CN107383939B - A kind of preparation method coating Prussian blue or Prussian blue analogue pigment - Google Patents

A kind of preparation method coating Prussian blue or Prussian blue analogue pigment Download PDF

Info

Publication number
CN107383939B
CN107383939B CN201710557722.0A CN201710557722A CN107383939B CN 107383939 B CN107383939 B CN 107383939B CN 201710557722 A CN201710557722 A CN 201710557722A CN 107383939 B CN107383939 B CN 107383939B
Authority
CN
China
Prior art keywords
prussian blue
ammonium
substrate
pigment
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710557722.0A
Other languages
Chinese (zh)
Other versions
CN107383939A (en
Inventor
林一中
王振兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201710557722.0A priority Critical patent/CN107383939B/en
Publication of CN107383939A publication Critical patent/CN107383939A/en
Application granted granted Critical
Publication of CN107383939B publication Critical patent/CN107383939B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation

Abstract

The present invention relates to a kind of preparation method for coating Prussian blue or Prussian blue analogue pigment, this method includes obtaining using Prussian blue or Prussian blue analogue is coated after Zeta potential adjustment auxiliary agent processing and coating Prussian blue or Prussian blue analogue pigment substrate.It is Prussian blue or Prussian blue analogue free that method of the invention can effectively solve the problems, such as that substrate coats.Prussian blue or Prussian blue analogue the pigment that the present invention prepares resulting cladding can be used in the industries such as cosmetics and coating, ink.

Description

A kind of preparation method coating Prussian blue or Prussian blue analogue pigment
Technical field
The present invention relates to a kind of preparation methods of pigment, more specifically to a kind of Prussian blue or class Prussia of cladding The preparation method of blue pigment.
Background technique
As hydrated iron [Fe (III) (H2O)6]3+[Fe (II) (CN)6]4-When reacting in aqueous solution, the indigo plant of generation The insoluble precipitating of color, it is referred to as Prussian blue (Prussian Blue).Its vivid color can be permanent holding, therefore people It is applied to industrial dye, paint ink and other fields relevant to color for Prussian blue.As Prussian blue research Continue, people replace [Fe (III) (H with the hydrated ion of other transition metal or rare earth metal2O)6]3+, and [Fe (II) (CN)6]4-It reacts in aqueous solution, the insoluble precipitating of generation, referred to as Prussian blue analogue compound.
Prussian blue and Prussian blue analogue compound has chromatic colour, is widely used in every profession and trade, but individually Phenomena such as will cause reunion using Prussian and influence to use.Therefore by Prussian blue or Prussian blue analogue substance packet Its reunion can not only be improved by being overlying on substrate, but also because color is superimposed with substrate and will form very attractive color.
Since E.I.Du Pont Company has developed pearlescent pigment since the eighties of last century 60, pearlescent pigment is widely used in painting The fields such as material, cosmetics, plastics, leather and ink.And colour saturation then can be improved in pearlescent pigment surface cladding absorbed layer, generates More charming color effects.General cladding mill base colorant can be using the side for coating mill base after substrate surface alclad again Formula, but this cladding mode, which can generate mill base, to fall off, fade and so on (Deutsche Bundespatent No.1192353 and the U.S. are special Benefit is 2995459).Coprecipitation is most commonly used for preparing Prussian blue and Prussian blue analogue particle.For example, using stirring The method mixed is containing [Fe (CN)6]4-Solution in be added excess chlorination ferrous solution, blue precipitate will be obtained, precipitating washed into paint Drying can be obtained Prussian blue.Therefore cladding Prussian blue analogue substance more uses directly in substrate surface Direct precipitation Mode.
The patent US3951679 use of Merck KGaA company is initially formed ferroferrocyanide Fe2[Fe(CN)6] white Substance forms Prussian blue (Fe in (such as potassium chlorate etc.) that oxidant is added4[Fe(CN)6]3) film.Between the method uses Connection forms Prussian blue in substrate surface, and technique is cumbersome.
United States Patent (USP) US4047969A1 disclose it is a kind of coat barba hispanica method, using soluble ferrocyanide with can Soluble chloride generation is Prussian blue, and this method is Prussian blue in substrate surface Direct precipitation, but in 3.5-5.5pH range It is interior, can there is a situation where Prussian blue free.
The pigment of chameleon pigment cladding barba hispanica substance is referred to for Merck & Co. Inc. WO2006005595, but not Refer to specific preparation method.
Female coloured silk patent 201110259368.6 is disclosed combines cladding preparation Prussia using potassium ferrocyanide with iron chloride The method of the effect pigment of indigo plant cladding, but according to its technique, 40 μm of flaky powder material is greater than especially for average grain diameter Material, which can generate, significantly to dissociate, and causes gloss after cladding to decline, filtration difficulty.Female coloured silk patent 201210405046.2 discloses one The Prussian blue pigment of the magnetic cladding of kind tool, with female color patent 201110259368.6 using similar method cladding, together Sample, which exists, is easy free, the free problem of the barba hispanica of especially big partial size substrate cladding.
Summary of the invention
The object of the present invention is to provide a kind of preparation method for coating Prussian blue or Prussian blue analogue pigment, this method Effectively improve the free situation for coating Prussian blue or Prussian blue analogue pigment.
To achieve the above object, the technical scheme is that
A kind of preparation method coating Prussian blue or Prussian blue analogue pigment, this method include that substrate is utilized Zeta Prussian blue or Prussian blue analogue is coated after current potential adjustment auxiliary agent processing, obtains and coats Prussian blue or Prussian blue analogue face Material.
In a preferred embodiment of the invention, the method comprising the steps of:
(1) by substrate and water or water content be more than 30% water and can be mixed into water the mixed solvent of homogeneous solvent by Solid and liquid weight ratio 1/4-20 is configured to slurry, and Zeta potential is added and adjusts auxiliary agent, in room temperature to stirring 0-10h at 100 DEG C,
Wherein, the ratio of Zeta potential adjustment auxiliary agent and substrate is 0.1/100-100/100 by weight；
(2) for adjustment system pH to 2.0-5.0, control system temperature is 40-95 DEG C, and the water-soluble of ferrocyanide is added Liquid, while aqueous metal salt is added, it is in the process 2.0-5.0 with acid or alkali maintenance system pH value；
(3) it is filtered, washed, obtains and coat Prussian blue or Prussian blue analogue pigment.
In a more preferred embodiment of the present invention, system temperature is 60-95 DEG C in step (1).
In a more preferred embodiment of the present invention, in step (2) adjustment system pH to 2.0-3.0 and then The aqueous solution and aqueous metal salt of ferrocyanide are added simultaneously.In a more preferred embodiment of the present invention, step (2) control system temperature is 60-80 DEG C in.In a more preferred embodiment of the present invention, ferrocyanide is being added Maintenance system pH value is 2.0-3.0 during aqueous solution and aqueous metal salt.
In a preferred embodiment of the invention, substrate is sheet substrate or non-sheet substrate；The flaky material Selected from natural mica, synthetic mica, sheet glass, titanium dioxide silicon wafer, alumina wafer, flake ferric oxide or bismuth oxychloride crystals, boron The mixture of silicate, platelet boron nitride or a variety of above substances, or metal and/or nonmetallic and/or metal are coated on it The natural mica of oxide and/or nonmetal oxide, synthetic mica, sheet glass, titanium dioxide silicon wafer, alumina wafer, sheet oxygen Change the pigment or a variety of mixtures with paint that iron or bismuth oxychloride crystals, borosilicate, platelet boron nitride are formed, it is described non- Sheet substrate is selected from kaolin, calcium carbonate, barium sulfate, diatomite, magnesium carbonate, magnesium silicate, barium carbonate, boron nitride, hydroxy-apatite Stone, zirconium oxide, calcium borosilicate, borsal or a variety of above substances mixture.
In a more preferred embodiment of the present invention, the average grain diameter of sheet substrate is 1-5000 μm, sheet substrate Average thickness be 0.1-7 μm.In another more preferred of the invention, the average grain diameter of sheet substrate is 10- 2000 μm, with a thickness of 0.1-5 μm.
In a more preferred embodiment of the present invention, average grain diameter (D50) 30um or more of sheet substrate, more preferably Average grain diameter (D50) 40um or more, further preferred average grain diameter (D50) 60um or more." D50 " refer to powder average grain diameter or Median, the equivalent diameter of the largest particles when further cumulative distribution is 50% in finger size distribution curve.For example, Partial size in the present invention is measured using America and Europe gram LS-POP (6) type laser particle size analyzer.
In a preferred embodiment of the invention, Zeta potential adjustment auxiliary agent is to contain NH4 +Compound or can be with Generate NH4 +Compound.
In a more preferred embodiment of the present invention, it is ammonium chloride, ammonium bromide, sulfuric acid that Zeta potential, which adjusts auxiliary agent, Ammonium, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium oxalate, ammonium nitrate, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, The mixture of ammonium hydroxide, urea or a variety of above substances.
In a preferred embodiment of the invention, ferrocyanide is selected from potassium ferrocyanide, sodium ferrocyanide, ferrous iron The mixture of ammonium cyanide or a variety of above substances.
In a preferred embodiment of the invention, metal salt is selected from water-soluble transition metal salt and/or solvable In or mixtures thereof the rare earth metal salt of water.
In a more preferred embodiment of the present invention, water-soluble transition metal salt is selected from Fe (III) salt, Co (II) salt, the mixing of Cr (III) salt, Cu (II), Mn (IV) salt, Ti (IV) salt, Ni (II) salt, Ba (II) or a variety of above salts Object.In another more preferred of the invention, water-soluble transition metal salt is selected from Fe (III) salt, Co (II) The mixture of salt Cu (II), Ti (IV) salt or a variety of above salts.
In a more preferred embodiment of the present invention, Fe (III) salt is selected from iron chloride and/or ferric sulfate.
In a more preferred embodiment of the present invention, Ti (IV) salt is selected from titanium tetrachloride.
In a more preferred embodiment of the present invention, water-soluble rare earth metal salt is selected from: lanthanum (La) salt, cerium (Ce) salt, praseodymium (Pr) salt, neodymium (Nd) salt, promethium (Pm) salt, samarium (Sm) salt, europium (Eu) salt, gadolinium (Gd) salt, terbium (Tb) salt, dysprosium (Dy) Salt, holmium (Ho) salt, erbium (Er) salt, thulium (Tm) salt, ytterbium (Yb) salt, lutetium (Lu) salt, scandium (Sc) salt, yttrium (Y) salt or a variety of above salt The mixture of class.In another more preferred of the invention, water-soluble rare earth metal salt is selected from: lanthanum (La), Cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), Ytterbium (Yb), lutetium (Lu), scandium (Sc), the hydrochloride of yttrium (Y), nitrate, sulfate or a variety of above salts mixture.
In a preferred embodiment of the invention, it can be mixed into homogeneous solvent with water and be selected from alcohol, the preferred first of the alcohol Alcohol and/or ethyl alcohol, more preferable ethyl alcohol.
In a preferred embodiment of the invention, the dosage M of ferrocyanide is (with Fe (CN)6 (IV)It is calculated as) (0.01mmol-100mmol)/g substrate, the dosage mi (Xi of metal saltYiMeter, wherein Y is the ioni valence of metal salt X) be (0.01mmol-100mmol)/g substrate；And meet:N is the positive integer less than 10.Such as to deposit Fe(III) 4[Fe(CN)6](IV) 3, such as use K4Fe(CN)6With FeCl3It is prepared as raw material, if K4Fe(CN)6For 3mol, then need FeCl3For 4mol, meet 4*3=4*3.
In a preferred embodiment of the invention, alkali used in adjustment, control or maintenance system pH is inorganic base, preferably Ground, the inorganic base are or mixtures thereof sodium hydroxide, potassium hydroxide, ammonium hydroxide.
In a preferred embodiment of the invention, acid used in adjustment, control or maintenance system pH is inorganic acid, preferably Ground, the inorganic acid are or mixtures thereof hydrochloric acid, sulfuric acid, oxalic acid.
It is a further object of the present invention to provide the cladding by method preparation of the invention is Prussian blue or Prussian blue analogue Pigment.
The Prussian blue or class Prussia coated in Prussian blue or Prussian blue analogue the pigment of cladding prepared by the present invention The average thickness of blue film is 1-300nm, more preferably, with a thickness of 10-200nm.
Prussian blue or Prussian blue analogue the pigment of cladding prepared by the present invention can be widely used in the change such as nail polish The industries such as cosmetic and coating, ink.
" a variety of " refer to two or more in the present invention.
" solution " unless otherwise specified, refers to aqueous solution in the present invention.
During preparation coats Prussian blue or Prussian blue analogue pigment, inventor is had surprisingly found that by adjusting base The Zeta potential on material surface can obviously improve Prussian blue or Prussian blue analogue cladding, highly effective reduction It is free, the compactness extent of cladding is improved, cost is reduced, pigment quality is improved, the cladding class Prussia of function admirable can be obtained Blue pigment especially can be convenient and inexpensively obtain big partial size substrate and coat Prussian blue or Prussian blue analogue pigment.
Influence about Zeta potential adjustment auxiliary agent to substrate surface Zeta potential is measured using zeta potential instrument, such as Shown in Fig. 1.Wherein DN4 indicates Zeta of the untreated substrate (hollow silicon dioxide ball, D50=4um) under certain pH value Current potential, DN4+A refer to Zeta potential adjustment auxiliary agent (ammonium chloride) treated substrate (hollow silicon dioxide ball) in certain pH Ze current potential under value.From figure 1 it appears that the Zeta potential on the surface DN4 has bright after Zeta potential adjustment auxiliary agent is added Aobvious change, within the scope of pH=2-5, Zeta potential adjustment auxiliary agent, which is added, can significantly improve the Zeta potential of powder surface, Think that this change is the main reason for causing Prussian blue or Prussian blue analogue cladding more efficient.
Detailed description of the invention
Fig. 1 is change of the Zeta potential adjustment auxiliary agent to the Zeta potential on hollow silicon dioxide ball surface, and wherein DN4 is indicated Zeta potential of the untreated substrate (hollow silicon dioxide ball) under certain pH value, DN4+A refers to be adjusted with Zeta potential Auxiliary agent (ammonium chloride) treated Zeta potential of the substrate (hollow silicon dioxide ball) under certain pH value.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.Test method without specific conditions in following example, usually according to conventional strip Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage is calculated by weight.
The charging rate is the average charging rate of material adding procedure.
The temperature is can have reasonable fluctuation in set temperature range, refers generally to set temperature ± 5 DEG C.
The pH is to allow to have error in instrument air precision, and general error range is ± 0.1pH, such as pH=2.5, then Allow then to allow worst error in 2.3-2.6 such as pH=2.4-2.5 for 2.4-2.6..
Embodiment 1
In the reactor, sheet glass of the 60g average grain diameter at 500 μm is added, 3 μm of thickness, water 800mL preparation is added and is slurried 4g ammonium chloride is added in liquid, is warming up to 78 DEG C, stirs 3h；System pH is adjusted to 2.5 with hydrochloric acid, with 10mL/ at 78 DEG C of temperature 20mL 0.25M ferrocyanide aqueous solutions of potassium is added in the speed of h, while water-soluble with the 1M iron chloride that 6.7mL is added in 3.33mL/h It is 2.5-2.6 that liquid, which is in the process pH using hydrochloric acid or sodium hydroxide maintenance, stirs 0.1h after charging；Filter later, Almost without dissociating, Prussian blue cladding sheet glass is obtained.
Covering amount is with Fe4[Fe(CN]6] meter theoretical amount be 1.43g, be computed covering amount be 1.40g, clad ratio be base The 2.3% of material weight, covering amount are the 97% of theoretical amount, illustrate that free situation has obtained fabulous control.
Embodiment 2
In the reactor, synthetic mica substrate chameleon of the 60g average grain diameter at 40 μm is added, according to solid and liquid weight than 1/ 10 addition 500g water and 100g ethyl alcohol are configured to slurry, and 2g ammonium chloride and 2g urea is added, is warming up to 85 DEG C of stirring 2h；Use sulfuric acid Adjustment system pH to 2.7 is added 60mL0.5M ferrocyanide ammonium salt solution at temperature 60 with 10mL/h, while being added with 10mL/h 60mL0.66M ferric chloride in aqueous solution is in the process pH in 2.7-2.8 using hydrochloric acid or sodium hydroxide maintenance, and charging finishes After stir 0.5h；It is filtered, washed, the pigment of chameleon cladding barba hispanica is obtained, almost without free.Covering amount is with Fe4[Fe (CN]6]3The theoretical amount of meter is 8.58g, and being computed covering amount is 8.26g, and clad ratio is the 13.8% of substrate weight, cladding Amount is the 96% of theoretical amount, illustrates that free situation has obtained fabulous control.
Embodiment 3
In the reactor, 60g average grain diameter is added in the green interference pearly-lustre face of 100 μm of synthetic mica cladding titanium dioxide Material is configured to slurry than 1/20 addition 1200g water according to solid and liquid weight, 2g ammonium sulfate and 2g ammonium bromide is added, is warming up to 85 DEG C, Stir 3h；System pH is adjusted to the 0.25M ferrocyanide ammonium salt solution that 15mL is added at 2.5,85 DEG C with 5ml/h using sulfuric acid, The mixture aqueous solution that 15mL has iron chloride 0.167M and titanium chloride 0.125M is added with 5mL/h simultaneously, is made in the process 0.5h is stirred after 2.5-2.6, charging with sodium hydroxide or hydrochloric acid maintenance system pH value；Be filtered, washed, free amount compared with It is few, the powder with green interference colours, green accumulation color is obtained after dry.Its theoretical covering amount is with Fe4Ti3[Fe(CN)6]6For 1.02g, being computed covering amount is 0.97g, and clad ratio is the 1.6% of substrate amount, and covering amount is the 95% of theoretical amount.
Embodiment 4
In the reactor, natural mica coated iron oxide, silica, iron oxide of the 60g average grain diameter at 30 μm is added Chameleon pearlescent pigment, than 1/4 plus water 240g is configured to slurry, 2g ammonium sulfate and 2g ammonium oxalate is added according to by solid and liquid weight Element is warming up to 85 DEG C, stirs 2h；System pH is adjusted to 2.3, with 30mL/h at 85 DEG C of temperature with hydrochloric acid and sulfuric acid mixture liquid 30mL0.25M ferrocyanide ammonium salt solution is added, while with the cobalt chloride solution of the 1M of 15ml/h addition 15mL, in the process 1h is stirred after 2.3-2.4, charging with sulfuric acid or potassium hydroxide maintenance system pH value；It is filtered, washed, it is ferrous to obtain cladding The chameleon powder of cobaltous cyanide cladding.Theoretical covering amount is with Co2Fe(CN)6It is calculated as 2.5g, practical cladding is calculated as 2.3g, swims It is only 7% or so from amount.
Embodiment 5
In the reactor, preparing spherical SiO 2 of the 60g average grain diameter at 3 μm is added, adds according to by solid and liquid weight than 1/20 Enter 1200g water and be configured to slurry, 10g aluminium chloride and 15g urea are added later, after 10h is stirred at room temperature, is warming up to 78 DEG C； System pH is adjusted to 2.8 with hydrochloric acid, 60mL0.25M ferrocyanide ammonium salt solution is added with 10mL/h at 78 DEG C of temperature, simultaneously The ferric chloride in aqueous solution of the 1M of 20mL is added with 3.33mL/h speed, uses hydrochloric acid or sodium hydroxide control system pH in the process Value stirs 0.5h after 2.8-2.9, charging；It is filtered, washed, obtains the silicon for having the cladding of blue accumulation color Prussian blue Ball.Theoretical covering amount is with Fe4[Fe(CN)6]3It is calculated as 4.3g, practical cladding is calculated as 4.1g, and covering amount is the 95% of theoretical amount Left and right.
Embodiment 6
In the reactor, sheet synthetic mica of the 60g average grain diameter at 4 μm is added, adds according to by solid and liquid weight than 1/10 Enter 600g water and be configured to slurry, 20g ammonium hydrogen carbonate is added, be warming up to 78 DEG C, stirs 1h；System pH is adjusted to 2.7 with hydrochloric acid, 40mL0.25M ferrocyanide ammonium salt solution is added with 10mL/h at 78 DEG C of temperature, while the 0.33M chlorination of 40mL being added with 10mL/h Water solution stirs 0.15h with hydrochloric acid or sodium hydroxide maintenance system pH value in the process after 2.7, charging；It crosses Filter, washing, have blue accumulation toner body, and swipe has highly transparent.Theoretical covering amount is with Fe4[Fe(CN)6]32.9g is calculated as, Practical cladding is calculated as 2.8g, and covering amount is 96% or so of theoretical amount.
Embodiment 7
In the reactor, titanium dioxide of the 60g average grain diameter at 2 μm is added, 900g water is added than 1/15 according to solid weight It is configured to slurry, 5g urea, 10g ammonium chloride, 1g ammonium hydrogen carbonate are added later, stirs 4h at 78 DEG C；With sulfuric acid by system pH It adjusts to 2.7,15mL0.25M ferrocyanide ammonium salt solution is added with 15mL/h at 78 DEG C of temperature, while 15mL/h is added 20mL0.20M iron chloride and 0.05M lanthanum chloride mixed aqueous solution, in the process with potassium hydroxide maintenance system pH value in 2.7- 2.8,0.5h is stirred after charging；It is filtered, washed, obtains the titanium dioxide of Prussian blue analogue cladding.Theoretical covering amount with Fe3.2La0.8[Fe(CN)6]3It is calculated as 1.2g, practical cladding is calculated as 1.1g, and covering amount is 95% or so.
Embodiment 8
In the reactor, 25Kg average grain diameter is added in the blue interference pearly-lustre face of 50 μm of foliated glass cladding titanium dioxide Material is made slurry than 1/10 addition 250Kg according to by solid and liquid weight, 200g ammonium sulfate and 100 ammonium bromides and 200g urea is added, 80 DEG C are warming up to, 1.5h is stirred；System pH is adjusted to 2.5 with hydrochloric acid, the 0.25M of 25L is added with 10L/h at 80 DEG C of temperature Ferrocyanide ammonium salt solution, while with the 0.33M ferric chloride in aqueous solution of 10L/h addition 25L, sodium hydroxide or salt are used in the process Sour maintenance system pH value stirs 0.5h after 2.5-2.6, charging, is filtered, washed, and almost without dissociating, obtaining has indigo plant The powder of color interference colours, blue accumulation color.Theoretical covering amount is with Fe4[Fe(CN)6]3It is calculated as 716g, practical cladding is calculated as 678g, covering amount are 95% or so.
Comparative example 1
In the reactor, 60g average grain diameter is added in 500 μm, 3 μm of thickness of sheet glass, water 800mL preparation is added and is slurried Liquid, system heat up 78 DEG C, and system pH is adjusted to 2.5 with hydrochloric acid, and 20mL is added in 78 DEG C of the temperature speed with 10mL/h 0.25M ferrocyanide aqueous solutions of potassium, while with the 1M ferric chloride in aqueous solution of 3.33mL/h addition 6.7mL, it uses in the process It is 2.5-2.6 that hydrochloric acid or sodium hydroxide maintenance, which are pH, stirs 0.1h after charging；It filters, filtration difficulty, sufficiently washs later Powder very slight color afterwards.Covering amount is with Fe4[Fe(CN]6] meter theoretical amount be 1.43g, be computed covering amount be 0.20g, packet The rate of covering is only the 0.33% of substrate weight, and covering amount is the 14.0% of theoretical amount, is illustrated free very serious.With embodiment 1 A pair of Prussian blue dissociating of comparative descriptions embodiment of the present invention method can be reduced obviously.
Comparative example 2
In the reactor, preparing spherical SiO 2 of the 60g average grain diameter at 3 μm is added, adds according to by solid and liquid weight than 1/20 Enter water 1200g and be configured to slurry, be warming up to 78 DEG C, is adjusted system pH to 2.8, until being added at 78 DEG C with 10mL/h with hydrochloric acid 60mL 0.25M ferrocyanide ammonium salt solution, while chlorination is added with the ferric chloride in aqueous solution that the 1M of 20mL is added in 3.33mL/h speed Water solution stirs 0.5h with hydrochloric acid or sodium hydroxide control system pH value in the process after 2.8-2.9, charging；Filtering, It is difficult to filter；Sufficiently after washing, silicon ball very slight color.Theoretical covering amount is with Fe4[Fe(CN)6]3It is calculated as 4.3g, practical cladding warp It is calculated as 1.1g, covering amount is 26% or so of theoretical amount.
It is general in cladding from comparative example as can be seen that in the case where helping processing substrate without Zeta potential adjustment Shandong scholar's indigo plant is easy to dissociate.
Preferred form of production according to the present invention has carried out the description that there is no limit to the present invention by example, still It should be appreciated that those skilled in the art can make a variety of changes and/or become in the range of the appended claims definition Type, without departing from relevant protection scope.

Claims (8)

1. a kind of preparation method for coating Prussian blue or Prussian blue analogue pigment, this method includes that substrate is utilized Zeta electricity Prussian blue or Prussian blue analogue is coated after position adjustment auxiliary agent processing, obtains and coats Prussian blue or Prussian blue analogue face Material,
The method comprising the steps of:
(1) by substrate and water or water content be more than 30% water with the mixed solvent of homogeneous solvent can be mixed into water by solid-liquid Weight ratio 1/4-20 is configured to slurry, and Zeta potential is added and adjusts auxiliary agent, in room temperature to stirring 0-10h at 100 DEG C,
Wherein the ratio of Zeta potential adjustment auxiliary agent and substrate is 0.1/100-100/100 by weight；
(2) for adjustment system pH to 2.0-5.0, control system temperature is 40-95 DEG C, the aqueous solution of ferrocyanide is added, together When aqueous metal salt is added, in the process using acid or alkali maintenance system pH value be 2.0-5.0,
(3) it is filtered, washed, obtains and coat Prussian blue or Prussian blue analogue pigment,
The Zeta potential adjustment auxiliary agent is to contain NH4 +Compound or NH can be generated4 +Compound.
2. preparation method according to claim 1, wherein the substrate is sheet substrate or non-sheet substrate；The sheet It is brilliant that material is selected from natural mica, synthetic mica, sheet glass, titanium dioxide silicon wafer, alumina wafer, flake ferric oxide or bismuth oxychloride Body, borosilicate, platelet boron nitride or a variety of above substances mixture, or coat on it metal and/or it is nonmetallic and/or The natural mica of metal oxide and/or nonmetal oxide, synthetic mica, sheet glass, titanium dioxide silicon wafer, alumina wafer, piece The pigment or a variety of mixtures with paint that shape iron oxide or bismuth oxychloride crystals, borosilicate, platelet boron nitride are formed, institute It states non-sheet substrate and is selected from kaolin, calcium carbonate, barium sulfate, diatomite, magnesium carbonate, magnesium silicate, barium carbonate, boron nitride, hydroxyl Apatite, zirconium oxide, calcium borosilicate, borsal or a variety of above substances mixture.
3. preparation method according to claim 1, wherein Zeta potential adjustment auxiliary agent is ammonium chloride, ammonium bromide, sulphur Sour ammonium, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium oxalate, ammonium nitrate, ammonium phosphate, ammonium hydrogen phosphate, phosphoric acid hydrogen two Ammonium, ammonium hydroxide, urea or a variety of above substances mixture.
4. preparation method according to claim 1, wherein the ferrocyanide is selected from potassium ferrocyanide, ferrocyanide The mixture of sodium, ferrous ammonium cyanide or a variety of above substances.
5. preparation method according to claim 1, wherein the metal salt be selected from water-soluble transition metal salt and/or Or mixtures thereof water-soluble rare earth metal salt.
6. preparation method according to claim 1, wherein described can be mixed into homogeneous solvent selected from alcohol with water.
7. preparation method according to claim 1, the dosage M of ferrocyanide is (with Fe (CN)6 (IV)Meter) be (0.01mmol-100mmol)/g substrate, the dosage mi of metal salt is (with XiYiMeter, wherein Yi is the ion of i-th kind of metal salt Xi Valence) it is (0.01mmol-100mmol)/g substrate；And meet:N is the positive integer less than or equal to 10.
8. being prepared according to the described in any item methods of preceding claims, wherein gained cladding is Prussian blue or Prussian blue analogue Prussian blue or Prussian blue analogue film the average thickness of pigment cladding is 1-300nm.
CN201710557722.0A 2017-07-10 2017-07-10 A kind of preparation method coating Prussian blue or Prussian blue analogue pigment Active CN107383939B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710557722.0A CN107383939B (en) 2017-07-10 2017-07-10 A kind of preparation method coating Prussian blue or Prussian blue analogue pigment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710557722.0A CN107383939B (en) 2017-07-10 2017-07-10 A kind of preparation method coating Prussian blue or Prussian blue analogue pigment

Publications (2)

Publication Number Publication Date
CN107383939A CN107383939A (en) 2017-11-24
CN107383939B true CN107383939B (en) 2019-04-30

Family

ID=60335614

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710557722.0A Active CN107383939B (en) 2017-07-10 2017-07-10 A kind of preparation method coating Prussian blue or Prussian blue analogue pigment

Country Status (1)

Country Link
CN (1) CN107383939B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109077941B (en) * 2018-07-13 2021-05-14 福建坤彩材料科技股份有限公司 Colored bismuth oxychloride pigment and preparation method and application thereof
CN114350179B (en) * 2021-12-31 2023-07-14 浙江凯色丽科技发展有限公司 Preparation method of liquid-phase synthesized iron blue coloring pearlescent pigment

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318091A (en) * 1998-09-19 2001-10-17 默克专利股份有限公司 Reduction pigments
CN102181176A (en) * 2011-06-03 2011-09-14 杭州弗沃德精细化工有限公司 Process for preparing iron blue with fantastic color effect
CN102443285A (en) * 2011-09-05 2012-05-09 福州坤彩精化有限公司 Prussian blue pearlescent pigment and preparation method thereof
CN102597131A (en) * 2009-10-28 2012-07-18 巴斯夫欧洲公司 Pigments with improved sparkling effect
CN103173058A (en) * 2011-12-21 2013-06-26 星铂联制造公司 Colored platelets
CN103183972A (en) * 2011-12-21 2013-07-03 默克专利股份有限公司 Effect pigments
CN103874654A (en) * 2011-10-18 2014-06-18 日本曹达株式会社 Surface-covered inorganic powder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318091A (en) * 1998-09-19 2001-10-17 默克专利股份有限公司 Reduction pigments
CN102597131A (en) * 2009-10-28 2012-07-18 巴斯夫欧洲公司 Pigments with improved sparkling effect
CN102181176A (en) * 2011-06-03 2011-09-14 杭州弗沃德精细化工有限公司 Process for preparing iron blue with fantastic color effect
CN102443285A (en) * 2011-09-05 2012-05-09 福州坤彩精化有限公司 Prussian blue pearlescent pigment and preparation method thereof
CN103874654A (en) * 2011-10-18 2014-06-18 日本曹达株式会社 Surface-covered inorganic powder
CN103173058A (en) * 2011-12-21 2013-06-26 星铂联制造公司 Colored platelets
CN103183972A (en) * 2011-12-21 2013-07-03 默克专利股份有限公司 Effect pigments

Also Published As

Publication number Publication date
CN107383939A (en) 2017-11-24

Similar Documents

Publication Publication Date Title
Yasukawa et al. Preparation and structure of calcium hydroxyapatite substituted with light rare earth ions
Opuchovic et al. Sol-gel synthesis, characterization and application of selected sub-microsized lanthanide (Ce, Pr, Nd, Tb) ferrites
CN107383939B (en) A kind of preparation method coating Prussian blue or Prussian blue analogue pigment
Zheng et al. Synthesis and characterization of blue TiO 2/CoAl 2 O 4 complex pigments with good colour and enhanced near-infrared reflectance properties
CN1160422C (en) Sulphide and oxysulphide pigments
CN110655807B (en) Preparation method of zirconium silicate coated iron oxide red for ceramic ink-jet printing
CN106132875B (en) Plate-like aluminum oxide and its preparation method
CN113479895B (en) Method for preparing superfine zirconium silicate and zirconium silicate-based coating pigment by one-step precipitation method
CN107365513B (en) A kind of preparation method coating Prussian blue or Prussian blue analogue pigment
EP3064553A1 (en) Iron oxide based black glossy pigment and method for preparing same
CN107325588A (en) A kind of preparation method for the pigment for coating high gorgeous degree iron oxide
CN109608906B (en) Superfine aluminum oxide coated bismuth molybdate yellow pigment and preparation method thereof
KR101782861B1 (en) Flaky aluminum oxide and method of producing thereof
JP4732969B2 (en) Iron oxide powder for red pigment
CN108394925B (en) Preparation method of YAG-coated gamma-Ce 2S3 red pigment
JP2003201122A (en) Method for manufacturing granular hematite particle powder
JP3601759B2 (en) Composite oxide green pigment and method for producing the same
JP7191693B2 (en) Coating method for substrate surface
CN107662938A (en) A kind of preparation method of little particle yittrium oxide cerium
JPH0252660B2 (en)
CN113173593A (en) Preparation method of stable nano yttrium oxide powder
Vicent et al. Differentiation between the green and Turkish Blue solid solutions of vanadium in a zircon lattice obtained by the sol-gel process
CN109880402A (en) A kind of nonmagnetic black ceramic ink dyestuff and its methods for making and using same
CN115386246A (en) Preparation method of double-layer coated cerium sulfide red pigment chemical coating film
CN116102044A (en) Needle-shaped and flake-shaped blended alumina powder and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant