CN102702934A - Fluorescent transparent coating capable of realizing full colors, preparation method and luminous device using fluorescent transparent coating - Google Patents
Fluorescent transparent coating capable of realizing full colors, preparation method and luminous device using fluorescent transparent coating Download PDFInfo
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- CN102702934A CN102702934A CN2012101731293A CN201210173129A CN102702934A CN 102702934 A CN102702934 A CN 102702934A CN 2012101731293 A CN2012101731293 A CN 2012101731293A CN 201210173129 A CN201210173129 A CN 201210173129A CN 102702934 A CN102702934 A CN 102702934A
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Abstract
The invention discloses a fluorescent transparent coating capable of realizing full colors. The fluorescent transparent coating comprises quantum dots and ultraviolet (UV) curing transparent ink. A method for preparing the fluorescent transparent coating comprises the following steps of: adding the quantum dots and the UV curing transparent ink into a charging bucket, and stirring by using a dispersion machine for 30 to 120 minutes; adding zirconium oxide beads of which the grain diameters are 0.2 millimeter, and grinding for 3 to 8 hours; printing the ground UV curing transparent ink containing the quantum dots on a base material by using an inkjet printer to form a target image; and irradiating by using ultraviolet light while printing the target image or after the target image is printed. According to the fluorescent transparent coating, the quantum dots which can emit fluorescent light of different wavelengths and the UV curing transparent ink are combined to realize full colors, and the image is printed by using the UV curing transparent ink through the inkjet printer; and the method is simple, high in efficiency and flexible and can be used for large-area inkjet, and the coating is high in curing speed and environment-friendly.
Description
Technical field
The present invention relates to the quantum dot Application Areas, be specifically related to a kind ofly realize full-color fluorescence Clear coating and preparation method thereof, and use the light-emitting device that this fluorescence Clear coating is formed.
Background technology
Quantum dot is called semiconductor nanocrystal again, and when the stimulation that receives light or electricity, quantum dot just can send specific fluorescent light, and the color of fluorescence is by the composition material and the size shape decision of quantum dot.This characteristic makes quantum dot can change the light color that excitation light source sends.Adopt the quantum dot of different compositions or size, can access coloury light.At present countries in the world are all in the application of research quantum dot aspect full-color, but mainly in the demonstration field.
Samsung has been developed the full color Active Matrix LCD At screen that adopts technology of quantum dots.Compare present mobile phone, MP3 uses screen, the quantum dot image display is brighter, more energy-conservation, price is also cheaper.The preparation method of its quantum dot coating is following: at first quantum dot solution is coated on the silicon plate; Evaporation then; Again jut is pressed into quantum dot layer, removes to change behind the top layer and be pressed onto on glass substrate or the plastic base, this process has just realized the transfer of quantum dot to substrate.
People such as the Polina Anikeeva of MIT (MIT) and Jonathan Halpert utilize CdSe, ZnS, ZnSe layer and semiconductor compound ZnCdS and ZnCdSe, and synthetic light emitting region is enough to contain the gluey quantum dot of visible light wave range.They adopt a kind of organic substrate that can be compatible with all kinds of quantum dots; And utilize a kind of simple method that quantum dot is deposited on the base material: on the elastomerics seal, to form quantum dot individual layer (QD monolayer) with rotation injection molding (spin casting) earlier, again this individual layer is imprinted in the component structure.This method can independently be made quantum dot, and therefore the quantum dot of all kinds of colors can use the components identical structure, deposits red, green and blue quantum dot simultaneously as picture element through simple and cheap step.
Though known several kinds of quantum dot coating processes respectively have advantage, exist also that coating production is more loaded down with trivial details, efficient is low, be difficult to carry out big area coating, curing speed waits shortcoming more slowly.
The UV curing inks is nearly three, the 40 years novel inks that just occur and rise; Its mechanism of action is through light trigger that in ink set self, adds and catalyzer; Absorb outside enough ultraviolet rays that apply and beam energy and excite cross-linking and curing reaction, finally reach and cause the film forming purpose of printing ink.Therefore UV curing inks rate of drying is fast, and particularly on non-absorbent substrate, the stock that can directly print is widest in area general.
Summary of the invention
But the object of the present invention is to provide a kind of simple, efficient, big area air brushing flexibly, curing speed is fast and can realize full-color fluorescence Clear coating and preparation method thereof.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
A kind ofly realize full-color fluorescence Clear coating, it is characterized in that, form by quantum dot and UV curing transparent China ink.
Described quantum dot is periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconductor compound or its corresponding nucleocapsid structure; Concrete described periodic table of elements II-VI family semiconductor compound comprises CdSe by binary compound, CdTe, ZnS, ZnSe, ZnTe, ZnO; HgS, HgSe, HgTe, ternary compound comprises CdSeS, CdSeTe, CdSTe, ZnSeS; ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe; CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe and quaternary compound comprise CdZnSeS, CdZnSeTe; CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe forms; Periodic table of elements III-V family semiconductor compound comprises GaN by binary compound, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb; InN, InP, InAs, InSb, ternary compound comprises GaNP, GaNAs, GaNSb, GaPAs, GaPSb; AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb; InPAs, InPSb, GaAlNP and quaternary compound comprise GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs; GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb forms; Periodic table of elements IV-VI family semiconductor compound comprises SnS by binary compound, SnSe, SnTe, PbS; PbSe, PbTe, ternary compound comprises SnSeS, SnSeTe, SnSTe; PbSeS, PbSeTe, PbSTe, SnPbS; SnPbSe, SnPbTe and quaternary compound comprise SnPbSSe, SnPbSeTe, SnPbSTe forms; Period of element Table IV family semiconductor compound, by Si, Ge and binary compound comprise SiC, SiGe forms; Said nucleocapsid structure is for being nuclear with foregoing periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconductor compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, one or more among the SiO2 are the nuclear shell structure quantum point of shell.
Above-mentioned quantum dot quality percentage composition is 1～25%,
Above-mentioned UV curing transparent China ink is: the commercial commercially available UV curing inks product that does not add pigment, for example one or more in epoxy acrylate class UV curing inks, urethane acrylate class UV curing inks, polyester acrylate class UV curing inks, polyether acrylate class UV curing inks, ROHM propyl ester and the unsaturated polyester class UV curing inks.Above-mentioned UV curing transparent China ink quality percentage composition is 75～99%.
A kind of preparation method who realizes full-color fluorescence Clear coating, this preparing method's step is:
Step 1: quantum dot and UV curing transparent China ink are joined in the charging basket through dispersion machine stirring 30～120min;
Step 2: adding particle diameter is the zirconium oxide bead of 0.2mm, grinds 3-8 hour;
Step 3: the ground UV curing transparent China ink that contains quantum dot is printed out target image through the air brushing machine on base material;
Step 4: in the printing target image or after the printing target image, carry out UV-irradiation and make it to solidify.
The above-mentioned UV curing transparent China ink that contains quantum dot is 3～100mPaS 30 ℃ viscosity.UV-irradiation solidified condition is: the radiation quantity of UV-light is 10～1500W/cm, and irradiation time is 0.5～300 second.
In addition, the present invention relates to the light-emitting device of using this fluorescence Clear coating, this light-emitting device specifically: be printed on the substrate according to the method described above after can realizing that full-color quantum dot and UV curing transparent are black and mixing; Then the above-mentioned substrate that is solidified with fluoresent coating is cut into the size and dimension that needs, and dresses up light-emitting device with the light sources of fluorescence excitation.
Above-mentioned substrate is glass or transparent resin.Transparent resin is one or more of polymethylmethacrylate (PMMA), PS (PS), SE (PVC), urethane (PU), polyethylene terephthalate (PET), polycarbonate (PC), Vestolen PP 7052 (PP).
The light source of above-mentioned fluorescence excitation is blue light or ultraviolet LED light source.The excitation wavelength that the light source of fluorescence excitation produces is 280nm～480nm.
Use the advantage of the fluorescence Clear coating of quantum dot and UV curing transparent China ink making to be: can regulate emission wavelength simply through the size of quantum point grain diameter, realize full-color; Fluorescence Clear coating rate of drying is fast, and particularly on non-absorbent substrate, the stock that can directly print is widest in area general; Solvent-free volatilization when the fluorescence Clear coating solidifies, the feature of environmental protection is good.
Compare with other coating productions, use quantum dot and the air brushing of UV curing transparent China ink to prepare to realize full-color fluorescence Clear coating to have that method is simple, efficient, Color conditioning is flexible, can carry out the big area air brushing, coating curing speed is fast, the feature of environmental protection good.
Description of drawings
Fig. 1 is the synoptic diagram of the embodiment of the invention 6;
The symbol explanation:
1, full-color quantum dot fluorescence Clear coating, wherein each letter among the POLYOE has different fluorescence colors;
2, substrate;
3, blue light or ultraviolet LED light source.
Embodiment
Embodiment 1
A kind ofly realize full-color fluorescence Clear coating, form by quantum dot and UV curing transparent China ink.Quantum dot is claimed semiconductor nanocrystal again, comprises periodic table of elements II-VI family or III-V family nano semiconductor material and corresponding nucleocapsid structure thereof; Specifically comprise CdSe, CdTe, CdS, ZnSe, ZnS, GaP, GaN, GaAs, InP, InN, InAs, InSb, PbS, quantum dots such as PbSe; Or be nuclear with the above-mentioned materials, with CdSe, CdS, ZnSe, ZnS, CdO, ZnO, SiO
2Deng the nano semiconductor material that forms for shell with nucleocapsid structure.The material of size and composition through the control quantum dot can be regulated the emission wavelength of quantum dot, obtains multiple distinguishable color.General quantum dot particle diameter is between 1～10nm.With (CdSe) ZnS core-shell quanta dots is example, when the CdSe core diameter is 1.8nm, and the emission blue light; When the CdSe core diameter is 7nm, red-emitting.The fluorescence of the CdSe of different size size can be contained whole visible spectrum.With the quality percentage composition is 1%, core diameter is 1.8nm (CdSe) ZnS core-shell quanta dots and quality percentage composition is that 99% UV curing transparent China ink mixes, adds in the charging basket through dispersion machine stirring 30min; Add the 0.2mm zirconium oxide bead, grind 3h, the ground UV curing transparent China ink that contains quantum dot is 3mPaS 30 ℃ of following viscosity; The ground UV curing transparent China ink that contains quantum dot is printed out target image through the air brushing machine on base material; Printing is carried out UV-irradiation target image the time or after printing makes it curing, and the radiation quantity of UV-light is 1500W/cm, and irradiation time is 0.5 second, and formed fluorescence Clear coating can send blue light after with the ultraviolet LED light source activation.Employing UV curing transparent China ink mixes the back and can realize full-color fluorescence Clear coating fully through air brushing mechanism with quantum dot, but has simple, efficient, the flexible big area air brushing of method, the fast advantage of curing speed.
Embodiment 2
The commercial commercially available UV curing inks product that does not add pigment comprises in epoxy acrylate class UV curing inks, urethane acrylate class UV curing inks, polyester acrylate class UV curing inks, polyether acrylate class UV curing inks, ROHM propyl ester and the unsaturated polyester class UV curing inks one or more.(CdSe) ZnS core-shell quanta dots that to be 75% UV curing transparent inkwood fat with the quality percentage composition be 25% with the quality percentage composition, core diameter is 7nm mixes, and adds in the charging basket and stirs 120min through dispersion machine; Add the 0.2mm zirconium oxide bead, grind 8h, the ground UV curing transparent China ink that contains quantum dot is 100mPaS 30 ℃ of following viscosity; With the ground UV curing transparent China ink that contains quantum dot through the air brushing machine at the target image that prints out on glass; Printing is carried out UV-irradiation target image the time or after printing makes it curing, and the radiation quantity of UV-light is 10W/cm, and irradiation time is 300 seconds, and formed fluorescence Clear coating can send ruddiness after with blue light or ultraviolet LED light source activation.The excitation wavelength that the light source of fluorescence excitation produces is preferably 280nm～480nm.Be cut into the size and dimension that needs to glass then, and dress up light-emitting device with the light sources of fluorescence excitation.
Embodiment 3
The CdSe quantum dot that to be 88% UV curing transparent China ink with the quality percentage composition be 12% with the quality percentage composition, particle diameter is 3.2nm mixes, in the adding charging basket through dispersion machine stirring 75min; Add the 0.2mm zirconium oxide bead, grind 5h, the ground UV curing transparent China ink that contains quantum dot is 50mPaS 30 ℃ of following viscosity; The ground UV curing transparent China ink that contains quantum dot is printed out target image through the air brushing machine on transparent resin; Printing is carried out UV-irradiation target image the time or after printing makes it curing, and the radiation quantity of UV-light is 1000W/cm, and irradiation time is 100 seconds, and formed fluorescence Clear coating can send green glow after with blue light or ultraviolet LED light source activation.Be cut into the size and dimension that needs to transparent resin then, and dress up light-emitting device with the light sources of fluorescence excitation.The excitation wavelength that the light source of fluorescence excitation produces is preferably 280nm～480nm.
Embodiment 4
The CdSe quantum dot that to be 80% UV curing transparent China ink with the quality percentage composition be 20% with the quality percentage composition, particle diameter is 3.2nm mixes, in the adding charging basket through dispersion machine stirring 50min; Add the 0.2mm zirconium oxide bead, grind 4h, the ground UV curing transparent China ink that contains quantum dot is 40mPaS 30 ℃ of following viscosity; With the ground UV curing transparent China ink that contains quantum dot through the air brushing machine at the target image that prints out on glass; Printing is carried out UV-irradiation target image the time or after printing makes it curing, and the radiation quantity of UV-light is 500W/cm, and irradiation time is 120 seconds, and formed fluorescence Clear coating can send green glow after with blue light or ultraviolet LED light source activation.Be cut into the size and dimension that needs to glass then, and dress up light-emitting device with the light sources of fluorescence excitation.The excitation wavelength that the light source of fluorescence excitation produces is preferably 280nm～480nm.
Embodiment 5
(CdSe) ZnS core-shell quanta dots that to be 90% UV curing transparent inkwood fat with the quality percentage composition be 10% with the quality percentage composition, core diameter is 7nm mixes, and adds in the charging basket and stirs 100min through dispersion machine; Add the 0.2mm zirconium oxide bead, grind 7h, the ground UV curing transparent China ink that contains quantum dot is 85mPaS 30 ℃ of following viscosity; The ground UV curing transparent China ink that contains quantum dot is printed out target image through the air brushing machine on transparent resin; Printing is carried out UV-irradiation target image the time or after printing makes it curing, and the radiation quantity of UV-light is 1200W/cm, and irradiation time is 40 seconds, and formed fluorescence Clear coating can send ruddiness after with blue light or ultraviolet LED light source activation.Dress up light-emitting device then the size and dimension of glass transparent resin one-tenth needs, and with the light sources of fluorescence excitation.The excitation wavelength that the light source of fluorescence excitation produces is preferably 280nm～480nm.
Embodiment 6
As shown in Figure 1; The quantum dot of different size is mixed the back according to the method shown in the foregoing description with UV curing transparent China ink; Through the air brushing machine with needed pattern; Like the printed words of POLYOE, be printed on glass or the transparent resin substrate 2, transparent resin is one or more of polymethylmethacrylate (PMMA), PS (PS), SE (PVC), urethane (PU), polyethylene terephthalate (PET), polycarbonate, Vestolen PP 7052 PP.Through behind the ultraviolet light polymerization, obtain full-color quantum dot fluorescence Clear coating 1, substrate 2 is cut into shape as shown in Figure 1, blue light or the ultraviolet LED light source 3 with fluorescence excitation is assembled into light-emitting device then.This light-emitting device can be used for aspects such as illumination, advertisement, decoration or displaying.Above-mentioned blue light or ultraviolet LED light source 3 are distributed in the both sides or the edge of light-emitting device, comprise one or more.
Can also full-color quantum dot fluorescence Clear coating be printed on glass or the transparent resin, form full-color scenery with hills and waters, personage's picture, the substrate cutting that will be printed with picture is again got off, and forms light-emitting device with the blue light or the ultraviolet LED light source of fluorescence excitation.This light-emitting device can be applied in upholstery, like glass door, window, aspects such as outdoor advertising.
Full-color quantum dot fluorescence Clear coating of the present invention is transparent not having under the state of light source activation, so after being applied on glass door, the window, daytime, glass door, window were transparent when not having light source activation; In the time of night, open the blue light or the ultraviolet LED light source of fluorescence excitation, just can the excitation quantum point, chromatic pattern just appears on transparent doors, the window, have special decoration and advertising results.
The present invention is not limited to above-mentioned embodiment; If various changes of the present invention or distortion are not broken away from the spirit and scope of the present invention; If these changes and distortion belong within claim of the present invention and the equivalent technologies scope, then the present invention also is intended to comprise these changes and distortion.
Claims (10)
1. can realize full-color fluorescence Clear coating for one kind, it is characterized in that, form by quantum dot and UV curing transparent China ink.
2. a kind of full-color fluorescence Clear coating of realizing according to claim 1 is characterized in that described quantum dot is periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconductor compound or its corresponding nucleocapsid structure; Concrete described periodic table of elements II-VI family semiconductor compound comprises CdSe by binary compound, CdTe, ZnS, ZnSe, ZnTe, ZnO; HgS, HgSe, HgTe, ternary compound comprises CdSeS, CdSeTe, CdSTe, ZnSeS; ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe; CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe and quaternary compound comprise CdZnSeS, CdZnSeTe; CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe forms; Periodic table of elements III-V family semiconductor compound comprises GaN by binary compound, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb; InN, InP, InAs, InSb, ternary compound comprises GaNP, GaNAs, GaNSb, GaPAs, GaPSb; AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb; InPAs, InPSb, GaAlNP and quaternary compound comprise GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs; GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb forms; Periodic table of elements IV-VI family semiconductor compound comprises SnS by binary compound, SnSe, SnTe, PbS; PbSe, PbTe, ternary compound comprises SnSeS, SnSeTe, SnSTe; PbSeS, PbSeTe, PbSTe, SnPbS; SnPbSe, SnPbTe and quaternary compound comprise SnPbSSe, SnPbSeTe, SnPbSTe forms; Period of element Table IV family semiconductor compound, by Si, Ge and binary compound comprise SiC, SiGe forms; Said nucleocapsid structure is for being nuclear with foregoing periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconductor compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, one or more among the SiO2 are the nuclear shell structure quantum point of shell.
3. a kind of full-color fluorescence Clear coating of realizing according to claim 1 is characterized in that described quantum dot quality percentage composition is 1～25%, and described UV curing transparent China ink quality percentage composition is 75～99%.
4. a kind of full-color fluorescence Clear coating of realizing according to claim 1 is characterized in that described UV curing transparent China ink does
:Do not add the UV curing inks product of pigment, comprise in epoxy acrylate class UV curing inks, urethane acrylate class UV curing inks, polyester acrylate class UV curing inks, polyether acrylate class UV curing inks, ROHM propyl ester and the unsaturated polyester class UV curing inks one or more.
5. preparation method that can realize full-color fluorescence Clear coating, it is characterized in that: this preparing method's step is:
Step 1: quantum dot and UV curing transparent China ink are joined in the charging basket through dispersion machine stirring 30～120min;
Step 2: adding particle diameter is the zirconium oxide bead of 0.2mm, grinds 3-8 hour;
Step 3: the ground UV curing transparent China ink that contains quantum dot is printed out target image through the air brushing machine on base material;
Step 4: in the printing target image or after the printing target image, carry out UV-irradiation and make it to solidify.
6. a kind of preparation method who realizes full-color fluorescence Clear coating according to claim 5 is characterized in that, the said UV curing transparent China ink that contains quantum dot is 3～100mPaS 30 ℃ viscosity.
7. according to power
SharpRequire 5 described a kind of preparing methods that realize full-color fluorescence Clear coating, it is characterized in that described UV-irradiation solidified condition is: the radiation quantity of UV-light is 10～1500W/cm, irradiation time is 0.5～300 second.
8. use the light-emitting device of this fluorescence Clear coating, it is characterized in that, can realize that full-color quantum dot mixes the back with UV curing transparent China ink and is printed on the substrate according to the described method of claim 5; Then the above-mentioned substrate that is solidified with fluoresent coating is cut into the size and dimension that needs, and dresses up light-emitting device with the light sources of fluorescence excitation.
9. light-emitting device according to claim 8 is characterized in that, described substrate is glass or transparent resin; Described transparent resin is one or more of polymethylmethacrylate (PMMA), PS (PS), SE (PVC), urethane (PU), polyethylene terephthalate (PET), polycarbonate (PC), Vestolen PP 7052 (PP).
10. light-emitting device according to claim 8 is characterized in that, the light source of described fluorescence excitation is blue light or ultraviolet LED light source; The excitation wavelength that the light source of described fluorescence excitation produces is 280nm～480nm.
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Application publication date: 20121003 |