CN102779929B - Fluorescent ink composite - Google Patents
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- CN102779929B CN102779929B CN201210266868.7A CN201210266868A CN102779929B CN 102779929 B CN102779929 B CN 102779929B CN 201210266868 A CN201210266868 A CN 201210266868A CN 102779929 B CN102779929 B CN 102779929B
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Abstract
The invention provides a kind of light that can be sent by LED efficiently becomes another wavelength fluorescent ink composite from a wavelength convert.This comprises cured resin composition and phosphor constituents for the fluorescent ink composite be deposited in LED matrix, and phosphor constituents is the nano fluorescent powder particles of the order of magnitude in 100 ~ 1000 nanometers.Especially, be distributed in nano-phosphor uniform particles in this fluorescent ink composite.Nano fluorescent powder particles is undertaken pulverizing processing procedure by the fluorescent powder grain that the particle diameter that to the order of magnitude is 1 ~ 50 micron is larger and is formed.Preferably, pulverizing processing procedure is based on solvent wet grinding.Present invention also offers and form nano fluorescent powder particles according to solvent wet grinding from the fluorescent powder grain of greater particle size and make the method for fluorescent ink composite.
Description
The cross reference of related application
The application is U.S. Patent application 13/103, the part continuity application of 117 (applying date is on May 9th, 2011), at this in conjunction with the application as a reference.
Technical field
The present invention relates generally to the fluorescent ink composite for LED and/or LED matrix.Particularly, the present invention relates to fluorescent ink composite with nano-scale fluorescent powder grain and preparation method thereof, the light that LED can send by this fluorescent ink composite efficiently becomes another kind of wavelength from a kind of wavelength convert.
Background technology
Light-emitting diode (LED) is a kind of semiconductor light sources.LED has lot of advantages compared with other light source such as incandescent lamp.LED has longer life-span, preferably stability, faster switching characteristic and lower energy consumption usually.The LED of latest development has and can compare or higher luminous efficiency (lm/W) with fluorescent lamp.
In circuit when the forward bias of LED exceedes its threshold voltage, make LED luminous due to the spontaneous compound of electron-hole pair.The wavelength of the light produced depends on and is forming the band gap between the material used in the p-n junction of LED.The wavelength of the light that LED produces is usually in the scope of infrared light, visible ray or UV.Details about LED in Cambridge University Press, can find in " the Light emitting diodes " of E.Fred Schubert, at this in conjunction with its entirety as a reference.Details about semiconductor optical in Springer publishing house, can find in " the Semiconductor optics " of Claus F.Klingshirn, at this in conjunction with its entirety as a reference.
For convenience of manufacturing, the most frequently used LED form of tradition is placed on substrate the plane square LED wafer of micron-scale.This semiconductor wafer is generally gallium nitride, and substrate can be the metal of such as aluminium, and it also plays heat sink effect.LED wafer realizes being connected by meticulous metal wire and the Circuits System on substrate.LED wafer itself can be installed on a surface of a substrate, or can be arranged in the groove of substrate.
When manufacturing the high-brightness LED light source being used for mankind's illumination, there is various challenge.First be the light extraction efficiency maximizing LED wafer itself.Because semi-conducting material has high index of refraction, so the wide majority produced can run into total internal reflection (TIR) at semiconductor-air interface place.In the prior art, the difference by reducing semiconductor surface place refractive index reduces the amount of TIR light.Because semiconductor refractive index is a kind of material behavior, reach above-mentioned effect by being packaged together with the encapsulating material with more high index of refraction by LED.Past uses epoxide resin material, and use silicones recently more, because it has relatively high transparency, colour stability and hot property.
The single LED do not encapsulated produces monochromatic light.Owing to using LED as the trend of lighting source, LED technology is all paid close attention in research in the last few years, and this LED technology makes LED wafer send the light of different colours.In synthesize white light, people have had sizable interest.The most frequently used is place material for transformation of wave length in the light-emitting area of the LED wafer of blue light-emitting, such as yellow fluorescent powder from the mode of single led generation white light.Material for transformation of wave length layer in LED wafer can absorb the photon that some LED send, and they are changed the light that (down-convert) is visible wavelength downwards, thus produces the double-colored light source with blue and yellow wavelengths light.If the gold-tinted produced and blue light have correct ratio, so human eye can experience white light.
In the prior art, material for transformation of wave length is added in the encapsulated layer surrounding LED wafer, using the substitute mode as Direct precipitation on wafer.The use of this encapsulating material can have distinct methods.Certain methods use is molded or encapsulating material is directly fixed on substrate by pre-molded, and certain methods erects dam around living LED wafer, then fills this dam.The latter is commonly called a glue, because encapsulating material provides in liquid form, then solidifies.In fact, in this dispensing method, fluorescent ink composite can be applied in LED wafer on the surface.
In prior art, the another kind of method be applied to by fluorescence coating in LED wafer uses ink-jet printer that fluorescent ink is injected in LED wafer on the surface.This inkjet printing methods, at U.S. Patent application 13/103, has description in 117, discloses as a reference in conjunction with it at this.
But, in traditional method for packing, particle diameter usually can be used at the Large stone fluorescent material of 5 ~ 25 microns.But the problem of fluorescent material sedimentation in use easily appears in the fluorescent material of Large stone, make fluorescent material skewness in colloid, cause the LED encapsulated out easily to occur misalignment thus.
Therefore, the fluorescent material improved for a glue or inkjet printing is necessary.
Summary of the invention
Particle diameter is at 1 ~ 50 micron, particularly the fluorescent material of Large stone of 5 ~ 25 microns has high fluorescence conversion efficiency. but, serious settlement issues is there is at the fluorescent powder grain of this particle size range, cause the change of the colour temperature of packaged LED inconsistent and color thus. therefore, the fluorescent powder grain of nano-scale causes the interest of people owing to having the very little rate of settling. but, the problem that existence one is serious for the fluorescent powder grain of current nano-scale, that is exactly the reduction by more than 50% compared with the fluorescent material of Large stone of its fluorescence conversion efficiency. the invention provides a kind of for a glue or inkjet printing fluorescent ink composite, this ink includes the nano fluorescent powder particles that the order of magnitude is 100 ~ 1000 nanometers, and very high light conversion efficiency can be reached, the LED using this fluorescent ink to encapsulate and/or LED matrix have excellent colour temperature and/or colour consistency and high brightness.
The invention provides one and be deposited on fluorescent ink composite on LED, its fluorescent powder grain has very little size, and can reach very high light transfer ratio.This ink comprises cured resin composition and phosphor constituents, and phosphor constituents comprises the nano fluorescent powder particles that the order of magnitude is 100 ~ 1000 nanometers.Nano fluorescent powder particles by the order of magnitude be the larger fluorescent powder grain of 1 ~ 50 micron carry out pulverize processing procedure formed.Preferably, pulverizing processing procedure is based on solvent wet grinding.
After crushing process, nano fluorescent powder particles has very little sedimentation rate.Therefore they can be evenly dispersed in described fluorescent ink composite, can be used for a glue or ink jet printing.So, consistent correlated colour temperature and/or color can be had with the LED of this ink encapsulation.
In addition, these nano fluorescent powder particles are becoming during another wavelength to have very high light conversion efficiency from a wavelength convert by LED light.With size 1 ~ 50 micron, particularly the Large stone fluorescent powder grain of 5 ~ 25 microns is compared, and the light conversion efficiency of nano fluorescent powder particles of the present invention can reach more than 90% of those Large stone fluorescent powder grain conversion efficiencies.On market, other existing nano fluorescent powder particles can not reach.
Fluorescent ink for dotting glue method can be obtained by mixing nano fluorescent powder particles and cured resin (preferably heat reactive resin).Heat reactive resin can be bi-component silicon resin.
Fluorescent ink for ink-jet printing process comprises above-mentioned phosphor constituents and cured resin, and cured resin is as polymer adhesive.Cured resin can be UV cured resin and/or heat reactive resin.In order to ensure the ink-jet ability of ink-jet printer, the viscosity of ink remains on below about 50 centipoises.Provide the solvent of q.s to control the viscosity of whole fluorescent ink.
Accompanying drawing explanation
Fig. 1 is the method flow diagram being formed nano fluorescent powder particles by solvent wet grinding from Large stone fluorescent powder grain.
Fig. 2 A be one embodiment of the invention make the method flow diagram of fluorescent ink composite based on forming nano fluorescent powder particles from Large stone fluorescent powder grain.
Fig. 2 B be another embodiment of the present invention make the method flow diagram of fluorescent ink composite based on forming nano fluorescent powder particles from Large stone fluorescent powder grain.
Embodiment
Be packaged with the combination of yellow fluorescent powder about blue led below and form " white " LED to describe ink of the present invention.But should be appreciated that, the present invention is applicable to any fluorescent material to be applied on the LED of any color, thus the color of LED is regulated to become the color arrived by Human Perception.No matter as used herein whether " fluorescent material " is " fluorescent material " that traditional sense is thought, here, term " fluorescent material " be broadly be used for describing an absorption wavelength light and send any material for transformation of wave length of another wavelength light.For blue led, Representative fluorescence powder for sending gold-tinted comprises yttrium-aluminium-garnet (YAG) sill (alternatively, doped with cerium), terbium aluminium garnet (TAG) sill and silicate-based material, sulfide material, nitride material or oxymtride material.Organic fluorescent powder and organic-inorganic composite material can also be used, for simplicity, be all called as " fluorescent material " as above.The combination of Single wavelength transition material or material for transformation of wave length can be selected in the luminescence desired by whole packaged LED.
For LED, the acceptable optimum range of fluorescent powder grain size is normally between 1 micron to about 50 microns.Such as, U.S. Patent application US20110045619 mentions typical LED fluorescent powder granular size between about 5 to 25 microns.Another example, US Patent No. 8125139 advises that average granular size is preferably between 3 to 20 microns.Another example, US Patent No. 8048338, US7887718, US8062549 and US7524437 suggestion, from the angle of luminous efficiency, the mean particle size of fluorescent material preferably between 1 to 50 microns, and does not preferably exceed 20 or 30 microns.
Although particle diameter is at 1 ~ 50 micron, particularly the fluorescent material of 5 ~ 25 microns has higher light conversion efficiency, but, the problem of fluorescent material sedimentation is in use easily there is at the fluorescent material of this particle size range, make fluorescent material skewness in colloid, cause the LED encapsulated out easily to occur misalignment thus.But, but the fluorescent powder grain of nano-scale causes the concern of people owing to having the very little rate of settling., there is a serious problem in existing nano-scale fluorescent powder grain, that is exactly the reduction by more than 50% compared with the fluorescent material of Large stone of its fluorescence conversion efficiency.
As one of them development, U.S. Patent application US20070024173 discloses and uses nano fluorescent powder particles, its size, between 1 to 50 nanometers, preferably between 2 to 20 nanometers, to be reflected by fluorescent powder grain or the part of scattering does not carry out the light of light conversion to minimize.Also mention size in the publication and can cause maximum light scattering at the fluorescent powder grain of 200 to 500 nanometers, therefore the fluorescent powder grain of this scope is not adopted.
Fluorescent powder grain size supported by studying in great detail of exporting of LED light at the optimum range of 1 to 50 microns, please refer to the people such as N.T.Tran " Effect of phosphor particle size on luminous efficacy of phosphor-converted white LED; " IEEE Journal of Lightwave Technology, vol.27, pp.5145-5150, November 2009, discloses as a reference in conjunction with it at this.From simulation result, the people such as N.T.Tran (2009) have shown, when fluorescent powder grain size is increased to 100 nanometer from 50 nanometers, light output obviously reduces, then in the scope of 100 to 500 nanometers, light output then rests in a minimum value, more afterwards when fluorescent powder grain size is increased to 1 micron, light output has slight increase.When fluorescent powder grain size continues to increase from 1 micron, light output then increases continually and steadily.In the scope of micron-scale, when fluorescent powder grain size is approximately 20 microns, light output reaches maximum, more backward, light output just have dropped.Be similar to US20070024173, the people such as Tran (2009) think fluorescent powder grain size light output in the scope of 100 to 500 nanometers to be minimum value are because light is obviously by fluorescent powder grain scattering.
Based on more than, those of ordinary skill in the art can not go to use fluorescent powder grain size in 100 to 1000 nanometer range, and particularly the fluorescent material of 100 to 500 nanometer range is used for LED.But this light is become another wavelength by luminescence generated by light (photoluminescence) from a wavelength convert after recently, present inventor proves fluorescent powder grain size by experiment fluorescent material can catch LED light expeditiously in 100 to 1000 nanometer range.With size 1 ~ 50 micron, particularly the Large stone fluorescent powder grain of 5 ~ 25 microns is compared, and present inventor finds can reach more than 90% of those Large stone fluorescent powder grain conversion efficiencies according to the light conversion efficiency of the fluorescent powder grain of the 100-1000 nanometer made of the present invention.This is that on market, other existing nano fluorescent powder particles can not reach, and their conversion efficiency can reduce by more than 50% as previously mentioned.
After having had this to find, inventor notices that US7126265 discloses a kind of spherical fluorescent powder grain, and it is formed at the major fluorescent powder particles (primary phosphor particles) of 100 to 1500 nanometers by the multiple average particle size particle size of polymerization.The nano fluorescent powder particles that the present invention discloses not is the major fluorescent powder particles that US7126265 discloses.Nano fluorescent powder particles disclosed here neither be intended to form one or more spherical fluorescent powder grain mentioned in US7126265 discloses.
Fluorescent ink of the present invention employs a kind of phosphor constituents, and it comprises the nano fluorescent powder particles of size in 100 to 1000 nanometers, and wherein nano-phosphor uniform particles ground dispersed throughout is in this ink composition.Can help the dispersed fluorescent powder grain that can prevent again to make the fluorescent powder grain of generation is deposited in fluorescent ink, needs accurate crushing technology.By larger be approximately that the fluorescent powder grain of 1 to 50 microns performs crushing process (size reduction process), and obtain nano fluorescent powder particles.Especially, crushing process is preferably based on solvent wet grinding (solvent wet milling).Solvent wet grinding is a kind of wet grinding.About the description of wet grinding, can see the Dispersion of Powders in Liquids and Stabilization of Suspensions of T.F.Tadros, Wiley, 2012, be incorporated into this disclosure as a reference at this.About solvent wet grinding, the optimization of process of lapping parameter can the people such as T.-H.Hou " Parameters optimization of a nano-particle wet milling process using the Taguchi method; response surface method and genetic algorithm; " Powder Technology, Volume 173, Issue 3, pp.153-162, find in 30 April 2007, at this in conjunction with its entirety as a reference.Discussion about solvent wet grinding can also see WO/2000/056486.
Inventor found through experiments; except reaching high light conversion efficiency; nano fluorescent powder particles also has other benefits, and compared with the fluorescent material of traditional about 5 to 25 micrometer fluorescent powder particles sizes, the sedimentation phenomenon of fluorescent material in cured resin is also improved.The size of cured resin and nano fluorescent powder particles can be selected, make fluorescent ink composite after being deposited on LED, before final solidification, the rate of settling of nano fluorescent powder particles in ink is quite slow, thus in LED matrix or LED, form the equally distributed solidification fluorescence coating of fluorescent material.
Nano-phosphor and the fluorescent ink composite comprising nano-phosphor and preparation method thereof will in following descriptions.
In order to make the fluorescent ink of the fluorescent powder grain including desirable size range, carefully controlling fluorescent powder grain size by accurate wet grinding, making the fluorescent powder grain size range energy minimization fluorescent powder grain sedimentation produced, namely keeping dispersity.Fig. 1 is described through the process that larger fluorescent powder grain is made nano fluorescent powder particles by solvent wet grinding.Fluorescent powder grain larger for particle diameter is scattered in solvent, forms suspension.Alternatively, in suspension, also can add dispersant, impel larger fluorescent powder grain to disperse in a solvent.Then in suspension, add mill ball medium and form mixture.Wet-milling is carried out to this mixture, until most larger fluorescent powder grain has become the particle of 100 to 1000 nanometers stirring in grinding machine/pulverizing mill.Therefore, nano fluorescent powder particles is just formed in the mixture, in order to check/guaranteeing that most larger fluorescent powder grain has become the particle of nano-scale, can take out sub-fraction sample mixtures and carry out particle size measurement.After the wet milling, using such as screen cloth to filter mixture, from wherein removing mill ball medium, then by such as centrifuge by other component separation in these particles and mixture, just obtaining nano-phosphor particle.
Preferably, do not carry out the physical separation of other compositions in nano fluorescent powder particles and mixture, just make fluorescent ink.Fig. 2 A shows and makes an embodiment of fluorescent ink, the viscosity that the viscosity of this fluorescent ink can make it meet dotting glue method or ink jet printing method to require by regulable control.First, Large stone fluorescent powder grain and cured resin composition are disperseed in a solvent, obtains suspension.
Large stone fluorescent material can be yttrium-aluminium-garnet (YAG) sill (as YAG:Ce), terbium aluminium garnet (TAG) sill (as TAG:Ce), silicate-based material (as SrBaSiO4:Eu), sulfide material (as CaS:Eu, SrS:Eu, SrGa2S4:Eu etc.), nitride material (as Sr2Si5N8:Eu, Ba2Si5N8:Eu etc.) or oxymtride material (as Ca-α-SiAlON:Eu, SrSi2O2N2:Eu etc.).
Cured resin composition can be UV cured resin (as Tego 2100, Tego 2200 etc.) or heat reactive resin (as DOW CORNING Dow Corning 6550, DOW CORNING Dow Corning 6551, SHIN-ETSU HANTOTAI Shin-Etsu 9022, LPS5547 etc.) or both combinations.If formula comprises UV cured resin, so need initator (as Irgacure 2959 etc.).
Solvent can be that any conventional organic solvent is as ethanol, acetone, 2 pentanone, 1-amylalcohol, isopropyl alcohol etc.
Alternatively, in suspension, add dispersant, dispersant can be enlightening height Tego 655, enlightening height Tego 710, Lu Borun Solsperse 22000, Zetasperse 2100 etc.
Then in suspension, add mill ball medium and form the first mixture.Wet-milling is carried out to this first mixture, until most Large stone fluorescent powder grain has become the particle of nano-scale.As mentioned above, the sub-fraction sample that can take out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain has diminished.After the wet milling, use filter (can be screen cloth) to filter the first mixture, from the first mixture, remove mill ball medium, obtain the second mixture.A part of solvent is evaporated, until the viscosity of the second mixture is close to the viscosity number required from the second mixture.Therefore, just fluorescent ink is obtained with the form of the second mixture after evaporation.
Fig. 2 B shows another embodiment making and require the fluorescent ink composite of viscosity.The difference of this embodiment and Fig. 2 A illustrated embodiment did not add cured resin composition before wet-milling.In the embodiment of Fig. 2 B, first by the dispersion of Large stone fluorescent powder grain in a solvent, obtain suspension.As mentioned above, dispersant can be added in suspension.Then in suspension, add mill ball medium and form the first mixture.Wet-milling first mixture, until carry out particle size measurement to the sub-fraction sample of the first mixture and detect that most of fluorescent powder grain all becomes nano-sized particles.Then, use filter (can be screen cloth) to filter the first mixture, from the first mixture, remove mill ball medium, obtain the second mixture.In this stage, in the second mixture, add cured resin composition and be dispersed in good condition in the second mixture, obtaining the 3rd mixture.From the 3rd mixture, evaporate a part of solvent, until the viscosity of the 3rd mixture is close to given viscosity number, obtain fluorescent ink.
According to different LED encapsulation method, as a glue or ink jet printing, can be different on the fluorescent ink composite composition containing nano-scale fluorescent material.
For dotting glue method, ink composition composition is as follows:
Ink composition as implied above is the embodiment of a suggestion.But, be appreciated that the application in the present invention, the ink composition of dotting glue method being applicable to the fluorescent material of any type in prior art, cured resin and dispersant.
Because for dotting glue method, all solvents in ink composition have all evaporated, so do not show the solvent composition in composition in superincumbent form.
Component listed by above table and ratio, will provide the specific embodiment prepared for the fluorescent ink composite of a glue below.
Example 1: add 6g Large stone fluorescent material YAG:Ce, 94g cured resin DOW CORNING Dow Corning 6550 in the acetone of 200cc, forms suspension, then in suspension, adds mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By all solvent evaporations in the second mixture, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for a glue.This ink is used to adopt some glue mode to encapsulate the Photoelectric Detection parameter of rear LED as follows:
From test data, the light conversion efficiency of the fluorescent powder grain of the 100-1000 nanometer made of the present invention can reach more than 90% of those Large stone fluorescent powder grain conversion efficiencies.
Example 2: add 1g Large stone fluorescent material YAG:Ce, 99g cured resin DOW CORNING Dow Corning 6550 in the acetone of 200cc, forms suspension, then in suspension, adds mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By all solvent evaporations in the second mixture, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for a glue.
Example 3: add 60g Large stone fluorescent material TAG:Ce, 40g cured resin DOW CORNING Dow Corning 6551 in the acetone of 200cc, forms suspension, then in suspension, adds mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most bulk fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By all solvent evaporations in the second mixture, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for a glue.
Example 4: add 54g Large stone fluorescent material YAG:Ce, 6gCa-α-SiAlON:Eu, 25g cured resin SHIN-ETSU HANTOTAI Shin-Etsu 9022,15g dispersant enlightening height Tego655 in the acetone of 200cc, form suspension, then in suspension, add mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most bulk fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By all solvent evaporations in the second mixture, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for a glue.
Example 5: add 30g Large stone fluorescent material YAG:Ce, 3g dispersant Zetasperse 2100 in the acetone of 200cc, forms suspension, then in suspension, adds mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until carry out particle size measurement to the sub-fraction sample of the first mixture and detect that most Large stone fluorescent powder grain has all been transformed into the particle of nano-scale.Then, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.In this stage, just add 67g cured resin composition SHIN-ETSU HANTOTAI LPS5547, be dispersed in the second mixture in good condition, form the 3rd mixture.By all solvent evaporations in the 3rd mixture, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for a glue.
For ink jet printing method, ink composition composition is as follows:
Ink composition as implied above is the embodiment of a suggestion.But, be appreciated that the application in the present invention, the ink composition of ink-jet printing process being applicable to the fluorescent material of any type in prior art, cured resin and dispersant.
Component listed by above table and ratio, will provide the specific embodiment prepared for the fluorescent ink composite of inkjet printing below.
Example 6: add in the 2 pentanone of 300cc that 1g Large stone fluorescent material YAG:Ce, 1g cured resin enlightening is high by 2100,0.2g UV initator, 0.2g dispersant Lu Borun Solsperse 22000, form suspension, then in suspension, add mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By the partial solvent evaporation in the second mixture, make residual solvent weight be 97.6g, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for inkjet printing.
Example 7: add in the isopropyl alcohol of 300cc that 15g Large stone fluorescent material YAG:Ce, 15g cured resin enlightening is high by 2100,4g UV initator, 15g dispersant enlightening height Tego 710, form suspension, then in suspension, add mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By the partial solvent evaporation in the second mixture, make residual solvent weight be 51g, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for inkjet printing.
Example 8: add in the 1-amylalcohol of 300cc that 5g Large stone fluorescent material SrBaSi:Eu, 10g cured resin enlightening is high by 2100,1g UV initator, 1g dispersant Lu Borun Solsperse 22000, form suspension, then in suspension, add mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.As mentioned above, the sub-fraction sample taking out the first mixture carries out particle size measurement, to detect and to guarantee that most Large stone fluorescent powder grain is all transformed into the particle of nano-scale.After the wet milling, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.By the partial solvent evaporation in the second mixture, make residual solvent weight be 83g, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for inkjet printing.
Example 9: add 10g Large stone fluorescent material YAG:Ce, 1gSr2Si5N8:Eu, 3g dispersant Zetasperse 2100 in the 1-amylalcohol of 300cc, forms suspension, then in suspension, adds mill ball medium, form the first mixture.Wet-milling is carried out to the first mixture, until carry out particle size measurement to the sub-fraction sample of the first mixture and detect that most Large stone fluorescent powder grain has all been transformed into the particle of nano-scale.Then, with screen cloth, the first mixture is filtered, from the first mixture, remove mill ball medium, thus obtain the second mixture.In this stage, just add 8g cured resin composition enlightening high 2200 and 0.4g UV initator, be dispersed in the second mixture in good condition, form the 3rd mixture.By the partial solvent evaporation in the 3rd mixture, make residual solvent weight be 77.6g, obtain the final fluorescent ink formula containing nano-scale fluorescent material, for inkjet printing.
Although describe aforementioned invention according to foregoing example embodiment, should be appreciated that various modifications and variations are fine.Therefore, these amendments and modification drop in the scope of appended claims the present invention for required protection.
Claims (20)
1., for being deposited on the fluorescent ink composite in LED or LED matrix, comprising:
Cured resin composition;
Phosphor constituents, it comprises the fluorescent powder grain that the order of magnitude is 200 ~ 300 nanometers, is distributed in whole fluorescent ink composite to described nano-phosphor uniform particles.
2. fluorescent ink composite according to claim 1, wherein said nano fluorescent powder particles is undertaken pulverizing processing procedure by the fluorescent powder grain of the greater particle size to the order of magnitude being 1 ~ 50 micron and is formed.
3. fluorescent ink composite according to claim 2, wherein said pulverizing processing procedure is based on solvent wet grinding.
4. fluorescent ink composite according to claim 1, wherein said phosphor constituents is from following selection: yttrium-aluminium-garnet sill, terbium aluminium garnet sill and silicate-based material, sulfide material, nitride material or oxymtride material.
5. fluorescent ink composite according to claim 1, wherein said cured resin composition comprise UV cured resin or heat reactive resin or both.
6. fluorescent ink composite according to claim 5, wherein said heat reactive resin composition is bi-component silicon resin.
7. fluorescent ink composite according to claim 5, wherein said UV cured resin is UV solidification of silicon resin or organosilicon acrylic fat.
8. fluorescent ink composite according to claim 1, the percentage by weight of content from the percentage by weight of 1% to 60% of wherein said phosphor constituents.
9. fluorescent ink composite according to claim 1, the percentage by weight of content from the percentage by weight of 25% to 99% of wherein said cured resin composition.
10. fluorescent ink composite according to claim 1, wherein said cured resin composition comprise UV cured resin or heat reactive resin or both, described fluorescent ink composite, has the viscosity being less than 50 centipoises, makes described fluorescent ink composite that ink-jet printer can be used to print.
11. fluorescent ink composite according to claim 10, also comprise the photoinitiator for UV solidification, the percentage by weight of content from the percentage by weight of 0.2% to 4% of wherein said photoinitiator.
12. fluorescent ink composite according to claim 10, also comprise solvent, the percentage by weight of content from the percentage by weight of 51% to 97.6% of wherein said solvent.
13. fluorescent ink composite according to claim 12, wherein said solvent is from following selection: isopropyl alcohol, 2 pentanone, 1-amylalcohol.
14. fluorescent ink composite according to claim 10, also comprise dispersant, the percentage by weight of content from the percentage by weight of 0.2% to 15% of wherein said dispersant.
15. fluorescent ink composite according to claim 10, the percentage by weight of content from the percentage by weight of 1% to 15% of wherein said phosphor constituents.
16. fluorescent ink composite according to claim 10, the percentage by weight of content from the percentage by weight of 1% to 15% of wherein said cured resin composition.
17. 1 kinds, for being deposited on the method for making of the nano-phosphor in LED or LED matrix, being carried out pulverizing processing procedure by the fluorescent powder grain that the particle diameter that to the order of magnitude is 1 ~ 50 micron is larger and form described nano-phosphor, comprising:
By fluorescent powder grain larger for described particle diameter dispersion in a solvent, suspension is formed;
Wet-milling is carried out to described suspension, until the larger fluorescent powder grain of most particle diameter has all been transformed into the fluorescent powder grain that the order of magnitude is 200 ~ 300 nanometers, and
By other component separation in nano fluorescent powder particles and suspension.
18. 1 kinds of methods made for being deposited on the fluorescent ink composite in LED or LED matrix, described fluorescent ink composite comprises cured resin composition and nano fluorescent powder particles, and the method comprises:
By the order of magnitude be fluorescent powder grain that the particle diameter of 1 ~ 50 micron is larger and the dispersion of described cured resin composition in a solvent, form suspension;
Wet-milling is carried out to described suspension, until the larger fluorescent powder grain of most particle diameter has all been transformed into the fluorescent powder grain that the order of magnitude is 200 ~ 300 nanometers, thus forms the suspension containing described nano fluorescent powder particles;
Described fluorescent ink composite is formed containing evaporating a part of solvent the suspension of nano fluorescent powder particles from described.
19. 1 kinds of methods made for being deposited on the fluorescent ink composite in LED or LED matrix, described fluorescent ink composite comprises cured resin composition and nano fluorescent powder particles, and the method comprises:
By the order of magnitude be fluorescent powder grain dispersion that the particle diameter of 1 ~ 50 micron is larger in a solvent, form suspension;
Wet-milling is carried out to described suspension, until the larger fluorescent powder grain of most particle diameter has all been transformed into the fluorescent powder grain that the order of magnitude is 200 ~ 300 nanometers, thus forms the suspension containing described nano fluorescent powder particles;
Add described cured resin composition in described containing in the suspension of nano fluorescent powder particles, form mixture;
From described mixture, evaporate a part of solvent form described fluorescent ink composite.
20. fluorescent ink composite according to claim 1, the selection of the size of wherein said cured resin composition and described nano fluorescent powder particles, be to make described nano fluorescent powder particles after deposition, can sedimentation extremely lentamente in described fluorescent ink composite before solidification, thus uniform curing fluorescence coating can be formed in LED matrix or LED.
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| CN1653157A (en) * | 2002-05-06 | 2005-08-10 | 奥斯兰姆奥普托半导体有限责任公司 | Wavelength-converting reactive resinous compound and light-emitting diode component |
| CN101126010A (en) * | 2007-08-08 | 2008-02-20 | 华南理工大学 | Bi-component silicon resin for sealing power-type LED and synthesis method thereof |
| CN102260438A (en) * | 2011-05-09 | 2011-11-30 | 香港应用科技研究院有限公司 | LED fluorescence ink composite used for ink jet printing |
| CN102575161A (en) * | 2009-08-06 | 2012-07-11 | 昭和电工株式会社 | Fluorescent substance, process for producing same, and luminescent device including same |
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| DE20308495U1 (en) * | 2003-05-28 | 2004-09-30 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH | Conversion LED |
| JP2007197612A (en) * | 2006-01-27 | 2007-08-09 | Kyocera Corp | Fluorescent substance, wavelength converter, and light emitting device |
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| CN1653157A (en) * | 2002-05-06 | 2005-08-10 | 奥斯兰姆奥普托半导体有限责任公司 | Wavelength-converting reactive resinous compound and light-emitting diode component |
| CN101126010A (en) * | 2007-08-08 | 2008-02-20 | 华南理工大学 | Bi-component silicon resin for sealing power-type LED and synthesis method thereof |
| CN102575161A (en) * | 2009-08-06 | 2012-07-11 | 昭和电工株式会社 | Fluorescent substance, process for producing same, and luminescent device including same |
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