CN114958036B - Pearlescent pigment and preparation method thereof - Google Patents
Pearlescent pigment and preparation method thereof Download PDFInfo
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- CN114958036B CN114958036B CN202210755160.1A CN202210755160A CN114958036B CN 114958036 B CN114958036 B CN 114958036B CN 202210755160 A CN202210755160 A CN 202210755160A CN 114958036 B CN114958036 B CN 114958036B
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- 239000000049 pigment Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010926 purge Methods 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 23
- 239000010937 tungsten Substances 0.000 claims abstract description 23
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 22
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 29
- 239000002932 luster Substances 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 18
- 229910044991 metal oxide Inorganic materials 0.000 description 16
- 150000004706 metal oxides Chemical class 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 11
- 230000006872 improvement Effects 0.000 description 8
- 238000001354 calcination Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- -1 automotive coatings Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- 230000007073 chemical hydrolysis Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
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
- C09C1/0078—Pigments consisting of flaky, non-metallic substrates, characterised by a surface-region containing free metal
-
- 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
- C09C1/62—Metallic pigments or fillers
- C09C1/627—Copper
-
- 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
- C09C3/066—Treatment or coating resulting in a free metal containing surface-region
-
- 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
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
-
- 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
- C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
- C09C2200/502—Metal particles
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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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
- C09C2200/505—Inorganic particles, e.g. oxides, nitrides or carbides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of pearlescent pigment, which comprises the following steps: s1, taking pigment substrate powder, placing the pigment substrate powder into atomic layer deposition equipment, vacuumizing, and setting the temperature to be 25-300 ℃; s2, leading in the precursor A as WF 6 The method comprises the steps of carrying out a first treatment on the surface of the S3, purging excessive precursor A and byproducts by purge gas; s4, introducing a reducing precursor B; s5, purging excessive reducing precursor B and byproducts by purge gas; s6, repeating the steps S2-S5 for 1-100 times to obtain the sparkling pearlescent pigment. Compared with the traditional technology, the scheme of the invention adopts an atomic layer deposition process to plate a uniform and compact tungsten metal layer on the surface of the pigment, so that the brightness and the chromaticity of the pigment are greatly improved, and the flickering effect is better. The method has simple operation steps, can accurately control the thickness of the covering layer by controlling the flow of the precursor, the deposition time and the times, has strong controllability and good repeatability, and can obtain firm interlayer combination of the tungsten layer and the adjacent covering layer, so that the pearlescent pigment can obtain good luster and is not easy to decolor.
Description
Technical Field
The invention relates to the technical field of pigments, in particular to a pearlescent pigment and a preparation method of the pearlescent pigment.
Background
Pearlescent pigments have been widely used in various industrial products such as automotive coatings, cosmetics, plastics, printed products and construction materials due to the attractive color and luster. Pearlescent pigments are generally prepared by depositing a single or multiple layers of metal oxides on a metal pigment and subsequent calcination. The metallic pigment mainly comprises aluminum powder (silver), copper powder (gold), zinc powder and the like. Typical metal oxide layers are composed of titanium oxide, iron oxide. Pearlescent pigments of different colors are mainly made according to the variation of the thickness or sequence of metal oxides on the metallic pigment. Titanium oxide is the most widely used optical metal oxide layer, and various colors (thin to thick order) such as silver, gold, red, violet, blue, green and the like can be presented by coating titanium oxide with different thicknesses on a metal pigment. The metal oxide layer is typically coated using a liquid phase process.
Patent application publication No. CN102876090A proposes to coat the surface of the substrate with multiple layers of metal oxides of different crystal forms to produce different refractive indexes, and finally obtain the pearlescent pigment with enhanced interference effect. In the coating process, a crystal form conversion promoter Sn02 needs to be added between each metal oxide layers to strengthen the interference effect, and the coated metal oxide adopts a wet chemical hydrolysis coating method. Chinese patent CN109054457B proposes a preparation method of black pearlescent pigment, which comprises coating indium oxide as crystal guide agent, and coating high refractive index ferric oxide layer and low refractive index cobalt oxide layer alternately on the substrate by hydrolysis coating method. The hydrolytic coating method of the two schemes has the following defects: the operation steps are complicated, the conditions required to be controlled, such as the PH value, the solvent concentration and the solution dropping rate, are too many, the thickness of each metal oxide layer is difficult to control, the thickness of each metal oxide layer is consistent, and the difference of the thickness can cause errors in the color and luster of the pearlescent pigment obtained each time.
Patent publication No. CN107567484B proposes a translucent pearlescent pigment obtained by coating a metal oxide having a low refractive index and a metal oxide having a high refractive index on the surface of a metal substrate sheet in this order. The coating step of the metal oxide is carried out by hydrolysis of one or more organometallic compounds and/or by precipitation of one or more dissolved metal salts (sol-gel process), followed by calcination of the substrate sheet thus coated to convert the metal substrate sheet into the corresponding metal oxide. The method has the defects that the deposition process and the calcination process are not easy to control, the coating layer is easy to be uneven, and the coated particles are easy to form agglomeration. The uniformity and compactness of the resulting coating will be less than ideal, as it is easy to add particles at too high a concentration or at too high a reaction rate.
Disclosure of Invention
At present, pearlescent pigments are prepared by coating a plurality of layers of metal or metal oxide on a color substrate and then performing a calcination process, wherein the coating method involved has the following disadvantages: the preparation process is complex, the reaction process takes a long time, the surface of the coating layer is uneven, defects are easy to generate, the thickness of the coating layer is difficult to control accurately, the adhesive force is poor, and the like. These coating methods affect the color purity, gloss, and performance of the pearlescent pigment.
In order to solve the above problems, the inventors prepared a pearlescent pigment comprising a metallic tungsten layer, wherein the coating of the metallic tungsten layer is achieved using an advanced Atomic Layer Deposition (ALD) process. Multiple cladding layers with different refractive indices can increase the refraction and reflection of light, and tungsten refractive index is between that of TiO 2 And Al 2 O 3 The pearlescent pigment with stronger luster can be obtained by coating with the tungsten film. The technical scheme adopted by the invention is as follows.
A preparation method of pearlescent pigment adopts an atomic layer deposition process to plate a uniform and compact tungsten metal layer on the surface of pigment substrate powder, and the preparation method comprises the following steps:
s1, taking pigment substrate powder, placing the pigment substrate powder into a reaction furnace of atomic layer deposition equipment, vacuumizing, and setting the temperature of the reaction furnace to be 25-300 ℃;
s2, introducing a precursor A into the reaction furnace, wherein the precursor A is WF 6 ；
S3, purging excessive precursor A and byproducts by purge gas;
s4, introducing a reducing precursor B into the reaction furnace;
s5, purging excessive reducing precursor B and byproducts by purge gas;
s6, repeating the steps S2-S5 for 1-100 times to obtain the pearlescent pigment with flashing light.
As a further improvement of the preparation method of the pearlescent pigment, in the step S2, the precursor A is introduced for 0.1 to 120S, the holding time is 1 to 60S, and the steps of introducing and holding are circularly performed for 1 to 20 times.
As a further improvement of the preparation method of the pearlescent pigment, in the step S4, the time of introducing the precursor B is 0.1-120S, the holding time is 1-60S, and the steps of introducing and holding are circularly performed for 1-20 times.
As a further improvement of the method for producing a pearlescent pigment of the present invention, in steps S3 and S5, the purge gas is each selected from any one of nitrogen gas and argon gas.
As a further improvement of the preparation method of the pearlescent pigment, the pigment base powder is pale yellow, and the yellow pearlescent pigment with flash luminescence is obtained.
As a further improvement of the preparation method of the pearlescent pigment, the pigment base powder is light blue, and the dark blue pearlescent pigment with flash luminescence is obtained.
As a further improvement of the preparation method of the pearlescent pigment of the present invention, the pigment base powder is metal powder, glass powder, mica powder.
As a further improvement of the method for producing a pearlescent pigment of the present invention, the metal powder is aluminum powder, copper powder or zinc powder.
As a further improvement of the process for producing pearlescent pigment of the present invention, the reducing precursor B is Si 2 H 6 、SiH 4 、B 2 H 6 、H 2 In (a) and (b)Any one of them.
The pearlescent pigment prepared by the preparation method comprises pigment base powder in an inner core and a compact uniform metal tungsten layer wrapping the surface of the pigment base powder.
Compared with the prior art, the pearlescent pigment and the preparation method thereof have the following beneficial effects:
1. the ALD process is adopted to prepare the pearlescent pigment, the operation steps of the method are simple, the thickness of the coated metal tungsten layer can be accurately controlled by controlling the flow rate, the deposition time and the times of the precursor, and the method is high in controllability and good in repeatability.
2. By utilizing the better refractive index and light absorption characteristics of the metal tungsten, the color is more shiny by depositing tungsten on the pearlescent material.
3. The tungsten film coated by the ALD technology is firmly combined with the pearlescent material, so that the pearlescent pigment can obtain good luster and is not easy to decolor, and the method can be popularized to the production of any other pearlescent pigment. The metal layer and the metal oxide layer can be uniformly coated by adopting an ALD (atomic layer deposition) process, the thickness is controllable, and the combination between the layers is firm.
4. ALD process coating can solve the problems of the traditional coating method: coating is uneven, thickness is uncontrollable, adhesion is poor, etc.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
A preparation method of pearlescent pigment adopts an atomic layer deposition process to plate a uniform and compact tungsten metal layer on the surface of pigment substrate powder, and the preparation method comprises the following steps:
s1, taking pigment substrate powder, placing the pigment substrate powder into a reaction furnace of atomic layer deposition equipment, vacuumizing, setting the temperature of the reaction furnace to be 25-300 ℃ and keeping the temperature for 0.5-2.0 h. The pigment base powder may be metal powder, glass powder, mica powder, but is not limited thereto. The metal powder is preferably aluminum powder, copper powder or zinc powder, has stable property and is not easy to rust.
S2, introducing a precursor A into the reaction furnace, wherein the precursor A is WF 6 . Optionally, the precursor A is introduced for 0.1 to 120 seconds, the holding (reaction) time is 1 to 60 seconds, and the steps of introducing and holding are circularly performed for 1 to 20 times.
S3, purging excessive precursor A and byproducts by purge gas for 1-60S and purging times for 1-20 times. The purge gas may be nitrogen or argon.
S4, introducing a reducing precursor B into the reaction furnace to lead WF to be formed 6 Reducing hexavalent tungsten to metal W; the reducing precursor B may be Si 2 H 6 、SiH 4 、B 2 H 6 、H 2 Any one of these, but is not limited thereto. Wherein, optionally, the time of introducing the precursor B is 0.1-120 s, the holding time is 1-60 s, and the steps of introducing and holding are circularly performed for 1-20 times.
S5, purging excessive reducing precursor B and byproducts by purge gas for 1-60S, wherein the number of times of purging is 1-20. The purge gas may be nitrogen or argon.
S6, repeating the steps S2-S5 for 1-100 times to obtain the pearlescent pigment capable of flashing, wherein the pearlescent pigment comprises pigment base powder in an inner core and a compact and uniform metal tungsten layer wrapping the surface of the pigment base powder.
Compared with the traditional pearlescent pigment, the pearlescent pigment provided by the invention has the advantages that the Atomic Layer Deposition (ALD) process is adopted to plate a uniform and compact tungsten metal layer on the surface of the pigment, the brightness and the chromaticity are greatly improved, and the flickering effect is better. The thickness of the metal tungsten layer is precisely controlled by controlling the cycle period, so that the color depth of the pearlescent pigment is changed (such as light blue to dark blue, and the other is unchanged). The method has simple operation steps, can accurately control the thickness of the covering layer by controlling the flow of the precursor, the deposition time and the times, has strong controllability and good repeatability, can obtain firm interlayer combination of the tungsten layer and the adjacent covering layer, can ensure that the pearlescent pigment has good luster and is not easy to decolor, and can be produced in a large scale. The prepared pearlescent pigment is suitable for cosmetics, paint, automobile-grade paint and the like.
Selected examples of the present invention will be described below.
Example 1
S1, placing pale yellow pearlescent pigment into a reaction furnace of atomic layer deposition equipment, vacuumizing to 0.001-1.0 torr, setting the reaction temperature to 200 ℃ and keeping for 0.5h;
s2, WF 6 As a W source precursor, WF was introduced into a reaction furnace 6 The charging time is 2s, the reaction time is 3s, and the reaction times are 2 times;
s3, introducing N 2 Or Ar gas is used for purging excessive WF 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s4, si is 2 H 6 As a reduction precursor, si is introduced into a reaction furnace 2 H 6 The charging time is 1s, the reaction time is 2s, and the reaction times are 2 times;
s5, introducing N 2 Or Ar gas is used for purging excessive Si 2 H 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s6, repeating the steps S2 to S5 for 20 times; a yellow pigment which shines in a sparkling manner is obtained.
Example 2
S1, placing light blue pearlescent pigment into a reaction furnace of atomic layer deposition equipment, vacuumizing to 0.001-1.0 torr, setting the reaction temperature to 200 ℃ and keeping for 0.5h;
s2, WF 6 As a W source precursor, WF was introduced into a reaction furnace 6 The charging time is 2s, the reaction time is 3s, and the reaction times are 2 times;
s3, introducing N 2 Or Ar gas is used for purging excessive WF6 and byproducts for 10s, and the purging times are 3 times;
s4, si is 2 H 6 As a reduction precursor, si is introduced into a reaction furnace 2 H 6 The charging time is 1s, the reaction time is 2s, and the reaction times are 2 times;
s5, introducing N 2 Or Ar gas is used for purging excessive Si 2 H 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s6, repeating the steps 2-5 times; a sparkling dark blue pigment is obtained.
Example 3
S1, placing muscovite powder into a reaction furnace of atomic layer deposition equipment, vacuumizing to 0.001-1.0 torr, setting the reaction temperature to 200 ℃ and keeping the reaction time for 0.5h;
s2, WF 6 As a W source precursor, WF was introduced into a reaction furnace 6 The charging time is 2s, the reaction time is 3s, and the reaction times are 2 times;
s3, introducing N 2 Or Ar gas is used for purging excessive WF 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s4, si is 2 H 6 As a reduction precursor, si is introduced into a reaction furnace 2 H 6 The charging time is 1s, the reaction time is 2s, and the reaction times are 2 times;
s5, introducing N 2 Or Ar gas is used for purging excessive Si 2 H 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s6, repeating the steps 2-5 times; a sparkling white pigment is obtained.
Example 4
S1, placing reddish brown copper powder into a reaction furnace of atomic layer deposition equipment, vacuumizing to 0.001-1.0 torr, setting the reaction temperature to 200 ℃ and keeping the reaction time for 0.5h;
s2, WF 6 As a W source precursor, WF was introduced into a reaction furnace 6 The charging time is 2s, the reaction time is 3s, and the reaction times are 2 times;
s3, introducing N 2 Or Ar gas is used for purging excessive WF 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s4, si is 2 H 6 As a precursor for the reduction of the precursor,introducing Si into a reaction furnace 2 H 6 The charging time is 1s, the reaction time is 2s, and the reaction times are 2 times;
s5, introducing N 2 Or Ar gas is used for purging excessive Si 2 H 6 And by-products, the purging time is 10s, and the purging times are 3 times;
s6, repeating the steps 2-5 times; a sparkling reddish brown pigment is obtained.
In summary, the pigments prepared in examples 1 to 4 have the following characteristics: by utilizing the characteristics of good refractive index and light absorption of the metal tungsten, tungsten is deposited on the pearlescent material, so that the color of the pigment is more shiny. The tungsten film coated by the ALD technology is firmly combined with the pearlescent material, so that the pearlescent pigment can obtain good luster and is not easy to decolor, and the method can be popularized to the production of any other pearlescent pigment. The pearlescent pigment and the preparation method thereof can be used in the fields of cosmetics, coatings, paints, automobile-grade paint spraying and the like, and have wide application prospect.
Claims (10)
1. A preparation method of pearlescent pigment is characterized in that an atomic layer deposition process is adopted to plate a uniform and compact tungsten metal layer on the surface of pigment base powder, and the preparation method comprises the following steps:
s1, taking pigment substrate powder, placing the pigment substrate powder into a reaction furnace of atomic layer deposition equipment, vacuumizing, and setting the temperature of the reaction furnace to be 25-300 ℃;
s2, introducing a precursor A into the reaction furnace, wherein the precursor A is WF 6 ；
S3, purging excessive precursor A and byproducts by purge gas;
s4, introducing a reducing precursor B into the reaction furnace;
s5, purging excessive reducing precursor B and byproducts by purge gas;
s6, repeating the steps S2-S5 for 1-100 times to obtain the pearlescent pigment with flashing light.
2. The method for producing a pearlescent pigment according to claim 1, wherein in the step S2, the step of introducing and holding is performed cyclically 1 to 20 times, wherein the precursor a is introduced for 0.1 to 120 seconds and the holding time is 1 to 60 seconds.
3. The method for producing a pearlescent pigment according to claim 2, wherein in the step S4, the step of introducing and holding is performed cyclically 1 to 20 times, wherein the precursor B is introduced for 0.1 to 120 seconds and the holding time is 1 to 60 seconds.
4. The method for producing a pearlescent pigment according to claim 1, wherein in steps S3 and S5, the purge gas is selected from any one of nitrogen and argon.
5. The method for preparing pearlescent pigment according to claim 1, wherein the pigment base powder is pale yellow to obtain a sparkling yellow pearlescent pigment.
6. The method for preparing pearlescent pigment according to claim 1, wherein the pigment base powder is light blue, resulting in a sparkling dark blue pearlescent pigment.
7. The method for preparing pearlescent pigment according to claim 1, wherein the pigment base powder is a metal powder, a glass powder, or a mica powder.
8. The method for producing a pearlescent pigment according to claim 7, wherein the metal powder is aluminum powder, copper powder or zinc powder.
9. The method for producing pearlescent pigment according to claim 1, wherein the reducing precursor B is Si 2 H 6 、SiH 4 、B 2 H 6 、H 2 Any one of the following.
10. A pearlescent pigment, characterized in that it is prepared according to the preparation method of any one of claims 1 to 9; the pearlescent pigment comprises pigment base powder in an inner core and a compact uniform tungsten metal layer wrapping the surface of the pigment base powder.
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