CN106280570A - Prussian blue sphere pigments used for cosmetic and preparation method thereof - Google Patents

Prussian blue sphere pigments used for cosmetic and preparation method thereof Download PDF

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Publication number
CN106280570A
CN106280570A CN201610653836.0A CN201610653836A CN106280570A CN 106280570 A CN106280570 A CN 106280570A CN 201610653836 A CN201610653836 A CN 201610653836A CN 106280570 A CN106280570 A CN 106280570A
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solution
suspension
value
constant temperature
prussian blue
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莫峰
林正交
熊小寒
章梦令
余慧忠
林敏立
丁苏扬
黄志仁
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GUANGXI CHESIR PEARL EFFECT MATERIAL Co Ltd
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GUANGXI CHESIR PEARL EFFECT MATERIAL Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
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    • 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
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • 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
    • C09C3/063—Coating
    • 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
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
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    • 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
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    • 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
    • C09C2200/20—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index
    • C09C2200/205—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index of coloured inorganic materials

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Abstract

The present invention relates to a kind of Prussian blue sphere pigments used for cosmetic and preparation method thereof, relate to fine chemistry industry field of material technology, with mean diameter D50Be the spherical base material of 1 μm～50 μm as pigment base material, be at least coated with SnO on the surface of described base material2、Al2O3And Fe4[Fe(CN)6]3Coating of metal oxides, its method, for first to put in ionized water by base material, makes suspension, by SnCl4Solution, AlCl3Solution and FeCl3Solution, K4Fe(CN)6Solution adds in suspension, when the color of suspension reaches required form and aspect, continue constant temperature stirring, then suspension filtered, be dried, calcine, compared with prior art, preparation method of the present invention is simple, its coating difficult drop-off of the product being prepared into, and has soft light effect, skinfeel is splendid, oil absorption is a low effect.

Description

Prussian blue sphere pigments used for cosmetic and preparation method thereof
Technical field
The invention belongs to fine chemistry industry Material Field, be specifically related to a kind of Prussian blue sphere pigments used for cosmetic and system thereof Preparation Method.
Background technology
At present, the pearlescent pigment commercially sold is mostly laminated structure, and flaky pearlescent pigment can rely on light to exist Refraction in different oxide skin(coating)s in pigment flakes, reflect, project and create difference form and aspect and gloss.Lamellar pearly-lustre face on market Material uses the mica sheet of different-grain diameter scope as base material mostly, and the surface coated nano titanium oxide of this substrate is mostly in island Shape is distributed, and because skinfeel is poor, oil absorption is bigger than normal, thus limits its application in cosmetics.
Use wet chemical method to be coated with sphere pigments prepared by many oxide at the surface alternatively layered of spherical base material, be Inorganic oxide, via high-temperature calcination, effect is permanent, and resistance to pressure and mobility are preferable, and the sphere pigments color of order colour is saturated Degree height, form and aspect are stable.But in the research process that pigment skinfeel is modified, rarely have the spherical base material of selection to be coated with.Main If because directly carrying out cladding on spherical base material and can causing cladding conversion ratio is low, color benefit is poor and clad can such as chicken The same problem split away off from spherical base material of eggshell.
Summary of the invention
One of the technical problem to be solved is to provide a kind of clad difficult drop-off, is evenly coated and oil absorption Low used for cosmetic Prussian blue sphere pigments and preparation method thereof.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
With mean diameter D50It is 1 μm～the SiO of 50 μm2Spherical base material, as pigment base material, at least wraps on the surface of described base material It is covered with SnO2、Al2O3And Fe4[Fe(CN)6]3Coating of metal oxides；Wherein, SnO2Coating is directly wrapped in described SiO2Spherical Substrate surface.
In technique scheme, more specifically scheme it may also is that the clad ratio 0.1% of described coating of metal oxides～ 50%。
Further: the coating being coated with successively on described spherical substrate surface is the one in A or B or C or D or E or F； Wherein A is SnO2、Al2O3、Fe4[Fe(CN)6]3；B is SnO2、Al2O3、Fe4[Fe(CN)6]3、SiO2；C is SnO2、Al2O3、Fe4 [Fe(CN)6]3、Al2O3；D is SnO2、Al2O3、Fe4[Fe(CN)6]3、Al2O3、SiO2；E is SnO2、TiO2、Al2O3、Fe4[Fe (CN)6]3、SiO2；F is SnO2、TiO2、Al2O3、Fe4[Fe(CN)6]3。
The preparation method of above-mentioned pigment may comprise steps of:
A. by mean diameter D50It is 1 μm～the SiO of 10 μm2Spherical base material puts in deionized water, makes the Ith suspension；
The most successively by SnCl4Solution, AlCl3Solution and FeCl3Solution, K4Fe(CN)6Solution joins the Ith Suspension obtains the IIth suspension, wherein, SnCl4After solution reaction terminates, then add AlCl3Solution, treats AlCl3Solution reaction After end, then drip FeCl3Solution and K4Fe(CN)6Solution；
C., when the color of the IIth suspension reaches to set form and aspect, add and account for SiO2The methyl of spherical substrate mass 0.01%～5% One in silicone oil or sodium silicate, and it is constant to control the holding of its pH value, obtains the IIIth suspension；
D. the IIIth suspension filtered, be dried, calcine.
Further: the conductivity of the deionized water used in described step A is not higher than 20 μ S/cm.
Further: SnCl described in step B4Solution, AlCl3Solution and FeCl3Solution, K4Fe(CN)6Specifically adding of solution Enter method as follows:
A. the Ith suspension is warming up to 65 DEG C～70 DEG C, and its pH value is adjusted to 1.0-1.5, then add under constant temperature stirs Account for described SiO2Spherical substrate mass 0.5 wt% SnCl4, and keep pH value constant in the process；As described SnCl4Add knot Shu Hou, continues constant temperature stirring 20～30 min；
B. the suspension after a step process is warming up to 70 DEG C～75 DEG C, and its pH value is adjusted to 5.0-6.0, then exist The lower addition of constant temperature stirring accounts for described SiO2The AlCl of spherical substrate mass 0.5%～5%3, and keep pH value constant in the process； As described AlCl3Add after terminating, continue constant temperature stirring 20～30 min；
C. the suspension after b step processes is warming up to 75 DEG C～85 DEG C, and its pH value is regulated 3.0～4.0, then exist It is simultaneously added dropwise FeCl under constant temperature stirring3Solution, K4Fe(CN)6Solution, controls the flow of two kinds of solution, keeps pH value constant, until The color of described suspension becomes Prussian blue；After the interpolation of the two solution terminates, continue constant temperature stirring 20～30 min.
The another kind of preparation method of above-mentioned pigment can comprise the steps:
A. by mean diameter D50It is 1 μm～the SiO of 10 μm2Spherical base material puts in deionized water, makes the Ith suspension；
B. the suspension after step A processes is heated up, successively by SnCl under constant temperature stirs4Solution, TiCl4Solution adds The IIth suspension is obtained in the Ith suspension, wherein, SnCl4After solution reaction terminates, then add TiCl4Solution, until described outstanding The color of supernatant liquid becomes silvery white；
C. after step B terminates, constant temperature stirs, and hangs suspension by the IIth and filters, is dried, and calcining thus prepares white spherical face Material granule；
D. put in deionized water for base material with white spherical pigment particles, make the IIIth suspension；
The most successively by AlCl3Solution and FeCl3Solution, K4Fe(CN)6Solution joins in the IIIth suspension, Obtain the IVth suspension；
F., when the color of the IVth suspension reaches to set form and aspect, add and account for white spherical pigment particles quality 0.01%～5% One in methyl-silicone oil or sodium silicate, and it is constant to control the holding of its pH value, obtains the Vth suspension；
G. the IIIth suspension filtered, be dried, calcine.
In technique scheme, more specifically scheme is it may also is that the conductivity of deionized water that uses in described a step Not higher than 20 μ S/cm.
Further: SnCl described in step B4Solution, TiCl4The concrete Adding Way of solution is as follows:
I. suspension is warming up to 65 DEG C～70 DEG C, and its pH value is adjusted to 1.0-1.5, then add under constant temperature stirs and account for institute State SiO2Spherical substrate mass 0.5 wt% SnCl4, and keep pH value constant in the process；As described SnCl4Interpolation terminates After, continue constant temperature stirring 20～30 min；
II. the suspension after I step process is warming up to 70 DEG C～75 DEG C, and its pH value is adjusted to 2.1, then at constant temperature Stirring is lower adds 2mol/L TiCl4Solution is until the color of described suspension becomes silvery white, and keeps pH value in the process Constant；
III. after II step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 120 DEG C are dried, forge for 740 DEG C Burn 5min, thus prepare white spherical pigment particles；
AlCl described in E step3Solution and FeCl3Solution, K4Fe(CN)6The concrete Adding Way of solution is as follows:
1). the IIIth suspension is warming up to 75 DEG C, and its pH value is adjusted to 5.5, be then slowly added dropwise under constant temperature stirs 0.5mol/L AlCl3Solution 60ml, and drip 20% sodium hydroxide in the process to keep pH value constant；When described solution Add after terminating, continue constant temperature stirring 20～30 min；
2). by through 1) suspension after step process is warming up to 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature Lower addition FeCl3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension Color become Prussian blue.
Clad ratio of the present invention refers to that the quality of the oxide being coated on base material accounts for the percentage ratio of substrate mass.
Owing to using technique scheme, the present invention obtains providing the benefit that:
1, owing to being coated with Al on the spherical base material of the present invention2O3Coating of metal oxides and Prussian blue before, first cladding one layer SnO2, it is possible to prevent clad to come off.
2, due to the fact that employing mean diameter D50Be the spherical base material of 1 μm～50 μm as pigment base material, and at base material Surface coating multiple layer metal oxide and Prussian blue, thus the Prussian blue sphere pigments obtained possesses soft light effect, skin Feel splendid, effect that oil absorption is low.
3, deionized water conductivity is limited to less than 20 μ S/cm by the present invention, can effectively reduce metal-oxide The impact of hydrolytic process.
5, the present invention is by adding methyl-silicone oil, sodium silicate or coupling agent etc. and controlling its consumption, effectively promotes face Material hydrophilic and oleophilic effect, improve its dispersibility etc., well applied in the industry such as cosmetics, ink.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the pigment top layer coating particle characterization of the uncoated tin layers that present example 1 prepares.
Fig. 2 is the SEM figure of the pigment top layer coating particle characterization of the cladding tin layers that present example 2 prepares.
Fig. 3 is the SEM figure of the pigment top layer coating particle characterization of the cladding tin layers that present example 3 prepares.
Detailed description of the invention
In order to better illustrate the present invention, below in conjunction with specific embodiment, the invention will be further described, and the present invention Protection domain be not intended to be limited to following example.
Embodiment 1:
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the solid spherical SiO that 50g mean diameter is 5 μm is weighed2, put in the reactor that volume is 2L, add 800ml and go Ionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 40ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
D. after step C terminates, with 20% sodium hydroxide, suspension pH value is regulated to 7, then add under constant temperature stirring condition 50ml methyl-silicone oil, and it is constant to control the holding of its pH value；
E. after D step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments.
The clad of the pigment of the present embodiment does not has tin layers, observes that clad can be such as egg under a scanning electron microscope Shell is the same to split away off, as shown in Figure 1 from spherical base material.
Embodiment 2:
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the solid spherical SiO that 50g mean diameter is 5 μm is weighed2, put in the reactor that volume is 2L, add 800ml and go Ionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 1.5, Then under constant temperature stirs, it is slowly added dropwise 0.5 wt% SnCl4Solution 30ml, and drip 20% sodium hydroxide in the process and protect Hold pH value constant；As described SnCl4After solution interpolation terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 40ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
D. the suspension after step C processes is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
E. after D step terminates, with 20% sodium hydroxide, suspension pH value is regulated to 7, then add under constant temperature stirring condition 50ml methyl-silicone oil, and it is constant to control the holding of its pH value；
F. after E step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments.
The pigment that the present embodiment obtains, is with solid spherical SiO2As base material, the coating that this substrate surface covers is followed successively by SnO2Layer, Al2O3Layer and Fe4[Fe(CN)6]3Layer, the clad ratio of coating is 5.10%；As in figure 2 it is shown, in scanning electron microscope Lower observation, granules of pigments is spherical, and microsphere surface particle is evenly coated, without obscission.
Embodiment 3
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the solid spherical SiO that 150g mean diameter is 2 μm is weighed2, put in the reactor that volume is 2L, add 800ml Deionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 1.5, Then under constant temperature stirs, it is slowly added dropwise 0.5 wt% SnCl4Solution 60ml, and drip 20% sodium hydroxide in the process and protect Hold pH value constant；As described SnCl4After solution interpolation terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 80ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
D. the suspension after step C processes is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
E. after D step terminates, with 20% sodium hydroxide, suspension pH value is regulated to 7, then add under constant temperature stirring condition 20ml methyl-silicone oil, and it is constant to control the holding of its pH value；
F. after E step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments.
The pigment that the present embodiment obtains, is with solid spherical SiO2As base material, the coating that this substrate surface covers is followed successively by SnO2Layer, Al2O3Layer, Fe4 [Fe (CN) 6] 3 layers and SiO2Layer, the clad ratio of whole coating is 21.55%；As it is shown on figure 3, sweeping Retouching observed under electron microscope, granules of pigments is spherical, and microsphere surface particle is evenly coated, without obscission.
Embodiment 4
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the solid spherical SiO that 50g mean diameter is 3 μm is weighed2, put in the reactor that volume is 2L, add 800ml and go Ionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 1.5, Then under constant temperature stirs, it is slowly added dropwise 0.5 wt% SnCl4Solution 40ml, and drip 20% sodium hydroxide in the process and protect Hold pH value constant；As described SnCl4After solution interpolation terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 40ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
D. the suspension after step C processes is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
E. after D step terminates, with 20% sodium hydroxide, suspension pH value is regulated to 7, then add under constant temperature stirring condition 40ml methyl-silicone oil, and it is constant to control the holding of its pH value；
F. after E step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments；
The pigment that the present embodiment obtains, is with solid spherical SiO2As base material, the coating that this substrate surface covers is followed successively by SnO2 Layer, Al2O3Layer, Fe4 [Fe (CN) 6] 3 layers and SiO2Layer, the clad ratio of whole coating is 18.90%.
Embodiment 5
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the solid spherical SiO that 100g mean diameter is 10 μm is weighed2, put in the reactor that volume is 2L, add 1000ml deionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 1.5, Then under constant temperature stirs, it is slowly added dropwise 0.5 wt% SnCl4Solution 60ml, and drip 20% sodium hydroxide in the process and protect Hold pH value constant；As described SnCl4After solution interpolation terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is warming up to 75 DEG C, and the pH value of described suspension is regulated 2.1, then exist Constant temperature stirring is lower adds 2mol/L TiCl4Solution is until the color of described suspension becomes silvery white, and keeps in the process PH value is constant；
D. after step C terminates, constant temperature stirring 20～30 min, then suspension is filtered, 120 DEG C are dried, 740 DEG C of calcinings 5min, thus prepares white sphere pigments；
E. weigh the white sphere pigments that 100g obtains through D step, put in the reactor that volume is 2L, add 1000ml and go Ionized water, stirring is allowed to dispersed formation suspension；
F. the suspension after E step process is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 60ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
G. the suspension after F step process is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
H., after G step terminates, with 20% sodium hydroxide, suspension pH value is regulated to 8.5, then add under constant temperature stirring condition Enter 0.5mol/L sodium silicate 30ml, and it is constant to control the holding of its pH value；
I. after H step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments.
The pigment that the present embodiment obtains, is with solid spherical SiO2As base material, the coating that this substrate surface covers is followed successively by SnO2Layer, TiO2Layer、Al2O3Layer, Fe4 [Fe (CN) 6] 3 layers and SiO2Layer, the clad ratio of whole coating is 6.85%.
Embodiment 6
The preparation method of this Prussian blue sphere pigments comprises the following steps:
A. the hollow ball shape SiO that 50g mean diameter is 5 μm is weighed2, put in the reactor that volume is 2L, add 800ml and go Ionized water, stirring is allowed to dispersed formation suspension；
B. the suspension after step A processes is warming up to 65 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 1.5, Then under constant temperature stirs, it is slowly added dropwise 0.5 wt% SnCl4Solution 30ml, and drip 20% sodium hydroxide in the process and protect Hold pH value constant；As described SnCl4After solution interpolation terminates, continue constant temperature stirring 20～30 min；
C. the suspension after step B processes is warming up to 75 DEG C, with dilute hydrochloric acid, the pH value of this suspension is regulated to 5.5, Then under constant temperature stirs, it is slowly added dropwise 0.5mol/L AlCl3Solution 40ml, and drip 20% sodium hydroxide in the process Keep pH value constant；After the interpolation of described solution terminates, continue constant temperature stirring 20～30 min；
D. the suspension after step C processes is kept temperature 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature FeCl will be added time lower3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension The color of liquid becomes Prussian blue；
E. after D step terminates, with 20% sodium hydroxide, suspension pH value is regulated to 7, then add under constant temperature stirring condition 30ml methyl-silicone oil, and it is constant to control the holding of its pH value；
F. after E step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 60 DEG C are dried, thus prepare general Shandong Scholar's indigo plant sphere pigments.
The pigment that the present embodiment obtains, is with solid spherical SiO2As base material, the coating that this substrate surface covers is followed successively by SnO2Layer, TiO2Layer、Al2O3Layer, Fe4[Fe(CN)6]3Layer and SiO2Layer, the clad ratio of whole coating is 4.70%.
Testing result
The detection of oil absorption:
Accurately weigh sample 1.0～1.5g, be accurate to 0.0001g, as on flat board, refine oleum lini with the dropping of glue head dropper, Every time sample-adding must not exceed 10, grinds by toolsetting pressure after adding, and makes oil penetrate into given the test agent, continue with this speed drop to oil and Till sample forms agglomerate.From that point on, need after often adding one to be fully ground with toolsetting, when the paste of formation homogenous consistency, Just do not split the most broken, when can stick on flat board again, be terminal.
Oil absorption oil quality needed for every 100g product represents, calculation is as follows:
m%= M/m * 100%
In formula: the consumption of M-expression oleum lini, g；
The quality of m-sample, g.
The detection of table 1 oil absorption
As can be seen from the above Table 1, this Prussian blue sphere pigments oil absorption is relatively low, it is adaptable to cosmetics, ink, coating, mould The fields such as material.
Two, pigment top layer characterizes coating particle characterization
Can be seen that from Fig. 1 to Fig. 3, granules of pigments is spherical, is evenly distributed；Can be seen that from the contrast of Fig. 1,2, uncoated SnO2's Spherical pigment particles surface has and comes off, and has been coated with SnO2Spherical pigment particles surface substantially without coming off, effect is obviously improved.

Claims (9)

1. a Prussian blue sphere pigments used for cosmetic, it is characterised in that: with mean diameter D50It is 1 μm～the SiO of 50 μm2Ball Shape base material, as pigment base material, is at least coated with SnO on the surface of described base material2、Al2O3And Fe4[Fe(CN)6]3Burning Thing coating；Wherein, SnO2Coating is directly wrapped in described SiO2Spherical substrate surface.
Prussian blue sphere pigments used for cosmetic the most according to claim 1, it is characterised in that: described metal-oxide is coated with The clad ratio 0.1%～50% of layer.
Prussian blue sphere pigments used for cosmetic the most according to claim 1 and 2, it is characterised in that: described spherical base material The coating being coated with successively on surface is the one in A or B or C or D or E or F；Wherein A is SnO2、Al2O3、Fe4[Fe(CN)6]3； B is SnO2、Al2O3、Fe4[Fe(CN)6]3、SiO2；C is SnO2、Al2O3、Fe4[Fe(CN)6]3、Al2O3；D is SnO2、Al2O3、 Fe4[Fe(CN)6]3、Al2O3、SiO2；E is SnO2、TiO2、Al2O3、Fe4[Fe(CN)6]3、SiO2；F is SnO2、TiO2、Al2O3、 Fe4[Fe(CN)6]3。
4. the preparation method of a Prussian blue sphere pigments used for cosmetic, it is characterised in that comprise the following steps:
A. by mean diameter D50It is 1 μm～the SiO of 10 μm2Spherical base material puts in deionized water, makes the Ith suspension；
The most successively by SnCl4Solution, AlCl3Solution and FeCl3Solution, K4Fe(CN)6Solution joins the Ith and hangs Supernatant liquid obtains the IIth suspension, wherein, SnCl4After solution reaction terminates, then add AlCl3Solution, treats AlCl3Solution reaction is tied Shu Hou, then drip FeCl3Solution and K4Fe(CN)6Solution；
C., when the color of the IIth suspension reaches to set form and aspect, add and account for SiO2The methyl silicon of spherical substrate mass 0.01%～5% One in oil or sodium silicate, and it is constant to control the holding of its pH value, obtains the IIIth suspension；
D. the IIIth suspension filtered, be dried, calcine.
The preparation method of Prussian blue sphere pigments used for cosmetic the most according to claim 4, it is characterised in that: described A The conductivity of the deionized water used in step is not higher than 20 μ S/cm.
6. according to the preparation method of the used for cosmetic Prussian blue sphere pigments described in claim 4 or 5, it is characterised in that:
SnCl described in step B4Solution, AlCl3Solution and FeCl3Solution, K4Fe(CN)6The concrete Adding Way of solution is as follows:
A. the Ith suspension is warming up to 65 DEG C～70 DEG C, and its pH value is adjusted to 1.0-1.5, then add under constant temperature stirs Account for described SiO2Spherical substrate mass 0.5 wt% SnCl4, and keep pH value constant in the process；As described SnCl4Add knot Shu Hou, continues constant temperature stirring 20～30 min；
B. the suspension after a step process is warming up to 70 DEG C～75 DEG C, and its pH value is adjusted to 5.0-6.0, then exist The lower addition of constant temperature stirring accounts for described SiO2The AlCl of spherical substrate mass 0.5%～5%3, and keep pH value constant in the process； As described AlCl3Add after terminating, continue constant temperature stirring 20～30 min；
C. the suspension after b step processes is warming up to 75 DEG C～85 DEG C, and its pH value is regulated 3.0～4.0, then exist It is simultaneously added dropwise FeCl under constant temperature stirring3Solution, K4Fe(CN)6Solution, controls the flow of two kinds of solution, keeps pH value constant, until The color of described suspension becomes Prussian blue；After the interpolation of the two solution terminates, continue constant temperature stirring 20～30 min.
7. the preparation method of a Prussian blue sphere pigments used for cosmetic, it is characterised in that comprise the following steps:
A. by mean diameter D50It is 1 μm～the SiO of 10 μm2Spherical base material puts in deionized water, makes the Ith suspension；
B. the suspension after step A processes is heated up, successively by SnCl under constant temperature stirs4Solution, TiCl4Solution adds The IIth suspension is obtained in the Ith suspension, wherein, SnCl4After solution reaction terminates, then add TiCl4Solution, until described outstanding The color of supernatant liquid becomes silvery white；
C. after step B terminates, constant temperature stirs, and hangs suspension by the IIth and filters, is dried, and calcining thus prepares white spherical face Material granule；
D. put in deionized water for base material with white spherical pigment particles, make the IIIth suspension；
The most successively by AlCl3Solution and FeCl3Solution, K4Fe(CN)6Solution joins in the IIIth suspension, Obtain the IVth suspension；
F., when the color of the IVth suspension reaches to set form and aspect, add and account for white spherical pigment particles quality 0.01%～5% One in methyl-silicone oil or sodium silicate, and it is constant to control the holding of its pH value, obtains the Vth suspension；
G. the IIIth suspension filtered, be dried, calcine.
The preparation method of Prussian blue sphere pigments used for cosmetic the most according to claim 7, it is characterised in that: described a The conductivity of the deionized water used in step is not higher than 20 μ S/cm.
9. according to the preparation method of the used for cosmetic Prussian blue sphere pigments described in claim 7 or 8, it is characterised in that:
SnCl described in step B4Solution, TiCl4The concrete Adding Way of solution is as follows:
I. suspension is warming up to 65 DEG C～70 DEG C, and its pH value is adjusted to 1.0-1.5, then add under constant temperature stirs and account for institute State SiO2Spherical substrate mass 0.5 wt% SnCl4, and keep pH value constant in the process；As described SnCl4Interpolation terminates After, continue constant temperature stirring 20～30 min；
II. the suspension after I step process is warming up to 70 DEG C～75 DEG C, and its pH value is adjusted to 2.1, then at constant temperature Stirring is lower adds 2mol/L TiCl4Solution is until the color of described suspension becomes silvery white, and keeps pH value in the process Constant；
III. after II step terminates, constant temperature stirring 20～30 min, then suspension is filtered, 120 DEG C are dried, forge for 740 DEG C Burn 5min, thus prepare white spherical pigment particles；
AlCl described in E step3Solution and FeCl3Solution, K4Fe(CN)6The concrete Adding Way of solution is as follows:
1). the IIIth suspension is warming up to 75 DEG C, and its pH value is adjusted to 5.5, be then slowly added dropwise under constant temperature stirs 0.5mol/L AlCl3Solution 60ml, and drip 20% sodium hydroxide in the process to keep pH value constant；When described solution Add after terminating, continue constant temperature stirring 20～30 min；
2). by through 1) suspension after step process is warming up to 75 DEG C, and its pH value is adjusted to 3.2, then stir at constant temperature Lower addition FeCl3Solution, K4Fe(CN)6Solution, the flow controlling two kinds of solution is constant with holding pH value, until described suspension Color become Prussian blue.
CN201610653836.0A 2016-08-11 2016-08-11 Prussian blue sphere pigments used for cosmetic and preparation method thereof Pending CN106280570A (en)

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