CN104341925A - Photoluminescent coating material and preparation method thereof - Google Patents

Photoluminescent coating material and preparation method thereof Download PDF

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Publication number
CN104341925A
CN104341925A CN201310318292.9A CN201310318292A CN104341925A CN 104341925 A CN104341925 A CN 104341925A CN 201310318292 A CN201310318292 A CN 201310318292A CN 104341925 A CN104341925 A CN 104341925A
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coating according
preparation
photoluminescence
embedded photoluminescent
photoluminescence coating
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CN104341925B (en
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王玮
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BYD Co Ltd
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The present invention provides a photoluminescent coating material, which comprises 12-35% of a photoluminescent material, 1-8% of natural muscovite powder, 2-6% of a dispersing agent, 1-3% of a film forming aid, 1-2% of a thickener, 0.5-2% of an antifoaming agent, 12-20% of a polymer emulsion, and the balance of deionized water. The present invention further provides a preparation method of the photoluminescent coating material. The photoluminescent coating material of the present invention has characteristics of stable performance and storage resistance of the coated product, good decoration effect, good luminescence luminosity, and high luminescence brightness, wherein the luminescence can last for more than 10 h after the photoluminescent coating material absorbs light for 1 h.

Description

A kind of photoluminescence coating and preparation method thereof
Technical field
The invention belongs to field of new, particularly relate to a kind of photoluminescence coating and preparation method thereof.
Background technology
Luminescent material, to refer under the effect of all kinds energy excitation can be luminous material, he is widely used in, in various instruction series products, making product shinny at dark place.Along with the development and progression of Materials science, the type of luminescent material is also changeful, and its application is variation gradually also, is extended the application such as instantaneous light emission, permanent shining and application decoration by initial indicative function.
Embedded photoluminescent material refers to UV-light, visible or infrared light excitation light-emitting material and the luminescence phenomenon that produces, and he is widely used in the application such as clock and watch, steamer, the panel board of aircraft, road lighting and buildings mark.Embedded photoluminescent material absorbs the energy of sunlight daytime, and then discharge in the evening, and be a kind of perfect green light source, the application prospect in safety precaution is extremely wide.
Photoluminescence roughly experiences absorption, transmission ofenergy and light emission three main phase.After embedded photoluminescent material is excited by external energy irradiation, energy directly can be absorbed (activator or impurity) by luminescence center, also can by the matrix absorption of luminescent material.Under the previous case, absorb or with the electronics in the Elektronenschale of activator to higher energy level transition; Or electronics and activator depart from completely, activator transits to ionization states and forms hole; Latter event, matrix absorption energy forms hole and electronics in matrix, and hole may be moved along crystal, and is bound on each luminescence center; Radiation is because electronics turns back to initial level, or caused by electronics and ion center combine again.Ionization is excited when the particle of external energy and the atom of luminous host collide and cause.Ionization unbound electron out has certain energy, and what can cause again other atoms excites ionization, when the atom of excited state or state of ionization comes back to stable state, will cause luminescence.The energy of absorption is changed into optical radiation by luminous host, the principle of Here it is embedded photoluminescent material stimulated luminescence.
Luminous paint seen is in the market main mainly with solvent based coating, not only when coating film forming by organic solvent harmful for volatilization, and often need the strict range of application of regulation and consumption in use, its range of application be restricted.
Publication number is that the Chinese patent of CN1396220A discloses a kind of water-borne coatings, it is aqueous luminous paint, its composition and weight percent are: emulsion polymerization 20-70, embedded photoluminescent material 5-60, dispersion agent 0.1-1.0, thickening material 0.2-1.5, film coalescence aid 1-5, sanitas 0.1-0.3, defoamer 0.1-0.5, water surplus.Although this patent is using water as solvent, in this coating, embedded photoluminescent material is comparatively large because of density, in a solvent than great, manufactures and there will be the problems such as precipitation, levelling property difference and film-forming properties are general in use procedure.
Summary of the invention
The present invention solves photoluminescence coating of the prior art to there is unstable properties, technical problem that intensity is low, provides a kind of stable performance, the photoluminescence coating with high strength and preparation method thereof.
The invention provides a kind of photoluminescence coating, comprise following composition and percentage composition:
Embedded photoluminescent material 12-35%
Natural muscovite powder 1-8%
Dispersion agent 2-6%
Film coalescence aid 1-3%
Thickening material 1-2%
Defoamer 0.5-2%
Polymer emulsion 12-20%
Deionized water surplus.
Present invention also offers the preparation method of this photoluminescence coating, the method comprises the steps:
S1, natural muscovite powder is put into stirrer, then add dispersion agent, film coalescence aid, thickening material and defoamer successively, be mixed to get the first mixture;
Add embedded photoluminescent material in S2, the first mixture of obtaining in step S1 and be mixed to get the second mixture;
S3, in the second mixture, add polymer emulsion and deionized water be uniformly dispersed and namely obtain photoluminescence coating.
(main component chemical constitution is KAl to the addition of natural muscovite powder in coating of the present invention 2(AlSi 3o 10) (OH) 2).White mica belongs to oblique system, macroscopic view tool vitreous luster, the light that can send coating itself has good refraction effect, coating compared with the same recipe of not adding white mica powder can make the briliancy of the coating in the present invention promote more than 30%, and the distance of coating luminescence is longer, wider, glossiness performance is better.Simultaneously, because white mica powder has higher insulativity, resistance toheat, acid-alkali-corrosive-resisting, and there is the performances such as thermal expansivity is little, the coating covering performance that with the addition of this powder significantly promotes, sticking power is also higher, and running under high-temperature condition, tool is not dangerous to make this coating, and there is safe value pole.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of photoluminescence coating, comprise following composition and percentage composition:
Embedded photoluminescent material 12-35%
Natural muscovite powder 1-8%
Dispersion agent 2-6%
Film coalescence aid 1-3%
Thickening material 1-2%
Defoamer 0.5-2%
Polymer emulsion 12-20%
Deionized water surplus.
Preferably, following composition and percentage composition is comprised:
Embedded photoluminescent material 12-20%
Natural muscovite powder 1-3%
Dispersion agent 2-4%
Film coalescence aid 2-3%
Thickening material 1.5-2%
Defoamer 0.5-0.8%
Polymer emulsion 12-18%
Deionized water surplus.
In order to better reflect the light that coating itself sends, preferably, the median size of described natural muscovite powder is for being less than 10 microns.Further be preferably 0.1-10 micron.
Photoluminescence coating provided by the present invention, described dispersion agent, membrane-forming agent, thickening material, defoamer and polymer emulsion have no particular limits, various dispersion agents, membrane-forming agent, thickening material, defoamer and the polymer emulsion that can commonly use for this area.In the present invention, at least one in the non-ammonium polyacrylate salt of described dispersion agent, poly-phosphate, alkylaryl sulphonate, quaternary ammonium salt, polyalkylene glycol alkyl phenolic ether, poly-methyl acrylate and polyacrylamide; Described film coalescence aid is at least one in ethanol, Virahol, ethylene glycol, glycerol, ether, ethylene glycol ethyl ether, phenylcarbinol and ethylene glycol ethyl ether; At least one in the non-methylcellulose gum of described thickening material, Vltra tears, Natvosol and carboxymethyl cellulose; At least one in the non-silicone emulsion of described defoamer, polyglycerol fatty acid ester and phosphoric acid ester; Described polymer emulsion is the one in pure-acrylic emulsion, benzene emulsion, ACRYLIC EMULSION and organosilicon crylic acid latex.
Photoluminescence coating provided by the present invention, wherein embedded photoluminescent material can be the photoluminescence coating of shades of colour.Preferred red light electroluminescent material, green light electroluminescent material and blue light electroluminescent material in the present invention.
In the present invention, red light electroluminescent material is α M ' S β MAl 2o 4: Eu xln y;
Wherein, M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe; M is the one in Mg, Ca, Be, Mo, Fe, Sb; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; α, β, x, y are mole coefficient: 2≤α≤4; 1≤β≤7; 0.0002≤x≤0.3; 0.02≤y≤0.1.Preferably, 2≤α≤4; 2≤β≤5; 0.01≤x≤0.2; 0.02≤y≤0.06.
In the present invention, green light electroluminescent material is α MLnS β Ln ' Al 2o 4: Eu xln y;
Wherein, M is the one in Mg, Ca, Be; Ln, Ln ' be separately independently one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ln and Ln ' is different; α, β, x, y are mole coefficient: 0.2≤α≤2; 1≤β≤5; 0.0002≤x≤0.3; 0.01≤y≤0.5; Preferably, 2≤α≤4; 1≤β≤7; 0.0001≤x≤0.15; 0.01≤y≤0.5.
In the present invention, blue light electroluminescent material is α M ' O β MAl 14o 25: Eu xln y;
Wherein, M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe, Bi; M is the one in Mg, Ca, Be; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; α, β, x, y are mole coefficient: 0.5≤α≤8; 2≤β≤6; 0.0001≤x≤0.15; 0.01≤y≤0.5.Preferably, 2≤α≤4; 1≤β≤7; 0.0001≤x≤0.15; 0.01≤y≤0.5.
Redness in the present invention, green luminescent material with the addition of sulfide.In sulfide, metal ion positive polarity is strong, and after hydrolysis, the aobvious alkalescence of solution, can not only increase the solvability of luminescent material in paint solvent to a certain extent, can also to balance in raw material other in acid composition.The most important thing is, different sulfide can increase the briliancy of different colours, as MnS, very effectively can strengthen the briliancy of green luminescent material, make the glossiness of coating and tone all meet expection.
Present invention also offers the preparation method of this photoluminescence coating, the method comprises the steps:
S1, natural muscovite powder is put into stirrer, then add dispersion agent, film coalescence aid, thickening material and defoamer successively, be mixed to get the first mixture;
Add embedded photoluminescent material in S2, the first mixture of obtaining in step S1 and be mixed to get the second mixture;
S3, in the second mixture, add polymer emulsion and deionized water be uniformly dispersed and namely obtain photoluminescence coating.
In the preparation method of photoluminescence coating provided by the present invention, wherein embedded photoluminescent material can be the photoluminescence coating of shades of colour.Preferred red light electroluminescent material, green light electroluminescent material and blue light electroluminescent material in the present invention.
Preferably, the preparation method of red light electroluminescent material is: by Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mol ratio be (1-7): (2-4): (1-7): (0.0001-0.15): (0.01-0.05); M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe; M is the one in Mg, Ca, Be, Mo, Fe, Sb; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
Preferably, Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mol ratio be (2-5): (2-4): (2-4.5): (0.005-0.1): (0.01-0.03).
Preferably, the preparation method of green light electroluminescent material is: by Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mol ratio be (1-5): (0.2-2): (0.05-1.0): (0.0001-0.15): (0.01-0.05); M is the one in Mg, Ca, Be; Ln, Ln ' be separately independently one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ln and Ln ' is different.
Preferably, Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mol ratio be (2-4): (1-2): (0.1-0.5): (0.005-0.1): (0.01-0.03).
Preferably, the preparation method of blue light electroluminescent material is: by Al 2o 3, MO, M ' CO 3, Eu 2o 3and Ln 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MO, M ' CO 3, Eu 2o 3, Ln 2o 3the mol ratio of adding is (14-75): (1-8): (2-8): (0.0001-0.15): (0.01-0.05); M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe, Bi; M is the one in Mg, Ca, Be; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
Preferably, Al 2o 3, MO, M ' CO 3, Eu 2o 3, Ln 2o 3the mol ratio of adding is (20-45): (3-5): (2-6): (0.005-0.1): (0.01-0.03).
In order to improve the performance of embedded photoluminescent material, preferably, described microwave frequency is 300MHZ-300GHz, and wavelength is 0.1-100cm, and heat-up time is 10-60 minute.Further preferably, described microwave frequency is 300MHZ-300GHz, and wavelength is 10-50cm, and heat-up time is 20-45 minute.
In order to improve the light intensity of embedded photoluminescent material, preferably, the particle diameter of described mixed powder is 1-10 μm.
Luminescent material preparation technology provided by the invention overcomes the intrinsic defect of prior synthesizing method, and as too high in high temperature solid-state method temperature of reaction, powder particles greatly and easily lump, in order to carry out the work such as follow-up stirring, filling, just must grind material.The process of grinding just seriously reduces the luminescent properties index of material.The present invention uses microwave method to prepare luminescent material, the method you enter to overcome all drawbacks of high temperature solid-state method, the fault in material that the inequality of being heated that causes because of heating in various chemical process causes can also be overcome.
The embedded photoluminescent material of red, green, blue provided by the invention three kinds of primary colors, as needed the luminescent material of other colors, then can be in harmonious proportion red, green, blue three look arbitrarily, allots desirable color matching.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
1, red illuminating material is prepared,
Raw material: Al 2o 3204 grams, MgS84 gram, CaCO 3175 grams, Eu 2o 31.76 grams, La 2o 33.26 gram.
Make mixed powder granularity be less than 10 μm above-mentioned raw materials mixed grinding, select microwave frequency to be 150GHz.Put into crucible after utilizing high velocity dispersators fully to be mixed by above-mentioned raw materials, be placed in microwave oven, heat taking-up after 40 minutes and cool and obtain red light electroluminescent material.
2, photoluminescence coating preparation:
Raw material: the embedded photoluminescent material that step 1 obtains 150 grams, 20 grams, natural muscovite powder, dispersion agent 20 grams, film coalescence aid 20 grams, thickening material 15 grams, defoamer 5 grams, polymer emulsion 150 grams, deionized water 620 grams.
First natural muscovite powder is put into stirrer, add stock dispersion agent, film coalescence aid, thickening material and defoamer successively under the low speed, after mixing, raw material embedded photoluminescent material is slowly added, add rear lifting stirrer speed.To be mixed evenly after add stock polymer emulsion and deionized water gradually, product A 1 can be obtained until be finally uniformly dispersed.
Embodiment 2-14
Prepare photoluminescence coating A2-A14 according to the method for embodiment 1, difference is: prepare each raw material of embedded photoluminescent material as table 1.
Table 1
Al 2O 3 MS M’CO 3 Eu 2O 3 Ln 2O 3 Mol ratio
Embodiment 2 Al 2O 3 CaS MgCO 3 Eu 2O 3 Ce 2O 3 1:3:1:0.0001:0.01
Embodiment 3 Al 2O 3 BeS SrCO 3 Eu 2O 3 Pr 2O 3 7:2:7:0.15:0.05
Embodiment 4 Al 2O 3 MoS BaCO 3 Eu 2O 3 Nd 2O 3 3:4:3:0.001:0.02
Embodiment 5 Al 2O 3 FeS CuCO 3 Eu 2O 3 Sm 2O 3 4:2.5:4:0.01:0.03
Embodiment 6 Al 2O 3 SbS ZnCO 3 Eu 2O 3 Eu 2O 3 5:3.5:5:0.05:0.04
Embodiment 7 Al 2O 3 CaS FeCO 3 Eu 2O 3 Gd 2O 3 6:3:6:0.01:0.01
Embodiment 8 Al 2O 3 CaS MgCO 3 Eu 2O 3 Tb 2O 3 2:3:1.5:0.0005:0.02
Embodiment 9 Al 2O 3 CaS MgCO 3 Eu 2O 3 Dy 2O 3 3:3:3:0.005:0.02
Embodiment 10 Al 2O 3 CaS MgCO 3 Eu 2O 3 Ho 2O 3 2:2:2:0.005:0.01
Embodiment 11 Al 2O 3 MgS CaCO 3 Eu 2O 3 Er 2O 3 5:4:4.5:0.1:0.03
Embodiment 12 Al 2O 3 MgS CaCO 3 Eu 2O 3 Tm 2O 3 3:3:3:0.01:0.02
Embodiment 13 Al 2O 3 MgS CaCO 3 Eu 2O 3 Yb 2O 3 3:2:5:0.008:0.015
Embodiment 14 Al 2O 3 MgS CaCO 3 Eu 2O 3 Lu 2O 3 4:3:4.5:0.08:0.025
Comparative example 1
Prepared by photoluminescence coating:
Raw material: the embedded photoluminescent material that step 1 obtains 150 grams, dispersion agent 20 grams, film coalescence aid 20 grams, thickening material 15 grams, defoamer 5 grams, polymer emulsion 150 grams, deionized water 640 grams.
After stock dispersion agent, film coalescence aid, thickening material and defoamer being mixed under stirrer low speed, raw material embedded photoluminescent material is slowly added, add rear lifting stirrer speed.To be mixed evenly after add stock polymer emulsion and deionized water gradually, can products C A1 be obtained until be finally uniformly dispersed.
Embodiment 15
1, green luminescent material is prepared,
Raw material: Al 2o 3204 grams, MnS44 gram, La 2o 333 grams, Eu 2o 31.76 grams, Dy 2o 33.73 gram.
Make mixed powder granularity be less than 10 μm above-mentioned raw materials mixed grinding, select microwave frequency to be 150GHz.Put into crucible after utilizing high velocity dispersators fully to be mixed by above-mentioned raw materials, be placed in microwave oven, heat taking-up after 40 minutes and cool and obtain green light electroluminescent material.
2, photoluminescence coating preparation:
Raw material: the embedded photoluminescent material that step 1 obtains 180 grams, 24 grams, natural muscovite powder, dispersion agent 20 grams, film coalescence aid 20 grams, thickening material 15 grams, defoamer 6 grams, polymer emulsion 270 grams, deionized water 565 grams.
First natural muscovite powder is put into stirrer, add stock dispersion agent, film coalescence aid, thickening material and defoamer successively under the low speed, after mixing, raw material embedded photoluminescent material is slowly added, add rear lifting stirrer speed.To be mixed evenly after add stock polymer emulsion and deionized water gradually, until the product A 15 that is finally uniformly dispersed to obtain.
Embodiment 16-28
Prepare photoluminescence coating A16-A28 according to the method for embodiment 15, difference is: prepare each raw material of embedded photoluminescent material as table 2.
Table 2
Al 2O 3 MS Ln 2O 3 Eu 2O 3 Ln’ 2O 3 Mol ratio
Embodiment 16 Al 2O 3 CaS Dy 2O 3 Eu 2O 3 Ce 2O 3 1:0.2:0.05:0.0001:0.01
Embodiment 17 Al 2O 3 BeS Ce 2O 3 Eu 2O 3 Pr 2O 3 2:0.5:0.08:0.001:0.02
Embodiment 18 Al 2O 3 BeS Pr 2O 3 Eu 2O 3 Nd 2O 3 3:1:0.1:0.01:0.03
Embodiment 19 Al 2O 3 BeS Nd 2O 3 Eu 2O 3 Sm 2O 3 4:1.5:0.5:0.1:0.04
Embodiment 20 Al 2O 3 BeS Sm 2O 3 Eu 2O 3 Eu 2O 3 5:2:1.0:0.15:0.05
Embodiment 21 Al 2O 3 CaS Eu 2O 3 Eu 2O 3 Gd 2O 3 2:1:0.1:0.005:0.01
Embodiment 22 Al 2O 3 CaS Gd 2O 3 Eu 2O 3 Tb 2O 3 4:2:0.5:0.1:0.03
Embodiment 23 Al 2O 3 CaS Tb 2O 3 Eu 2O 3 Dy 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 24 Al 2O 3 CaS Dy 2O 3 Eu 2O 3 Ho 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 25 Al 2O 3 MgS Ho 2O 3 Eu 2O 3 Er 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 26 Al 2O 3 MgS Er 2O 3 Eu 2O 3 Tm 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 27 Al 2O 3 MgS Tm 2O 3 Eu 2O 3 Yb 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 28 Al 2O 3 MgS Yb 2O 3 Eu 2O 3 Lu 2O 3 3:1.5:0.2:0.05:0.02
Embodiment 29
1, blue light electroluminescent material is prepared,
Raw material: Al 2o 3408 grams, MgO20 gram, CaCO 350 grams, Eu 2o 30.04 gram, Dy 2o 30.8 gram.
Grinding makes mixed powder granularity be less than 10 μm, selects microwave frequency to be 150GHz.Put into crucible after utilizing high velocity dispersators fully to be mixed by above-mentioned raw materials, be placed in microwave oven, heat taking-up after 40 minutes and cool and obtain blue light electroluminescent material.
2, photoluminescence coating preparation:
Raw material: the embedded photoluminescent material that step 1 obtains 200 grams, 20 grams, natural muscovite powder, dispersion agent 30 grams, film coalescence aid 30 grams, thickening material 20 grams, defoamer 5 grams, polymer emulsion 150 grams, deionized water 545 grams.
First natural muscovite powder is put into stirrer, add stock dispersion agent, film coalescence aid, thickening material and defoamer successively under the low speed, after mixing, raw material embedded photoluminescent material is slowly added, add rear lifting stirrer speed.To be mixed evenly after add stock polymer emulsion and deionized water gradually, product A 29 can be obtained until be finally uniformly dispersed.
Embodiment 30-42
Prepare photoluminescence coating A30-A42 according to the method for embodiment 29, difference is: prepare each raw material of embedded photoluminescent material as table 3.
Table 3
Al 2O 3 MO M’CO 3 Eu 2O 3 Ln 2O 3 Mol ratio
Embodiment 30 Al 2O 3 CaO MgCO 3 Eu 2O 3 Ce 2O 3 14:1:2:0.0001:0.01
Embodiment 31 Al 2O 3 Be O SrCO 3 Eu 2O 3 Pr 2O 3 20:2:2.5:0.0005:0.02
Embodiment 32 Al 2O 3 Be O BaCO 3 Eu 2O 3 Nd 2O 3 25:2.5:3:0.001:0.03
Embodiment 33 Al 2O 3 BeO CuCO 3 Eu 2O 3 Sm 2O 3 30:3:3.5:0.005:0.04
Embodiment 34 Al 2O 3 BeO ZnCO 3 Eu 2O 3 Eu 2O 3 35:3.5:4:0.01:0.05
Embodiment 35 Al 2O 3 CaO FeCO 3 Eu 2O 3 Gd 2O 3 40:4:4.5:0.05:0.02
Embodiment 36 Al 2O 3 CaO BiCO 3 Eu 2O 3 Tb 2O 3 45:4.5:5:0.1:0.01
Embodiment 37 Al 2O 3 CaO ZnCO 3 Eu 2O 3 La 2O 3 50:5:5.5:0.15:0.03
Embodiment 38 Al 2O 3 MgO ZnCO 3 Eu 2O 3 Ho 2O 3 55:5.5:6:0.05:0.02
Embodiment 39 Al 2O 3 MgO Ca CO 3 Eu 2O 3 Er 2O 3 60:6:6.5:0.01:0.02
Embodiment 40 Al 2O 3 MgO Ca CO 3 Eu 2O 3 Tm 2O 3 65:6.5:7:0.1:0.03
Embodiment 41 Al 2O 3 MgO Ca CO 3 Eu 2O 3 Yb 2O 3 70:7:7.5:0.15:0.02
Embodiment 42 Al 2O 3 MgO MgCO 3 Eu 2O 3 Lu 2O 3 75:8:8:0.15:0.02
Testing method and data
Photoluminescence coating A1-A42 and CA1 is coated in substrate surface, and coating thickness is 180 μm, obtains product S1-S42 and CS1.
1, stability test
Under respectively one barrel of coating A1-A42 and CA1 being positioned over the same environment in laboratory, observe the change of its painting color, whether have layering, be used further to brushing, contrast with brand-new coating application effect after leaving standstill for some time, whether range estimation has significant change.The results are shown in Table 4.
2, outward appearance
Detect by an unaided eye the outward appearance of product S1-S42 and CS1, the results are shown in Table 4.
3, light emission luminosity
Product S1-S42 and CS1 is placed on extinction 1h under same light source, then places it in same environment and carry out luminescence, record its fluorescent lifetime, the results are shown in Table 4.
4, briliancy
By the briliancy of brightness photometer measure product S1-S42 and CS1, the results are shown in Table 4.
Table 4
As can be seen from Table 4, the product performance of photoluminescence paint of the present invention are stable, resistance to be deposited, and good decorating effect, light emission luminosity is good, and sustainable luminous more than the 10h of extinction 1h, glorious degrees is large.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (23)

1. a photoluminescence coating, is characterized in that, comprises following composition and percentage composition:
Embedded photoluminescent material 12-35%
Natural muscovite powder 1-8%
Dispersion agent 2-6%
Film coalescence aid 1-3%
Thickening material 1-2%
Defoamer 0.5-2%
Polymer emulsion 12-20%
Deionized water surplus.
2. photoluminescence coating according to claim 1, is characterized in that, comprises following composition and percentage composition:
Embedded photoluminescent material 12-20%
Natural muscovite powder 1-3%
Dispersion agent 2-4%
Film coalescence aid 2-3%
Thickening material 1.5-2%
Defoamer 0.5-0.8%
Polymer emulsion 12-18%
Deionized water surplus.
3. photoluminescence coating according to claim 1, is characterized in that, the median size of described natural muscovite powder is for being less than 10 microns.
4. photoluminescence coating according to claim 1, it is characterized in that, at least one in the non-ammonium polyacrylate salt of described dispersion agent, poly-phosphate, alkylaryl sulphonate, quaternary ammonium salt, polyalkylene glycol alkyl phenolic ether, poly-methyl acrylate and polyacrylamide.
5. photoluminescence coating according to claim 1, is characterized in that, described film coalescence aid is at least one in ethanol, Virahol, ethylene glycol, glycerol, ether, ethylene glycol ethyl ether, phenylcarbinol and ethylene glycol ethyl ether.
6. photoluminescence coating according to claim 1, is characterized in that, at least one in the non-methylcellulose gum of described thickening material, Vltra tears, Natvosol and carboxymethyl cellulose.
7. embedded photoluminescent material according to claim 1, is characterized in that, at least one in the non-silicone emulsion of described defoamer, polyglycerol fatty acid ester and phosphoric acid ester.
8. photoluminescence coating according to claim 1, is characterized in that, described polymer emulsion is the one in pure-acrylic emulsion, benzene emulsion, ACRYLIC EMULSION and organosilicon crylic acid latex.
9. the photoluminescence coating according to claim 1-8 any one, is characterized in that, described embedded photoluminescent material is α M ' S β MAl 2o 4: Eu xln y;
Wherein, M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe; M is the one in Mg, Ca, Be, Mo, Fe, Sb; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; α, β, x, y are mole coefficient: 2≤α≤4; 1≤β≤7; 0.0002≤x≤0.3; 0.02≤y≤0.1.
10. photoluminescence coating according to claim 9, is characterized in that, 2≤α≤4; 2≤β≤5; 0.01≤x≤0.2; 0.02≤y≤0.06.
11. photoluminescence coating according to claim 1-8 any one, it is characterized in that, described embedded photoluminescent material is α MLnS β Ln ' Al 2o 4: Eu xln y;
Wherein, M is the one in Mg, Ca, Be; Ln, Ln ' be separately independently one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ln and Ln ' is different; α, β, x, y are mole coefficient: 0.2≤α≤2; 1≤β≤5; 0.0002≤x≤0.3; 0.01≤y≤0.5.
12. photoluminescence coating according to claim 11, is characterized in that, 2≤α≤4; 1≤β≤7; 0.0001≤x≤0.15; 0.01≤y≤0.5.
13. photoluminescence coating as described in claim 1-8 any one, it is characterized in that, described embedded photoluminescent material is α M ' O β MAl 14o 25: Eu xln y;
Wherein, M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe, Bi; M is the one in Mg, Ca, Be; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; α, β, x, y are mole coefficient: 0.5≤α≤8; 2≤β≤6; 0.0001≤x≤0.15; 0.01≤y≤0.5.
The preparation method of 14. 1 kinds of photoluminescence coating according to claim 1, it is characterized in that, the method comprises the steps:
S1, natural muscovite powder is put into stirrer, then add dispersion agent, film coalescence aid, thickening material and defoamer successively, be mixed to get the first mixture;
Add embedded photoluminescent material in S2, the first mixture of obtaining in step S1 and be mixed to get the second mixture;
S3, in the second mixture, add polymer emulsion and deionized water be uniformly dispersed and namely obtain photoluminescence coating.
The preparation method of 15. photoluminescence coating according to claim 14, is characterized in that, the preparation method of described embedded photoluminescent material is: by Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mol ratio be (1-7): (2-4): (1-7): (0.0001-0.15): (0.01-0.05); M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe; M is the one in Mg, Ca, Be, Mo, Fe, Sb; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
The preparation method of 16. photoluminescence coating according to claim 15, is characterized in that, Al 2o 3, MS, M ' CO 3, Eu 2o 3and Ln 2o 3mol ratio be (2-5): (2-4): (2-4.5): (0.005-0.1): (0.01-0.03).
The preparation method of 17. photoluminescence coating according to claim 14, is characterized in that, the preparation method of described embedded photoluminescent material is: by Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mol ratio be (1-5): (0.2-2): (0.05-1.0): (0.0001-0.15): (0.01-0.05); M is the one in Mg, Ca, Be; Ln, Ln ' be separately independently one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ln and Ln1 is different.
The preparation method of 18. photoluminescence coating according to claim 17, is characterized in that, Al 2o 3, MS, Ln 2o 3, Eu 2o 3and Ln ' 2o 3mol ratio be (2-4): (1-2): (0.1-0.5): (0.005-0.1): (0.01-0.03).
The preparation method of 19. photoluminescence coating according to claim 14, is characterized in that, the preparation method of described embedded photoluminescent material is: by Al 2o 3, MO, M ' CO 3,eu 2o 3and Ln 2o 3mixed grinding obtains mixed powder; Mixed powder is put into crucible, is placed in microwave oven, heating, then take out and cool and obtain embedded photoluminescent material;
Wherein, Al 2o 3, MO, M ' CO 3, Eu 2o 3, Ln 2o 3the mol ratio of adding is (14-75): (1-8): (2-8): (0.0001-0.15): (0.01-0.05); M ' is the one in Mg, Ca, Sr, Ba, Cu, Zn, Fe, Bi; M is the one in Mg, Ca, Be; Ln is the one in lanthanon La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
The preparation method of 20. photoluminescence coating according to claim 19, is characterized in that, Al 2o 3, MO, M ' CO 3, Eu 2o 3, Ln 2o 3the mol ratio of adding is (20-45): (3-5): (2-6): (0.005-0.1): (0.01-0.03).
The preparation method of 21. photoluminescence coating according to claim 14-20 any one, it is characterized in that, described microwave frequency is 300MHZ-300GHz, and wavelength is 0.1-100cm, and heat-up time is 10-60 minute.
The preparation method of 22. photoluminescence coating according to claim 21, it is characterized in that, described microwave frequency is 300MHZ-300GHz, wavelength is 10-50cm, and heat-up time is 20-45 minute.
The preparation method of 23. photoluminescence coating according to claim 14-20 any one, it is characterized in that, the particle diameter of described mixed powder is 1-10 μm.
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