride (such as magnesium fluoride) and the multilayered structure containing silica in the sedimentary of core material precursor；According to It only can remove the remover of peelable separation layer, then can get the multilayered structure containing fluoride；If by above-mentioned processed Sample use acid to be handled again, or when carrying out demoulding processing using peelable separation layer and fluorination can be removed simultaneously The remover of object may then obtain the silicon dioxide layer of surface roughization, and carrying out subsequent cladding with the material can be hidden The good pigment of lid power.The processing mode to form air layer is required supplementation with,

Using the above material of acquisition as core material precursor, subsequent cladding is carried out.The material of external coating can be selected from metal Oxide, metal hydroxides, nonmetal oxide, Non-metal hydroxides, metal suboxides, metal fluoride, metal In oxyhalide, metal chalogenides, metal sulfide, metal nitride, metal oxynitrides and metal carbides It is one or more, and at least one layer of material has rate of penetrating higher than 1.6 in the clad.For example, TiO₂, Fe₂O₃, TiFe₂O₅, Fe₃O₄, BiOCl, Cr₂O₃, ZrO₂, ZnO, SnO₂, CoO, Co₃O₄, VO₂, V₂O₃, iron titanate, Ti₂O₃, pucherite, aluminium Sour cobalt, SiO₂、Al₂O₃、Al(OH)₃、MgF₂、B₂O₃, one of ZnS or a variety of.The subsequent preferred wet chemical method packet of cladding It covers.Cladding each layer can according to the case where different core material precursors and external coating situation respectively organic solvent system and/ Or the pigment that cladding obtains different structure and effect is carried out under aqueous systems.The especially core containing sulfurized layer and/or fluoride The method that the structure of material precursor can be coated according to subsequent wet-chemical is obtained containing sulfurized layer or fluoride or sulfide Or the pigment of structure that fluoride layer is substituted by air layer.For example, the core material precursor containing zinc sulfide layer is in subsequent wet chemical side Hydrochloric acid adjustment system pH to acidic leach, which is added, after method one layer of certain thickness silicon dioxide layer of cladding removes zinc sulphide, Zinc sulfide layer is replaced by air in final product.

Containing metallic aluminium core material precursor subsequent wet chemical method coat one layer of certain thickness silicon dioxide layer after It adds hydrochloric acid and adjusts system pH to acidic leach removing aluminium, replaced in final product aluminium layer by air.

In the case where for the core material precursor such as containing materials such as silica, aluminium dioxides, because using PVD method system Standby material is particularly smooth, and thickness distribution is very concentrated, and uses it as substrate progress outer cladding object and is coated When, the not obtainable effect of general substrate can be obtained.Therefore the pigment bright for we, in order to reach expected specific face Color effect, the requirement to thickness and clad is stringenter than common substrate, also passes through preferred color effects also not It is that general mica etc. has the pigment institute of very wide base material thickness distribution attainable.Such as the present invention uses PVD method system The standby earth silicon material with a thickness of 150nm (thickness deviation is less than 1.5nm), on it single layer cladding titanium dioxide (50nm Left and right) or di-iron trioxide (40nm or so), can be obtained the extraordinary optical color variable pigment of colour saturation, and partial size very Can still have extraordinary excitation purity and color changeable effect in the case where thin.And with dioxy that used by Merck prepared by belt mode The pigment of SiClx substrate preparation is compared, the substrate prepared using PVD method, can have more outstanding flatness and narrower Thickness distribution, more outstanding pigment property can be obtained.It is not in variegated.And for 80nm thickness (thickness deviation Silica substrate 1nm), the di-iron trioxide for coating one layer of 80nm thickness on it can be obtained very pure red, complete It is complete not variegated.

For the core material precursor being made of multilayer reflective layers and/or dielectric layer, can be selected not according to different layer structures Same method for coating obtains the pigment of different-effect.As core material precursor central core be silver when because its have it is very outstanding The property of acid and alkali-resistance is used directly for coating various metals and nonmetallic oxide or hydroxide, and obtaining has well Excitation purity, brightness and covering power pigment.

For using zinc sulphide as the core material precursor of intermediate symmetry layer, such as successively by silica, zinc sulphide and silica The core material precursor of composition, if layer of silicon dioxide layer is coated under alkaline condition first, later by the pH value for the system that adjusts to acid Property, zinc sulphide is removed, coats the metal and/or nonmetal oxide and/or hydrogen of high refractive index under certain conditions later Oxide, the pigment of acquisition is because preparing for core material is smooth, and middle layer becomes air layer in final pigment, further increases Refringence strengthens the effect of pigment, and because of outer layer silicon dioxide layer, maintains the mechanically stable of entire pigment Property.

For using fluoride as the core material precursor of middle layer, coated silica under alkaline condition first adjusts later PH value is removed fluoride to acidity, and because the reason of generating hydrogen fluoride, the internal layer of silica is by slight corruption Erosion, further improves the covering power of powder.The metal of cladding high refractive index or nonmetallic oxidation under certain conditions later Object or hydroxide, obtaining has fine brightness, the very product of high covering power and excitation purity.

For the core material precursor containing aluminium layer, selection coats one layer of certain thickness dioxy first under organic solvent system The protective layer of SiClx, carrying out refractive index again later is more than 1.6 oxide or the cladding of hydroxide, then can get and retain aluminium layer The pigment of structure makes pigment have very high brightness and covering power.

For defect existing for existing pigment, the present inventor has obtained a kind of pigment containing smooth air layer.

The core material with air layer of the pigment of high brightness of the invention be by the core material precursor for preparing PVD again after What the method that continuous processing removes air layer precursor layer obtained.The core material can be the air layer of monolayer formation, be also possible to The combination of few one layer of smooth air and at least one layer of dielectric layer and/or at least one layer of reflecting layer.

The material in reflecting layer of the invention can be selected from the metal with high reflectance and low transmission rate, metal oxide, non- One of metal, nonmetal oxide are a variety of.For example, one kind or combinations thereof in silver, copper, gold, titanium, tantalum, niobium, chromium, nickel.

The material of dielectric layer of the invention can be selected from metal oxide of the refractive index lower than 1.8, metal fluoride, metal sulphur One of compound, nonmetal oxide, nonmetallic fluoride and nonmetallic sulfide are a variety of.For example, SiO₂、MgF₂、 Al₂O₃、AlF₃、Na AlF₆、BaF₂、NdF3、CaF₃、LiF。

Stainless steel lining bottom that the present invention selects design or glass are as substrate, using physical vapour deposition (PVD) (PVD) (any combination that such as thermal resistance evaporation, electron beam evaporation, one kind of sputtering sedimentation or above-mentioned three kinds of modes can be used) Peelable separation layer is prepared on the bottom liner, before then depositing one layer of smooth air layer according to design on peelable separation layer Body layer, or at least one layer of smooth air layer precursor layer and at least one layer of reflecting layer and/or at least one layer of anti-dielectric layer, one The smooth air layer precursor layer of layer, or at least one layer of smooth air layer precursor layer and at least one layer of reflecting layer and/or at least After the combined deposition of one dielectric layer is complete, peelable separation layer is deposited again, in this way, to deposit one layer of peelable separation layer With one layer of smooth air layer precursor layer, or at least one layer of smooth air layer precursor layer and at least one layer of reflecting layer and/or The group of at least one layer of dielectric layer is combined into a cycle, and repeatedly the period 1-50 times, preferably 5-30 times, to guarantee to take out in primary installation Under conditions of vacuum, equipment capacity is improved to greatest extent, equipment power dissipation is reduced, improves production efficiency.And guarantee the phase of coat To smooth, fine and close and complete.Using the method complete deposition after, rigidity substrate on form multiple peelable separation layers and The combination of multiple smooth air layer precursor layers or smooth air layer precursor layer and reflecting layer and/or dielectric layer (can also be with It is single peelable separation layer and single smooth air layer precursor layer, or single at least one layer of smooth air layer precursor layer With the combination of at least one layer of reflecting layer and/or at least one layer of dielectric layer) the periodical composite construction of composition, the above-mentioned period will be carried Property composite construction rigid substrate carry out demoulding process using specific demoulding solvent, peelable separation layer will be dissolved in remover In, will stripping down from rigid substrate for above-mentioned periodicity composite construction can also be sent out between each core material precursor layer unit It is estranged from, then they are collected rinsed, filtered, crushed, classification is handled, obtain core material precursor.

It, can be in organic solvent condition for the core material precursor for being smooth air layer precursor layer including metallic aluminum It is lower first to coat one layer of hydrated SiO 2 layer (the first external coating precursor layer), it is molten to acidity to add hydrochloric acid adjustment system pH Solution removes aluminium layer, is replaced in final product aluminium layer by smooth air layer.Coat high refractive index under certain conditions later Metal and/or nonmetal oxide and/or hydroxide, the pigment of acquisition is because preparing for core material is smooth, in final face Air layer precursor becomes smooth air layer in material, further increases refringence, strengthens the effect of pigment, and because Outer layer silicon dioxide layer maintains the mechanical stability of entire pigment.

It, can be in organic solvent condition for the core material precursor for being smooth air layer precursor layer including metallic aluminum It is lower first to coat layer of silicon dioxide layer (the first external coating precursor layer), powder is filtered, washed and/or dried later and/or It disperses dissolution in hydrochloric acid solution again by powder after calcining and removes aluminium layer, is taken in final product aluminium layer by smooth air layer Generation.Coat the metal and/or nonmetal oxide and/or hydroxide of high refractive index under certain conditions later, acquisition For pigment because preparing for core material is smooth, air layer precursor becomes smooth air layer in final pigment, further increases Refringence strengthens the effect of pigment, and because of outer layer silicon dioxide layer, maintains the mechanical stability of entire pigment.

For include zinc sulfide layer be smooth air layer precursor layer core material precursor for, such as successively by silica, For the core material precursor of zinc sulphide and silica composition, layer of silicon dioxide layer can be first coated under alkaline condition, later will The pH value of adjustment system removes zinc sulphide to acidity, coats the metal of high refractive index and/or non-under certain conditions later Metal oxide and/or hydroxide, the pigment of acquisition is because core material prepares smooth, the above-mentioned middle layer in final pigment Become smooth air layer, further increase refringence, strengthens the effect of pigment, and because outer layer silica Layer, maintains the mechanical stability of entire pigment.

For include zinc sulfide layer be smooth air layer precursor layer core material precursor for, such as successively by silica, For the core material precursor of zinc sulphide and silica composition, layer of silicon dioxide layer can be first coated under alkaline condition, later will Powder disperses powder in after being filtered, washed and/or dry and/or calcining dissolution in hydrochloric acid solution again and removes zinc sulfide layer, Coat the metal and/or nonmetal oxide and/or hydroxide of high refractive index, the pigment of acquisition under certain conditions later Because preparing for core material is smooth, above-mentioned middle layer becomes smooth air layer in final pigment, further increases refraction Rate is poor, strengthens the effect of pigment, and because of outer layer silicon dioxide layer, maintains the mechanical stability of entire pigment.

For include zinc sulfide layer be smooth air layer precursor layer core material precursor for, such as successively by silica, For the core material precursor of zinc sulphide and silica composition, layer of silicon dioxide layer can be first coated under the conditions of organic solvent, it Afterwards by the pH value for the system that adjusts to acidity, zinc sulphide is removed, later under certain conditions coat high refractive index metal and/ Or nonmetal oxide and/or hydroxide, the pigment of acquisition is because preparing for core material is smooth, in final pigment among the above Interbed becomes smooth air layer, further increases refringence, strengthens the effect of pigment, and because outer layer titanium dioxide Silicon layer maintains the mechanical stability of entire pigment.

For include zinc sulfide layer be smooth air layer precursor layer core material precursor for, such as successively by silica, For the core material precursor of zinc sulphide and silica composition, layer of silicon dioxide layer can be first coated under the conditions of organic solvent, it It disperses dissolution in hydrochloric acid solution again by powder after powder is filtered, washed and/or is dried and/or calcined afterwards and removes zinc sulphide Layer coats the metal and/or nonmetal oxide and/or hydroxide of high refractive index under certain conditions later, acquisition For pigment because preparing for core material is smooth, above-mentioned middle layer becomes smooth air layer in final pigment, further increases Refringence strengthens the effect of pigment, and because of outer layer silicon dioxide layer, maintains the mechanical stability of entire pigment.

It, can first under alkaline condition for the core material precursor for being smooth air layer precursor layer including fluoride layer Coated silica, adjusting pH value later is removed fluoride to acidity, and because the reason of generating hydrogen fluoride, dioxy The internal layer of SiClx further improves the covering power of powder by slight corrosion.The high refraction of cladding under certain conditions later The metal or nonmetal oxide or hydroxide of rate, obtaining has fine brightness, the very product of high covering power and excitation purity.

It, can first under alkaline condition for the core material precursor for being smooth air layer precursor layer including fluoride layer Coated silica disperses hydrochloric acid solution for powder after powder is filtered, washed and/or is dried and/or calcined later again Middle dissolution removes fluoride layer, and because the reason of generating hydrogen fluoride, the internal layer of silica is by slight corrosion, further Improve the covering power of powder.Coat the metal or nonmetal oxide or hydroxide of high refractive index under certain conditions later Object, obtaining has fine brightness, the very product of high covering power and excitation purity.

It, can be first in organic solvent item for the core material precursor for being smooth air layer precursor layer including fluoride layer Coated silica under part, adjusting pH value later is removed fluoride to acidity, and because of the reason of generating hydrogen fluoride, The internal layer of silica further improves the covering power of powder by slight corrosion.Cladding is high under certain conditions later The metal or nonmetal oxide or hydroxide of refractive index, obtaining has fine brightness, very high covering power and excitation purity Product.

It, can be first in organic solvent item for the core material precursor for being smooth air layer precursor layer including fluoride layer Coated silica under part disperses hydrochloric acid for powder after powder is filtered, washed and/or is dried and/or calcined later again Dissolution removes fluoride layer in solution, and because of the reason of generating hydrogen fluoride, the internal layer of silica by slight corrosion, into One step improves the covering power of powder.Coat the metal or nonmetal oxide or hydrogen of high refractive index under certain conditions later Oxide, obtaining has fine brightness, the very product of high covering power and excitation purity.

For the cladding of wet-chemical in the present invention, can be carried out using typically now existing process conditions.According to specific Situation directly can carry out next layer of cladding by regularization condition after one layer of cladding terminates, can also first will be at feed liquid Investment reaction kettle is coated again again after reason, washing, filtration treatment.

In a preferred embodiment, core material precursor obtains after the coated silica under organic solvent system With acid proof substrate, mill base coloring treatment is reused later, obtains the pigment of coloring.

Thickness for core material obtained as substrate illustrates: for the common mica powder or glass obtained by grinding For glass powder, there is wider particle diameter distribution and thickness distribution, because its thickness is a wider distribution, base material thickness pair The synthesis result of the influence of color is that excitation purity is poor but be not in apparent variegated, therefore causes the reason of thickness distribution Mica base material thickness is unobvious on the influence of the interference colours of final products, and color is mainly by the refractive index and packet of the clad on substrate The thickness of coating determines.For the core material precursor for using PVD method of the present invention to obtain, because its surface is very smooth, Therefore after carrying out wet chemical method deposition coating on it, core material can be represented the reflection of light and refraction action.Cause If this thickness distribution is uneven, the color that will cause the substrate generation of different-thickness has different interference colours, causes " variegated " Phenomenon, this can than because mica thickness it is different caused by it is variegated serious more；Therefore it is obtained for of the invention by PVD method Core material precursor, the distribution of thickness is generally narrower than glass etc., but because the core material precursor flatness is very high, at this time Because the difference of thickness cause the difference of the color of whole powder performance will clearly, for core of the invention Material precursor, the requirement to the thickness of its overall thickness and each layer is very high, generally require its deviation be no more than its thickness 1% or 5nm, this is also the range that PVD method can control, and guarantees that the color effects of the pigment obtained are not in miscellaneous in the range Color, especially in the angle faced.

" peelable separation layer " herein refers to the sedimentary that can use remover removing in subsequent processes, Cause bottom liner core material precursor layer to be detached from after removing, and is used to form 1-20 layer dielectric layer, 1-20 layers of reflecting layer or the 2- of core material The multilayered structure of 19 layers of dielectric layer and one layer of reflecting layer composition, or be used to form one layer of 1-6 layer of core material precursor layer it is smooth Air layer, or the combination at least one layer of smooth air layer and at least one layer of dielectric layer and/or at least one layer of reflecting layer Multilayered structure is mutually disengaged, to form free core material precursor.Peelable separation layer is selected generally from that organic solvent is solvable or water Soluble coating, for example, soluble polymer such as acrylic resin or sodium chloride, corresponding remover is that can dissolve having for its Solvent, such as acetone or acetone soln or deionized water etc..It, can also be by conduct when for sulfide as dielectric layer material Peelable separation layer, the acid that can dissolve the sulfide can be used as remover use.For example, zinc sulphide in the present invention It can be used as peelable separation layer, using hydrochloric acid as remover.It, can also be by conduct when for fluoride as dielectric layer material Peelable separation layer, the acid that can dissolve the fluoride can be used as remover use.For example, magnesium zinc in the present invention It can be used as peelable separation layer, using hydrochloric acid as remover.

In the present invention, " core material precursor " is the precursor of the core material of final pigment.The pigment of this law is first using physical vapor Deposition (PVD) method prepares core material precursor, then carries out the external coating that wet-chemical cladding obtains.It is coated in later wet-chemical Certain dielectric layers or reflecting layer in condition in core material precursor may be removed, it is also possible to be removed without layer, therefore core The structure of material may be not identical as core material precursor, it is also possible to identical.It is further preferred that coating treatment process core in later wet-chemical Air layer precursor in material precursor is removed to form air layer, therefore the structure of core material and core material precursor be not identical.

Herein " air precursor layer " refer to it is subsequent under the conditions of can be dissolved removing and form smooth air layer Layer of material.For example, aluminium layer dissolves in subsequent hydrochloric acid or sulfuric acid solution and forms smooth air layer；Magnesium fluoride layer or fluorine Change calcium layer to dissolve in subsequent hydrochloric acid or sulfuric acid solution and form smooth air layer.

" the first external coating precursor layer " refers to herein forms in final products after drying, heating and/or calcining The first external coating material, which coated before smooth air layer precursor layer is removed 's.It herein means the hydrate of the corresponding coating formed in wet-chemical cladding, the hydrate of coating can generally pass through height Temperature calcining obtains corresponding coating.For example, when the first external coating is silica, the first external coating precursor layer can be with It is core material precursor to be put into the ethanol solution of ethyl orthosilicate, and the mixed solution of 2g water and ammonium hydroxide is added in the solution (NH₃Concentration 10%) under conditions of one layer of hydrated SiO 2 layer coating.

" the second external coating precursor layer " is that air layer precursor layer is wrapped after being removed in core material precursor herein The layer covered refers to the second external coating material formed in final products after drying, heating and/or calcining.It herein means wet The hydrate of the corresponding coating formed in chemistry cladding, the hydrate of coating can generally be obtained corresponding by high-temperature calcination Coating.For example, the second external coating precursor layer is to be put into core material precursor when the second external coating is di-iron trioxide One layer of aqua oxidation iron layer of formation is coated in the aqueous solution of iron chloride under the conditions of pH=3.

" remaining external coating precursor layer " refers to herein forms in final products after drying, heating and/or calcining Remaining external coating material.

In the present invention, the metal of high reflectance is nonmetallic or two or more of oxides refer to that reflectivity is higher than 50% Metal is nonmetallic or two or more of oxides.

In the present invention, " metal suboxide " refers to oxide of the metal state lower than the highest valence state state of the metal.

This method is combined using PVD method and wet process surrounding phase, and the pigment with smooth air layer core material of preparation has High brightness advantage, the effect pigment cost than the preparation of pure PVD method can be lower, and can obtain simple PVD method not Obtainable pigment structure, and pigment is handled by complete outer cladding, there is no be easy to react destroy pigment property and The section of color effects, more stable, use scope is wider；And the wet process surrounding phase ratio with use common substrate, because having More smooth, particularly narrower thickness distribution substrate can obtain better color effects.

Present invention will be further explained below with reference to specific examples.Specific embodiment is to be with technical solution of the present invention Under the premise of implemented, give detailed embodiment and operating process.It should be understood that these embodiments are merely to illustrate this It invents rather than limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal Rule condition carries out.Unless otherwise indicated, percentage and number be by weight.

Embodiment 1

The core material of the pigment of the present embodiment is single layer silica, and external coating is titanium dioxide.

The zinc sulphide for first being deposited one layer of about 10nm or so on bottom liner glass plate using vacuum sputtering technique, is and then deposited Silica, until reaching 170nm, the zinc sulphide of redeposited 10nm or so then proceedes to deposition silica 1 70nm, repeatedly Above procedure is repeated, is repeated 10 times circulation, overall thickness reaches 2um or so.The material is immersed into hydrochloric acid (concentration 35%) later Middle about 30 minutes, zinc sulphide is removed, acquisition surface smoothness is high, and thickness is washed in the titanium dioxide silicon wafer of 170nm by subsequent It washs, be classified processing and obtain the core material precursor that particle diameter distribution is 20-100um, as subsequent cladding substrate, with a thickness of 170 ± 2nm。

Then it disperses core material precursor 40g in 1L water, is heated to 78 DEG C, later extremely with dilute hydrochloric acid adjustment system pH 2.0 or so, it is added dropwise to titanium tetrachloride aqueous solution (concentration 2mol/L), while sodium hydroxide solution is added with the pH of maintenance system Stabilization, stop charging when coating thickness reaches about 50nm, and system pH is slowly raised 6.0 or so, later mistake Filter, 100 DEG C of dryings obtain the pigment with golden red color changeable effect after 500 DEG C of calcinings, have very excellent brightness.With it is present The chameleon pigment ratio obtained using grinding mica substrate, excitation purity is higher, and there are few variegated, the more obvious face of color changeable effect Material.

Core material precursor is consistent with the core material structure after cladding external coating in the pigment.

Embodiment 2

The core material of the pigment of the present embodiment is single layer silica, the mixing of external coating titanium dioxide and di-iron trioxide Clad.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on substrate glasses plate using vacuum sputtering technique, And then silica is deposited, until reaching 80nm, organic peelable separation layer of redeposited 10nm or so then proceedes to deposit Silica 80nm, is iteratively repeated above procedure, is repeated 20 times circulation, and overall thickness reaches 2um or so.The material is immersed later In remover, peelable separation layer being removed, obtaining that surface smoothness is high, for thickness in the titanium dioxide silicon wafer of 80nm, process is subsequent Washing, classification processing obtain the substrate that coats as subsequent wet chemical of core material precursor that particle diameter distribution is 10-60um, thickness For 80 ± 4nm.

Then it disperses substrate 40g in 1L water, is heated to 78 DEG C, with hydrochloric acid adjustment system pH to 3.0 or so, add Enter 0.7mol/L iron chloride and the titanium tetrachloride mixed solution of 2.2mol/L, while ammonium hydroxide is added with the steady of the pH of maintenance system Fixed, coating thickness stops charging when reaching 80nm, and system pH is slowly raised 6.0 or so, filters later.110℃ It is dry, the pigment with gold effect is obtained after 800 DEG C of calcinings, there is very excellent brightness.It is produced with coating process is used The substrate of silica is compared, and has purer form and aspect, not variegated.

Embodiment 3

The core material of the pigment of the present embodiment is single layer aluminum oxide, and external coating is di-iron trioxide.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on bottom liner glass plate using vacuum sputtering technique, And then aluminum oxide is deposited, until reaching 100nm, the peelable separation layer of redeposited 10nm or so then proceedes to deposit Aluminum oxide 100nm, is iteratively repeated above procedure, is repeated 20 times circulation, and overall thickness reaches 2um or so.Later by the material Immerse in organic remover, remove peelable separation layer, obtain that surface smoothness is high, thickness 100nm aluminum oxide, The core material precursor that particle diameter distribution is 40-80um is obtained by subsequent washing, classification processing, the base as subsequent wet chemical cladding Material, with a thickness of 100 ± 1.5nm.

Then it disperses substrate 40g in 1L water, is heated to 78 DEG C, with hydrochloric acid adjustment system pH to 3.0 or so, add Enter 1.0mol/L ferric chloride in aqueous solution, while ammonium hydroxide is added with the stabilization of the pH of maintenance system, when coating thickness reaches 100nm Stop charging, and system pH is slowly raised 6.0 or so, filter later, 110 DEG C of dryings, is had after 500 DEG C of calcinings The pigment of red effect has very excellent brightness.Compared with the pigment for using molten-salt growth method to prepare alchlor substrate, because The substrate has very consistent thickness, and very even curface, excitation purity, brightness is all more superior.

Embodiment 4

The core material of the pigment of the present embodiment be two layers of silicon dioxide layer and the air layer between two layers of silicon dioxide layer, External coating is silica and di-iron trioxide.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on bottom liner glass plate using vacuum sputtering technique, And then the silicon dioxide layer of 40nm is deposited, redeposited 20nm zinc sulphide then proceedes to deposition 40nm silicon dioxide layer, Zhi Houchen Organic peelable separation layer of product 10nm, then it is iteratively repeated above procedure, it is repeated 20 times circulation, overall thickness reaches 2um or so.It The material is immersed in organic remover afterwards, removes peelable separation layer, acquisition surface smoothness is high, and thickness is respectively 40/ The silica of 20/40nm thickness/three layers of zinc sulphide/silica substrate obtains partial size by subsequent washing, classification processing It is distributed as the core material precursor of 10-40um, as the substrate of subsequent wet chemical cladding, with a thickness of 100nm ± 2nm.

Then it disperses substrate 40g in 1L water, is heated to 78 DEG C, sodium hydroxide solution adjusts system pH to 8.5 Left and right, is added the sodium silicate aqueous solution of 1mol/L, while dilute hydrochloric acid is added with the stabilization of the pH of maintenance system, coating thickness reaches Stop charging when to about 40nm, and system pH is slowly decreased to 1.0 or so, and raise the temperature to 90 DEG C, sufficiently stirs Reaction is mixed so that zinc sulphide reacts completely, is filtered later, sufficiently washs, then powder is put into reactor again, is scattered in In 1L water, 78 DEG C are heated to, under being 3.0 with hydrochloric acid adjustment pH, the ferric chloride solution of 1mol/L is added, and by the way that hydroxide is added The pH value of sodium maintenance system.Cladding thickness can obtain the higher golden pigment of excitation purity after 80nm, 100 DEG C of dryings.Because There are voided layer, the excitation purity Gao Genggao of color among the pigment.Core material precursor and the face for having coated external coating in the pigment Core material structure in material is different, because the zinc sulfide layer in core material precursor is coating during the wet-chemical of pigment cladding It is removed after relatively thin layer of silicon dioxide layer by the way that hydrochloric acid is added, the layer is substituted by air in final pigment.

Embodiment 5

The core material of the pigment of the present embodiment be two layers of silicon dioxide layer and the silver layer between two layers of silicon dioxide layer, outside Clad is titanium dioxide.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on bottom liner glass plate using vacuum sputtering technique, And then silica is deposited, until reaching 60nm or so, redeposited 20nm silver then proceedes to deposition silica 60nm, it The separation layer of 10nm is deposited afterwards, then is iteratively repeated above procedure, is repeated 20 times circulation, overall thickness reaches 2um or so.Later should Material immerses in organic remover, removes peelable separation layer, acquisition surface smoothness is high, and thickness is respectively 60/20/60nm Three layers of substrate of silica/silver/silicon dioxide of thickness, obtaining particle diameter distribution by subsequent washing, classification processing is 10- The core material precursor of 40um, as the substrate of subsequent wet chemical cladding, with a thickness of 100nm ± 4nm.

Then it disperses above-mentioned substrate 40g in 1L water, is heated to 78 DEG C, adjust system pH to 2.0 left sides with dilute hydrochloric acid The right side, is added the titanium tetrachloride aqueous solution of 2mol/L, while sodium hydroxide is added with the stabilization of the pH of maintenance system, coating thickness Stop charging when reaching about 10nm, and system pH is slowly decreased to 6.0 or so, filter later, sufficiently washs, 100 DEG C The pigment with high brightness is obtained after drying.

Embodiment 6

The core material of the pigment of the present embodiment be two layers of silicon dioxide layer and the aluminium layer between two layers of silicon dioxide layer, outside Clad is silica and di-iron trioxide.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on bottom liner glass plate using vacuum sputtering technique, And then silica is deposited, until reaching 60nm, redeposited 20nm aluminium then proceedes to deposition silica 60nm, Zhi Houchen Organic peelable separation layer of product 10nm, then it is iteratively repeated above procedure, it is repeated 20 times circulation, overall thickness reaches 2um or so, it The material is immersed in remover afterwards, removes peelable separation layer, acquisition surface smoothness is high, and thickness is respectively 60/20/ The silica of 60nm thickness/three layers of aluminium/silica substrate, obtaining particle diameter distribution by subsequent washing, classification processing is The core material precursor of 10-50um, as the substrate of subsequent wet chemical cladding, with a thickness of 140nm ± 2nm.

Then it disperses substrate 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl alcohol of the ethyl orthosilicate of 1mol/L is added Solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 10%), the coating thickness on above-mentioned substrate reaches about The silica of 60nm, is filtered, washed later, and powder is dispersed in water again, is heated to 70 DEG C, and system pH is used Hydrochloric acid is adjusted to 3.0 or so, the aqueous solution of the iron chloride of 1mol/L is added, and use the pH value of 30% ammonium hydroxide maintenance system, packet It covers after iron oxide thickness reaches 50nm, filtering is sufficiently washed, 100 DEG C of dryings, and obtaining after 400 DEG C of calcinings has very good covering The golden powder of power.

Core material precursor is identical as the core material structure after cladding external coating in the pigment.

Embodiment 7

The core material of the pigment of the present embodiment is successively by silica, zinc sulphide, silica, zinc sulphide, silica structure At external coating is silica and aluminium hydroxide and carbon black.

Organic peelable separation layer of one layer of about 10nm or so is first deposited on bottom liner glass plate using vacuum sputtering technique, And then 100nm silica is deposited, redeposited 20nm zinc sulphide then proceedes to deposition silica 1 00nm silica, it The zinc sulphide of 20nm thickness, redeposited silica 1 00nm are deposited afterwards；Organic strippable separation layer redeposited later, then repeatedly Above procedure is repeated, is repeated 7 times circulation, overall thickness reaches 2um or so.The material is immersed in organic remover later, is removed Peelable separation layer, obtain surface smoothness it is high, thickness be respectively 100/20/100/20/100nm thickness silica/ Zinc sulphide/silica/five layers of zinc sulphide/silica substrate, obtaining particle diameter distribution by subsequent washing, classification processing is The core material precursor of 10-100um, as the substrate of subsequent wet chemical deposition, with a thickness of 340nm ± 4nm.

Then it disperses core material precursor 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl orthosilicate of 1.5mol/L is added Ethanol solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 15%), reach in the coating thickness of above-mentioned core material The silica of about 70nm, is filtered, washed later, is dispersed in water again later and by powder, is heated to 40 DEG C, and by body It is that pH value is adjusted to 6.5 or so, 1mol/L aluminum chloride aqueous solution is added, is added later carbon black color paste (including 1g carbon black), filtering, Sufficiently washing obtains the powder of carbon black coloring after 100 DEG C of dryings.

The measurement method of following example 8-10 and the glossiness of the product of comparative example 9-1 and 9-2 preparation is as follows: light The measurement of damp degree (brightness): weighing 0.2g powder, and 2g polyurethane resin is added, and is uniformly mixed in after slurry, in black and white paper jam On scratched using the wet film maker of 100um, later by wet coating after 100 DEG C of baking ovens dry 1min, taking-up will be put after swipe It is placed in drying box after 1h, usesBGD 519HAZE GLOSSMETER (vancometer) measures 60 degree of lower gloss: 6 points of grab sample, results are averaged.

Embodiment 8

The core material of the pigment of the present embodiment is single-layer air layer, and external coating is silica and titanium dioxide layer.

The sodium chloride separation layer for first being deposited one layer of 50nm on bottom liner glass plate using vacuum sputtering technique, is and then deposited 20nm simple substance aluminium layer, (to deposit 50nm sodium chloride separation layer, then proceeding to deposition 20nm simple substance aluminium layer is a circulation), repeats The above circulation 14 times, overall thickness reaches 1um or so.The material is immersed in deionized water about 30 minutes later, by the above multilayer Sedimentary is removed from bottom liner glass plate, and further removes the separation layer between aluminium layer, and acquisition surface smoothness is high, and thickness exists The aluminum membranous layer of 20nm obtains the aluminium flake that size distribution is 5-25 by subsequent washing, classification processing, as subsequent cladding core Material precursor.

Then it disperses substrate 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl alcohol of the ethyl orthosilicate of 1mol/L is added Solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 10%), the coating thickness on above-mentioned substrate reaches 60nm Hydrated SiO 2 (the first external coating precursor layer) after, be filtered, washed, and disperse powder in again 5% hydrochloric acid it is molten In liquid, 70 DEG C are heated to, is stirred to react 1h, filtering later, sufficiently washing, dry, the material that acquisition aluminium layer is replaced by air layer (material comprising core material air layer and the first external coating precursor layer).

Above-mentioned powder body material is dispersed in water again later, regulation system temperature adjusts system pH=3, add to 78 DEG C Enter the aqueous solution of the iron chloride of 1mol/L, and using the pH value of 30% ammonium hydroxide maintenance system, coated iron oxide thickness reaches 60nm Afterwards, it filters, sufficiently washs, 100 DEG C of dryings, gold interference powder is obtained after 400 DEG C of calcinings.

The electromicroscopic photograph of the section of its pigment is shown in attached drawing 4, it is seen that powder includes inner air layer and the first external coating Silicon dioxide layer, the second external coating hematite layer.

Swipe is prepared according to preceding method, measuring its swipe brightness is 54.

Embodiment 9

The core material of the pigment of the present embodiment is with air layer/silica/air layer three-decker, the first outer cladding Layer is silica, and the second external coating is the mixing clad of titanium dioxide and di-iron trioxide.

The peelable separation layer of sodium chloride of one layer of 50nm or so is first deposited on substrate glasses plate using vacuum sputtering technique, And then the aluminium layer for depositing 30nm, deposits 80nm silica, the aluminium layer of redeposited 30nm later；The chlorine of redeposition 50nm later Change the peelable separation layer of sodium, (to deposit the peelable separation layer of sodium chloride of one layer of 50nm or so, and then deposits the aluminium of 30nm Layer, deposits 80nm silica later, and the aluminium layer of redeposited 30nm is a circulation)；Repeat the above circulation 10 times, overall thickness reaches Arrive 2um or so.The material is immersed in the agent of deionized water mould later, removes peelable separation layer, acquisition surface smoothness is high, With 30nm aluminium layer/80nm silicon dioxide layer/30nm aluminium layer three-decker piece, handled by subsequent washing, classification Obtain the substrate that the core material precursor that size distribution is 10-60um is coated as subsequent wet chemical.

Then it disperses substrate 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl alcohol of the ethyl orthosilicate of 1mol/L is added Solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 10%), the coating thickness on above-mentioned substrate reaches 40nm Hydrated SiO 2 (precursor layer of the first external coating silicon dioxide layer), be filtered, washed later, and powder is dispersed again In 5% aqueous hydrochloric acid solution, 70 DEG C are heated to, stirring 30min removes aluminium layer therein, and filtering later sufficiently washs, is dry It is dry, obtain aluminium layer by air layer replace with air layer/silica/air layer core material structure and being coated with the first outsourcing The material of coating precursor layer hydrated SiO 2；

Then it disperses the above-mentioned material comprising air layer in 1L water, is heated to 78 DEG C, adjust system pH with hydrochloric acid To 2.6 or so the titanium tetrachloride mixed solution of 0.7mol/L iron chloride and 2.2mol/L is added, while ammonium hydroxide is added to maintain in value The stabilization of the pH of system, coating thickness stops charging when reaching 30nm, and system pH is slowly raised 6.0 or so, it After filter.110 DEG C of dryings obtain the pigment with color changeable effect after 600 DEG C of calcinings.

Comparative example 9-1

The core material of the pigment of the present embodiment is with silicon dioxide layer, and the first external coating is silica, the second outsourcing Coating is the mixing clad of titanium dioxide and di-iron trioxide.

The peelable separation layer of sodium chloride of one layer of 50nm or so is first deposited on substrate glasses plate using vacuum sputtering technique, And then the silica of 140nm is deposited；The peelable separation layer of sodium chloride of redeposition 50nm or so later, (with one layer of deposition The organic peelable separation layer of the sodium chloride of 50nm or so, the silica for and then depositing 140nm is a circulation)；Repeat with Upper circulation 10 times, overall thickness reaches 2um or so.The material is immersed in deionized water remover later, removes peelable isolation Layer, acquisition surface smoothness is high, the titanium dioxide silicon wafer with 140nm, by subsequent washing, classification processing acquisition granularity point Cloth is the substrate that the core material precursor of 10-60um is coated as subsequent wet chemical.

Then it disperses substrate 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl alcohol of the ethyl orthosilicate of 1mol/L is added Solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 10%), the coating thickness on above-mentioned substrate reaches 40nm Hydrated SiO 2, be filtered, washed, dry later, obtain hydrated SiO 2 cladding titanium dioxide silicon wafer；

Then it disperses the above material in 1L water, is heated to 78 DEG C, with hydrochloric acid adjustment system pH to 2.6 or so, add Enter 0.7mol/L iron chloride and the titanium tetrachloride mixed solution of 2.2mol/L, while ammonium hydroxide is added with the steady of the pH of maintenance system Fixed, coating thickness stops charging when reaching 30nm, and system pH is slowly raised 6.0 or so, filters later.110℃ It is dry, the pigment with color changeable effect is obtained after 600 DEG C of calcinings.

Comparative example 9-2

The core material of the pigment of the present embodiment is with silicon dioxide layer, and clad is the mixed of titanium dioxide and di-iron trioxide Close clad.

The peelable separation layer of sodium chloride of one layer of 50nm or so is first deposited on substrate glasses plate using vacuum sputtering technique, And then the silica of 220nm is deposited；The peelable separation layer of sodium chloride of redeposition 50nm or so later, (with one layer of deposition The organic peelable separation layer of the sodium chloride of 50nm or so, the silica for and then depositing 220nm is a circulation)；Repeat with Upper circulation 7 times, overall thickness reaches 2um or so.The material is immersed in deionized water remover later, removes peelable isolation Layer, acquisition surface smoothness is high, the titanium dioxide silicon wafer with 220nm, by subsequent washing, classification processing acquisition granularity point The core material precursor that cloth is 10-60um is coated for subsequent wet chemical.

Then it disperses substrate 40g in 1L water, is heated to 78 DEG C, with hydrochloric acid adjustment system pH to 2.6 or so, add Enter 0.7mol/L iron chloride and the titanium tetrachloride mixed solution of 2.2mol/L, while ammonium hydroxide is added with the steady of the pH of maintenance system Fixed, coating thickness stops charging when reaching 80nm, and system pH is slowly raised 6.0 or so, filters later.110℃ It is dry, the pigment with color changeable effect is obtained after 600 DEG C of calcinings.

By powder made above according to preceding method swipe, measure swipe brightness (glossiness), the results showed that, embodiment The swipe brightness of the powder of 2 example is 68, and the swipe brightness of the powder of comparative example 9-1 is 59, comparative example 9-2 Powder swipe brightness be 60.

For result above, because the powder whole silica sections of comparative example 9-2 are prepared by PVD process , the silicon dioxide layer 140nm in comparative example 9-1 is prepared by PVD process, and the first clad silica is by Hydrolyze method Cladding, causes surfacing degree slightly worse compared with comparative example 9-2, but difference is little.And comparative example 9-1 and 9-2 Air layer is all not present in core material structure；The brightness for being corresponding in turn to swipe is lower, but difference is little again；And for implementing 9, Core material is 30nm air layer/80nm silicon dioxide layer/30nm air layer, overall thickness 140nm, in addition the first clad dioxy SiClx is prepared by Hydrolyze method.Because of the presence of air layer, causes brightness and improve a lot compared with comparative example 9-1 and 9-2.

Embodiment 10

The core material of the pigment of the present embodiment is with silica/air layer/silica three-decker, external coating For silica and coated by titanium dioxide layer.

The peelable isolation of sodium chloride of one layer of about 50nm or so is first deposited on substrate glasses plate using vacuum sputtering technique And then layer deposits the silica of 50nm, deposit the aluminium layer after 30nm later, deposit 50nm silica later；Later again The peelable separation layer of sodium chloride for depositing 50nm or so repeats the above deposition process and coats repeatedly to be repeated 15 times circulation later, always Thickness reaches 2um or so.The material is immersed in deionized water remover later, removes the peelable separation layer of sodium chloride, is obtained Surface smoothness is high, has the layer structure of thickness 50nm/30nm/50nm with silicon dioxide layer/aluminium layer/silicon dioxide layer Piece, by it is subsequent washing, classification processing obtain size distribution be 10-100um core material precursor as subsequent wet chemical packet The substrate covered.

Then it disperses substrate 40g in 1L ethyl alcohol, is heated to 40 DEG C, the ethyl alcohol of the ethyl orthosilicate of 1mol/L is added Solution, and the mixed solution (NH of 2g water and ammonium hydroxide is added₃Concentration 10%), the coating thickness on above-mentioned substrate reaches about The hydrated SiO 2 (the first external coating precursor layer) of 30nm, is filtered, washed, and disperse 5% again for powder later In aqueous hydrochloric acid solution, 70 DEG C, stirring 30min are heated to, filtering later, sufficiently washing, drying, what acquisition aluminium layer was replaced has Silica/air layer/silica and the material for being coated with the first external coating precursor layer hydrated SiO 2；

Then it disperses the above material in 1L water, is heated to 78 DEG C, with hydrochloric acid adjustment system pH to 2.0 or so, add Enter the titanium tetrachloride solution of 2.2mol/L, while sodium hydroxide is added with the stabilization of the pH of maintenance system, coating thickness reaches Stop charging when 40nm, and system pH is slowly raised 6.0 or so, filters later.110 DEG C of dryings obtain after 800 DEG C of calcinings There must be the pigment of golden red color changeable effect, there is very excellent brightness.

By powder made above according to preceding method swipe, measure swipe brightness (glossiness), the results showed that, the powder Swipe brightness be 76.

The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims

1. a kind of pigment of high brightness, the pigment include core material and external coating, which is characterized in that

The core material is 1-6 layers of structure, including one layer of smooth air layer, or at least one layer of smooth air layer and at least one The combination in layer dielectric layer and/or at least one layer of reflecting layer；

The overall thickness of the core material is 20-1000nm,

The thickness in monolayer of the dielectric layer is, the thickness in monolayer in the reflecting layer is 20-100nm, and

The thickness in monolayer deviation in the overall thickness of the core material and the dielectric layer or the reflecting layer is no more than overall thickness and accordingly 1% or 5nm of the average value of thickness degree,

The external coating is 2-6 layer, and the overall thickness of the external coating is 20-1000nm, every layer of clad with a thickness of 10- 300nm。

2. pigment according to claim 1, which is characterized in that the material of the dielectric layer is selected from SiO₂、MgF₂、Al₂O₃、 AlF₃、Na AlF₆、BaF₂、NdF₃、CaF₂, one of LiF, ZnS, CoS, MnS, FeS, CuS or a variety of.

3. pigment according to claim 1, which is characterized in that the reflecting layer be selected from silver, copper, gold, titanium, tantalum, niobium, chromium, One of nickel is a variety of.

4. pigment according to claim 1, which is characterized in that in the external coating, close to the outer cladding of the core material Layer is the first external coating；The external coating being coated on first external coating is the second external coating, and so on, Described in the first external coating be selected from silica and/or aluminum oxide；The material of second external coating and remaining external coating Material each is selected from TiO₂, Fe₂O₃, TiFe₂O₅, Fe₃O₄, BiOCl, Cr₂O₃, ZrO₂, ZnO, SnO₂, CoO, Co₃O₄, VO₂, V₂O₃, titanium Sour iron, Ti₂O₃, pucherite, one of cobalt aluminate or a variety of.

5. pigment according to claim 1-4, which is characterized in that the core material is 3-6 layers of structure, including smooth Air layer and dielectric layer, and the smooth air layer and the dielectric layer are alternately distributed.

6. pigment according to claim 5, which is characterized in that the core material is 3-tier architecture, including one layer of smooth air layer With two layers of silica, one layer of smooth air layer is between two layers of the silica.

7. pigment according to claim 5, which is characterized in that the core material be 3-tier architecture, including layer of silicon dioxide layer and 2 layers of smooth air layer, the silicon dioxide layer is between 2 layers of smooth air layer.

8. a kind of preparation method of the pigment of high brightness, which is characterized in that the method comprising the steps of:

1) preparation of core material precursor:

1.2) one layer of peelable separation layer is deposited on the bottom liner using PVD method, then deposit one layer using PVD method and put down Whole air layer precursor layer, or at least one layer of smooth air layer precursor layer and at least one layer of dielectric layer and/or at least one layer The combination in reflecting layer, redeposited one layer of peelable separation layer, in this way, smooth with one layer of one layer of peelable separation layer of deposition and deposition Air layer precursor layer, or at least one layer of smooth air layer precursor layer and at least one layer of dielectric layer precursor layer and/or at least The group of one layer of reflecting layer precursor layer is combined into a cycle, repeats the period 1-50 times；

1.3) the peelable separation layer in step 1.2) resulting materials is removed using remover, is washed out and is classified and is made a reservation for The core material precursor of particle diameter distribution；

2.1) the resulting core material precursor dispersion of step 1.3) is coated in the solution for not destroying the core material front body structure One external coating precursor layer, then, being filtered, washed and/or dry and/or calcining acquisition has smooth air layer precursor layer simultaneously Coat the powder of the first external coating；

2.2) powder with smooth air layer precursor layer and the first external coating of cladding for obtaining 2.1) step is scattered in Air layer precursor layer in the core material precursor can be dissolved to be formed in the solution of smooth air layer, in the core material Air layer precursor layer in precursor, which is dissolved, to be formed after smooth air layer, and filtering, sufficiently washing, drying are obtained containing free Gas-bearing formation and the powder for being coated with the first external coating or the first external coating precursor layer；

3) the second external coating precursor layer is coated:

Or

2.1) powder with air layer precursor layer and the first external coating precursor of cladding that step is obtained is without step 2.2) it is directly scattered under the reaction condition for being used to form the second external coating precursor layer and under this condition can be by institute The air layer precursor layer dissolution in core material precursor is stated to be formed in the solution of smooth air layer, in second external coating Precursor layer reaches predetermined thickness and the air layer precursor layer is dissolved and is formed after smooth air layer, is filtered, washed, does Dry and/or calcining；

4) cladding (if any) for carrying out remaining external coating, the mistake after all external coating precursor layers are covered to complete Filter, washing and dry and/or calcining obtain the pigment of high brightness.

9. preparation method according to claim 8, which is characterized in that the material of the smooth air layer precursor layer is selected from One of metal simple-substance, fluoride, sulfide are a variety of.

10. preparation method according to claim 9, which is characterized in that the metal simple-substance is selected from aluminium and/or zinc.

11. preparation method according to claim 9, which is characterized in that the fluoride is selected from magnesium fluoride and/or fluorination Calcium.

12. preparation method according to claim 9, which is characterized in that the sulfide is selected from zinc sulphide.

13. the preparation of any one of the pigment or claim 8-12 of the described in any item high brightness of claim 1-7 preparation method Purposes of the pigment of high brightness in coating, ink, cosmetics, color make-up.