CN103980714A - High-refraction-index LED (Light Emitting Diode) organic silicon packaging material and preparation method thereof - Google Patents

High-refraction-index LED (Light Emitting Diode) organic silicon packaging material and preparation method thereof Download PDF

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CN103980714A
CN103980714A CN201410243296.XA CN201410243296A CN103980714A CN 103980714 A CN103980714 A CN 103980714A CN 201410243296 A CN201410243296 A CN 201410243296A CN 103980714 A CN103980714 A CN 103980714A
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sio
component
vinyl
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修建东
梁圆
刘大为
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Yantai Li Nuo Electronic Science And Technology Co Ltd
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Yantai Li Nuo Electronic Science And Technology Co Ltd
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Abstract

The invention discloses a high-refraction-index LED (Light Emitting Diode) organic silicon packaging material and a preparation method thereof. The material consists of a component A and a component B, wherein the mass ratio of the component A to the component B is 5:1; the component A is prepared from the following raw materials in parts by mass: 140-160 parts of methyl high-phenyl vinyl silicon resin, 90-110 parts of vinyl phenyl silicon oil and 0.2-0.6 parts of platinum catalyst; the component B comprises 25-35 parts of high-phenyl vinyl silicon resin, 15-25 parts of methyl phenyl hydrogen silicon resin and 0.3-1 part of inhibitor. The methyl high-phenyl vinyl silicon resin is adopted to be reasonably combined with the vinyl phenyl silicon oil to provide silicon-vinyl, the high-phenyl vinyl silicon resin is adopted to be reasonably combined with the methyl phenyl hydrogen silicon resin to provide silicon hydrogen, in the presence of the catalyst and the inhibitor, the organic silicon packaging material obtained by uniformly mixing and stirring the components can have addition curing reaction when being heated, and can be applied to LED packaging to achieve the purpose of high light emission rate of an LED.

Description

High-refractive-index LED organosilicon packaging material and preparation method thereof
Technical Field
The invention relates to the technical field of LED organic silicon packaging materials, in particular to a high-refractive-index LED organic silicon packaging material and a preparation method thereof.
Background
The LED is composed of a chip, a lead, a bracket, conductive adhesive, packaging materials and the like, liquid rubber is poured into a device provided with electronic elements and circuits in a filling, encapsulating or mould pressing mode for packaging, the main chain of organic silicon is Si-O-Si side group which is methyl, the whole molecular chain is spiral, and the special mixed chain molecular structure endows the device with a plurality of excellent performances, such as: the Si-O bond length and the bond angle are relatively large, the steric hindrance of the bond to the rotation of the side group is small, and the chain segment is very flexible, so that the low-temperature resistance is good, meanwhile, the Si-O bond energy is relatively high, so that the Si-O bond has good thermal stability and weather resistance, can work within a wide temperature range (-50-250 ℃), and has good hydrophobicity due to low surface energy (21-22 mN/m); low surface tension and flexibility can increase the permeability of polymer systems. The characteristics enable the organic silicon to have high light transmittance, good thermal stability, strong ultraviolet resistance, small internal stress, low hygroscopicity, and obviously better performance than epoxy resin, and become an ideal choice of LED packaging materials, however, the organic silicon material has a lower refractive index, the low refractive index can influence the light-emitting rate of the LED, and in order to improve the refractive index and radiation resistance of the material, the organic silicon packaging materials are generally prepared by vinyl silicon resin containing a certain amount of diphenyl siloxane chain links or methyl phenyl siloxane chain links and hydrogen-containing silicon oil, and the materials have low shrinkage and good cold and heat shock resistance.
Disclosure of Invention
The invention relates to a high-refractive-index LED (light-emitting diode) organic silicon packaging material and a preparation method thereof, and is characterized in that methyl high-phenyl vinyl silicone resin is reasonably matched with vinyl phenyl silicone oil to provide silicon-vinyl, high-phenyl hydrogen base silicone resin is reasonably matched with methyl phenyl hydrogen base silicone resin to provide silicon hydrogen base, and the organic silicon packaging material which is uniformly mixed and stirred can generate addition curing reaction by heating in the presence of a catalyst and an inhibitor, and can be used for LED packaging to achieve the purpose of high light-emitting rate of an LED.
In order to achieve the purpose, the technical solution of the invention is as follows: the LED organic silicon packaging material with the high refractive index consists of a component A and a component B, wherein the mass ratio of the component A to the component B is 5: 1, and the component A comprises the following raw materials in parts by mass: 140-160 parts of methyl high phenyl vinyl silicone resin, 90-110 parts of vinyl phenyl silicone oil and 0.2-0.6 part of platinum catalyst; the component B comprises 25-35 parts of high phenyl hydrogen silicon resin, 15-25 parts of methyl phenyl hydrogen silicon resin and 0.3-1 part of inhibitor.
On the basis of the scheme, the invention can be further improved as follows:
further, the methyl high phenyl vinyl silicone resin has a chemical general formula of (PhSiO)3/2) x1(Ph2SiO)x2 (Me2SiO)x3 (ViMe2SiO1/2) x4A compound of formula (I), wherein PhSiO3/2Is a trifunctional link, in which Ph2SiO、Me2SiO is a difunctional mer, ViMe2SiO1/2Is a monofunctional link; wherein Ph is phenyl, Me is methyl, Vi is vinyl, x1= 0.55-0.60, x2= 0.02-0.04, x3= 0.02-0.04, x4= 0.35-0.45, and the sum of the values is x1+ x2+ x3+ x4= 1;
the vinyl phenyl silicone oil has a chemical general formula of ViMe2 SiO ( Si Me2O)m (SiPh2O)n Si Me2A compound Vi, wherein Ph is phenyl, Me is methyl, Vi is vinyl, m and n are integers which are more than 10 and m + n is less than 50, and the molar percentage of the vinyl is 0.78%; 5 mol% phenyl and a viscosity of 3050mPa @;
the high phenyl hydrogen-based silicone resin has three functional chain links, two functional chain links and one functional chain linkHigher viscosity MDT resins of (a); has the chemical general formula of (PhSiO)3/2)y1(Ph2SiO)y2(Ph3SiO1/2) y3 (HMe2SiO1/2) y4A compound of formula (I), wherein PhSiO3/2Is a trifunctional link, in which Ph2SiO is a difunctional chain member, Ph3SiO1/2、HMe2SiO1/2Is a monofunctional link; ph is phenyl, Me is methyl, Vi is vinyl, y1= 0.5-0.6, y2= 0.02-0.03, y3= 0.02-0.03, y4= 0.3-0.4, and the sum of the values is y1+ y2+ y3+ y4= 1;
the methylphenylhydrosilicon resin is a lower viscosity MDT resin with trifunctional chain link, bifunctional chain link and monofunctional chain link; has the chemical general formula of (PhSiO)3/2)z1(Me2SiO)z2(Me3SiO1/2)z3 (HMe2SiO1/2) z4A compound of formula (I), wherein PhSiO3/2Is a trifunctional mer of formula Me2SiO is a difunctional mer, (Me)3SiO1/2)、(HMe2SiO1/2) Is a monofunctional link; wherein Ph is phenyl, Me is methyl, Vi is vinyl, z1= 0.45-0.55, z2= 0.08-0.09, z3= 0.06-0.07, z4= 0.30-0.35, and the sum of the values is z1+ z2+ z3+ z4= 1;
the platinum catalyst is one selected from platinum-1, 3-dimethyl-1, 3-diphenyl-1, 3-divinyl siloxane complex, platinum-1, 1, 3, 3-tetramethyl-1, 3-divinyl-disiloxane complex and chloroplatinic acid-divinyl tetramethyl disiloxane complex;
the inhibitor is one or more than one selected from 1-ethynylcyclohexanol, 3-diphenyl-1, 5-divinyl-1, 1, 5, 5-tetramethyltrisiloxane, 3-phenyl-1, 5-divinyl-1, 1, 3, 5, 5-pentamethyltrisiloxane and phenyl tris (dimethylvinylsiloxy) silane.
The preparation method of the high-refractive-index LED organosilicon packaging material comprises the steps of preparing a component A and preparing a component B; wherein,
the preparation of the component A comprises the following steps: sequentially adding 140-160 parts by mass of methyl high phenyl vinyl silicone resin, 90-110 parts by mass of vinyl phenyl silicone oil and 0.2-0.6 part by mass of platinum catalyst into a stirrer, and uniformly stirring to obtain the component A;
the preparation of the component B comprises the following steps: sequentially adding 25-35 parts by mass of high phenyl hydrogen silicone resin, 15-25 parts by mass of methyl phenyl hydrogen silicone resin and 0.1-0.3 part by mass of inhibitor into a stirrer, and uniformly stirring to obtain the component B;
during the use, will component A and component B according to the ratio of mass ratio 5: 1, carry out the misce bene, vacuum deaeration 30 ~ 45 minutes, glue or the filling is on waiting to encapsulate LED chip spare, slowly heats to 150 ℃ to solidification 2 ~ 3 hours at 150 ℃ constant temperature, stop heating, the cooling accomplishes the solidification.
The invention has the advantages and characteristics that: the component A of the high-refractive-index LED organosilicon encapsulating material provides silicon-vinyl for addition reaction during curing reaction and inhibits side reaction from occurring, so that a platinum catalyst generated by black substances is avoided; the component B provides a silicon-hydrogen group for addition reaction and an inhibitor during curing reaction; both the A component and the B component provide phenyl groups capable of improving refractive index and silicone resin for improving adhesion and adhesion; according to the improved scheme, the vinyl phenyl silicone oil with high viscosity and low viscosity in the component A is used in a matching way, and the MDT resin with high viscosity and low viscosity in the component B is used in a matching way, so that the components are favorably stirred and uniformly mixed.
Detailed Description
Example 1
Preparation of component A: sequentially adding 160 g of methyl high phenyl vinyl silicone resin, 90 g of vinyl phenyl silicone oil and 0.6 g of platinum-1, 3-dimethyl-1, 3-diphenyl-1, 3-divinyl siloxane complex into a stirrer, and stirring uniformly to obtain the component A;
the preparation of the component B comprises the following steps: sequentially adding 32 g of high phenyl hydrogen silicon resin, 20 g of methyl phenyl hydrogen silicon resin and 0.2 g of 3-phenyl-1, 5-divinyl-1, 1, 3, 5, 5-pentamethyl trisiloxane into a stirrer, and uniformly stirring to obtain the component B;
during the use, will component A and component B according to the ratio of mass ratio 5: 1, carry out the misce bene, vacuum deaeration 30 ~ 45 minutes, glue or the filling is on waiting to encapsulate LED chip spare, slowly heats to 150 ℃ to solidification 2 ~ 3 hours at 150 ℃ constant temperature, stop heating, the cooling accomplishes the solidification.
Example 2
Preparation of component A: sequentially adding 140 g of methyl high phenyl vinyl silicone resin, 110 g of vinyl phenyl silicone oil and 0.2 g of chloroplatinic acid-divinyl tetramethyl disiloxane complex into a stirrer, and uniformly stirring to obtain the component A;
the preparation of the component B comprises the following steps: sequentially adding 25 g of high phenyl hydrogen silicon resin, 25 g of methyl phenyl hydrogen silicon resin and 0.1 g of 1-ethynylcyclohexanol in parts by mass into a stirrer, and uniformly stirring to obtain the component B;
during the use, will component A and component B according to the ratio of mass ratio 5: 1, carry out the misce bene, vacuum deaeration 30 ~ 45 minutes, glue or the filling is on waiting to encapsulate LED chip spare, slowly heats to 150 ℃ to solidification 2 ~ 3 hours at 150 ℃ constant temperature, stop heating, the cooling accomplishes the solidification.
Example 3
Preparation of component A: sequentially adding 150 g of methyl high phenyl vinyl silicone resin, 100 g of vinyl phenyl silicone oil and 0.4 g of platinum-1, 1, 3, 3-tetramethyl-1, 3-divinyl-disiloxane complex into a stirrer, and stirring uniformly to obtain the component A;
the preparation of the component B comprises the following steps: sequentially adding 35 g of high phenyl hydrogen silicon resin, 15 g of methyl phenyl hydrogen silicon resin and 0.3 g of phenyl tri (dimethyl vinyl siloxy) silane into a stirrer, and uniformly stirring to obtain the component B;
during the use, will component A and component B according to the ratio of mass ratio 5: 1, carry out the misce bene, vacuum deaeration 30 ~ 45 minutes, glue or the filling is on waiting to encapsulate LED chip spare, slowly heats to 150 ℃ to solidification 2 ~ 3 hours at 150 ℃ constant temperature, stop heating, the cooling accomplishes the solidification.
Uniformly mixing the component A and the component B described in the embodiments 1, 2 and 3 according to respective mass ratio, defoaming in vacuum for 30 minutes, leveling the mixture in a mold tank according to the requirements of GB/T528-2009, slowly heating to 130 ℃, curing at 130 ℃ for 2-3 hours at constant temperature, stopping heating, cooling, finishing curing, and preparing into a sheet. Testing one: according to GB2410-80
Testing the transmittance of the sheet sample; and (2) testing: preparing a dumbbell-shaped silica gel sample according to the GB/T528-2009 requirements, testing the tensile strength of the silica gel sample, and testing three: testing the hardness of the silica gel sample according to GB/T2411-2008; and (3) testing: the refractive index of the silica gel sample was measured using an Abbe refractometer.
Table one: performance index table
Performance index ﹨ sample Example 1 Example 2 Example 3
Transmittance after curing (%) 95.5/(585nm) 95.3/(585nm) 95.7/(585nm)
Tensile Strength (MPa) 6.55 6.17 6.39
Hardness after curing (A) 65 69 67
Refractive index 1.51 1.52 1.51
As can be seen from the table I, the light transmittance of the cured sheet samples (1 mm thick) of the samples of examples 1, 2 and 3 is above 95% at a wavelength of 585 nm, the tensile strength is above 6.17MPa, the hardness after curing is 66A-69A, and the refractive index is above 1.51, which all reach the expected target and are suitable for packaging power LEDs.
The above-mentioned embodiments are merely descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims (2)

1. A high-refractive-index LED organic silicon packaging material and a preparation method thereof are characterized in that: the LED organosilicon packaging material with the high refractive index is composed of a component A and a component B, wherein the mass ratio of the component A to the component B is 5: 1, and the component A comprises the following raw materials in parts by mass: 140-160 parts of methyl high phenyl vinyl silicone resin, 90-110 parts of vinyl phenyl silicone oil and 0.2-0.6 part of platinum catalyst; the component B comprises 25-35 parts of high phenyl hydrogen silicone resin, 15-25 parts of methyl phenyl hydrogen silicone resin and 0.3-1 part of inhibitor;
the preparation method of the LED organic silicon packaging material with the high refractive index comprises the preparation of a component A and the preparation of a component B; wherein,
the preparation of the component A comprises the following steps: sequentially adding 140-160 parts by mass of methyl high phenyl vinyl silicone resin, 90-110 parts by mass of vinyl phenyl silicone oil and 0.2-0.6 part by mass of platinum catalyst into a stirrer, and uniformly stirring to obtain the component A;
the preparation of the component B comprises the following steps: sequentially adding 25-35 parts by mass of high phenyl hydrogen silicone resin, 15-25 parts by mass of methyl phenyl hydrogen silicone resin and 0.1-0.3 part by mass of inhibitor into a stirrer, and uniformly stirring to obtain the component B.
2. The high-refractive-index LED organosilicon encapsulating material and the preparation method thereof according to claim 1, wherein the high-refractive-index LED organosilicon encapsulating material is characterized in that: the methyl high phenyl vinyl silicone resin has a chemical general formula of (PhSiO)3/2) x1 (Ph2SiO)x2 (Me2SiO)x3 (ViMe2SiO1/2) x4A compound of formula (I), wherein PhSiO3/2Is a trifunctional link, in which Ph2SiO、Me2SiO is a difunctional mer, ViMe2SiO1/2Is a monofunctional link; wherein Ph is phenyl, Me is methyl, Vi is vinyl, x1= 0.55-0.60, x2= 0.02-0.04, x3= 0.02-0.04, x4= 0.35-0.45, and the sum of the values is x1+ x2+ x3+ x4= 1; the vinyl phenyl silicone oil has a chemical general formula of ViMe2 SiO ( Si Me2O)m (SiPh2O)n Si Me2A compound Vi, wherein Ph is phenyl, Me is methyl, Vi is vinyl, m and n are integers which are more than 10 and m + n is less than 50, and the molar percentage of the vinyl is 0.78%; 5 mol% phenyl and a viscosity of 3050mPa @; the high phenyl hydrogen-based silicone resin is a higher viscosity MDT resin with trifunctional chain links, bifunctional chain links and monofunctional chain links; has the chemical general formula of (PhSiO)3/2)y1(Ph2SiO)y2(Ph3SiO1/2) y3 (HMe2SiO1/2) y4A compound of formula (I), wherein PhSiO3/2Is a trifunctional link, in which Ph2SiO is a difunctional chain member, Ph3SiO1/2、HMe2SiO1/2Is a monofunctional link; ph is phenyl, Me is methyl, Vi is vinyl, y1= 0.5-0.6, y2= 0.02-0.03, y3= 0.02-0.03, y4= 0.3-0.4, and the sum of the values is y1+ y2+ y3+ y4= 1; the methylphenylhydrosilicon resin is a lower viscosity MDT resin with trifunctional chain link, bifunctional chain link and monofunctional chain link; has the chemical general formula of (PhSiO)3/2)z1(Me2SiO)z2(Me3SiO1/2)z3 (HMe2SiO1/2) z4A compound of formula (I), wherein PhSiO3/2Is a trifunctional mer of formula Me2SiO is a difunctional mer, (Me)3SiO1/2)、(HMe2SiO1/2) Is a monofunctional link; wherein Ph is phenyl, Me is methyl, Vi is vinyl, z1= 0.45-0.55, z2= 0.08-0.09, z3= 0.06-0.07, z4= 0.30-0.35, and the sum of the values is z1+ z2+ z3+ z4= 1; the platinum catalyst is one selected from platinum-1, 3-dimethyl-1, 3-diphenyl-1, 3-divinyl siloxane complex, platinum-1, 1, 3, 3-tetramethyl-1, 3-divinyl-disiloxane complex and chloroplatinic acid-divinyl tetramethyl disiloxane complex; the inhibitor is one or more than one selected from 1-ethynylcyclohexanol, 3-diphenyl-1, 5-divinyl-1, 1, 5, 5-tetramethyltrisiloxane, 3-phenyl-1, 5-divinyl-1, 1, 3, 5, 5-pentamethyltrisiloxane and phenyl tris (dimethylvinylsiloxy) silane.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104212408A (en) * 2014-08-15 2014-12-17 华中师范大学 Phenyl-series high-refractive-index LED loading glue and preparation method thereof
CN104788961A (en) * 2015-05-20 2015-07-22 龚灿锋 LED encapsulating material
CN105176483A (en) * 2015-08-14 2015-12-23 烟台德邦先进硅材料有限公司 High-refractive-index, high-toughness and vulcanization-resistant LED packaging silicone rubber
CN105400488A (en) * 2015-11-28 2016-03-16 烟台德邦先进硅材料有限公司 Low-thermal-resistance and vulcanization-resistant COB (chip on board) integrated packaging adhesive
CN105713552A (en) * 2016-03-24 2016-06-29 深圳市安品有机硅材料有限公司 Preparation method of thixotropic organic silicon packaging adhesive
CN105838319A (en) * 2016-03-24 2016-08-10 深圳市安品有机硅材料有限公司 Preparation method of pre-dispersed high-thixotropy packaging silica gel
CN105969295A (en) * 2016-07-30 2016-09-28 江苏罗化新材料有限公司 Formula of high-refraction and high-tenacity silicone rubber for fluorescent film
CN106380862A (en) * 2016-10-26 2017-02-08 三友(天津)高分子技术有限公司 Organic polysiloxane composition for packaging ultraviolet light-emitting diode and preparation method thereof
CN107418214A (en) * 2017-07-31 2017-12-01 无锡市永兴金属软管有限公司 A kind of diode package modified silicon rubber and preparation method thereof
CN109266013A (en) * 2018-09-07 2019-01-25 苏州歌诗夫新材料有限公司 Height refraction, color inhibition add-on type silica gel material and preparation method thereof
CN111777941A (en) * 2020-06-12 2020-10-16 广东省石油与精细化工研究院 Curable organic silicon composition and preparation method and application thereof
CN112251190A (en) * 2020-09-10 2021-01-22 烟台德邦科技有限公司 LED packaging adhesive composition

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104212408B (en) * 2014-08-15 2016-04-06 华中师范大学 Filling glue of a kind of phenyl system high refractive index LED and preparation method thereof
CN104212408A (en) * 2014-08-15 2014-12-17 华中师范大学 Phenyl-series high-refractive-index LED loading glue and preparation method thereof
CN104788961A (en) * 2015-05-20 2015-07-22 龚灿锋 LED encapsulating material
CN105176483B (en) * 2015-08-14 2018-02-06 烟台德邦先进硅材料有限公司 A kind of LED of resistance to vulcanization packaging silicon rubbers of high index of refraction high tenacity
CN105176483A (en) * 2015-08-14 2015-12-23 烟台德邦先进硅材料有限公司 High-refractive-index, high-toughness and vulcanization-resistant LED packaging silicone rubber
CN105400488A (en) * 2015-11-28 2016-03-16 烟台德邦先进硅材料有限公司 Low-thermal-resistance and vulcanization-resistant COB (chip on board) integrated packaging adhesive
CN105838319B (en) * 2016-03-24 2019-01-04 深圳市安品有机硅材料有限公司 Preparation method of pre-dispersed high-thixotropy packaging silica gel
CN105838319A (en) * 2016-03-24 2016-08-10 深圳市安品有机硅材料有限公司 Preparation method of pre-dispersed high-thixotropy packaging silica gel
CN105713552B (en) * 2016-03-24 2018-09-18 深圳市安品有机硅材料有限公司 Preparation method of thixotropic organic silicon packaging adhesive
CN105713552A (en) * 2016-03-24 2016-06-29 深圳市安品有机硅材料有限公司 Preparation method of thixotropic organic silicon packaging adhesive
CN105969295A (en) * 2016-07-30 2016-09-28 江苏罗化新材料有限公司 Formula of high-refraction and high-tenacity silicone rubber for fluorescent film
CN106380862A (en) * 2016-10-26 2017-02-08 三友(天津)高分子技术有限公司 Organic polysiloxane composition for packaging ultraviolet light-emitting diode and preparation method thereof
CN107418214A (en) * 2017-07-31 2017-12-01 无锡市永兴金属软管有限公司 A kind of diode package modified silicon rubber and preparation method thereof
CN109266013A (en) * 2018-09-07 2019-01-25 苏州歌诗夫新材料有限公司 Height refraction, color inhibition add-on type silica gel material and preparation method thereof
CN111777941A (en) * 2020-06-12 2020-10-16 广东省石油与精细化工研究院 Curable organic silicon composition and preparation method and application thereof
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CN112251190B (en) * 2020-09-10 2022-08-19 烟台德邦科技股份有限公司 LED packaging adhesive composition

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