JP2021528503A - Encapsulating resin composition for surface mount discrete devices of LED displays and its applications - Google Patents

Abstract

The present invention discloses a sealing resin composition for a surface-mounted discrete device of an LED display and its use, and the composition includes a first epoxy resin, a second epoxy resin, an acid anhydride, and inorganic oxidation. It contains physical beads, organic polymer fine particles, and a black color material. The encapsulating resin composition of the present invention can be applied to a surface mount discrete device RGB device for a display, in which the device is a five-sided light emitting independent light source including a set of R, G and B chips. Including, a modularized light source (4in1) including four sets of RGB chips may be included. When the sealing composition of the present invention is applied to the above-mentioned device sealing, it improves the moisture resistance and light emission uniformity of the device, improves the contrast, and reduces the warp generated in the sealing process. Can be made to. The encapsulating resin composition further has a low light attenuation property with respect to a blue light source in an RGB device, and extends the service life of the RGB device.

Description

The present invention relates to a sealing resin composition for a surface mount discrete device of an LED display and its use.

In recent years, as big size displays have developed into high-definition display effects of 4K and 8K, LED devices tend to be compact, and the chip size and the pitch of lamp beads are synchronously reduced. Conventional LED encapsulation materials exhibit many defects in the materials and techniques in the following points.

(1) Five-sided emission type EMC lamp beads are smaller in size and denser in pitch than conventional liquid epoxy resin injection type reflective cup devices, and there is a risk of exposure of leads or pins after cutting. big. Moreover, as the sealing layer becomes thinner, the protective effect on the chip gradually weakens. Therefore, since it is necessary to enhance the airtightness protection against the chip, the sealing material is required to have high reliability, particularly moisture resistance. However, the conventional sealing material has low moisture resistance, which reduces the reliability of the chip.

(2) A thin substrate is used so as to satisfy the demand for reducing the size of the light emitting device, and the conventional sealing material tends to cause a large warp of the substrate, which is disadvantageous to the subsequent cutting process.

(3) RGB display devices are required to have a sealing resin having good resistance to light attenuation. While the resistance of the organic silicone resin to light attenuation is superior to that of the epoxy resin, the hardness of the organic silicone resin is low, the adhesive force to the substrate is low, and the airtightness is poor. Therefore, it is difficult to realize high reliability requirements. However, ordinary epoxy resins have poor resistance to light attenuation and are difficult to meet optical requirements.

(4) As a display device, the chips of the three colors R, G, and B have non-uniform light emission from each angle due to the currently used sealing material, and are viewed from a large angle with respect to the viewing angle. There is a terrible color deviation and when the RGB chips are assembled into the display, the screen colors do not match. These optical defects are severe enough to limit the widespread application of RGB devices.

(5) As an optical semiconductor device, the encapsulating resin is required to have good translucency. However, the higher the transparency of the conventional encapsulating material, the more severe the warp, while the warp is. The smaller it is, the less transparent it is. Currently, there are no reports that resolve the contradiction between translucency and warpage.

Improvements in contrast and heat dissipation are also inevitable requirements for the application of compact, high-density displays.

Chinese patent CN105229808A submitted to solve the warpage problem by adding an inorganic filler, which is not a sealing material for sealing and protecting chips, but metal leadframes and light in optical semiconductor devices. It is applied as a reflector material formed around a semiconductor device. The problem solved by the patent is not the warp that occurs after injection molding the sealing material, but the warp problem that occurs in the holder itself where the reflector is located. The epoxy resin composition disclosed in the patent does not have translucency because it needs to have a strong reflective action.

The patent CN105518882A realizes the purpose of improving the light output efficiency by using a light scattering organic filler. In order to realize the object of the invention, the average particle size of the organic filler used is 5 to 15 μm. If the average particle size is too large and the difference from the light wave wavelength is too large, it is advantageous for light transmission, but the scattering effect is reduced.

In the patent CN109243313A, a black color material having a total weight of 1 ‰ to 6 ‰ of the epoxy resin is blended so as to improve the contrast of the display. If the amount of the black color material added is too large, it affects the heat dissipation and translucency of the LED device. If the amount of the black color material added exceeds 0.1%, the brightness of the light emitting chip is reduced to 1% or less, which limits its application in the display field.

In the present invention, in order to eliminate defects in the prior art, the surface of an LED display having low light attenuation, good resistance to warpage, good resistance to moisture, uniform light emission from each angle, and high contrast. It is an object of the present invention to provide a sealing resin composition for a mountable discrete device.

A second object of the present invention is to provide an application of a sealing resin composition for a surface mount discrete device of an LED display.

The outline of the technical solution of the present invention is as follows.
A sealing resin composition for a surface-mounted discrete device of an LED display, which is a first epoxy resin, a second epoxy resin, an acid anhydride, an inorganic oxide bead, an organic polymer fine particle, and a black color material. It is characterized by including and.

The mass of the first epoxy resin is 10 to 61 parts, the mass of the second epoxy resin is 0 to 60 parts, and the amount of acid anhydride used is equal to that of the epoxy groups of the first epoxy resin and the second epoxy resin. It is a molar ratio, the mass of the inorganic oxide beads is 5 to 60 parts, and the mass of the organic polymer fine particles is 0.1 of the total mass of the first epoxy resin, the second epoxy resin, the acid anhydride and the inorganic oxide beads. % To 1%, and the mass of the black color material is 0.01% to 0.1% of the total mass of the first epoxy resin, the second epoxy resin, the acid anhydride and the inorganic oxide beads.

The first epoxy resin is at least one of an alicyclic epoxy resin and glycidyl isocyanurate.
The alicyclic epoxy resin is a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3', 4'-epoxycyclohexanecarboxylic acid 3. , 4-Epoxycyclohexylmethyl or Dycel CELLOXIDE8000.

The glycidyl isocyanurate is triglycidyl isocyanurate, diglycidyl isocyanurate or monoglycidyl isocyanurate.

The second epoxy resin is a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or an epoxy silicone composite epoxy resin.

The acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, maleic anhydride, and methyltetrahydrophthalic anhydride. Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadicic acid anhydride, dodecenylsuccinic anhydride, methylnadic acid anhydride, hydrogenated methylnagic acid anhydride, glutaric acid anhydride, tylcyclohexenetetracarboxylic acid diacid anhydride At least one of them.

The general formula of the inorganic oxide beads is Na _(1-x-y-z-u) O _{(1-x-y-z-u) / 2} · Si _x O _2x · M1 _y O _{3y / 2} · M2. _z O _z · Zr _u O _2u , of which M1 = B, Al, M2 = Mg, Ca, Sr, Zn, the contents of each element are 0.4 ≦ x ≦ 0.7, 0.1 ≦ y ≦ 0.3, z ≦ 0.3, u ≦ 0.3, x + y + z + u ≧ 0.9, of which z, u and 1-x-y-z-u cannot be set to zero at the same time. It is possible, and the central particle size of the inorganic oxide beads is 5 to 30 μm.

7. The organic polymer fine particles are at least one of organic silicon polymer fine particles phenol resin fine particles, polystyrene fine particles, and polymethyl methacrylate fine particles, and the average particle size of the organic polymer fine particles is 5 μm or less. Item 2. The composition according to Item 1 or 2.

The black color material is at least one of nanocarbon black, nanocopper oxide and nanomanganese oxide.

Application of the above composition in encapsulation of surface mount RGB discrete devices for LED displays.

The advantages of the present invention are as follows.
1) Reduce warpage,
2) Greatly improved moisture resistance,
3) It has a predetermined light scattering effect and realizes the light distribution effect of Idemitsu.
4) It has the effect of improving the heat transfer coefficient of the complex.
5) It has the effect of improving the contrast of the LED device.
6) Improve the performance described above and maintain good transmittance of the device.

The encapsulating resin composition of the present invention can be applied to a surface mount discrete device RGB device for a display, in which the device is a five-sided light emitting independent light source including a set of R, G and B chips. Including, a modularized light source (4in1) including four sets of RGB chips may be included. When applied to the sealing of the above devices, the sealing composition of the present invention improves the moisture resistance and light emission uniformity of the device, improves the contrast, and reduces the warpage generated in the sealing process. be able to. The encapsulating resin composition further has a low light attenuation property with respect to a blue light source in an RGB device, and extends the service life of the RGB device.

It is a schematic diagram of the surface mount type discrete RGB device of the LED display sealed with the sealing resin composition of this invention. FIG. 5 is a schematic front view of a discrete device (4in1) of a modularized light source including four sets of surface mount RGB chips of an LED display sealed with a sealing resin composition.

Hereinafter, the present invention will be further described with reference to specific examples.

Each component substance used in the present invention is as follows.

First epoxy resin:
Alicyclic epoxy resin 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct: trade name EHPE-3150, epoxy equivalent 177, Daicel Kako Co., Ltd. Made, abbreviation EHPE-3150,
3', 4'-Epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl: trade name CELLOXIDE 2021P, epoxy equivalent 125, manufactured by Daicel Kako Co., Ltd., abbreviation CELLOXIDE 2021P,
Daicel CELLOXIDE 8000: Epoxy equivalent 100, manufactured by Daicel Kako Co., Ltd., abbreviation CELLOXIDE 8000.

Glycidyl isocyanurate:
Triglycidyl isocyanurate: TGIC-D, epoxy equivalent 100, manufactured by Changzhou City Beef Chemical Industry Co., Ltd., abbreviation TGIC-D.

Diglycidyl isocyanurate: epoxy equivalent 120, abbreviation DGIC.

Monoglycidyl isocyanurate: Epoxy equivalent 185, abbreviation MGIC.

Second epoxy resin:
Bisphenol A type epoxy resin:
Bisphenol A type epoxy resin: JER1002, epoxy equivalent 600-700, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1002.

Bisphenol A type epoxy resin: JER1004, epoxy equivalent 875-975, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1004.

Bisphenol A type epoxy resin: JER1007, epoxy equivalent 1750-2200, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1007.

Bisphenol A type epoxy resin: JER1009, epoxy equivalent 2400-3300, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1009.

Bisphenol A type epoxy resin: JER1010, epoxy equivalent 3000-5000, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1010.

Bisphenol A type epoxy resin: JER1003F, epoxy equivalent 700-800, manufactured by Mitsubishi Chemical Corporation, abbreviation JER1003F.

Bisphenol A type epoxy resin: NPES-301, epoxy equivalent 450-500, Nan Ya Plastics Co., Ltd., abbreviation NPES-301.

Bisphenol A type epoxy resin: NPES-302, epoxy equivalent 600-700, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-302.

Bisphenol A type epoxy resin: NPES-303, epoxy equivalent 800-900, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-303.

Bisphenol A type epoxy resin: NPES-304, epoxy equivalent 900-1000, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-304.

Bisphenol A type epoxy resin: NPES-901, epoxy equivalent 450-500, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-901.

Bisphenol A type epoxy resin: NPES-902, epoxy equivalent 600-650, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-902.

Bisphenol A type epoxy resin: NPES-903, epoxy equivalent 70-750, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-903.

Bisphenol A type epoxy resin: NPES-904, epoxy equivalent 780 to 850, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPES-904.

Bisphenol A type epoxy resin: NPES-905, epoxy equivalent 930-960, Nan Ya Plastics Co., Ltd., abbreviation NPES-905.

Hydrogenated bisphenol A type epoxy resin:
Hydrogenated bisphenol A type epoxy resin: YX-8000, epoxy equivalent 205, manufactured by Mitsubishi Chemical Corporation, abbreviation YX-8000.

Hydrogenated bisphenol A type epoxy resin: YX-8040, epoxy equivalent 1000, manufactured by Mitsubishi Chemical Corporation, abbreviation YX-8040.

Hydrogenated bisphenol A type epoxy resin: YX-8034, epoxy equivalent 290, manufactured by Mitsubishi Chemical Corporation, abbreviation YX-8034.

Hydrogenated bisphenol A type epoxy resin: YL-6753, epoxy equivalent 180, manufactured by Mitsubishi Chemical Corporation, abbreviation YL-6753.

Bisphenol F type epoxy resin:
Bisphenol F type epoxy resin: NPEF-170, epoxy equivalent 160-180, Nan Ya Plastics Co., Ltd., abbreviation NPEF-170.

Bisphenol F type epoxy resin: NPEF-175, epoxy equivalent 160-180, Nan Ya Plastics Co., Ltd., abbreviation NPEF-175.

Bisphenol F type epoxy resin: NPEF-176, epoxy equivalent 170-190, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPEF-176.

Bisphenol F type epoxy resin: NPEF-185, epoxy equivalent 170-190, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPEF-185.

Bisphenol F type epoxy resin: NPEF-187, epoxy equivalent 175-185, manufactured by Nan Ya Plastics Co., Ltd., abbreviation NPEF-187.

Bisphenol F type epoxy resin: NPEF-500, epoxy equivalent 164-170, Nan Ya Plastics Co., Ltd., abbreviation NPEF-500.

Epoxy Silicone Composite Epoxy Resin:
Epoxy Silicone Composite Epoxy Resin: ERS-Si1200, Epoxy Equivalent 1100-1200, manufactured by Mitsubishi Chemical Corporation, abbreviation ERS-Si1200.

Epoxy silicone composite epoxy resin: ERS-Si1700, epoxy equivalent 200, manufactured by Mitsubishi Chemical Corporation, abbreviation ERS-Si1700.
Epoxy Silicone Composite Epoxy Resin: XP833, Epoxy Equivalent 300, manufactured by Mitsubishi Chemical Corporation, abbreviation XP833.

Acid anhydride:
Tetrahydrophthalic anhydride (THPA): Acid anhydride equivalent 152, Nan Ya Plastics Co., Ltd., abbreviation THPA.

Phthalic anhydride: Acid anhydride equivalent 148, manufactured by Nan Ya Plastics Co., Ltd.

Trimellitic anhydride: acid anhydride equivalent 92.

Pyromellitic acid anhydride: Acid anhydride equivalent 218, manufactured by Rakuho Kako Co., Ltd.

Hydrogenated pyromellitic acid anhydride: acid anhydride equivalent 224.

Maleic anhydride: Acid anhydride equivalent 98.

Methyltetrahydrophthalic anhydride: Acid anhydride equivalent 166, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Hexahydrophthalic anhydride: Acid anhydride equivalent 154, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Methylhexahydrophthalic anhydride: Acid anhydride equivalent 168, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Nasic Acid Anhydride: Acid anhydride equivalent 164, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Dodecenyl succinic anhydride: Acid anhydride equivalent 266, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Methylnadic acid anhydride: Acid anhydride equivalent 178, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Hydrogenated methylnadic acid anhydride: Acid anhydride equivalent 180, Puyang Keisei Electronic Materials Crotch ▲ Minute ▼ Made by Co., Ltd.

Glutaric acid anhydride: Acid anhydride equivalent 114, manufactured by Liaoyang Hengqing Chemical Co., Ltd.

Methylcyclohexenetetracarboxylic dianhydride: Acid anhydride equivalent 132.

Inorganic oxide beads:
Inorganic oxide beads-1: Chemical composition Si _0.55 O _1.1 · B _0.2 O _0.3 · Ca _0.15 O _0.15 · Zr _0.1 O _0.2 , center particle size D50 = 20 μm, abbreviation Inorganic oxide beads-1.

Inorganic oxide beads-2: Chemical composition Na _0.1 O _0.05 · Si _0.5 O _1.0 · B _0.1 O _0.15 · Zr _0.3 O _0.6 , center particle size D50 = 10 μm, abbreviation inorganic oxide beads-2.

Inorganic oxide beads-3: Chemical composition Na _0.04 O _0.02 · Si _0.6 O _1.2 · B _0.16 O _0.24 · Zr _0.2 O _0.4 , center particle size D50 = 5 μm, abbreviation inorganic oxide beads-3.

Inorganic oxide beads-4: Chemical composition Si _0.4 O _0.8 , Al _0.3 O _0.45 , Ca _0.1 O _0.1 , Mg _0.2 O _0.2 , center particle size D50 = 12 μm, abbreviation inorganic oxide beads-4.

Inorganic oxide beads-5: Chemical composition Si _0.6 O _1.2 , Al _0.1 O _0.15 , Ca _0.2 O _0.2 , Zn _0.1 O _0.1 , center particle size D50 = 15 μm, abbreviation inorganic oxide beads-5.

Inorganic oxide beads-6: Chemical composition Na _0.06 O _0.03・ Si _0.56 O _1.12・ Al _0.28 O _0.42・ Ca _0.1 O _0.1 , center particle size D50 = 25 μm, abbreviation inorganic oxide beads-6.

Inorganic oxide beads-7: Chemical composition Si _0.7 O _1.4 , Al _0.05 O _0.075 , B _0.15 O _0.225 , Mg _0.1 O _0.1 , center particle size D50 = 30 μm, abbreviation inorganic oxide beads-7.

Inorganic oxide beads-8: Chemical composition Si _0.45 O _0.9 / Al _0.2 O _0.3 / B _0.1 O _0.15 / Ca _0.15 O _0.15 / Zn _0.1 O _0.1 , center particle size D50 = 8 μm, abbreviation inorganic oxide beads-8.

Inorganic oxide beads-9: Chemical composition Na _0.04 O _0.02 , Si _0.6 O _1.2 , Al _0.1 O _0.15 , Ca _0.26 O _0.26 , center particle size D50 = 25 μm, abbreviation inorganic oxide beads-9.

Inorganic oxide beads-10: Chemical composition Si _0.5 O _1.0 · B _0.3 O _0.45 · Mg _0.1 O _0.1 · Sr _0.1 O _0.1 , center particle size D50 = 15 μm, abbreviation inorganic oxide beads-10.

Inorganic oxide beads-11: Chemical composition Si _0.6 O _1.2・ Al _0.2 O _0.3・ Mg _0.15 O _0.15・ Sr _0.05 O _0.05 , center particle size D50 = 24 μm, abbreviation inorganic oxide beads-11.

Inorganic oxide beads-12: Chemical composition Si _0.6 O _1.2 / Al _0.2 O _0.3 / Zr _0.2 O _0.4 , center particle size D50 = 30 μm, abbreviation Inorganic oxide beads-12 ..

The method for preparing inorganic oxide beads is to weigh the powdery precursors (including oxides, carbonates, and hydroxides) of each element at the target compounding ratio, ball mill, mix, pressurize, and dry. Then, high-temperature sintering, coarse pulverization, secondary ball milling, and spray drying are performed to obtain inorganic oxide beads having a fixed component.

Inorganic oxide beads: Alumina, center particle size D50 = 5 μm, Jiangsu Lianlui new material crotch ▼ manufactured by Co., Ltd., abbreviation alumina.

Inorganic oxide beads: calcium oxide, center particle size D50 = 10 μm, abbreviation calcium oxide.

Inorganic oxide beads: magnesium oxide, center particle size D50 = 15 μm, abbreviation magnesium oxide.

Inorganic oxide beads: silica, center particle size D50 = 20 μm, Jiangsu Lianlui new material crotch ▼ manufactured by Co., Ltd., abbreviation silica.

Organic Polymer Fine Particles-Organic Silicone Polymer Fine Particles:
Organic polymer fine particles: KMP-590, organic silicon polymer fine particles, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KMP-590.

Organic polymer fine particles: KMP-597, organic silicon polymer fine particles, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KMP-597.

Organic polymer fine particles: KMP-701, organic silicon polymer fine particles, average particle size 3.5 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KMP-701.

Organic polymer fine particles: KMP-600, organic silicon polymer fine particles, average particle size 5 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KMP-600.

Organic polymer fine particles: KMP-605, organic silicon polymer fine particles, average particle size 2 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation KMP-605.

Organic polymer fine particles: X-52-7030, organic silicon polymer fine particles, average particle size 0.8 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation X-52-7030.

Organic polymer fine particles: X-52-854, organic silicon polymer fine particles, average particle size 0.8 μm, manufactured by Shin-Etsu Chemical Co., Ltd., abbreviation X-52-854.

Organic Polymer Fine Particles-Phenol Resin:
Organic polymer fine particles: phenol resin, number average molecular weight 20000 to 50000, average particle size 1 um, abbreviation phenol resin-1.

Organic polymer fine particles: phenol resin, number average molecular weight 30,000 to 80,000, average particle size 3 um, abbreviation phenol resin-2.

Organic polymer fine particles: phenol resin, number average molecular weight 50,000 to 100,000, average particle size 5 um, abbreviation phenol resin-3.

Organic Polymer Fine Particles-Polystyrene Fine Particles:
Organic polymer fine particles: polystyrene fine particles, average particle size 0.5 um, abbreviation polystyrene fine particles-1.

Organic polymer fine particles: polystyrene fine particles, average particle size 2um, abbreviation polystyrene fine particles-2.

Organic polymer fine particles: KM-503, polystyrene fine particles, average particle size 3 μm, manufactured by Dongguan City Kaoru New Materials Co., Ltd., abbreviation KM-503.

Organic polymer fine particles: KM-5030, polystyrene fine particles, average particle size 3 μm, manufactured by Dongguan City Kaoru New Materials Co., Ltd., abbreviation KM-5030.

Organic Polymer Fine Particles-Polymethylmethacrylate Fine Particles:
Organic polymer fine particles: LD-015, polymethylmethacrylate fine particles, average particle size 1.5 μm, Dongguan City Shinsei Chemical Technology Co., Ltd.

Organic polymer fine particles: KMR-3EA, polymethylmethacrylate fine particles, average particle size 3 μm, manufactured by Soken Chemical Co., Ltd., abbreviation KER-3EA.

Organic polymer fine particles: KMR-3TA, polymethylmethacrylate fine particles, average particle size 3 μm, manufactured by Soken Chemical Co., Ltd., abbreviation KMR-3TA.

Black color material: Nano carbon black 2300 #, average particle size 15 nm, Mitsubishi Chemical Corporation.

Black color material: nano-copper oxide, average particle size 40nm, Beijing Tokushinajima Gold Technology Co., Ltd.

Black color material: Nano manganese oxide, average particle size 50 nm, Shanghai Higashi New Materials Technology Co., Ltd.

The examples of the present invention are for those skilled in the art to understand the present invention well, and are not any restrictions on the present invention.

The sealing resin compositions prepared according to the examples and comparative examples in the present invention are tested for their respective performances by the following methods.

Blue light attenuation: A hexagonal substrate with a blue light chip and lead welded together is placed in the mold of the molding equipment, and then the prepared encapsulating resin composition is preheated in the molding equipment and extruded into the mold cavity. Embed the chip and expose the leads of the hexagonal substrate. This sample needs to be cured at 150 ° C. for 4 hours. An integrating sphere is then used to test the initial luminous flux of this embedded chip when lit at a particular current. A series of encapsulating resin compositions to be tested were prepared by this method into a sample to be tested, then the samples were connected in series and continuously lit at room temperature for 200 hours using a 200 mA current (acceleration test). Retest the luminous flux remaining at a particular current. (Initial Luminous Flux-Residual Luminous Flux) / Initial Luminous Flux provides blue light attenuation for this single sample. The number of samples for each test of each sealing resin composition is 3 or more, and the average value is adopted.

The integrating sphere device used in this test is a photometric integrating sphere R98 with an aluminum base manufactured by Hangzhou Far Photoelectric Information Co., Ltd.

Molding shrinkage: 20 g of the prepared sealing resin composition powder or granules or blocks are weighed and injected into a specific mold at 150 ° C. for curing. The mold cavity is circular with a diameter of 60 mm and a thickness of about 3 mm. The cured molding resin is taken out and left at room temperature for 24 hours. Next, the diameter of the cured resin in the vertical direction is measured, the average value thereof is obtained, and the difference between the diameter and the diameter of the mold is divided by the diameter of the mold to obtain the mold shrinkage ratio. The number of samples for each test of each sealing resin composition is 3 or more, and the average value is adopted.

Water absorption: A sample having a diameter of 60 mm and a thickness of about 3 mm is obtained in the same manner as in the mold and injection molding conditions when preparing the sample used for the mold shrinkage rate. Continue curing for 4 hours under the condition of 150 ° C. After taking out the sample and leaving it at room temperature, the mass of the sample is weighed to obtain the initial weight. Next, put it in boiling water and keep boiling for 1 hour, take out the sample, wipe off the water, and weigh the sample. Divide the difference between the two masses by the initial mass to obtain the water absorption of the sample. The number of samples for each test of each sealing resin composition is 3 or more, and the average value is adopted.

Idemitsu: The obtained encapsulating resin composition was extruded into a mold having a cavity with a side length of 30 mm and a depth of 0.40 mm, cured at 150 ° C. for 2 minutes, and then transferred to an oven at 150 ° C. for curing for 4 hours. A sample having a side length of about 30 mm * 30 mm and a thickness of 0.40 mm is obtained, and the light transmittance at 450 nm is tested using a spectrophotometer to obtain the light output rate.

Idemitsu uniformity: The prepared encapsulating resin composition is encapsulated on a red LED chip by an injection molding method, and then the radiant intensity distribution data of this chip, that is, the radiant intensity at various angles, is tested. , Judge the light emission effect.

Chip surface temperature: A hexagonal substrate with a blue light chip and leads welded is placed in the mold of the molding equipment, and then the prepared encapsulating resin composition is preheated by the molding equipment and extruded into the mold cavity. The chip is embedded with an embedding thickness of 1 mm to expose the leads of the hexagonal substrate. This sample needs to be cured at 150 ° C. for 4 hours. Next, a series of encapsulating resin compositions that need to be tested were prepared by this method into a sample to be tested, then the samples were connected in series and continued for 1 hour at room temperature using a 200 mA current (acceleration test). Turn on and test the chip surface temperature under these conditions with an infrared thermal imager. Obtain the blue light attenuation of this single sample. The number of samples for each test of each sealing resin composition is 3 or more, and the average value is adopted.

The infrared thermal imager is RX-500 manufactured by Dongguan City Fubon Electronics Co., Ltd.

The preparation method of the sealing resin composition (abbreviated as the sealing resin composition) for the surface mount type discrete device of the LED display prepared in the examples of the present invention and the sealing resin composition in the comparative example is as follows. there were.

The compounding ratio of each example is shown in Table 1, and the first epoxy resin (added if there is a second epoxy resin), acid anhydride, inorganic oxide beads, organic polymer fine particles, and black coloring material are taken. After mixing well, the mixture was uniformly kneaded at 100 ° C. using a twin-screw extruder, cooled and pulverized to obtain a powdery sealing resin composition.

Table 2 shows the test results of Examples 1 to 11 of the present invention.

In the comparative example of the present invention, each substance is mixed at the compounding ratio shown in Table 3, uniformly kneaded at a temperature of 100 ° C. using a twin-screw extruder, cooled and pulverized, and sealed in powder form. A resin composition was obtained.

Table 3 shows the test results of Comparative Examples 1 to 9 of the present invention.

From the results of Examples 1 to 3 and 7 to 11 in Table 1, it was found that when all the components of the epoxy resin were the first epoxy resin, the obtained sealing resin composition had remarkable blue light resistance. rice field.

In Examples 4 to 6, when the first epoxy resin and the second epoxy resin were used in combination, the obtained sealing resin composition had good blue light attenuation.

By replacing EHPE-3150 of Example 1 with the first epoxy resin CELLOXIDE 2021P, CELLOXIDE 8000, DGIC or MGIC, similar resistance to blue light attenuation was obtained.

In Comparative Example 1, since the second epoxy resin (JER1002) was used as the main agent, the obtained sealing resin composition of Comparative Example had poor blue light attenuation performance.

Second epoxy resin (bisphenol A type epoxy resin NPES-301, NPES-303, NPES-304, NPES-901, NPES-902, NPES-903, NPES-904, NPES-905, JER1004, JER1007, JER1009, JER1010, And JER1003F; hydrogenated bisphenol A type epoxy resin YX-8040, YX-8040, YX-8034 and YL-6753; bisphenol F type epoxy resin NPEF-170, NPEF-175, NPEF-176, NPEF-185, NPEF-187 , And NPEF-500; Epoxy Silicone Composite Epoxy Resins ERS-Si1200, ERS-Si1700, and XP833) replaced JER1002 with similar resistance to blue light attenuation.

From the results of Examples 1, 2 and 6, and Comparative Examples 2 and 7, since the sealing resin composition contains the inorganic oxide beads 1, the molding shrinkage rate and the water absorption rate of the sealing resin composition are significantly reduced. And, as the content of the inorganic oxide beads increases, the degree of decrease is further increased, and it has been found that while maintaining a high light emission rate, it maintains considerable transparency, which is for light emitting LED devices. It was very important.

From Examples 2, 3, 5, 9 and 10, to include inorganic oxide beads-2, inorganic oxide beads-3, inorganic oxide beads-4, inorganic oxide beads-5 and inorganic oxide beads-6. It was found that the molding shrinkage and water absorption of the sealing resin composition were significantly reduced, the light emission rate was high, and the transparency was good.

Inorganic oxide beads-7, inorganic oxide beads-8, inorganic oxide beads-9, inorganic oxide beads-10, inorganic oxide beads-11, or inorganic oxide beads-12 in the inorganic oxide of Example 1. Similar effects were obtained when replacing beads-1.

In Comparative Example 2, since the inorganic oxide beads were not added, the obtained sealing resin composition had a high molding shrinkage rate and a poor water absorption rate.

In Comparative Example 3, since silica, which is an ordinary inorganic oxide bead, was used, the molding shrinkage and water absorption of the obtained sealing resin composition were significantly reduced, but the light emission rate was very low, and the light emitting device had a very low light emission rate. Has no effect when added and has not been suitable for use in RGB displays.

From Comparative Example 1 and Comparative Example 7, it was found that the sealing resin composition had a constant and uniform light emitting effect even when the organic polymer fine particles were not used. Therefore, the inorganic oxide beads used in the present invention also play a role in balancing the light emission from each angle.

From Examples 1, 2, 7 and 8, when the organic polymer fine particles KMP-590 are contained, the light emission curve shape of the sealing resin composition is a smooth arc shape, so that the light emission from each angle is uniform. It was found that the organic polymer fine particles KMP-590 play a role in balancing the light emission from each angle.

From Examples 3 to 5, it was found that the encapsulating resin composition obtained by adding phenol resin-1, KM-503 and KMR-3EA as the organic polymer fine particles had a smooth arcuate emission curve. rice field. This indicates that the organic polymer fine particles phenol resin-1, KM-503, and KMR-3EA also play a role in balancing the light emission from each angle.

From Comparative Example 7, it was found that the encapsulating resin composition to which the organic polymer fine particles were not added had a large difference in light emission intensity measured at each angle, the curved shape became zigzag, and light could not be emitted uniformly at each angle. ..

Organic polymer fine particles KMP-597, KMP-701, KMP-600, KMP-605, X-52-7030, X-52-854, phenol resin-2, phenol resin-3, polystyrene fine particles-1, polystyrene fine particles-2 Replacing the organic polymer fine particles KMP-590 of Example 1 with KM-5030, LD-015 and KMR-3TA, the emission curves of the resulting encapsulating resin composition can produce similar effects.

Further, from Examples 2, 7 and 8, it was found that when the amount of the organic polymer fine particles KMP-590 is large, the water absorption rate of the sealing resin composition is significantly improved and the risk of poor reliability is increased. .. Therefore, the organic polymer fine particles cannot be used alone, and in order to eliminate the risk due to the increase in water absorption, it is necessary to combine them with the inorganic oxide beads.

In Examples 1 to 11, by using nanoscale carbon black 2300 # (average particle diameter 15 nm) which is a black color material and nanoscale copper oxide (average particle diameter 40 nm) which is a black color material, the light emission rate and The effect of improving contrast was achieved while ensuring a lower chip surface temperature.

In Comparative Example 9, when nanocarbon black 2300 #, which is a black color material, was excessively added, the light emission rate was significantly reduced, while the black color material absorbed heat and accumulated heat in the sealing device, resulting in long-term lighting. As the temperature rises, the risk of failure of long-used LED devices has increased.

Similar effects were obtained by using nanomanganese oxide (average particle size 50 nm) instead of nanocarbon black 2300 # (average particle size 15 nm), which is the black color material of Example 1.

Trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, dodecenyl succinic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid Similar effects were obtained when the anhydride, glutaric anhydride, and methylcyclohexenetetracarboxylic acid diichydride were replaced with maleic anhydride in Example 1.

From the above results, the encapsulating resin composition for the surface mount type discrete device of the LED display of the present invention is characterized by having resistance to blue light attenuation and low water absorption, whereby it is compact. -It can be seen that the airtight protection and reliability of the thin device are improved. Further, in order to reduce the molding shrinkage rate of this epoxy resin composition, warpage after mounting the small pitch / high density chip is effectively suppressed, and the problem of workability in the mounting factory is improved.

From the viewpoint of application experience, the sealing resin composition of the present invention constitutes a screen from a sealed chipset by balancing the light emission intensity from each angle of the R, G and B chips, and constitutes a front surface. After adjusting the white balance, the color deviation caused by a large angle with respect to the viewing angle disappears. By adding a suitable black color material with high precision, the contrast can be improved without causing the temperature rise of the chip.

note:
1) Class I: It has a smooth arc shape, and the amount of light emitted from each angle is uniform.

2) Class II: It is jagged and the difference in the amount of light emitted from each angle is huge.

3) Class III: An arc shape with a slightly concave center angle, and the amount of light emitted from the center angle is slightly low.

4) *: Since the light emission rate is low, the blue light attenuation and the light emission curve shape cannot be measured.

5) In Tables 1 and 3, the numbers in the brackets represent the number of moles of epoxy resin or acid anhydride.

The present invention screens the first and second epoxy resin systems, adds acid anhydrides, and further introduces inorganic oxide beads. The present invention uses screened inorganic oxide beads in consideration of the light transmittance of the light emitting device, and has a high transmittance. Moreover, the content of the inorganic oxide beads accounts for 5 to 60 parts of the first epoxy resin, the second epoxy resin and the inorganic oxide beads. The heat transfer coefficient of the inorganic oxide beads is generally larger than that of the epoxy resin, and therefore, to a certain extent, the heat dissipation effect of the composition is further improved.

The present invention has submitted that inorganic oxide beads are added and organic polymer fine particles are composited in order to further enhance the light distribution effect (light emission uniformity) of light emission, and the organic polymer fine particles are R, G. It can play a role of mixing the light emitted from the three chips, B and B, and can display the light emitted from each angle in a large angle in a well-balanced manner. After adjusting the white balance on the front of the assembled big size display, observe the presence or absence of red from a large angle on the side.

The present invention submits the addition of a black color material so as to achieve the object of improving the contrast, but the black color material absorbs the amount of heat to raise the temperature of the light emitting device and the addition of the black color material. When the amount is large, the amount of the black color material used is strictly limited to 0.1% by weight or less in view of the feature that the translucency of the light emitting device is sharply lowered.

As a result, the light attenuation is low, the resistance to warpage and the resistance to moisture are good, and a sealing resin composition is obtained, the light emission is balanced, the contrast and heat dissipation are improved, and the experience of the terminal user is improved. Can be improved.

In the sealed LED device of the present invention, the thickness of the sealing layer is generally 0.2 to 0.6 mm.

Claims (9)

For surface mount discrete devices of LED displays comprising a first epoxy resin, a second epoxy resin, an acid anhydride, inorganic oxide beads, organic polymer fine particles, and a black color material. Encapsulating resin composition. The mass of the first epoxy resin is 10 to 61 parts, the mass of the second epoxy resin is 0 to 60 parts, and the amount of acid anhydride used is equal to that of the epoxy groups of the first epoxy resin and the second epoxy resin. It is a molar ratio, the mass of the inorganic oxide beads is 5 to 60 parts, and the mass of the organic polymer fine particles is 0.1 of the total mass of the first epoxy resin, the second epoxy resin, the acid anhydride and the inorganic oxide beads. % To 1%, and the mass of the black color material is 0.01% to 0.1% of the total mass of the first epoxy resin, the second epoxy resin, the acid anhydride and the inorganic oxide beads. The composition according to claim 1. The first epoxy resin is at least one of an alicyclic epoxy resin and glycidyl isocyanurate.
The alicyclic epoxy resin is a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, 3', 4'-epoxycyclohexanecarboxylic acid 3. , 4-Epoxycyclohexylmethyl or Dycel CELLOXIDE8000,
The composition according to claim 1 or 2, wherein the glycidyl isocyanurate is triglycidyl isocyanurate, diglycidyl isocyanurate or monoglycidyl isocyanurate. The composition according to claim 1 or 2, wherein the second epoxy resin is a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or an epoxy silicone composite epoxy resin. .. The acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, maleic anhydride, and methyltetrahydrophthalic anhydride. Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadicic acid anhydride, dodecenylsuccinic anhydride, methylnadic acid anhydride, hydrogenated methylnagic acid anhydride, glutaric acid anhydride, tylcyclohexenetetracarboxylic acid diacid anhydride The composition according to claim 1 or 2, wherein the composition is at least one of. The general formula of the inorganic oxide beads is Na _(1-x-y-z-u) O _{(1-x-y-z-u) / 2} · Si _x O _2x · M1 _y O _{3y / 2} · M2. _z O _z · Zr _u O _2u , of which M1 = B, Al, M2 = Mg, Ca, Sr, Zn, the contents of each element are 0.4 ≦ x ≦ 0.7, 0.1 ≦ y ≦ 0.3, z ≦ 0.3, u ≦ 0.3, x + y + z + u ≧ 0.9, of which z, u and 1-x-y-z-u cannot be set to zero at the same time. The composition according to claim 1 or 2, which is possible and has a central particle size of the inorganic oxide beads of 5 to 30 μm. The organic polymer fine particles are at least one of phenol resin fine particles, polystyrene fine particles, and polymethylmethacrylate fine particles as organic silicon polymer fine particles, and the average particle size of the organic polymer fine particles is 5 μm or less. The composition according to claim 1 or 2. The composition according to claim 1 or 2, wherein the black color material is at least one of nanocarbon black, nanocopper oxide, and nanomanganese oxide. An application of the composition according to any one of claims 1 to 8 in encapsulation of a surface mount RGB discrete device for an LED display.

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