CN106867280A - Iron system pearlescent pigment of high chroma high brightness based on synthetic mica and its production and use - Google Patents
Iron system pearlescent pigment of high chroma high brightness based on synthetic mica and its production and use Download PDFInfo
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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
- C09C1/40—Compounds of aluminium
- C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- 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
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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
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/66—Hue (H*)
Abstract
The present invention relates to a kind of iron system pearlescent pigment of the high chroma high brightness based on synthetic mica, it includes (a) synthetic mica substrate successively, b () thickness is the oxide skin(coating) of the low-refraction of 5-20nm for iron oxide layer (c) thickness of high index of refraction in substrate of 50-300nm, the iron oxide layer of the high index of refraction of (d) thickness 20-50nm, the oxide skin(coating) of the low-refraction of (e) thickness 100-300nm, f () thickness is the iron oxide layer of the high index of refraction of 50-300nm, and (g) optional outer layer or process layer.By controlling and adjust different pH values, the corresponding soluble-salt of each layer material is hydrolyzed alternately be coated in synthetic mica substrate and is formed multiple interfaces, with increase light reflection and folding so as to improve chroma luminance.The pearlescent pigment can be applied to paint, coating, plastics, colored leather, wallpaper, cosmetics etc..
Description
Technical field
The present invention relates to pearlescent pigment, specifically relate in synthetic mica substrate by using alternately cladding height refractive index
The pearlescent pigment of the high chroma high brightness of the sandwich construction that oxide is formed.
Background technology
Pearlescent pigment is gradually widely used in traditional organic and inorganic, metallic pigments application fields as a kind of novel pigment.
Design feature based on pearlescent pigment, pearlescent pigment not only has the color of traditional inorganic organic pigment, and with certain
The luster effect of metallic pigments, while safety and environmental protection.With the development of society, the lifting of people's aesthetic standards, to the color of pigment
The requirement more and more higher of color and Safety and Environmental Protection, the research of pearlescent pigment substitution conventional pigment also necessarily turns into trend.
Be commercialized the pearlescent pigment of the TiO 2 series with stronger interference color effect that common two major class is at present, with interference colours
With the iron oxide pearlescent pigment for absorbing color.Just because of the characteristics of the absorption color and interference colours of iron oxide pearlescent pigment, make its into
It is that the inorganic iron oxide pigment of substitution and organic red pigment are possibly realized, therefore, this also result in extensive research both at home and abroad.
It is roughly divided into following aspect：1st, coated by other slaines that adulterate in soluble iron salt solutions, for example
CN101517011B changes structure and obtains color by the formation ferrite such as the zinc that adulterates, copper.2nd, carried out using special base material
It is prepared by cladding soluble iron salting liquid, such as DE102005002124.7 descriptions by be precisely controlled silica base material thickness and
The thickness sum of iron oxide obtains strong red effect pigment in 470-500nm.3rd, one is adulterated by the iron oxide layer of cladding
Prepared by the mode of the certain thickness low refraction oxide of layer, such as CN10242312, CN103797076 point out logical formation folding high
The rate of penetrating/grazing shot rate/refraction structure high can obtain high chroma pigment.Compared to traditional iron oxide pearlescent pigment, exist by with upper type
Can be improved in colourity, but, there is certain deficiency in terms of synthesis technique and product colourity, brightness.
Existing theory thinks, when the iron oxide layer of high index of refraction replaces cladding substrate with the oxide skin(coating) of low-refraction, compared to
Traditional mono-layer oxidized iron cladding mode, the colourity of pearlescent pigment and brightness are significantly improved, and pearlescent pigment is wanted to show
Excellent colourity and brightness, it is necessary to ensure that iron oxide layer has enough thickness.The iron oxide layer thickness of CN103797076 descriptions
Not enough, therefore colour saturation is not high.CN102492312 describes iron oxide layer enough thickness, yet with iron oxide and mica
Thermal coefficient of expansion it is different, when sufficiently thick oxide layer is coated on carries out high-temperature calcination on mica, inevitably result in iron oxide
There is crackle with the interfacial separation of mica or the iron oxide layer itself of thickness in layer, influences the quality of pearly-lustre.Therefore, in order to solve with
Present on problem, the technology that the present invention is provided is while ensureing iron oxide layer thickness, to draw by thick iron oxide layer
Enter certain thickness silicon dioxide layer cushioning effect and solve the problems, such as that crackle occur in interfacial separation and iron oxide layer itself.
The content of the invention
The present invention is intended to provide a kind of iron system pearlescent pigment of the high chroma high brightness based on synthetic mica and preparation method thereof.The method
Key problem in technology is, with synthetic mica base material, multiple inhomogenous interfaces to be formed by the oxide of alternately cladding height refractive index,
And control the thickness of pearl each clad to form the pearlescent pigment of enhancing chroma luminance.
" optional " expression in this application is with or without." optionally " representing carries out or does not carry out.
The iron system pearlescent pigment of the high chroma high brightness based on synthetic mica of the invention includes (a) synthetic mica substrate, (b) successively
Thickness is the iron oxide layer of the high index of refraction coated in substrate of 50-300nm, and (c) thickness is the low-refraction of 5-20nm
Oxide skin(coating) (such as silicon dioxide layer or alumina layer), magnesium fluoride layer or magnesium silicate layer, the refraction high of (d) thickness 20-50nm
The iron oxide layer of rate, the oxide skin(coating) (such as silica or aluminum oxide) of the low-refraction of (e) thickness 100-300nm, fluorination
Magnesium layer or magnesium silicate layer, (f) thickness is the iron oxide layer of the high index of refraction of 50-300nm, and (g) optional outer layer or place
Reason layer or protective layer (such as thickness 5-25nm).
The high index of refraction refers to that refractive index is more than 1.8, and especially refractive index is more than 2.5, such as 2.94-3.22, such as 3.01.
The low-refraction refers to that refractive index is less than 1.7, preferably shorter than 1.6, more preferably less than 1.5.
Preferably, the thickness of the layer (b) be 50-300nm, more preferably preferably 60-200nm, 70-180nm, more preferably
80-150nm.The thickness of the layer (c) is 5-20nm, preferably more preferably 7-18nm, 10-15nm.The thickness of the layer (d) is
20-50nm, more preferably 25-45nm, more preferably 30-40nm.The thickness of the layer (e) is 100-300nm, more preferably
130-270nm, preferably 150-250nm, more preferably 160-220nm.The thickness of the layer (f) be 50-300nm, preferably 60-200nm,
More preferably 70-180nm, more preferably 80-150nm.
The synthetic mica is preferably fluorophologopite, and particle size range is 1--100 μm, more preferably preferably 3-60 μm, 5-45
μm.Average grain diameter is 5-60 μm, preferably 7-45 μm, more preferably more preferably 10-40 μm, 15-28 μm.
Invention additionally provides the preparation method of above-mentioned pearlescent pigment, the method includes：
(A) synthetic mica is added water and is made slurry；
(B) water-soluble molysite corresponding with iron oxide is added in slurry prepared by step (A), by hydrolyzing cladding refraction high
The iron oxide layer of rate so that its thickness is 50-300nm；
(C) by using the soluble silicate (such as sodium metasilicate or potassium silicate or lithium metasilicate) corresponding with the oxide of low-refraction
Or aluminum soluble salt (such as alchlor or aluminum nitrate) is hydrolyzed, or by soluble fluoride (such as potassium fluoride or sodium fluoride or fluorine
Change lithium) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), or by soluble silicate (such as sodium metasilicate or potassium silicate or
Lithium metasilicate) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), coated on the iron oxide layer of step (B) cladding low
The oxide skin(coating) (such as silicon dioxide layer or alumina layer) of refractive index, magnesium fluoride layer or magnesium silicate layer so that its thickness is
5-20nm；
(D) wrapped in the film layer of the low-refraction coated in step (C) by hydrolysis using water-soluble molysite corresponding with iron oxide
Cover the iron oxide layer of high index of refraction so that its thickness is 20-50nm；
(E) by using the soluble silicate (such as sodium metasilicate or potassium silicate or lithium metasilicate) corresponding with the oxide of low-refraction
Or aluminum soluble salt (such as alchlor or aluminum nitrate) is hydrolyzed, or by soluble fluoride (such as potassium fluoride or sodium fluoride or fluorine
Change lithium) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), or by soluble silicate (such as sodium metasilicate or potassium silicate or
Lithium metasilicate) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), coated on the iron oxide layer of step (D) cladding low
The oxide skin(coating) (such as silicon dioxide layer or alumina layer) of refractive index, magnesium fluoride layer or magnesium silicate layer so that its thickness is
100-300nm；
(F) wrapped in the film layer of the low-refraction coated in step (E) by hydrolysis using water-soluble molysite corresponding with iron oxide
Cover the iron oxide layer of high index of refraction so that its thickness is 50-300nm, then filters mixture, washs, dries；
(G) material that step (F) is obtained is calcined, is such as calcined at 800-900 DEG C, obtained pearlescent pigment product；
With
Optionally, (H) coats (such as thickness on the pearlescent pigment product surface that step (G) is obtained with organo silane coupling agent
5-25nm's) organo silane coupling agent layer (as outer layer or process layer or protective layer), then gained mixture is filtered, wash
Wash, dry.
The water-soluble molysite is, for example, iron chloride, ferric nitrate, ferric sulfate etc., preferably iron chloride.As a example by aqueous solution mass fraction
Such as 10%-20%, 10% is preferably.
The corresponding soluble-salt of oxide on low-refraction, such as silica is by silicate such as sodium metasilicate precipitation generation；
Aluminum oxide is that by aluminium chloride, aluminum nitrate etc. is formed；Magnesium fluoride is by soluble fluoride such as potassium fluoride or sodium fluoride and soluble magnesium salt
Such as magnesium chloride sedimentation generation, magnesium silicate is by such as magnesium chloride sedimentation generation of soluble silicate such as sodium metasilicate and soluble magnesium salt.
Form and aspect according to final products determine membrane wrapping thickness, and thickness can be corresponding solvable by the oxide of Fe salt, low-refraction
The addition of property salt is controlled.For example, being relative to conjunction to coat the consumption of the water-soluble molysite such as iron chloride that (b) layer is used
Into the 10-60% (weight) of mica.For the consumption for coating the compound of the low-refraction that (c) layer is used is relative to synthetic mica
1-5% (weight).For the consumption for coating the water-soluble molysite such as iron chloride that (d) layer is used is the 4-10% relative to synthetic mica
(weight).For the consumption for coating the low-refraction compound that (e) layer is used is relative to the 20-60% of synthetic mica (weight).
For the iron chloride that cladding (f) layer is used is relative to the 10-60% of synthetic mica (weight).
Optional outer layer or process layer are for example for increasing weatherability, percetage by weight of the organosilan consumption relative to synthetic mica
Scope is 1-5%, and thickness is usually 5-25nm.
It is preferred that, step (H) is cladding outer layer or process layer or protective layer：The pearlescent pigment obtained after step (F) adds water and beats
Slurry, obtains pearlescent pigment slurry, is warming up to 70-90 DEG C, preferably from about 75-80 DEG C, adjusts pH to 8.0-10.0, preferably from about 8.5-9.5,
The metasilicate pentahydrate sodium (adding in form of an aqueous solutions) of the 2-5 weight % relative to pearlescent pigment is slowly added, in adding procedure
Middle holding pH stabilizations are added and for pH to be reduced to 5.0-7.0, preferably from about 6.0-7.0 in 8.0-10.0, preferably from about 8.5-9.5,
Add the cerous nitrate of 0.1-0.5 weight % and the aluminum nitrate of 0.1-0.3 weight % relative to pearlescent pigment and be sufficiently stirred for, by pH
5.0-7.0, preferably 6.0-7.0 are reduced to, the 1-4% relative to pearlescent pigment weight, preferably from about 2% γ-glycidol is added
Ether oxygen propyl trimethoxy silicane and 1-4%, preferably from about 2%3- aminopropyl triethoxysilanes, are sufficiently stirred for, filter, wash,
Drying.
The synthetic mica is preferably fluorophologopite, and particle diameter is 1--300 μm, preferably 10-60 μm.
In addition, when the special synthetic mica piece, especially fluorophologopite piece of selection, gained pigment is obtained in that good optics effect
Should, especially as narrower particle size distribution (1.5-4.5), effect is more notable.
Described hydrolyzed PH value is 2--10, preferential 3-8.Preferably, step (B), (D), the hydrolysis of (F) be in pH2-4,
Carried out under preferably from about pH3, the step (C), the hydrolysis of (E) are carried out under pH7-10, preferably from about 7.5-8.5.
Described high-temperature calcination temperature is 700-850 DEG C, preferably 720-760 DEG C.
It is prepared according to the method described above, in the case where the corresponding soluble-salt of oxide of low-refraction is for silicate, cladding
Material is synthetic mica+Fe by the structure after calcining2O3+SiO2+Fe2O3+SiO2+Fe2O3, by adjusting what iron oxide was coated
Thickness can obtain the color of different high chromas for example：It is orange, red etc..
The present invention also provides the purposes of above-mentioned pearlescent pigment, can be widely used in coating, paint, plastics, cosmetics, leather,
The fields such as wallpaper.
Beneficial effects of the present invention：
1st, iron series of products common compared in the market, the structure that the clad of the pearlescent pigment is designed to many bed boundarys can be effective
Increase the reflection and refraction of light, and then highlight and colourity.The common iron series pearly-lustre face of high chroma high brightness can not only be obtained
The rufous of material, claret.And excellent orange series pearlescent pigment can be arrived.
2nd, the preparation method of cladding substrate is replaced with the oxide skin(coating) of low-refraction compared to the iron oxide layer of current high index of refraction,
The technology of the present invention can not only make the iron oxide layer have enough thickness the color and high brightness of high chroma is presented, while by thick
Certain thickness silicon dioxide layer is introduced in iron oxide layer, is solved because the thermal coefficient of expansion difference of iron oxide and mica causes
There is crack problem in the interfacial separation or the iron oxide layer itself of thickness occurred in high-temperature calcination.
Specific embodiment
Following examples be to further instruction of the invention, but the present invention is not limited to the following example.
Embodiment 1
Under agitation, the 100g fluorophologopite that particle size range is 5-45 μm (average grain diameter is 27 μm) is added to 2L
In soft water, and 80 DEG C are heated to, with 1:1 hydrochloric acid (concentrated hydrochloric acid (about 37%~38%) of 1 parts by volume and the water of 1 parts by volume
Mix, similarly hereinafter) by pH value regulation to 3.0, then start the liquor ferri trichloridi of slow metered 900ml 10%,
Constant pH value is carried out with 30% sodium hydroxide solution in the meantime constant, after PH then is risen into 8.0, under this pH value
The sodium silicate solution of slow metered 100ml 20%, while being controlled with 10% hydrochloric acid and keeping PH=8.0 constant.After adding
After continuing to stir half an hour, with 1:PH value is down to 3.0 by 1 hydrochloric acid, continues the tri-chlorination of slow metered 300ml 10%
Ferrous solution, it is constant to carry out constant pH value with 30% sodium hydroxide solution, continues to stir half an hour after adding, then by pH value
After rising to 8.0, the sodium silicate solution of slow metered 2000ml 20%, while being controlled with 10% hydrochloric acid and keeping PH=8.0
It is constant.After continuing to stir half an hour after adding, with 1:PH value is down to 3.0 by 1 hydrochloric acid, continues slow metered 1000ml
10% liquor ferri trichloridi, it is constant to carry out constant pH value with 30% sodium hydroxide solution, continues to stir half an hour after adding,
Filtered, wash after at 110 DEG C dry 12 hours, most 760 DEG C calcine 0.5 hour.Obtain orange pearl pigment,
The thickness of each coating layer is successively：B () iron oxide layer thickness is 75nm；C () silicon dioxide layer thickness is 15nm；(d) oxygen
It is 35nm to change iron layer thickness；E () silicon dioxide layer thickness is 160nm；(f) iron oxide layer thickness is 68nm.
Embodiment 2
Under agitation, the 100g fluorophologopite that particle size range is 5-45 μm (average grain diameter is 27 μm) is added to 2L
In soft water, and 80 DEG C are heated to, with 1:1 hydrochloric acid adjusts to 3.0 pH value, then starts slow metered 1200ml 10%
Liquor ferri trichloridi, it is constant to carry out constant pH value with 30% sodium hydroxide solution in the meantime, and PH then is risen into 8.0
Afterwards, under this pH value slow metered 100ml 20% sodium silicate solution, while being controlled and being kept with 10% hydrochloric acid
PH=8.0 is constant.After continuing to stir half an hour after adding, with 1:PH value is down to 3.0 by 1 hydrochloric acid, continues slow metered
The liquor ferri trichloridi of 600ml 10%, it is constant to carry out constant pH value with 30% sodium hydroxide solution, continues to stir half after adding
Hour, after pH value then is risen into 8.0, the sodium silicate solution of slow metered 2500ml 20%, while with 10% salt
Acid control simultaneously keeps PH=8.0 constant.After continuing to stir half an hour after adding, with 1:PH value is down to 3.0 by 1 hydrochloric acid, is continued
The liquor ferri trichloridi of slow metered 1150ml 10%, it is constant to carry out constant pH value with 30% sodium hydroxide solution, plus
It is complete after continue stir half an hour, filtered, wash after at 110 DEG C dry 12 hours, most 760 DEG C calcine 0.5 hour.
Salmon pink pearlescent pigment is obtained, the thickness of each coating layer is successively：B () iron oxide layer thickness is 84nm；(c) silicon dioxide layer
Thickness is 14nm；D () iron oxide layer thickness is 48nm；E () silicon dioxide layer thickness is 180nm；(f) iron oxide layer
Thickness is 76nm.
Embodiment 3
Under agitation, the 100g fluorophologopite that particle size range is 5-45 μm (average grain diameter is 27 μm) is added to 2L
In soft water, and 80 DEG C are heated to, with 1:1 hydrochloric acid adjusts to 3.0 pH value, then starts slow metered 1400ml 10%
Liquor ferri trichloridi, it is constant to carry out constant pH value with 30% sodium hydroxide solution in the meantime, and PH then is risen into 8.0
Afterwards, under this pH value slow metered 80ml 20% sodium silicate solution, while being controlled with 10% hydrochloric acid and keeping PH=8.0
It is constant.After continuing to stir half an hour after adding, with 1:PH value is down to 3.0 by 1 hydrochloric acid, continues slow metered 250ml 10%
Liquor ferri trichloridi, it is constant to carry out constant pH value with 30% sodium hydroxide solution, continues to stir half an hour after adding, so
After pH value is risen into 8.0 afterwards, the sodium silicate solution of slow metered 3000ml 20%, while being controlled simultaneously with 10% hydrochloric acid
Keep PH=8.0 constant.After continuing to stir half an hour after adding, with 1:PH value is down to 3.0 by 1 hydrochloric acid, continues slow metering
The liquor ferri trichloridi of 1000ml 10% is added, it is constant to carry out constant pH value with 30% sodium hydroxide solution, continued after adding
Stirring half an hour, filtered, wash after at 110 DEG C dry 12 hours, most 760 DEG C calcine 0.5 hour.Obtain red
Color pearlescent pigment, the thickness of each coating layer is successively：B () iron oxide layer thickness is 98nm；C () silicon dioxide layer thickness is
9nm；D () iron oxide layer thickness is 27nm；E () silicon dioxide layer thickness is 210nm；(f) iron oxide layer thickness is
63nm。
Embodiment 4
The orange pearl pigment that embodiment 1 is obtained carries out the weather-proof treatment in surface.100g pearlescent pigments add water mashing, add water to
666ml, is warmed up to 78 DEG C, calls liquid caustic soda slowly to rise PH：9.0,5% metasilicate pentahydrate sodium solution 60mL, flow：0.5mL/min,
With 5% tartaric acid control PH：9.0.Add and use 1.5mol hydrochloric acid, flow：PH to 6.5 drops in 0.6mL/min, adds 1.0g 20.2%
Ce(NO3)3, 3.5g 4.3%Al (NO3)39H2O, stirs 15min, adjusts pH to 6.5, adds 2.0g γ-glycidol
Ether oxygen propyl trimethoxy silicane and 3- aminopropyl triethoxysilane 2.0g, stir 1 hour, filtering, washing, drying.
Gained sample is applied to the application field that automotive grade is painted and has weather-proof requirement.
The Performance Evaluation of sample：
The method that the quality evaluation of sample is stamped the card or sprayed plate using common coating.By certain pearlescent pigment be added to resin or
After being stirred in person's paint, plate is then coated with or sprays, then color and luster and finish are tested with X-Rite MA68 color difference meters.Such as
Shown in following table：
Embodiment 2 is sample of the invention with embodiment 3, (h ° of value generation close with existing product KC9502 and KC9504 form and aspect
Table form and aspect).In close form and aspect, color saturation (C* values) and brightness (L* values) are improved.Particularly colour saturation
Degree (C* values) is obviously improved.
KC9502 and 9504 is iron oxide cladding natural mica, and 9502 total coating layer thickness is about 90 nanometers, 9504
Total coating layer is 120 nanometers.
Application Example
The pearlescent pigment of above example 1-4 can apply to paint, coating, plastics, colored leather, wallpaper, powdery paints,
The fields such as cosmetics.Pearlescent pigment of the invention for example is added in paint or plastics, very excellent color and luster and color can be shown
Color effect.
Application Example 1：By taking paint spraying as an example
4.00 grams of pearlescent pigments of embodiment 2 of precise, add 4.0 grams of butyl acetates and 8.0 grams of polyester car paint resins,
Dispersed with stirring 10 minutes under agitator are placed in, are continued to add 84.0 grams of car paint resin system and is stirred 5 minutes.Before spraying first
Adjust the viscosity of coating to Ford 4 cup 14-15 seconds.It is 25 degrees Celsius, relative humidity that the temperature between spraying is controlled during spraying
It is 60%.Twice of spraying, dodges and does 10 minutes back cover varnish, dodges to do again and is toasted 30 minutes after 140 degrees Celsius.
Application Example 2：As a example by being molded application:
It is accurate to weigh polypropylene (PP) dried at 200 grams 105 DEG C and expect in plastic sealing bag, add 1 milliliter gloss oil (
It is dispersed oil) and then vibration, allow gloss oil to be sufficiently mixed with polypropylene material.Prepared to weigh 4.000 grams of embodiment 2 with assay balance
Pearl essence is added in plastic sealing bag, is vibrated again, is rubbed, and makes pearl essence full and uniform dispersion in PP particles.Barrel temperature
Reach after setting value (usually 180 DEG C~200 DEG C), the polypropylene material for preparing is added hopper the inside, use injection and melten gel function
Original clout extrusion in barrel, until extruding virgin material untill, extrusion virgin material should be glossy, free from admixture, without stain, without burning,
Bubble-free；Meanwhile, nozzle should be without clogging during injection.After two panels is as good as before and after plastic sheet out, reproduction is out
Plastic sheet is stablizes qualified product, can enter automatically normal production.
Claims (10)
1. a kind of iron system pearlescent pigment of the high chroma high brightness based on synthetic mica, it includes (a) synthetic mica substrate successively,
B () thickness is the iron oxide layer of the high index of refraction coated in substrate of 50-300nm, (c) thickness is the low folding of 5-20nm
Oxide skin(coating) (such as silicon dioxide layer or alumina layer), magnesium fluoride layer or the magnesium silicate layer of rate are penetrated, (d) thickness 20-50nm's
The iron oxide layer of high index of refraction, the oxide skin(coating) (such as silica or aluminum oxide) of the low-refraction of (e) thickness 100-300nm,
Magnesium fluoride layer or magnesium silicate layer, (f) thickness for 50-300nm high index of refraction iron oxide layer, and (g) optional outer layer or
Person's process layer or protective layer.
2. iron system according to claim 1 pearlescent pigment, wherein, the high index of refraction refer to refractive index more than 1.8, especially
Its refractive index is more than 2.5, such as 2.94-3.22, such as 3.01；And/or
The low-refraction refers to that refractive index is less than 1.7, preferably shorter than 1.6, more preferably less than 1.5.
3. iron system according to claim 1 and 2 pearlescent pigment, wherein, the thickness of the layer (b) is 60-200nm, more
It is preferred that 70-180nm, more preferably 80-150nm；And/or, the thickness of the layer (c) is 7-18nm, preferably 10-15nm.
4. the iron system pearlescent pigment according to any one of claim 1-3, wherein, the thickness of the layer (d) is
25-45nm, more preferably 30-40nm；And/or,
The thickness of the layer (e) is 130-270nm, more preferably preferably 150-250nm, 160-220nm；And/or,
The thickness of the layer (f) is 60-200nm, more preferably more preferably 70-180nm, 80-150nm.
5. the iron system pearlescent pigment according to any one of claim 1-4, wherein, the synthetic mica is fluorophologopite,
The particle size range of fluorophologopite is 1-100 μm, more preferably preferably 3-60 μm, 5-45 μm.
6. iron system according to claim 5 pearlescent pigment, wherein, the average grain diameter of fluorophologopite is 5-60 μm, preferably
7-45 μm, more preferably more preferably 10-40 μm, 15-28 μm.
7. the preparation method of the iron system pearlescent pigment any one of claim 1-6, the method includes：
(A) synthetic mica is added water and is made slurry；
(B) water-soluble molysite corresponding with iron oxide is added in slurry prepared by step (A), by hydrolyzing cladding refraction high
The iron oxide layer of rate so that its thickness is 50-300nm；
(C) by using the soluble silicate (such as sodium metasilicate or potassium silicate or lithium metasilicate) corresponding with the oxide of low-refraction
Or aluminum soluble salt (such as alchlor or aluminum nitrate) is hydrolyzed, or by soluble fluoride (such as potassium fluoride or sodium fluoride or fluorine
Change lithium) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), or by soluble silicate (such as sodium metasilicate or potassium silicate or
Lithium metasilicate) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), coated on the iron oxide layer of step (B) cladding low
The oxide skin(coating) (such as silicon dioxide layer or alumina layer) of refractive index, magnesium fluoride layer or magnesium silicate layer so that its thickness is
5-20nm；
(D) wrapped in the film layer of the low-refraction coated in step (C) by hydrolysis using water-soluble molysite corresponding with iron oxide
Cover the iron oxide layer of high index of refraction so that its thickness is 20-50nm；
(E) by using the soluble silicate (such as sodium metasilicate or potassium silicate or lithium metasilicate) corresponding with the oxide of low-refraction
Or aluminum soluble salt (such as alchlor or aluminum nitrate) is hydrolyzed, or by soluble fluoride (such as potassium fluoride or sodium fluoride or fluorine
Change lithium) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), or by soluble silicate (such as sodium metasilicate or potassium silicate or
Lithium metasilicate) reacted with soluble magnesium salt (such as magnesium chloride or magnesium nitrate), coated on the iron oxide layer of step (D) cladding low
The oxide skin(coating) (such as silicon dioxide layer or alumina layer) of refractive index, magnesium fluoride layer or magnesium silicate layer so that its thickness is
100-300nm；
(F) wrapped in the film layer of the low-refraction coated in step (E) by hydrolysis using water-soluble molysite corresponding with iron oxide
Cover the iron oxide layer of high index of refraction so that its thickness is 50-300nm, mixture is filtered, washed, dried；
(G) calcined material for obtaining step (F), such as calcine at 800-900 DEG C, obtains pearlescent pigment product；With
Optionally, (H) coats (such as thickness on the pearlescent pigment product surface that step (G) is obtained with organo silane coupling agent
5-25nm's) organo silane coupling agent layer, then gained mixture is filtered, wash, dry.
8. method according to claim 7, wherein the use of the water-soluble molysite such as iron chloride used for cladding (b) layer
Amount be relative to the 10-60% of synthetic mica (weight), and/or, be the use of the compound of low-refraction that cladding (c) layer is used
Amount be relative to the 1-5% of synthetic mica (weight), and/or, be the use of water-soluble molysite such as iron chloride that cladding (d) layer is used
Amount be relative to the 4-10% of synthetic mica (weight), and/or, be the consumption of low-refraction compound that cladding (e) layer is used
Be relative to the 20-60% of synthetic mica (weight), and/or, for the cladding iron chloride that uses of (f) layer is relative to synthetic mica
10-60% (weight).
9. the method according to any one of claim 7-9, wherein step (H) are cladding outer layer or process layer or protective layers：
The pearlescent pigment obtained after step (F) adds water mashing, acquisition pearlescent pigment slurry, is warming up to 70-90 DEG C, preferably from about 75-80
DEG C, pH to 8.0-10.0, preferably from about 8.5-9.5 are adjusted, it is slowly added the inclined silicon of five water of the 2-5 weight % relative to pearlescent pigment
Sour sodium (adding in form of an aqueous solutions), keeps pH stabilizations in 8.0-10.0, preferably from about 8.5-9.5 in adding procedure, adds
PH is reduced to 5.0-7.0, preferably from about 6.0-7.0, the cerous nitrate and 0.1-0.3 of the 0.1-0.5 weight % relative to pearlescent pigment is added
The aluminum nitrate of weight % is simultaneously sufficiently stirred for, and pH is reduced into 5.0-7.0, preferably 6.0-7.0, is added relative to pearlescent pigment weight
1-4%, preferably from about 2% γ-glycidyl ether oxygen propyl trimethoxy silicane and 1-4%, the preferably from about second of 2%3- aminopropyls three
TMOS, is sufficiently stirred for, and filters, washs, dries.
10. iron system pearlescent pigment according to any one of claim 1-6 or by any one of claim 7-9
The iron system pearlescent pigment that method is obtained is applied to the purposes of coating, paint, plastics, cosmetics, leather or wallpaper.
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| CN110358327A (en) * | 2019-07-25 | 2019-10-22 | 汕头市镇发珠光颜料有限公司 | A kind of high-purity red pearl effect pigment and preparation method thereof |
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| CN103797076A (en) * | 2012-09-10 | 2014-05-14 | Cqv株式会社 | Interference pigment having higher color intensity and method for preparing same |
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