CN103773083B - Optical interference color change pigment and its preparation method and application - Google Patents
Optical interference color change pigment and its preparation method and application Download PDFInfo
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- CN103773083B CN103773083B CN201210396799.1A CN201210396799A CN103773083B CN 103773083 B CN103773083 B CN 103773083B CN 201210396799 A CN201210396799 A CN 201210396799A CN 103773083 B CN103773083 B CN 103773083B
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Abstract
The invention relates to a preparation method of an optical interference pigment, and characterized in that: by an atomic layer deposition technology, alternately depositing high refractive index and low refractive index multilayer oxide thin films on a sheet substrate, and by accurate adjustment and control of the refractive index and thickness of thin film materials, obtaining the optical interference pigment with the color changed with change of visual angles. The atomic layer deposition technology can guarantee the inherent smoothness of the sheet substrate surface, has excellent covering power, and full realizes the expression of optical interference color. The preparation method of the optical interference color change pigment is used in the industries of paints, coatings, plastics, ceramics, glass and cosmetics.
Description
Technical field
The present invention designs a kind of pigment and its preparation method and application, particularly relates to a kind of optical interference camouflage paint and its preparation method and application.
Background technology
Light interfere pigment is metal oxide or the nonmetal oxide of alternately deposit high refractive index and low-refraction on flat substrates, utilize optical interference to produce color, can be used in paint, coating, plastics, pottery, glass, makeup and printing-ink industry.The interference color of pigment are determined by the light refractive index of oxide skin and thickness.If thin-film refractive index and gauge control improper, will coated interference pigment be made to reflect too many light at whole visible light wave range, cause human eye perceives very bright, but do not have coloured phenomenon.Therefore, in order to obtain the colour index of controlling diaphragm system, the necessary fine adjustment each other of thickness of each layer, controls thickness error in the scope of Ethylmercurichlorendimide level.Main application wet-chemical coating method prepares light interfere pigment on the flat substrates such as mica, glass, tinsel at present.Such as, but wet chemical method, sol-gel method, accurately can not control the thickness of each rete within the scope of Ethylmercurichlorendimide level.In addition, wet chemical method can cause the intrinsic smoothness deterioration on the surface of sheet material, and the dispersity of particle is not enough, causes irregular reflection, can not make full use of the reflected light of slice surfaces, fully can not realize the expression of interference color.Ald (Atomic Layer Deposition, ALD) technology can well solve above-mentioned technical problem.The presoma reacted keeps being separated each other, does not directly occur to react between gas phase, only surface chemical reaction occurs.Deposit film can reach the control of atomic level, film thickness simply and accurately controls by the cycle number of reaction, the multilayer film of heterogeneity also can directly obtain, and has the ability of big area, batch deposition film, and film has excellent model keeping character and repeatability.Atomic layer deposition method also can ensure the intrinsic smoothness on sheet material surface, has fabulous covering power, fully realizes the expression of optical interference look.
Summary of the invention
Object of the present invention is for the deficiency of current techniques, a kind of preparation method of brand-new optical interference pigment is provided, namely use technique for atomic layer deposition on flat substrates, alternately prepare the oxide membranous layer of high refractive index and low-refraction, the thickness of accurate control rete, obtains the coated interference pigment reflecting different colours light with viewing angle difference.
The surface albedo of a film structure determined is the function of lambda1-wavelength and input angle.When a given input angle, just can obtain this film structure under this condition by the reflection spectrum curve of Wavelength distribution, each film structure determined has corresponding reflection spectrum, and the change with input angle changes by this reflection spectrum.Carry out Film Design as required, reasonable computation apolegamy film material and thicknesses of layers, change refractive index and film thickness value, just can reach predetermined reflection spectrum index.The optical thin film with interference structure can be obtained light interfere pigment after a series of process such as pulverizing, classification, surface treatment.Under certain vacuum condition, utilize technique for atomic layer deposition the oxide material of different refractivity successively alternating deposition on flat substrates, homogeneity and the compactness of rete can be ensured, and the error of thicknesses of layers can control in the scope of Ethylmercurichlorendimide level, this ensure that in technique, and optical interference pigment performance is stablized, compact structure, can not fade, have strong weathering resistance and shear resistant.
The invention provides a kind of preparation method of optical interference pigment, it is characterized in that, on flat substrates, the multilevel oxide film of deposit high refractive index and low-refraction is replaced by technique for atomic layer deposition, fine adjustment and the specific refractory power and the thickness that control thin-film material, obtain the light interfere pigment that color changes with visual angle change.
Described ald at flat substrates deposit high refractive index sull is: the reaction chamber of atomic layer deposition apparatus is evacuated to 10 ~ 16 hPa, question response cavity temperature reaches 100 ~ 300 DEG C, start the first reactant zinc, or tin, or the high pure nitrogen pulse that the presoma of titanium passes into 0.1 ~ 0.3 second enters reaction chamber, by being chemically adsorbed on flat substrates, pass into 3 ~ 5 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excess zinc in reaction chamber again, or tin, or titanium precursors; Then 0.1 ~ 0.3 second water vapor is passed into, or other oxygen source presoma pulses, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 3 ~ 5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain certain thickness high refractive index layer.
Described ald refers at flat substrates deposition low-refraction sull: the reaction chamber of atomic layer deposition apparatus is evacuated to 10 ~ 16 hPa, question response cavity temperature reaches 100 ~ 300 DEG C, start the first reactant aluminium, or the high pure nitrogen pulse that the presoma of silicon passes into 0.1 ~ 0.3 second enters reaction chamber, by being chemically adsorbed on flat substrates, pass into 3 ~ 5 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excess of aluminum in reaction chamber again, or silicon precursor; Then 0.1 ~ 0.3 second water vapor is passed into, or other oxygen source presoma pulses, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 3 ~ 5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain a low-index layer.
Described high-index material be not less than in visible light wave range specific refractory power 2 oxide material, be specially zinc oxide or titanium oxide or stannic oxide; Described low-index material be visible light wave range specific refractory power not higher than 1.8 oxide material, be specially aluminum oxide or silicon oxide.
Described multilevel oxide thin film has following film structure feature: H/L/ ... / H, H is the oxide membranous layer of high refractive index, L is the oxide membranous layer of low-refraction, high low-index film H and L alternating deposit, and last one deck is high refractive index layer H, total number of plies of whole film structure is an odd number, and is less than or equal to 9.
The thickness of described individual layer high refractive index layer (H) and individual layer low-index film (L) is 20 nanometer to 200 nanometers.
Described flat substrates is mica, or tinsel, or glass.
The flat substrates of deposition oxide film is pulverized, obtains optical interference pigment.
The invention provides a kind of optical interference pigment prepared by aforesaid method.
The present invention also provides the application of the optical interference camouflage paint prepared by aforesaid method in paint, coating, plastics, pottery, glass, cosmetic industry.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
Flat substrates mica (size is 20 ~ 60 microns) is put into atomic layer deposition apparatus carry powdered sample annex after be placed in reaction chamber again, be evacuated between 10 ~ 16hPa.Question response cavity temperature reaches 150 DEG C, start the process of ald zinc oxide film (H layer): the high pure nitrogen pulse that zinc ethyl presoma passes into 0.1 second enters reaction chamber, by being chemically adsorbed on mica, then pass into 3 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excessive zinc ethyls in reaction chamber; Then pass into water vapor pulse in 0.1 second, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the zinc-oxide film of a circulation, repeats the zinc oxide film (H layer) that said process obtains thickness about 54 nanometer for 271 times.After H layer has deposited, deposit L layer alumina layer again: the trimethyl aluminium presoma pulse continuing to pass into reaction chamber 0.1 second, make it with the mode saturated adsorption of chemistry on the surface of zinc oxide film, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, and repetition said process obtains the alumina layer (L layer) that thickness is about 64 nanometers for 638 times.Finally, continue the zinc oxide film of deposition 54 nanometer as previously described, complete the optical interference pigment of H/L/H trilamellar membrane architecture.When observation visual angle is changed by Vertical dimension level, the color of coated interference pigment is changed to redness through purple by hyacinthine.
Embodiment 2:
Flat substrates mica (size is 20 ~ 60 microns) is put into atomic layer deposition apparatus carry powdered sample annex after be placed in reaction chamber again, be evacuated between 10 ~ 16hPa.Question response cavity temperature reaches 150 DEG C, start the process of ald zinc oxide film (H layer): the high pure nitrogen pulse that zinc ethyl presoma passes into 0.1 second enters reaction chamber, by being chemically adsorbed on mica, then pass into 3 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excessive zinc ethyls in reaction chamber; Then pass into water vapor pulse in 0.1 second, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the zinc-oxide film of a circulation, repeats the zinc oxide film (H layer) that said process obtains thickness about 54 nanometer for 271 times.After H layer has deposited, deposit L layer alumina layer again: the trimethyl aluminium presoma pulse continuing to pass into reaction chamber 0.1 second, make it with the mode saturated adsorption of chemistry on the surface of zinc oxide film, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, and repetition said process obtains the alumina layer (L layer) that thickness is about 64 nanometers for 638 times.Continue the zinc oxide film of repeated deposition 54 nanometer and the alumina layer of 64 nanometers successively.Finally, continue the zinc oxide film of deposition 54 nanometer as previously described, complete the optical interference pigment of H/L/H/lH five tunic architecture.When observation visual angle is changed by Vertical dimension level, the color of coated interference pigment changes with embodiment 1 described in similar through purple to redness by hyacinthine, but the saturation ratio of color is higher.
Embodiment 3:
Flat substrates mica (size is 20 ~ 60 microns) is put into atomic layer deposition apparatus carry powdered sample annex after be placed in reaction chamber again, be evacuated between 10 ~ 16hPa.Question response cavity temperature reaches 150 DEG C, start the process of ald titanium oxide layer (H layer): the high pure nitrogen pulse that four (dimethylamine) titanium precursors passes into 1 second enters reaction chamber, by being chemically adsorbed on mica, then pass into 3 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excessive four (dimethylamine) titaniums in reaction chamber; Then pass into water vapor pulse in 0.1 second, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 4 seconds high pure nitrogen pulse cleanings.Said process completes the deposition of the thin film of titanium oxide of a circulation, repeats the titanium oxide layer (H layer) that said process obtains thickness about 51 nanometer for 729 times.After H layer has deposited, deposit L layer alumina layer again: the trimethyl aluminium presoma pulse continuing to pass into reaction chamber 0.1 second, make it with the mode saturated adsorption of chemistry on the surface of titanium oxide layer, then fall unnecessary trimethyl aluminium presoma with 3 seconds high pure nitrogen pulse cleanings; Then pass into water vapor pulse 0.1 second, then fall unnecessary water vapor with the high pure nitrogen pulse cleaning of 4 seconds.Said process completes the deposition of the aluminum oxide of a circulation, and repetition said process obtains the alumina layer (L layer) that thickness is about 72 nanometers for 716 times.Finally, continue the titanium oxide layer of deposition 51 nanometer as previously described, complete the optical interference pigment of H/L/H trilamellar membrane architecture.When observation visual angle is changed by Vertical dimension level, the color of coated interference pigment is changed to purple through bluish-green, blue by green.
Claims (4)
1. the preparation method of an optical interference pigment, it is characterized in that, on flat substrates, the multilevel oxide film of deposit high refractive index and low-refraction is replaced by technique for atomic layer deposition, fine adjustment and the specific refractory power and the thickness that control thin-film material, obtain the light interfere pigment that color changes with visual angle change;
Described ald at flat substrates deposit high refractive index sull is: the reaction chamber of atomic layer deposition apparatus is evacuated to 10 ~ 16 hPa, question response cavity temperature reaches 100 ~ 300 DEG C, start the first reactant zinc, or tin, or the high pure nitrogen pulse that the presoma of titanium passes into 0.1 ~ 0.3 second enters reaction chamber, by being chemically adsorbed on flat substrates, pass into 3 ~ 5 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excess zinc in reaction chamber again, or tin, or titanium precursors; Then 0.1 ~ 0.3 second water vapor is passed into, or other oxygen source presoma pulses, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 3 ~ 5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain certain thickness high refractive index layer;
Described ald refers at flat substrates deposition low-refraction sull: the reaction chamber of atomic layer deposition apparatus is evacuated to 10 ~ 16 hPa, question response cavity temperature reaches 100 ~ 300 DEG C, start the first reactant aluminium, or the high pure nitrogen pulse that the presoma of silicon passes into 0.1 ~ 0.3 second enters reaction chamber, by being chemically adsorbed on flat substrates, pass into 3 ~ 5 seconds high pure nitrogen pulse cleaning substrate adsorbs for physically, excess of aluminum in reaction chamber again, or silicon precursor; Then 0.1 ~ 0.3 second water vapor is passed into, or other oxygen source presoma pulses, be chemically adsorbed to the first reactive material, then fall unnecessary water vapor with 3 ~ 5 seconds high pure nitrogen pulse cleanings, or other oxygen source presomas; Repeat said process and obtain a low-index layer;
Described high-index material be not less than in visible light wave range specific refractory power 2 oxide material, be specially zinc oxide or titanium oxide or stannic oxide; Described low-index material be visible light wave range specific refractory power not higher than 1.8 oxide material, be specially aluminum oxide or silicon oxide;
Described multilevel oxide thin film has following film structure feature: H/L/ ... / H, H is the oxide membranous layer of high refractive index, L is the oxide membranous layer of low-refraction, high low-index film H and L alternating deposit, and last one deck is high refractive index layer H, total number of plies of whole film structure is an odd number, and is less than or equal to 9;
The thickness of described individual layer high refractive index layer (H) and individual layer low-index film (L) is 50 nanometer to 70 nanometers;
The flat substrates of deposition oxide film is pulverized, obtains optical interference pigment.
2. the preparation method of a kind of optical interference camouflage paint according to claim 1, is characterized in that, described flat substrates is mica, or tinsel, or glass.
3. the optical interference pigment prepared by the method described in claim 1 ~ 2 any one.
4. by the application of optical interference camouflage paint in paint, coating, plastics, pottery, glass, cosmetic industry described in claim described in 3.
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| CN107400403A (en) * | 2017-06-28 | 2017-11-28 | 浙江伟星实业发展股份有限公司 | A kind of Summoning slide fastener of changeable colour and preparation method thereof |
| CN108867025B (en) * | 2018-06-01 | 2020-12-11 | 大连理工大学 | Colored carbon fiber material based on one-dimensional photonic crystal and preparation method thereof |
| CN109343215B (en) * | 2018-10-17 | 2021-03-05 | 宁波融光纳米科技有限公司 | Method for automatically designing structural color pigment optical film |
| CN109322142A (en) * | 2018-10-25 | 2019-02-12 | 武汉纺织大学 | A kind of processing method of antibacterial textile |
| CN111103638A (en) * | 2018-10-26 | 2020-05-05 | 深圳市融光纳米科技有限公司 | Optical film with protective layer, nano-structure color crystal and preparation method |
| CN109355641B (en) * | 2018-11-06 | 2020-12-04 | 华中科技大学无锡研究院 | Method for modifying surface of inorganic pigment |
| CN112558192B (en) * | 2019-09-25 | 2023-06-02 | 深圳市融光纳米科技有限公司 | Optical film, nano-structure color crystal, and mixture and preparation method thereof |
| CN110885972A (en) * | 2019-10-30 | 2020-03-17 | 杭州美迪凯光电科技股份有限公司 | ALD preparation method for eliminating dot defects of camera module and product thereof |
| CN110767668B (en) * | 2019-12-30 | 2020-03-27 | 杭州美迪凯光电科技股份有限公司 | CLCC packaging body cover plate with nanoscale surface, packaging body and camera module |
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