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WO2013061781A1 - Composition de revêtement et procédé de production de dispositif électroluminescent - Google Patents

Composition de revêtement et procédé de production de dispositif électroluminescent Download PDF

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Publication number
WO2013061781A1
WO2013061781A1 PCT/JP2012/076261 JP2012076261W WO2013061781A1 WO 2013061781 A1 WO2013061781 A1 WO 2013061781A1 JP 2012076261 W JP2012076261 W JP 2012076261W WO 2013061781 A1 WO2013061781 A1 WO 2013061781A1
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Prior art keywords
phosphor layer
light emitting
organic solvent
phosphor
coating liquid
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PCT/JP2012/076261
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English (en)
Japanese (ja)
Inventor
正好 山内
仲島　厚志
禄人 田口
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Konica Minolta IJ Technologies Inc
Konica Minolta Advanced Layers Inc
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Konica Minolta IJ Technologies Inc
Konica Minolta Advanced Layers Inc
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Priority to JP2013540717A priority Critical patent/JP5862675B2/ja
Publication of WO2013061781A1 publication Critical patent/WO2013061781A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8515—Wavelength conversion means not being in contact with the bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
    • H10W74/00—
    • H10W90/724—

Definitions

  • the present invention relates to a technique for forming a wavelength conversion layer on a light emitting element.
  • a technique for obtaining a white light emitting device in which a phosphor such as a YAG (yttrium, aluminum, garnet) phosphor is disposed in the vicinity of a gallium nitride (GaN) blue LED (Light Emitting Diode) chip has been widely used. It has been.
  • white light is emitted by a color mixture of blue light emitted from the blue LED chip and yellow light emitted when the phosphor receives blue light and emits secondary light.
  • a technique of emitting white light by mixing color of blue light emitted from the blue LED chip and red light and green light emitted by each phosphor receiving blue light and secondary light emission is also used. Yes.
  • Such white light emitting devices have various uses, for example, there is a demand as an alternative to fluorescent lamps and incandescent lamps. In addition, it is also being used for lighting devices such as automobile headlights that require extremely high luminance. Since the headlight is required to have high visibility with respect to an object such as a distant sign, high performance is also required in terms of the color of the white light emitting device and the color uniformity of the irradiation range.
  • a method of sealing an LED chip (hereinafter sometimes referred to as “light emitting element”) or a mounting portion using a transparent resin in which a phosphor is dispersed is generally used.
  • the specific gravity of the phosphor particles is larger than that of the transparent resin. There is a problem that the phosphor settles before the transparent resin is cured, and color unevenness occurs during light emission.
  • Patent Document 1 proposes a technique of sealing a light emitting element with a ceramic (glass) containing a phosphor. Specifically, the phosphor particles are dispersed in a solution containing a metal alkoxide or a ceramic precursor composition, and this is applied onto the light emitting element and heated to form a glass film on the light emitting element.
  • the first coating liquid containing the phosphor is applied onto the light emitting element and dried to orient the phosphor on the chip, and then the second coating liquid containing the translucent ceramic material is applied. Therefore, a technique for protecting the voids and the surface of the phosphor layer with a translucent ceramic material has been studied. According to this technique, it is possible to reduce unevenness in light emission by orienting the phosphor on the light emitting element, and to improve heat resistance by protecting with a translucent ceramic material.
  • both the first coating solution and the second coating solution are applied by the spray method.
  • the phosphor layer formed by the first coating liquid may be peeled off from the light emitting element by the wind pressure of the second coating liquid spray.
  • a mask is generally used to protect a portion where the coating liquid is not applied. . For this reason, since the coating liquid is applied to portions other than the light emitting element, there is a problem that material loss is large.
  • the present invention is capable of locally applying the second coating liquid onto the light emitting element, and preventing the phosphor layer from peeling off from the light emitting element when the second coating liquid is applied. With the goal.
  • the invention described in claim 1 is a coating composition applied by an ink jet method to form a glass film on a phosphor layer formed on a light emitting element, wherein a translucent ceramic material and an organic material are applied.
  • a coating composition comprising a solvent and having a contact angle with respect to the phosphor layer of 0 to 10 degrees when coated on the phosphor layer.
  • the invention according to claim 2 is the coating composition according to claim 1, wherein the organic solvent has a surface tension of 20 mN / m to 30 mN / m and a viscosity of 1 mPa ⁇ s.
  • the invention according to claim 3 is the coating composition according to claim 1 or 2, wherein the organic solvent contains a monovalent or polyhydric alcohol or a derivative of the alcohol.
  • the invention according to claim 4 is the coating composition according to any one of claims 1 to 3, wherein the translucent ceramic material has R as an organic group and n as an integer.
  • the invention according to claim 5 is the coating composition according to any one of claims 1 to 4, wherein the coating composition contains oxide particles.
  • the invention according to claim 6 includes a step of applying a first coating solution containing a phosphor on a light emitting element, a step of forming a phosphor layer by heating and drying the first coating solution, A second coating liquid comprising a translucent ceramic material and an organic solvent and having a contact angle with respect to the phosphor layer of 0 to 10 degrees when coated on the phosphor layer is the fluorescence. And a step of coating the body layer by an ink jet method.
  • the invention described in claim 7 is the method for manufacturing the light emitting device according to claim 6, wherein the organic solvent has a surface tension of 20 mN / m to 30 mN / m and a viscosity of 1 mPa.
  • the invention according to claim 8 is the method for manufacturing the light emitting device according to claim 6 or claim 7, wherein the organic solvent includes a monovalent or polyvalent alcohol or a derivative of the alcohol. It is characterized by that.
  • the invention according to claim 9 is the method for manufacturing a light emitting device according to any one of claims 6 to 8, wherein the translucent ceramic material is formed by using R as an organic group and n as a light emitting device.
  • the invention according to claim 10 is the method for manufacturing a light emitting device according to any one of claims 6 to 9, wherein the second coating liquid contains oxide particles. It is characterized by.
  • the invention according to claim 11 is the method for manufacturing the light emitting device according to any one of claims 6 to 10, wherein the first coating liquid contains a layered silicate mineral. It is characterized by that.
  • the invention described in claim 12 is the method for manufacturing the light-emitting device according to claim 11, wherein the layered silicate mineral is smectite.
  • a coating liquid (coating composition) containing a translucent ceramic material and an organic solvent is applied onto the phosphor layer by an inkjet method. Therefore, damage to the phosphor layer can be reduced as compared with the case where the second coating liquid is applied by a spray method.
  • the contact angle of the coating liquid to the phosphor layer is 0 ° or more and 10 ° or less, the translucent ceramic material is uniformly distributed inside the phosphor layer, and peeling of the phosphor layer can be prevented. It becomes possible.
  • the coating liquid is locally applied by the inkjet method, it is possible to reduce material loss compared to the case of applying by the spray method.
  • the light emitting device 100 includes an LED substrate 1 having a concave cross section.
  • a metal portion 2 is provided in a concave portion (bottom portion) of the LED substrate 1, and a rectangular parallelepiped LED element 3 is disposed on the metal portion 2.
  • the LED element 3 is an example of a light emitting element that emits light of a predetermined wavelength.
  • a protruding electrode 4 is provided on the surface of the LED element 3 facing the metal portion 2, and the metal portion 2 and the LED element 3 are connected via the protruding electrode 4 (flip chip type).
  • a configuration in which one LED element 3 is provided for one LED substrate 1 is illustrated, but a plurality of LED elements 3 may be provided in a concave portion of one LED substrate 1.
  • a blue LED element is used as the LED element 3.
  • the blue LED element is formed, for example, by laminating an n-GaN-based cladding layer, an InGaN light-emitting layer, a p-GaN-based cladding layer, and a transparent electrode on a sapphire substrate.
  • the wavelength conversion layer 5 is formed around the LED element 3 in the recess of the LED substrate 1.
  • the wavelength conversion layer 5 is formed by laminating a phosphor layer 51 and a translucent ceramic layer 52 on the LED element 3 in this order.
  • the phosphor layer 51 contains a phosphor. This phosphor is excited by light of a predetermined wavelength (excitation light) in the emitted light of the LED element 3, and emits fluorescence having a wavelength different from the wavelength of the excitation light.
  • the translucent ceramic layer 52 includes a translucent ceramic material, and binds and protects the phosphor layer 51 on the LED element 3 as a binder.
  • the thickness of the wavelength conversion layer 5 is preferably 5 to 200 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 10 to 100 ⁇ m.
  • the wavelength conversion layer 5 may be configured to be provided only on the upper surface of the LED element 3.
  • a method of providing the wavelength conversion layer 5 only on the upper surface of the LED element 3 a method of installing a mask when forming the wavelength conversion layer 5 is used.
  • the phosphor layer 51 is formed by applying a first coating solution containing a phosphor and drying it. Moreover, the translucent ceramic layer 52 gives the 2nd coating liquid containing translucent ceramic material on the fluorescent substance layer 51, a 2nd coating liquid osmose
  • the compositions of the first coating solution and the second coating solution are summarized below.
  • the first coating liquid includes at least a phosphor and a solvent.
  • the solvent for example, water or an organic solvent is used.
  • the first coating liquid preferably contains a layered silicate mineral. Below, these details contained in the 1st coating liquid are put together.
  • the phosphor is excited by the emitted light from the LED element 3 and emits fluorescence having a wavelength different from the wavelength of the emitted light.
  • a YAG (yttrium aluminum garnet) phosphor that is excited by blue light (wavelength 420 nm to 485 nm) emitted from a blue LED element and emits yellow light (wavelength 550 nm to 650 nm) is used. .
  • a YAG phosphor In order to produce such a YAG phosphor, first, an oxide of Y, Gd, Ce, Sm, Al, La, Ga, or a compound that easily becomes an oxide at a high temperature is used, and these are stoichiometrically converted. Thorough mixing is performed at a theoretical ratio to obtain a mixed raw material. Alternatively, a coprecipitated oxide obtained by firing a solution obtained by coprecipitation of oxalic acid from a solution obtained by dissolving rare earth elements of Y, Gd, Ce, and Sm in an acid at a stoichiometric ratio with aluminum oxide and gallium oxide Mix to obtain a mixed raw material.
  • an appropriate amount of fluoride such as ammonium fluoride is mixed with the obtained mixed raw material as a flux and pressed to obtain a molded body.
  • the obtained molded body is packed in a crucible and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a sintered body having phosphor emission characteristics.
  • the YAG phosphor is used.
  • the type of the phosphor is not limited to this.
  • other phosphors such as non-garnet phosphor and silicate not containing Ce are used.
  • the luminous efficiency increases as the particle size of the phosphor increases, whereas the film strength of the wavelength conversion layer decreases as the particle size increases. Therefore, it is preferable to use one having a volume average particle diameter of 1 ⁇ m or more and 50 ⁇ m or less from the viewpoint of luminous efficiency and film strength.
  • the volume average particle diameter of the phosphor can be measured by, for example, a Coulter counter method or a laser diffraction / scattering particle diameter measuring apparatus.
  • the layered silicate mineral increases the viscosity of the mixed solution by being added to the first coating solution, and functions to suppress sedimentation of the phosphor.
  • a swellable clay mineral having a mica structure, a kaolinite structure, a smectite structure, or the like is preferable, and a swellable smectite structure is particularly preferable.
  • the content of the layered silicate mineral in the first coating solution is less than 0.5% by weight, the effect of increasing the viscosity of the first coating solution cannot be obtained sufficiently.
  • the content of the layered silicate mineral exceeds 20% by weight, the strength of the transparent ceramic layer formed by heating decreases. Accordingly, the content of the layered silicate mineral is preferably 0.5 wt% or more and 20 wt% or less, and more preferably 0.5 wt% or more and 10 wt% or less.
  • Smectite-structured swellable clay minerals have a thickening effect, but the higher the ratio, the higher the viscosity of the mixture.
  • the viscosity of the mixture is different from that of other components such as water, organic solvents, and phosphors. Determined by ratio.
  • a layered silicate mineral whose surface is modified (surface treatment) with an ammonium salt or the like can be used as appropriate.
  • Water has a role of swelling hydrophilic swellable particles.
  • hydrophilic swellable particles For example, when water is added to a hydrophilic layered silicate mineral that has not been surface-treated, water enters between the layers of the layered silicate mineral, increasing the viscosity of the mixture, thereby suppressing phosphor settling. can do.
  • swelling since there exists a possibility that swelling may be inhibited when the impurity is contained in water, it is necessary to use the pure water which does not contain an impurity as the water to add.
  • Organic solvent is used for improving the wettability of the mixed solution and adjusting the viscosity.
  • the organic solvent is methanol, ethanol, or propanol with excellent water compatibility. It is preferable to use alcohols such as butanol.
  • lipophilic swellable particles such as surface-treated lipophilic layered silicate minerals, water does not act on the swelling of the swellable particles, but the viscosity increases by adding water.
  • an organic solvent excellent in compatibility with the organic solvent By using a high-boiling organic solvent, the pot life of the mixed solution is not shortened, and the handleability is excellent.
  • a layered silicate mineral whose surface is modified (surface treatment) with an ammonium salt or the like can be used as appropriate.
  • the second coating liquid includes at least a translucent ceramic material (transparent resin material) and a solvent.
  • a solvent for example, an organic solvent is used.
  • oxide particles it is preferable to add oxide particles to the second coating solution.
  • the translucent ceramic material used in the second coating solution is composed of an organometallic compound or an inorganic polymer.
  • organometallic compound include metal alkoxides, metal acetylacetonates, metal carboxylates, and the like, but metal alkoxides that are easily gelled by hydrolysis and polymerization reaction are preferable.
  • the metal alkoxide may be a single molecule such as tetraethoxysilane, or may be silsesquioxane (polysiloxane) in which an organic siloxane compound is linked in a chain or cyclic form.
  • silsesquioxane polysiloxane
  • an organic siloxane compound is linked in a chain or cyclic form.
  • Examples of the inorganic polymer include polysilazane, but perhydropolysilazane having a low curing condition of curing to a ceramic at a low temperature and a low humidity is preferable.
  • Polysilazane is represented by the following [Formula 1]. [Formula 1] (R1R2SiNR3) n
  • R1 to R3 each independently represent a hydrogen atom, an alkyl group, an aryl group, a vinyl group, or a cycloalkyl group, and at least one of R1 to R3 is a hydrogen atom, and all are hydrogen The case where it is an atom is perhydropolysilazane.
  • n is an integer of 1 to 60.
  • the molecular shape of the polysilazane may be any shape, for example, linear or cyclic.
  • the polysilazane shown in [Formula 1] and a reaction accelerator as required are dissolved in an appropriate solvent, applied, and cured by heating, excimer light treatment, or UV (ultraviolet) light treatment, heat resistance, light resistance It is possible to produce an excellent ceramic layer.
  • reaction accelerator it is preferable to use an acid, a base or the like, but it is not always necessary to use it.
  • the reaction accelerator include triethylamine, diethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, hydrochloric acid, oxalic acid, fumaric acid, sulfonic acid, acetic acid, nickel, iron, palladium , Metal carboxylates containing iridium, platinum, titanium, and aluminum, but are not limited thereto.
  • reaction accelerator is a metal carboxylate, and the addition amount is preferably 0.01 to 5 mol% based on polysilazane.
  • a silsesquioxane represented by a composition formula (R—SiO3 / 2) n, that is, a trifunctional (T unit) siloxane is more preferable.
  • R represents an organic group.
  • the organic group “R” for example, those to which a hydrocarbon group such as a methyl group, an ethyl group, or a phenyl group is added are used.
  • Silsesquioxane includes cage, ladder, and random three-dimensional structures.
  • a silsesquioxane having a cage-type structure having robustness is used as the translucent ceramic material (transparent resin material) of this embodiment.
  • the silicon atoms form a skeleton of a triangular prism, a pentagonal column, a hexagonal column, and a heptagonal column, respectively.
  • the second coating liquid is adapted to the composition of the phosphor layer 51 (first coating liquid) so that the contact angle of the second coating liquid with respect to the phosphor layer 51 is not less than 0 degrees and not more than 10 degrees. Adjust the composition. This is because if the contact angle of the second coating solution with respect to the phosphor layer 51 is larger than 10 degrees, the second coating solution does not easily penetrate into the phosphor layer 51 and the phosphor layer 51 is sufficiently resistant to film peeling. Is not. If the contact angle is 10 degrees or less, the permeability of the second coating liquid increases to the phosphor layer 51, and the translucent ceramic material penetrates uniformly into the phosphor layer 51. Therefore, the phosphor layer 51 is peeled off. Resistance to is improved. Specific means for setting the contact angle to the above value include selection of a solvent used in the second coating solution and addition of a surfactant. The solvent conditions for the second coating solution will be described later.
  • organic solvent As the organic solvent used in the second coating solution of the invention, a solvent which makes the contact angle to the phosphor the above value is used. They may be used alone or in combination. Examples of the organic solvent include hydrocarbons, ethers, esters, alcohols, ketones, nitrogen-containing compounds and derivatives thereof.
  • the organic solvent used in the second coating solution of the present invention is preferably two or more kinds of organic solvents in order to improve both the inkjet suitability and the wettability to the phosphor.
  • it is preferably composed of two or more kinds of an organic solvent having a surface tension of 20 mN / m to 30 mN / m and a viscosity of 1 mPa ⁇ s to 50 mPa ⁇ s, and an organic solvent having a boiling point of 150 ° C. to 250 ° C. .
  • An organic solvent having a surface tension of 20 mN / m to 30 mN / m and a viscosity of 1 mPa ⁇ s to 50 mPa ⁇ s improves wettability to the phosphor layer 51.
  • the surface tension is less than 20 mN / m, ink adheres to the nozzle plate of the ink jet head, and it becomes difficult to form a meniscus in the nozzle, and the emission stability deteriorates.
  • the surface tension is greater than 30 mN / m, the desired wettability to the phosphor cannot be obtained.
  • a viscosity exceeds the said range the light emission in an inkjet will fall.
  • An organic solvent having a boiling point of 150 ° C. or more and 250 ° C. or less exhibits a drying prevention function in an inkjet head. If the boiling point is lower than 150 ° C., the moisture retaining property of the ink jet head cannot be maintained, and the head is dried and the nozzle, that is, the drop velocity is likely to decrease. If the boiling point is higher than 250 ° C., the drying load such as the drying temperature and drying time for drying the second coating liquid increases, which causes problems such as a decrease in productivity and damage to the housing of the LED module due to high temperature drying. There is a case.
  • the surface tension (mN / m) of the organic solvent used in the present invention is the value of the surface tension measured at 25 ° C.
  • Examples of the measuring method include annulus method (Dunoi method), platinum plate method ( Wilhelmy method).
  • organic solvents used in the second coating solution monovalent or polyhydric alcohols and derivatives thereof are more preferably used.
  • the second coating solution of the present invention preferably has a solvent volatilization time at 150 ° C. of 15 minutes or less. Thereby, it is possible to reduce the drying load of the second coating liquid and minimize the tact time. Moreover, damage to the housing of the LED module can be reduced.
  • the solvent volatility is adjusted by appropriately selecting the solvent of the second coating solution.
  • oxide particles It is preferable to add oxide particles to the second coating solution. By adding oxide particles to the second coating liquid, the strength of the translucent ceramic material is improved. Known oxide particles such as silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconia oxide (ZrO 2 ) are used. In addition, in consideration of compatibility with a translucent ceramic material or an organic solvent, a material obtained by treating the surface of oxide particles with a silane coupling agent or a titanium coupling agent can be used as appropriate.
  • additives can be added to the second coating solution as necessary.
  • additive commonly used ones such as an antioxidant, a stabilizer, an antistatic agent, a leveling agent and a viscosity modifier can be used.
  • the 1st coating liquid containing fluorescent substance is heat-dried, after apply
  • a coating method a known method such as a spray method or a dispenser method can be used.
  • the dry film thickness of the first coating solution is 5 to 200 ⁇ m, more preferably 10 to 200 ⁇ m, still more preferably 10 to 100 ⁇ m from the viewpoint of light emission intensity, film strength, and the like.
  • a phosphor having a particle diameter of 10 ⁇ m is applied with a dry film thickness of 30 ⁇ m, three phosphor particles are stacked on the LED element 3 in the vertical direction. If the number of phosphor particles is small, the wavelength conversion efficiency is lowered and the emission intensity cannot be obtained sufficiently. Moreover, when there are many fluorescent substance particles, the intensity
  • the second coating liquid is applied onto the phosphor layer 51 by an ink jet method.
  • the ink jet method a known method can be used.
  • Drop-on-demand methods include electromechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electro-thermal conversion methods (eg, thermal ink jet) Type, bubble jet (registered trademark) type), electrostatic attraction type (for example, electric field control type, slit jet type, etc.) and discharge type (for example, spark jet type).
  • an electro-mechanical conversion type or an electro-thermal conversion type head it is preferable to use an electro-mechanical conversion type or an electro-thermal conversion type head.
  • a method of dropping droplets (for example, the second coating liquid) by an inkjet method may be referred to as an “inkjet method”.
  • the second coating liquid By applying the second coating liquid by the ink jet method, it is possible to suppress the wind pressure at the time of coating compared to the case of using the spray method or the like, and it is possible to further reduce the damage to the phosphor layer 51. . Thereby, it is possible to prevent the phosphor particles (phosphor layer 51) from being peeled off from the LED element 3.
  • the phosphor particles have a large particle size of several tens of ⁇ m. For this reason, the conventional spray method has a large amount of liquid that is difficult to penetrate into the gaps in the phosphor layer.
  • the ink jet method When the ink jet method is applied, the diameter of the droplet can be suppressed to about several tens of ⁇ m, and the second coating liquid can easily penetrate into the gap between the phosphor layers 51.
  • the translucent ceramic material uniformly penetrates to the inside of the phosphor layer 51, and the film peeling of the phosphor layer 51 can be prevented.
  • the ink jet method it is possible to locally apply the second coating liquid only to a necessary portion.
  • the second coating liquid can be applied only on the LED element 3 having a size of, for example, several hundred ⁇ squares. Therefore, a mask is not required unlike the spray method, and material loss and efficiency are improved. It is much more advantageous in terms.
  • the wavelength conversion layer 5 may be sealed with a silicone resin (that is, covered with a silicone layer). Thereby, the time-dependent deterioration of the wavelength conversion layer 5 can be suppressed, and the adhesiveness of the wavelength conversion layer 5 to the LED substrate 1 and the LED element 3 can be improved.
  • the wavelength conversion layer 5 may not contain a phosphor, but instead may contain a phosphor in a silicone resin.
  • LED chip samples in which the compositions of the first coating liquid and the second coating liquid were changed were prepared as Comparative Examples 1 to 3 and Examples 1 to 9, and for each sample, “ Color unevenness evaluation, film strength evaluation, solvent volatility evaluation, contact angle measurement, and ejection stability evaluation were performed.
  • conditions for preparing LED chips used as samples, “examples of adjusting phosphors”, and “examples of adjusting silsesquioxane” will be described.
  • each evaluation method (or measurement method) of “Evaluation of uneven color”, “Evaluation of film strength”, “Evaluation of solvent volatility”, “Measurement of contact angle”, and “Evaluation of ejection stability” is explained.
  • the specific conditions of each comparative example and each example and the results of each evaluation are summarized.
  • the evaluation results are summarized in FIG. FIG. 3 summarizes the physical properties of the solvent used, that is, the viscosity, surface tension, and boiling point.
  • LED chip creation conditions A sample in which a blue LED having a size of 200 ⁇ m in length, 200 ⁇ m in width and 200 ⁇ m in height is mounted in a flip chip type in a circular package having an opening diameter of 3 mm, a bottom surface diameter of 2 mm, and a wall surface angle of 60 ° is used.
  • Phosphor preparation example Phosphor used in the Examples and Comparative Examples, mixing the phosphor material, Y 2 O 3 7.41g, Gd 2 O 3 4.01g, CeO 2 0.63g, the Al 2 O 3 7.77 g fully
  • An aluminum crucible mixed with an appropriate amount of ammonium fluoride as a flux is filled in an aluminum crucible and fired at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours in a reducing atmosphere in which hydrogen-containing nitrogen gas is circulated.
  • a fired product ((Y 0.72 Gd 0.24 ) 3 Al 5 O 12 : Ce 0.04 ) is produced.
  • Yellow phosphor particles having a volume average particle diameter of about 1 ⁇ m obtained by pulverizing, washing, separating and drying the obtained fired product are used.
  • this phosphor has a peak wavelength at a wavelength of approximately 570 nm when the emission wavelength of excitation light having a wavelength of 465 nm is measured.
  • silsesquioxane was synthesized using methylethoxysilane as a starting material while controlling the solvent, monomer concentration, base catalyst, pH value, and reaction temperature.
  • the synthesized silsesquioxane is analyzed by an analyzer such as 29Si-NMR (Si29 nuclear magnetic resonance) or GPC (Gel Permeation Chromatography), thereby obtaining a cage type of T6, T8, T10, T12, and T14. It has been confirmed that all of the structural silsesquioxane is included.
  • the second coating solution was dropped on the phosphor layer 51 formed on the glass plate, and the contact angle was measured using DM-500 manufactured by Kyowa Interface Chemical Co., Ltd.
  • the measured value is a value one second after the second coating solution is dropped.
  • a first coating solution was prepared by mixing and dispersing 30.2 g of phosphor and 69.8 g of pure water.
  • a second coating solution was prepared by mixing 3 g of polysiloxane and 97 g of ethylene glycol.
  • the first coating solution was applied by a spray method using a mask so that the first coating solution was applied only on the LED element 3 so that the film thickness after drying was 20 ⁇ m.
  • the phosphor layer 51 was formed by heating at 150 ° C. for 10 minutes to dry.
  • the LED element provided with the phosphor layer 51 by adjusting the droplet amount and resolution so that the wet film thickness is 33 ⁇ m using the Konica Minolta inkjet evaluation apparatus EB-150 and XY-100 with a KM512L head.
  • a second coating solution was applied onto 3 and dried at 150 ° C. for 15 minutes. Thereafter, heat treatment was performed at 150 ° C. for 1 hour to prepare a sample of an LED module.
  • the contact angle of the second coating solution in this comparative example is “40 degrees”.
  • the result of the evaluation of the color unevenness in this example is “ ⁇ ”.
  • the second coating liquid did not penetrate into the phosphor layer 51. Therefore, the result of this evaluation is “x”.
  • the ethylene glycol used in the second coating solution has a high viscosity of “20 mPa ⁇ s” and a surface tension of “48.4 mN / m”. Therefore, the evaluation result of ejection stability was “x”.
  • Comparative Example 2 A second coating solution was prepared by mixing 3 g of polysiloxane, 4.85 g of 2-propanol, and 92.15 g of ethylene glycol.
  • the first coating liquid is the same as that in Comparative Example 1.
  • the method for preparing the LED module sample is the same as in Comparative Example 1.
  • the contact angle of the second coating solution in this comparative example is “28.5 degrees”.
  • the result of evaluation of the color unevenness in this comparative example is “ ⁇ ”.
  • the second coating liquid did not penetrate into the phosphor layer 51. Therefore, the result of this evaluation is “x”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • the first coating solution was applied by a spray method using a mask so that the first coating solution was applied only on the LED element 3 so that the film thickness after drying was 20 ⁇ m.
  • the phosphor layer 51 was formed by heating at 150 ° C. for 10 minutes to dry.
  • the second coating liquid was applied on the LED element 3 provided with the phosphor layer 51 by a spray method so as to have a wet film thickness of 33 ⁇ m and dried at 150 ° C. for 15 minutes. Thereafter, heat treatment was performed at 150 ° C. for 1 hour to prepare a sample of an LED module.
  • the discharge stability is not evaluated.
  • the contact angle of the second coating solution in this comparative example is “3.9 degrees”.
  • the phosphor layer 51 may be peeled off by the wind pressure of the spray. Therefore, the result of this evaluation is “x”.
  • the evaluation result of the film strength is “ ⁇ ”.
  • Example 1 As Example 1, a first coating solution was prepared by mixing and dispersing 30.2 g of phosphor and 69.8 g of pure water. A second coating solution was prepared by mixing 3 g of polysiloxane and 97 g of 2-propanol.
  • the first coating liquid was applied by a spray method using a mask so as to be applied only on the LED element 3 so that the film thickness after drying was 20 ⁇ m.
  • the phosphor layer 51 was formed by heating at 150 ° C. for 10 minutes to dry. Further, the LED element provided with the phosphor layer 51 by adjusting the droplet amount and resolution so that the wet film thickness is 33 ⁇ m using the Konica Minolta inkjet evaluation apparatus EB-150 and XY-100 with a KM512L head.
  • a second coating solution was applied onto 3 and then dried at 150 ° C. for 15 minutes. Thereafter, heat treatment was performed at 150 ° C. for 1 hour to prepare a sample of an LED module.
  • the contact angle of the second coating solution in this example is “3.9 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • 2-propanol has a low viscosity of “1.6 mPa ⁇ s”, a surface tension of “22 mN / m”, and a low boiling point of “82 ° C.”.
  • the meniscus formation became unstable and drying on the nozzle surface was observed, and the evaluation result of the discharge stability was “ ⁇ ”.
  • Example 2 As Example 2, a second coating solution was prepared by mixing 3 g of polysiloxane and 97 g of diethylene glycol monoethyl ether. The composition of the first coating solution is the same as in Example 1. The method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating solution in this example is “1.4 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • diethylene glycol monoethyl ether has a low viscosity of “3.9 mPa ⁇ s”. Therefore, meniscus formation on the nozzle surface became unstable, and the result of evaluation of ejection stability was “ ⁇ ”.
  • Example 3 As Example 3, a second coating solution was prepared by mixing 3 g of polysiloxane, 9.7 g of 2-propanol, and 87.3 g of ethylene glycol. The composition of the first coating solution is the same as in Example 1. The method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating solution in this example is “10 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the second coating liquid according to this example had high surface tension and viscosity, and therefore, the evaluation result of the ejection stability was “ ⁇ ”.
  • Example 4 As Example 4, a second coating solution was prepared by mixing 3 g of polysiloxane, 29.1 g of 2-propanol, and 67.9 g of 2methyl-2,4-pentanediol. The composition of the first coating solution is the same as in Example 1. The method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating solution in this example is “5.3 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • Example 5 As Example 5, a second coating solution was prepared by mixing 3 g of polysiloxane, 92.15 g of 2-propanol, and 4.85 g of glycerin. The composition of the first coating solution is the same as in Example 1. The method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating solution in this example is “8.4 degrees”.
  • the volatilization time was “15 minutes or more”.
  • the result of the evaluation of color unevenness is “ ⁇ ”.
  • residual glycerin was detected. Therefore, the result of this evaluation is “ ⁇ ”.
  • the nozzle was found to be dried. Therefore, the result of this evaluation is “ ⁇ ”.
  • Example 6 As Example 6, a second coating solution was prepared by mixing 3 g of trifunctional silsesquioxane, 29.1 g of 2-propanol, and 67.9 g of 2-methyl-2,4-pentanediol.
  • the composition of the first coating solution is the same as in Example 1.
  • the method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating solution in this example is “6.1 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • Example 7 As Example 7, a second coating solution was prepared by mixing 3 g of polysiloxane, 3 g of zirconia oxide, 28.2 g of 2-propanol, and 65.8 g of 2methyl-2,4-pentanediol.
  • the composition of the first coating solution is the same as in Example 1.
  • the method for preparing the LED module sample is the same as that of the first embodiment.
  • the contact angle of the second coating liquid in this example is “5.8 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • Example 8 As Example 8, a first coating solution was prepared by mixing and dispersing 30.2 g of phosphor, 3.3 g of mica, and 66.5 g of pure water. A second coating solution was prepared by mixing 3 g of polysiloxane, 29.1 g of 2-propanol, and 67.9 g of 2-methyl-2,4-pentanediol. The method for producing the LED module sample is the same as in Example 1.
  • the contact angle of the second coating solution in this example is “5.7 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • Example 9 As Example 9, a first coating solution was prepared by mixing and dispersing 30.2 g of phosphor, 3.3 g of smectite, and 66.5 g of pure water. A second coating solution was prepared by mixing 3 g of trifunctional silsesquioxane, 3 g of zirconia oxide (ZrO), 28.2 g of 2-propanol, and 67.9 g of 2-methyl-2,4-pentanediol. . The method for producing the LED module sample is the same as in Example 1.
  • the contact angle of the second coating solution in this example is “6.3 degrees”.
  • the volatilization time was “15 minutes or less”.
  • the result of evaluation of color unevenness is “ ⁇ ”
  • the result of evaluation of film strength is “ ⁇ ”.
  • the evaluation result of the ejection stability is “ ⁇ ”.
  • the solvent of the second coating solution is an organic solvent having a surface tension of 20 mN / m to 30 mN / m and a viscosity of 1 mPa ⁇ s to 50 mPa ⁇ s, and a boiling point of 150 ° C. to 250 ° C.
  • the second organic solvent By including the second organic solvent, it is possible to improve ejection stability.
  • the coating liquid is locally applied by the inkjet method, it is possible to reduce material loss compared to the case of applying by the spray method.

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  • Led Device Packages (AREA)

Abstract

La présente invention porte sur une composition de revêtement, ladite composition de revêtement rendant possible d'appliquer localement un liquide de revêtement sur une couche de luminophore formée sur un élément électroluminescent et, dans le processus d'application du liquide de revêtement, d'empêcher le pelage de la couche de luminophore de l'élément électroluminescent. La présente invention porte également sur une solution de revêtement à appliquer par le procédé de jet d'encre pour former un film de verre sur une couche de luminophore formée sur un élément électroluminescent, ladite composition de revêtement étant caractérisée en ce qu'elle comprend une matière de céramique translucide et un solvant organique et, après avoir été appliquée sur la couche de luminophore, en ce qu'elle a un angle de contact par rapport à la couche de luminophore de 0-10° inclus.
PCT/JP2012/076261 2011-10-24 2012-10-11 Composition de revêtement et procédé de production de dispositif électroluminescent Ceased WO2013061781A1 (fr)

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JP2002374006A (ja) * 2001-06-15 2002-12-26 Toyoda Gosei Co Ltd 発光装置
JP2004153109A (ja) * 2002-10-31 2004-05-27 Matsushita Electric Works Ltd 発光装置及びその製造方法
JP2005019662A (ja) * 2003-06-26 2005-01-20 Nichia Chem Ind Ltd 発光装置
JP2005089601A (ja) * 2003-09-17 2005-04-07 Stanley Electric Co Ltd 熱硬化性樹脂組成物、該熱硬化性樹脂組成物で発光素子を封止した発光ダイオードおよび色変換型発光ダイオード
JP2007036030A (ja) * 2005-07-28 2007-02-08 Nichia Chem Ind Ltd 発光装置及びその製造方法
JP2009076749A (ja) * 2007-09-21 2009-04-09 Toyoda Gosei Co Ltd Ｌｅｄ装置及びその製造方法

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JPS61183843A (ja) * 1985-02-08 1986-08-16 Hitachi Ltd 光学的接着性を向上させた粉体塗布層の形成方法
JP2001181614A (ja) * 1999-12-24 2001-07-03 Teikoku Tsushin Kogyo Co Ltd Ｅｌ素子用蛍光体ペースト及びその製造方法
WO2002059208A1 (fr) * 2001-01-24 2002-08-01 Asahi Kasei Kabushiki Kaisha Compositions de résines à base d'éther de polyphénylène contenant des composés de silicium
JP2002374006A (ja) * 2001-06-15 2002-12-26 Toyoda Gosei Co Ltd 発光装置
JP2004153109A (ja) * 2002-10-31 2004-05-27 Matsushita Electric Works Ltd 発光装置及びその製造方法
JP2005019662A (ja) * 2003-06-26 2005-01-20 Nichia Chem Ind Ltd 発光装置
JP2005089601A (ja) * 2003-09-17 2005-04-07 Stanley Electric Co Ltd 熱硬化性樹脂組成物、該熱硬化性樹脂組成物で発光素子を封止した発光ダイオードおよび色変換型発光ダイオード
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JP2009076749A (ja) * 2007-09-21 2009-04-09 Toyoda Gosei Co Ltd Ｌｅｄ装置及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016062014A (ja) * 2014-09-19 2016-04-25 日本碍子株式会社 光学部品

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