CN102153865A - Organic silicon material for packaging high-power light-emitting diode - Google Patents
Organic silicon material for packaging high-power light-emitting diode Download PDFInfo
- Publication number
- CN102153865A CN102153865A CN 201010111927 CN201010111927A CN102153865A CN 102153865 A CN102153865 A CN 102153865A CN 201010111927 CN201010111927 CN 201010111927 CN 201010111927 A CN201010111927 A CN 201010111927A CN 102153865 A CN102153865 A CN 102153865A
- Authority
- CN
- China
- Prior art keywords
- organosilane monomer
- organosilane
- component
- monomer
- mentioned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention relates to an organic silicon material for packaging a high-power light-emitting diode, which has high refractive index and high optical transparency. Before being cured, the organic silicon material is of a double-component form, wherein the double components are a component A containing silicon vinyl groups and a component B containing silicon hydrogen groups. When the organic silicon material is in use, the two components are mixed in a molar ratio of vinyl in the silicon vinyl groups to silicon hydrogen in the silicon hydrogen groups of 0.5 to 2; and the two components are subjected to heat curing under the action of a catalyst to obtain the organic silicon material. The refractive index of the organic silicon material is in the range of 1.52 to 1.57. When the thickness of the organic silicon material is 1cm, the transmittance of light with the wavelength of 400 nanometers is more than or equal to 90 percent. The organic silicon material for packaging the high-power light-emitting diode can be used as a packaging material of a light-emitting or optical device or be used as an optical adhesive, is particularly suitable for being used as the packaging material of the high-power (more than or equal to 1W) LED (light-emitting diode).
Description
Technical field
The invention belongs to the organosilicon macromolecule field, particularly be suitable for the organosilicon material of large-power light-emitting diodes (LED) encapsulation with high refractive index, high optical transparency.
Background technology
The ageing-resistant performance of LED packaged material is to there being very important influence its work-ing life.Characteristics such as in the past few decades, Resins, epoxy has the good mechanical performance because of it, and high transparent and cost are low and be widely used as the LED packaged material.But along with improving constantly of LED power and brightness, traditional Resins, epoxy can not satisfy actual requirement aspect ageing-resistant performance.For example, in use because the irradiation and the thermal ageing of UV-light all can make it its colour changed into yellow occur, transmittance descends Resins, epoxy, thereby has shortened the work-ing life of LED greatly.In recent years, organosilicon material is because of it has outstanding ultraviolet resistance and heat aging performance, makes organosilicon material attract the concern of increasing LED manufacturers, is considered to promise to be most the packaged material of great power LED of future generation.
Along with to how improving constantly the further investigation of LED device luminous efficiency, new requirement has been proposed the refractive index as the organosilicon material of packaged material.Because the GaN chip has high specific refractory power (being about 2.2), in order effectively to reduce the light loss that interfacial refraction brings, improve as far as possible and get optical efficiency, require the specific refractory power of LED packaged material high as far as possible.For example, if specific refractory power is increased to 1.6 from 1.5, gets optical efficiency and can improve about 20%.The traditional silica gel or the refractive index of silicone material only are 1.41, and the refractive index of desirable packaged material should be as much as possible near the refractive index of GaN.
Silica gel and silicone resin are the organosilicon macromolecule materials that molecular backbone chain is made up of siloxane bond.The organosilicon macromolecule material has good optical transparence; Simultaneously, because the bond energy of siloxane bond is very high, silica gel and silicone resin have excellent ultraviolet resistance and heat aging performance.Silica gel and silicone resin mainly carry out anionoid polymerization by organosilane monomer (as cyclosiloxane monomer, chlorosilane) or hydrolytic condensation prepares.According to the difference of curing mechanism, silica gel and silicone resin are divided into add-on type and condensed type two classes.Because condensed type silica gel and silicone resin have small molecules to discharge, therefore generally be not suitable for being used for the LED encapsulation in solidification process.The curing of add-on type silica gel and silicone resin is generally carried out addition reaction of silicon with hydrogen by si-h bond and silico ethylene base and is realized in the presence of platinum catalyst.The silica gel and the silicone resin that are used for the LED encapsulation all have specific requirement to purity, mechanical property, optical property and processing performance, wherein the most important thing is how to improve the refractive index of silica gel and silicone resin when keeping high printing opacity.
Introducing the refractive index that the silicon phenyl can improve silica gel and silicone resin effectively in structure, also almost is the unique method that obtains high refractive index silica gel and silicone resin at present.Studies show that the introducing of silicon phenyl is to the almost not influence of ageing-resistant performance of material.Refractive index is reached more than 1.55, and phenyl content (phenyl and all substituent mol ratios) need reach more than 55%.So high phenyl content has proposed very high requirement to molecular designing and synthetic technology.If structure design is improper, perhaps synthetic technological condition control is improper, will cause problems such as transmittance reduction, mechanical property and the processing performance of final product be too poor.
The patent report of the preparation of at present more existing high refractive index silica gel, silicone resin, as U.S. Pat 6432137B1, US 2004/0198924A1, US 7009023B2 etc.These patents mainly are on molecular structure unit is formed certain variation to be arranged, and employed synthetic method all is general polymerization or hydrolytic condensation method, and key is to control well the synthetic processing condition.Though above-mentioned patent also has refractive index at the report more than 1.55, but the synthetic method that provides according to patent, when the refractive index of product 1.55 when above, at the transmittance of 400 nano wave lengths at (1cm thickness) below 75%, if as the LED packaged material, will reduce the luminous efficiency of LED greatly.The invention provides a kind of organosilicon material and synthetic method thereof with high refractive index and high-clarity, its refractive index can reach 1.57, and the transmittance at 400 nano wave lengths reaches more than 90% simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of high refractive index that has, the large-power light-emitting diodes encapsulation organosilicon material of high-clarity.
Of the present invention have a high refractive index, and the large-power light-emitting diodes encapsulation of high-clarity is add-on type curing with organosilicon material.Be two component forms before solidifying, contain silico ethylene base group (Si-CH=CH
2) component A and contain the component B of silicon hydrogen group (Si-H).During use, two kinds of components are 0.5～2 mixed by containing vinyl and the molar ratio that contains the silicon hydrogen in the silicon hydrogen group in the silico ethylene base group, two kinds of components carry out thermofixation under catalyst action, thereby obtain refractive index is 1.52～1.57, when the thickness of organosilicon material was 1cm, the transmitance of 400 nano wave length light was more than or equal to 90% simultaneously.
The content of described catalyzer is with respect to the 5～50ppm of the component A that contains silico ethylene base group with the gross weight of the component B that contains silicon hydrogen group.
Described catalyzer is H
2PtCl
6, Rh (PPh
3)
3Cl or Rh (PPh
3)
3Cl
2Deng; PPh wherein
3It is triphenylphosphine.
The described silico ethylene base group (Si-CH=CH that contains
2) component A be the organosilicon macromolecule polymkeric substance, form by four sense silica structural units, trifunctional silica structural unit, difunctionality silica structural unit and simple function silica structural unit, have following structure:
Wherein: R
1, R
2, R
3, R
4, R
5, R
6Be CH
3, CH
2=CH-, C
2H
5Perhaps C
6H
5In a kind of, and substituent R
1, R
2, R
3, R
4, R
5, R
6In have at least one to be CH
2=CH-has one to be C
6H
5R
1, R
2, R
3, R
4, R
5, R
6Can be identical or inequality; X, Y, Z, W are above-mentioned functional group shared separately molfractions in described organosilicon macromolecule polymkeric substance, X+Y+Z+W=100%, and its ratio can be adjusted as required, wherein, X=0～25%, Y=10～80%, Z=10～80%, W=10～80%.
The described silico ethylene base group (Si-CH=CH that contains
2) component A have very high transparency and refractive index, when light path was 1cm, the transmitance of 400 nano wave length light was more than or equal to 90%.The refractive index of component A can be regulated by regulating phenyl group shared molfraction in all substituted radicals of component A; When the molfraction of phenyl 50%～60% variation, refractive index can be regulated between 1.54～1.57.The contents of ethylene of component A can be regulated by the molfraction that changes vinyl-containing monomers.
The described silico ethylene base group (Si-CH=CH that contains
2) component A obtain through condensation reaction by four sense organosilane monomers, trifunctional organosilane monomer, dual functional organosilane monomer and simple function organosilane monomer.Condensation reaction divides hydrolytic condensation and two steps of alkali condensation.
(1) condensation that at first is hydrolyzed, with four sense organosilane monomers, the trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer are according to four sense organosilane monomers: trifunctional organosilane monomer: difunctionality organosilane monomer: the mol ratio of simple function organosilane monomer is 0～0.25: 0.1～0.8: mix at 0.1～0.8: 0.1～0.8, be cooled to 0 ℃, in rare gas element (as nitrogen) protection with stir the mixing solutions of dropping methyl alcohol and deionized water down, wherein the mole number of the mole number of methyl alcohol and deionized water is respectively 1～4 times of total mole number of above-mentioned 4 kinds of organosilane monomer hydrolysis functional groups; The a large amount of hydrochloric acid that produce in the dropping process absorb with inorganic alkali lye, and make the temperature of reaction system between 0～45 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with methods such as frozen water coolings; After dropwising, reaction soln continues to stir 2～5 hours, stops then stirring and standing demix; Layer oily matter after the layering is separated with organic solvent (toluene, dimethylbenzene, normal hexane or any mixture between them etc.) dissolving, and extremely neutral with deionized water wash, filter then and obtain colourless transparent solution.Used organic solvent when under temperature is the pressure condition of 80～100 ℃ and 3～5mm Hg, removing dissolving oil shape thing, in the process of removing organic solvent with rare gas element (as nitrogen) protection.The gained hydrolysis condensation product is the colourless bright oily liquids with certain viscosity.
(2) adding in the hydrolysis condensation product that step (1) obtains is the alkali of hydrolysis condensation product weight 0.01%～1%; be warming up to 100～200 ℃ in rare gas element (as nitrogen) protection with under stirring; and under this temperature, carry out alkali condensation reaction 6～12 hours; with the product that obtains after alkali condensation reaction organic solvent (toluene, dimethylbenzene, normal hexane or any mixture between them etc.) dissolving and extremely neutral for several times with deionized water wash, filtration obtains colourless transparent solution then.Be to remove organic solvent (toluene, dimethylbenzene, normal hexane or any mixture between them etc.) under the pressure condition of 80～100 ℃ and 3～5mm Hg to obtain the above-mentioned component A that contains silico ethylene base group in temperature, in the process of removing organic solvent with rare gas element (as nitrogen) protection.Product is the colourless bright liquid with big viscosity.
Above-mentioned four sense organosilane monomers can be chlorosilane (silicon tetrachlorides), also can be organosilane monomer that other can hydrolysis such as methoxy silane (tetramethoxy-silicane), oxyethyl group siloxanes (tetraethoxysilane) etc., or the mixture of above-mentioned four sense organosilane monomers; Above-mentioned trifunctional organosilane monomer can be organochlorosilane (trichlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (Trimethoxy silane), oxyethyl group siloxanes (triethoxyl silane) etc., or the mixture of above-mentioned trifunctional organosilane monomer; Above-mentioned difunctionality organosilane monomer can be organochlorosilane (dichlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (dimethoxy silane), oxyethyl group siloxanes (diethoxy silane) etc., or the mixture of above-mentioned difunctionality organosilane monomer.The simple function organosilane monomer can be organochlorosilane (chlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (methoxy silane), oxyethyl group siloxanes (Ethoxysilane) etc., or the mixture of above-mentioned simple function organosilane monomer.
Above-mentioned four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer preferably have high purity (purity is preferably in more than 98%), have preferably just purified by distillation.If the time that monomer is deposited after purifying is oversize, the transmittance of the component A that contains silico ethylene base group is reduced greatly.
In the said hydrolyzed condensation course, need to make temperature of reaction system be no more than 45 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with methods such as frozen water coolings; If the temperature of system surpasses 45 ℃, will cause containing the component A jaundice of silico ethylene base group, transmittance reduces greatly.
Wherein the mole number of the mole number of methyl alcohol and deionized water is respectively 1～4 times of total mole number of above-mentioned 4 kinds of organosilane monomer hydrolysis functional groups.If the consumption of water very little, hydrolysis is incomplete, and the consumption of water surpasses 4 times, and is very little to the reaction influence.If the consumption of methyl alcohol is very little, react bad control, cause product to turn white easily, transmittance reduces, and the consumption of methyl alcohol surpasses 4 times, and is very little to the reaction influence.
The temperature of above-mentioned alkali condensation reaction should be controlled in 100～200 ℃ of scopes, is preferably in 120～160 ℃ of scopes.If condensation temp is too high, will cause containing the component A jaundice of silico ethylene base group, transmittance reduces greatly; Otherwise if condensation temp is too low, condensation reaction is difficult to carry out, and this will cause two aspect problems.On the one hand, the viscosity of component A that contains silico ethylene base group is too little, is not suitable for the LED packaging process; On the other hand, the component A that contains silico ethylene base group contains a lot of silicon hydroxyls, causes final cured silicone material to turn white, and transmittance reduces.
The time of above-mentioned alkali condensation reaction should be controlled at 6～12 hours, if the reaction times is lower than 6 hours, condensation reaction is carried out not too complete, and after the reaction times was longer than 12 hours, to almost not influence of condensation reaction.
In above-mentioned alkali condensation reaction, used alkali is highly basic.Can be inorganic strong alkali, a kind of as in potassium hydroxide, sodium hydroxide, the lithium hydroxide; Also can be organic alkali, as tetramethyl-oxyammonia ((CH
3)
4NOH).Can regulate viscosity and the molecular weight of the component A that contains silico ethylene base group by the consumption of regulating alkali; The consumption of alkali is 0.01%～1% of a hydrolysis condensation product weight, and the viscosity that the condenses that obtains contains the component A of silico ethylene base group can be regulated between 200～10000 centipoises.
In the said hydrolyzed condensation reaction, be 10～20% NaOH solution but absorb the employed inorganic alkali lye mass concentration of hydrochloric acid with inorganic alkali lye.
The described component B that contains silicon hydrogen group (Si-H) is the organosilicon macromolecule polymkeric substance, is made up of four sense silica structural units, trifunctional silica structural unit, difunctionality silica structural unit and simple function silica structural unit, has following structure:
Wherein: R
1', R
2', R
3', R
4', R
5', R
6' be H, CH
3, C
2H
5Perhaps C
6H
5That plants is a kind of; And substituent R
1, R
2, R
3, R
4, R
5, R
6In have at least one to be H, have one to be C
6H
5R
1, R
2, R
3, R
4, R
5, R
6Can be identical or inequality; X ', Y ', Z ', W ' they are above-mentioned functional group shared molfractions in described organosilicon macromolecule polymkeric substance, X '+Y '+Z '+W '=100%, and its ratio can be adjusted as required; Wherein, X '=0～25%, Y '=10～80%, Z '=10～80%, W '=10～80%.
The described component B that contains silicon hydrogen group has very high transparency and refractive index, and when light path was 1cm, the transmitance of 400 nano wave length light was more than or equal to 90%.The refractive index that contains the component B of silicon hydrogen group can recently be regulated by regulating phenyl group shared mole in all substituted radicals of component B; The mol ratio of phenyl changes refractive index at 50%～60% and can regulate between 1.52～1.56.The silicon hydrogen group content of component B can recently be regulated by changing the monomeric mole of siliceous hydrogen base.
The above-mentioned component B that contains silicon hydrogen group obtains by four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and the condensation of simple function organosilane monomer cohydrolysis, and building-up process is as follows:
With four sense organosilane monomers, the trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer are according to four sense organosilane monomers: trifunctional organosilane monomer: difunctionality organosilane monomer: the mol ratio of simple function organosilane monomer is: 0～0.25%: 0.1～0.8: 0.1～0.8: 0.1～0.8 mixes, be cooled to 0 ℃, mixture with methyl alcohol and deionized water in rare gas element (as nitrogen) protection and under stirring evenly is added drop-wise in the organosilane monomer mixture, and wherein the mole number of the mole number of methyl alcohol and deionized water is respectively 1～4 times of total mole number of above-mentioned organosilane monomer hydrolysis functional group; The a large amount of hydrochloric acid that produce in the dropping process absorb with alkali lye, and make temperature of reaction system be no more than 5 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with methods such as frozen water coolings; After dropwising, reaction soln continues to stir 2～5 hours, stops then stirring and standing demix; Layer oily matter after the layering is separated with organic solvent (toluene, dimethylbenzene, normal hexane or any mixture between them etc.) dissolving, and extremely neutral with deionized water wash, filter then and obtain colourless transparent solution; Used organic solvent when under temperature is the pressure condition of 60～80 ℃ and 3～5mm Hg, removing dissolving oil shape thing; in the process of removing organic solvent, protect with rare gas element (as nitrogen); the gained hydrolysis condensation product is component B, for having the colourless bright oily liquids of certain viscosity.
Above-mentioned four sense organosilane monomers can be chlorosilane (silicon tetrachlorides), also can be organosilane monomer that other can hydrolysis such as methoxy silane (tetramethoxy-silicane), oxyethyl group siloxanes (tetraethoxysilane) etc., or the mixture of above-mentioned four sense organosilane monomers; Above-mentioned trifunctional organosilane monomer can be organochlorosilane (trichlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (Trimethoxy silane), oxyethyl group siloxanes (triethoxyl silane) etc., or the mixture of above-mentioned trifunctional organosilane monomer; Above-mentioned difunctionality organosilane monomer can be organochlorosilane (dichlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (dimethoxy silane), oxyethyl group siloxanes (diethoxy silane) etc., or the mixture of above-mentioned difunctionality organosilane monomer.The simple function organosilane monomer can be organochlorosilane (chlorosilane), also can be organosilane monomer that other can hydrolysis such as methoxy silane (methoxy silane), oxyethyl group siloxanes (Ethoxysilane) etc., or the mixture of above-mentioned simple function organosilane monomer.
Above-mentioned four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer need high purity (purity is preferably in more than 98%), have preferably just purified by distillation.If the time that monomer is deposited after purifying is oversize, the transmittance of the component B that contains silicon hydrogen group is reduced greatly.
In the said hydrolyzed condensation course, need to make temperature of reaction system be no more than 5 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with methods such as frozen water coolings; If the temperature of system surpasses 5 ℃, will cause the fracture of si-h bond, make the content of silicon hydrogen group among the component B that contains silicon hydrogen group be significantly less than the content of the silicon hydrogen group that calculates by the reaction raw materials proportioning, transmittance reduces simultaneously.
In the said hydrolyzed condensation course, the consumption of methyl alcohol and deionized water (mole number) is respectively 1～4 times of total mole number of above-mentioned organosilane monomer hydrolysis functional group.If the consumption of water very little, hydrolysis is incomplete, and the consumption of water surpasses 4 times, and is very little to the reaction influence.If the consumption of methyl alcohol is very little, react bad control, cause product to turn white easily, transmittance reduces, and the consumption of methyl alcohol surpasses 4 times, and is very little to the reaction influence.
The viscosity of component B that contains silicon hydrogen group is between 200～1500 centipoises.Mainly control by the relative molar ratio of regulating four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer, the simple function organosilane monomer is many more, and the viscosity of product is low more.
Described but to absorb the employed alkali lye concentration of hydrochloric acid with alkali lye be 10%～20% NaOH solution.
Silico ethylene group among the above-mentioned component A and the si-h bond among the component B carry out addition reaction of silicon with hydrogen and realize solidifying in the presence of catalyzer, thereby obtain the described high refractive index that has, the large-power light-emitting diodes encapsulation organosilicon material of high-clarity.
Solidifying employed catalyzer is the common employed catalyzer of silicon hydrogen addition, as H
2PtCl
6, Rh (PPh
3)
3Cl or Rh (PPh
3)
3Cl
2Deng.For the convenience on using, generally catalyzer is mixed in advance mutually with component A.For example, can be with H
2PtCl
6Solution with isopropanol to certain concentration, mix with the component A of certain mass and stir, then removal of solvent under reduced pressure Virahol at room temperature.The content of Pt is 5～50ppm with respect to the total amount of component A and component B, if content is too low, will cause curing reaction incomplete, if consumption is too high, will cause the transmittance of cured silicone material and ageing-resistant performance to reduce.
To be mixed with the component A of (or then add) catalyzer and component B during curing according to must ratio mixing, stir and vacuum outgas, be 120～180 ℃ in temperature then and solidify down and just can obtain described refractive index in 0.5～3 hour and reach as high as 1.57, encapsulate at the large-power light-emitting diodes more than 90% at the transmittance of 400 nano wave lengths simultaneously and use organosilicon material.
The encapsulation of described large-power light-emitting diodes is different with the molar ratio of si-h bond among the component B and change along with vinyl among the component A with the performance of organosilicon material, when the mol ratio of vinyl and si-h bond changes between 0.5～2, cured product can be the silicone resin with certain degree of hardness, also can be soft silicon gel.
In the above-mentioned solidification process, temperature is controlled at 120～180 ℃ of scopes.Preferred temperature is 140～160 ℃.If solidification value is higher than 180 ℃, gained cured silicone material will turn to be yellow, and transmittance is reduced, if solidification value is lower than 120 ℃, need prolong set time significantly, is unfavorable for practical application.
Because large-power light-emitting diodes of the present invention encapsulation has good optical transparence and high to 1.57 refractive index with organosilicon material, therefore can be used for the packaged material of luminous or optics or, be particularly suitable for packaged material as high-power (power is more than or equal to 1W) LED as optical adhesive.
Embodiment
Specify the present invention below by specific embodiment, but the present invention is not limited to following embodiment.
Embodiment 1: component A's is synthetic
With organosilane monomer PhSiCl
3(0.315mol, 66.6g) (Ph is phenyl, and is as follows), ViCH
3SiCl
2(0.315mol, 44.4g) (Vi is vinyl, and is as follows), Ph
2SiCl
2(0.708mol is 179.3g) with (CH
3)
2ViSiOSiVi (CH
3)
2(0.206mol, 38.3g) mix the there-necked flask that places 2000ml, and be cooled to 0 ℃ with ice bath, under logical nitrogen and stirring, drip the mixing solutions of methyl alcohol 434.0 and deionized water 244.2g by constant pressure funnel, rate of addition is relatively slow at first, and a large amount of hydrochloric acid mass concentrations of generation are 10% NaOH solution absorption.The dropping process continues about 4 hours, the promotion to 5 of the temperature of system ℃ in the dropping process.Dropwise the back and continued to stir (stirring velocity can appropriately be accelerated) 3 hours.Stop to stir, standing demix, incline supernatant liquid after, the oily matter n-hexane dissolution of lower floor, and with deionized water wash 5 times, until neutrality.Filter above-mentioned solution, under nitrogen protection, remove the normal hexane solvent then, obtain colourless bright liquid at 100 ℃/3-5mmHg.
Get said hydrolyzed thing 50g, add the NaOH that is equivalent to hydrolyzate quality 0.01%, under nitrogen protection, stir and be warming up to about 6 hours of 200 ℃ of condensations.Behind the cool to room temperature, add normal hexane or the toluene dissolving condenses of 80ml, use then the deionized water wash of each 80ml about 5 times until neutrality.Organic layer after the washing is filtered, under nitrogen protection, except that desolvating and low-boiling-point substance, obtain component A then at 150 ℃/3-5mmHg.The transmitance of the viscosity of component A, refractive index, 400 nano wave length light is as shown in table 1.
Embodiment 2: component A's is synthetic
Get the hydrolyzate 50g among the embodiment 1, add the NaOH that is equivalent to hydrolyzate quality 0.1%, under nitrogen protection, stir and be warming up to about 8 hours of 150 ℃ of condensations.Other operation obtains component A with embodiment 1.The transmitance of the viscosity of component A, refractive index, 400 nano wave length light is as shown in table 1.
Embodiment 3: component A's is synthetic
Get the hydrolyzate 50g among the embodiment 1, add the NaOH that is equivalent to hydrolyzate quality 1%, under nitrogen protection, stir and be warming up to about 12 hours of 100 ℃ of condensations.Other operation obtains component A with embodiment 1.The transmitance of the viscosity of component A, refractive index, 400 nano wave length light is as shown in table 1.
Embodiment 4: component A's is synthetic
Operation and embodiment 1 are basic identical, but the mixing solutions of first alcohol and water dropwised in 2 hours, and the system temperature of reaction rises to 40 ℃ in the dropping process.Get component A at last, the transmitance of its viscosity, refractive index, 400 nano wave length light is as shown in table 1.
Embodiment 5: component A's is synthetic
With organosilane monomer (C
2H
5O)
4Si (0.01mol, 2.08g), PhSiCl
3(0.0315mol, 6.66g), ViCH
3SiCl
2(0.0315mol, 4.44g), Ph
2SiCl
2(0.0708mol is 17.93g) with (CH
3)
2ViSiOSiVi (CH
3)
2(0.0206mol, 0.383g) mix the there-necked flask that places 250ml, and be cooled to 0 ℃ with ice bath, under logical nitrogen and stirring, drip the mixing solutions of methyl alcohol 43.40g and deionized water 24.42g by constant pressure funnel, other step obtains component A with embodiment 1.The transmitance of the viscosity of component A, refractive index, 400 nano wave length light is as shown in table 1.
Comparative example 1: component A's is synthetic
Operation and embodiment 1 are basic identical, but the mixing solutions of first alcohol and water dropwised in 1 hour, and the system temperature of reaction rises to 50 ℃ in the dropping process.Obtain being with slight xanchromatic component A at last, the transmitance of its viscosity, refractive index, 400 nano wave length light is as shown in table 1.As can be seen from Table 1, system temperature surpasses 45 ℃ in the mixing solutions dropping process of first alcohol and water, and the transmittance of the component A that obtains reduces greatly.
Comparative example 2: component A's is synthetic
Operation and embodiment 1 are basic identical, but the mixing solutions of first alcohol and water dropwised in half an hour, and the system temperature of reaction rises to 65 ℃ in the dropping process.Obtain being with slight xanchromatic component A at last, the transmitance of its viscosity, refractive index, 400 nano wave length light is as shown in table 1.As can be seen from Table 1, system temperature surpasses 45 ℃ in the mixing solutions dropping process of first alcohol and water, and the transmittance of the component A that obtains reduces greatly.
The performance of table 1. component A
Example 6: component B's is synthetic
With organosilane monomer PhSiCl
3(0.0265mol, 5.60g), Ph
2SiCl
2(0.0404mol, 10.90g) and (CH
3)
2HSiOSiH (CH
3)
2(0.04mol 5.36g) mixes the there-necked flask that places 250ml, and is cooled to 0 ℃ with ice bath, drips the mixing solutions of methyl alcohol 32.06g and deionized water 17.30g under logical nitrogen and stirring by constant pressure funnel, and rate of addition is relatively slow at first.Rate of addition can suitably be accelerated behind the mixing solutions of dropping 1/4th.The a large amount of hydrochloric acid that produce absorb with alkali lye.The dropping process continues about 8 hours, the promotion to 3 of the temperature of system ℃ in the dropping process, and, dropwise the back and continued to stir (stirring velocity can appropriateness accelerate) 4 hours.Stop to stir, standing demix, incline supernatant liquid after, the oily matter of lower floor dissolves with toluene, and washes 5 times until neutrality with deionized water.Organic layer after the washing is filtered, under nitrogen protection, at 70 ℃/3-5mmHg place to go solvent.After being cooled to room temperature, obtain colourless bright liquid, be component B.The transmitance of the viscosity of component B, refractive index, 400 nano wave length light is as shown in table 2.
Embodiment 7: component B's is synthetic
With organosilane monomer PhSiCl
3(0.0315mol, 6.66g), Ph
2SiCl
2(0.0708mol, 17.93g), CH
3SiHCl
2(0.0315,3.63) and (CH
3)
2SiHCl (0.04mol, 3.78) mix the there-necked flask that places 250ml, and be cooled to 0 ℃ with ice bath, under logical nitrogen and stirring, drip the mixing solutions of methyl alcohol 43.40g and deionized water 24.42g by constant pressure funnel, other operation obtains component B with embodiment 6.The transmittance of the viscosity of component B, refractive index, 400 nano wave lengths is as shown in table 2.
Embodiment 8: component B's is synthetic
With organosilane monomer (C
2H
5O)
4Si (0.01mol, 2.08g), PhSiCl
3(0.0315mol, 6.66g), Ph
2SiCl
2(0.0708mol, 17.93g), CH
3SiHCl
2(0.0315,3.63) and (CH
3)
2SiHCl (0.04mol, 3.78) mix the there-necked flask that places 250ml, and be cooled to 0 ℃ with ice bath, under logical nitrogen and stirring, drip the mixing solutions of methyl alcohol 43.40g and deionized water 24.42g by constant pressure funnel, other operation obtains component B with embodiment 6.The transmitance of the viscosity of component B, refractive index, 400 nano wave length light is as shown in table 2.
Comparative example 3:
Operation and embodiment 6 are basic identical, but the mixing solutions of first alcohol and water dropwised in 4 hours, and the system temperature of reaction rises to 10 ℃ in the dropping process.Obtain the component B that a little turns white at last, the transmitance of its viscosity, refractive index, 400 nano wave length light is as shown in table 2.As can be seen from Table 2, when hydrolysis-condensation reaction surpasses 5 ℃, the transmittance of component B reduces greatly.Simultaneously, nuclear magnetic resonance spectroscopy shows: the content of silicon hydrogen group is significantly less than the content of the silicon hydrogen group that is calculated by the reaction raw materials proportioning.
Comparative example 4:
Operation and embodiment 6 are basic identical, but the mixing solutions of first alcohol and water dropwised in 2 hours, and the system temperature of reaction rises to 40 ℃ in the dropping process.Obtain the component B that a little turns white at last, the transmitance of its viscosity, refractive index, 400 nano wave length light is as shown in table 2.As can be seen from Table 2, when hydrolysis-condensation reaction surpasses 5 ℃, the transmittance of component B reduces greatly.Simultaneously, nuclear magnetic resonance spectroscopy shows: the content of silicon hydrogen group is significantly less than the content of the silicon hydrogen group that is calculated by the reaction raw materials proportioning.
The performance of table 2. component B
Embodiment 9: the cured silicone material preparation
With catalyzer H
2PtCl
6, the component B that obtains among the component A that obtains among the embodiment 3 and the embodiment 7 is according to the mixed of table 3, the content of catalyzer is the 10ppm of whole mixture quality.After stirring, the vacuum outgas bubble does not have bubble to exist until its system, under 150 ℃, solidifies 1.5 hours then.The performance of the cured silicone material that obtains is as shown in table 3.As can be seen from Table 3, by changing the proportioning of component A and component B, can obtain having the cured silicone material of high refractive index, high optical transparency, different hardness.
The performance of table 3. cured silicone material (thickness of sample is 1cm)
UV-4802 type twin-beam ultraviolet-visible pectrophotometer (UNICO's production) is adopted in the test of the transmitance of light in the foregoing description and the comparative example, viscosity test adopts DV-II+PRO type viscometer (production of U.S. Brookfield company), hardness test LX-D type Shore durometer (production of Leqing city Hypon Instr Ltd.).
Claims (10)
1. organosilicon material is used in a large-power light-emitting diodes encapsulation, it is characterized in that: be component A that contains silico ethylene base group and the two component forms that contain the component B of silicon hydrogen group before described organosilicon material solidifies; Two kinds of components are 0.5～2 mixed by containing vinyl and the molar ratio that contains the silicon hydrogen in the silicon hydrogen group in the silico ethylene base group, and two kinds of components carry out obtaining described organosilicon material after the thermofixation under catalyst action.
2. organosilicon material is used in large-power light-emitting diodes encapsulation according to claim 1, and it is characterized in that: the refractive index of described organosilicon material is 1.52～1.57.
3. organosilicon material is used in large-power light-emitting diodes encapsulation according to claim 1 and 2, and it is characterized in that: when described organosilicon material was 1cm at thickness, the transmitance of 400 nano wave length light was more than or equal to 90%.
4. organosilicon material is used in large-power light-emitting diodes encapsulation according to claim 1, it is characterized in that: the content of described catalyzer is with respect to the 5～50ppm of the component A that contains silico ethylene base group with the gross weight of the component B that contains silicon hydrogen group;
Described catalyzer is H
2PtCl
6, Rh (PPh
3)
3Cl or Rh (PPh
3)
3Cl
2PPh wherein
3It is triphenylphosphine.
5. according to claim 1 or 4 described large-power light-emitting diodes encapsulation organosilicon materials, it is characterized in that: the described component A that contains silico ethylene base group is the organosilicon macromolecule polymkeric substance, form by four sense silica structural units, trifunctional silica structural unit, difunctionality silica structural unit and simple function silica structural unit, have following structure:
Wherein: R
1, R
2, R
3, R
4, R
5, R
6Be CH
3, CH
2=CH-, C
2H
5Perhaps C
6H
5In a kind of, and substituent R
1, R
2, R
3, R
4, R
5, R
6In have at least one to be CH
2=CH-has one to be C
6H
5R
1, R
2, R
3, R
4, R
5, R
6Can be identical or inequality; X, Y, Z, W are above-mentioned functional group shared separately molfractions in described organosilicon macromolecule polymkeric substance, X+Y+Z+W=100%, wherein, X=0～25%, Y=10～80%, Z=10～80%, W=10～80%.
6. organosilicon material is used in large-power light-emitting diodes encapsulation according to claim 5, and it is characterized in that: the described component A that contains silico ethylene base group obtains through condensation reaction by four sense organosilane monomers, trifunctional organosilane monomer, dual functional organosilane monomer and simple function organosilane monomer; Described condensation reaction divides hydrolytic condensation and two steps of alkali condensation;
(1) condensation that at first is hydrolyzed, with four sense organosilane monomers, the trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer are according to four sense organosilane monomers: trifunctional organosilane monomer: difunctionality organosilane monomer: the mol ratio of simple function organosilane monomer is 0～0.25: 0.1～0.8: mix at 0.1～0.8: 0.1～0.8, be cooled to 0 ℃, in protection of inert gas with drip the mixing solutions of methyl alcohol and deionized water under stirring, wherein the mole number of the mole number of methyl alcohol and deionized water is respectively 1～4 times of total mole number of above-mentioned 4 kinds of organosilane monomer hydrolysis functional groups; The a large amount of hydrochloric acid that produce in the dropping process absorb with inorganic alkali lye, and make the temperature of reaction system between 0～45 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with frozen water refrigerative method; After dropwising, reaction soln continues to stir 2～5 hours, stops then stirring and standing demix; Layer oily matter after the layering separated uses organic solvent dissolution, and with deionized water wash to neutral, filter then and obtain colourless transparent solution; Used organic solvent when under temperature is the pressure condition of 80～100 ℃ and 3～5mmHg, removing dissolving oil shape thing, blanketing with inert gas in the process of removing organic solvent; Obtain hydrolysis condensation product;
(2) adding in the hydrolysis condensation product that step (1) obtains is the alkali of hydrolysis condensation product weight 0.01%～1%, be warming up to 100～200 ℃ in protection of inert gas with under stirring, and under this temperature, carry out alkali condensation reaction 6～12 hours, with the product that obtains after the alkali condensation reaction with organic solvent dissolution and with deionized water wash to neutral, filter then and obtain colourless transparent solution; Be to remove the component A that organic solvent obtains containing silico ethylene base group, blanketing with inert gas in the process of removing organic solvent under the pressure condition of 80～100 ℃ and 3～5mmHg in temperature;
Above-mentioned four sense organosilane monomers are silicon tetrachloride, tetramethoxy-silicane, tetraethoxysilane or any mixture between them; Above-mentioned trifunctional organosilane monomer is trichlorosilane, Trimethoxy silane, triethoxyl silane or any mixture between them; Above-mentioned difunctionality organosilane monomer is dichlorosilane, dimethoxy silane, diethoxy silane or any mixture between them; Above-mentioned simple function organosilane monomer is a chlorosilane, methoxy silane, Ethoxysilane or any mixture between them.
7. according to claim 1 or 4 described large-power light-emitting diodes encapsulation organosilicon materials, it is characterized in that: the described component B that contains silicon hydrogen group is the organosilicon macromolecule polymkeric substance that contains silicon hydrogen group, form by four sense silica structural units, trifunctional silica structural unit, difunctionality silica structural unit and simple function silica structural unit, have following structure:
Wherein: R
1', R
2', R
3', R
4', R
5', R
6' be H, CH
3, C
2H
5Perhaps C
6H
5In a kind of; And substituent R
1, R
2, R
3, R
5, R
6In have at least one to be H, have one to be C
6H
5R
1, R
2, R
3, R
4, R
5, R
6Can be identical or inequality; X ', Y ', Z ', W ' are above-mentioned functional group shared molfractions in described organosilicon macromolecule polymkeric substance, X '+Y '+Z '+W '=100%; Wherein, X '=0～25%, Y '=10～80%, Z '=10～80%, W '=10～80%.
8. large-power light-emitting diodes encapsulation organosilicon material according to claim 7, it is characterized in that: the described component B that contains silicon hydrogen group obtains by four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and the condensation of simple function organosilane monomer cohydrolysis, and building-up process is:
With four sense organosilane monomers, the trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer are according to four sense organosilane monomers: trifunctional organosilane monomer: difunctionality organosilane monomer: the mol ratio of simple function organosilane monomer is: 0～0.25%: 0.1～0.8: 0.1～0.8: 0.1～0.8 mixes, be cooled to 0 ℃, mixture with methyl alcohol and deionized water in protection of inert gas and under stirring evenly is added drop-wise in the organosilane monomer mixture, and wherein the mole number of the mole number of methyl alcohol and deionized water is respectively 1～4 times of total mole number of above-mentioned organosilane monomer hydrolysis functional group; The a large amount of hydrochloric acid that produce in the dropping process absorb with alkali lye, and make temperature of reaction system be no more than 5 ℃ by the rate of addition of control methyl alcohol and deionized water mixed solution and/or with frozen water refrigerative method; After dropwising, reaction soln continues to stir 2～5 hours, stops then stirring and standing demix; Layer oily matter after the layering separated uses organic solvent dissolution, and with deionized water wash to neutral, filter then and obtain colourless transparent solution; Used organic solvent when under temperature is the pressure condition of 60～80 ℃ and 3～5mmHg, removing dissolving oil shape thing, blanketing with inert gas in the process of removing organic solvent, the gained hydrolysis condensation product is the component B that contains silicon hydrogen group;
Above-mentioned four sense organosilane monomers are silicon tetrachloride, tetramethoxy-silicane, tetraethoxysilane or any mixture between them; Above-mentioned trifunctional organosilane monomer is trichlorosilane, Trimethoxy silane, triethoxyl silane or any mixture between them; Above-mentioned difunctionality organosilane monomer is dichlorosilane, dimethoxy silane, diethoxy silane or any mixture between them; Above-mentioned simple function organosilane monomer is a chlorosilane, methoxy silane, Ethoxysilane or any mixture between them.
9. use organosilicon material according to claim 6 or the encapsulation of 8 described large-power light-emitting diodes, it is characterized in that: described alkali is a kind of in potassium hydroxide, sodium hydroxide, lithium hydroxide, the tetramethyl-oxyammonia;
Described inorganic alkali lye is that mass concentration is 10～20% NaOH solution;
Described organic solvent is toluene, dimethylbenzene, normal hexane or any mixture between them.
10. use organosilicon material according to claim 6 or 8 described large-power light-emitting diodes encapsulation, it is characterized in that: the purity of described four sense organosilane monomers, trifunctional organosilane monomer, difunctionality organosilane monomer and simple function organosilane monomer is all more than 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010111927 CN102153865A (en) | 2010-02-11 | 2010-02-11 | Organic silicon material for packaging high-power light-emitting diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010111927 CN102153865A (en) | 2010-02-11 | 2010-02-11 | Organic silicon material for packaging high-power light-emitting diode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102153865A true CN102153865A (en) | 2011-08-17 |
Family
ID=44435558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010111927 Pending CN102153865A (en) | 2010-02-11 | 2010-02-11 | Organic silicon material for packaging high-power light-emitting diode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153865A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433005A (en) * | 2011-08-25 | 2012-05-02 | 文仁光 | Liquid phenyl silica gel for LED and its preparation method |
| CN110922939A (en) * | 2019-12-16 | 2020-03-27 | 苏州瑞力博新材科技有限公司 | Organosilicon gel with conductivity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608068A (en) * | 2009-07-10 | 2009-12-23 | 茂名市信翼化工有限公司 | A kind of organosilicon material and synthetic method thereof of power-type LED encapsulation usefulness |
-
2010
- 2010-02-11 CN CN 201010111927 patent/CN102153865A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608068A (en) * | 2009-07-10 | 2009-12-23 | 茂名市信翼化工有限公司 | A kind of organosilicon material and synthetic method thereof of power-type LED encapsulation usefulness |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433005A (en) * | 2011-08-25 | 2012-05-02 | 文仁光 | Liquid phenyl silica gel for LED and its preparation method |
| CN102433005B (en) * | 2011-08-25 | 2014-04-02 | 文仁光 | Liquid phenyl silica gel for LED and preparation method thereof |
| CN110922939A (en) * | 2019-12-16 | 2020-03-27 | 苏州瑞力博新材科技有限公司 | Organosilicon gel with conductivity |
| CN110922939B (en) * | 2019-12-16 | 2021-10-22 | 苏州瑞力博新材科技有限公司 | Organosilicon gel with conductivity |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103122149B (en) | Optical package high refractive index High-transparency silicon rubber and its preparation method | |
| CN101215381B (en) | Method for preparing methylphenyl hydrogen-containing silicone oil | |
| CN102898649B (en) | Refractive index-adjustable MDT silicone resin and preparation method thereof | |
| CN101343365A (en) | Preparation method for methyl phenyl vinyl polysiloxane for packaging LED | |
| CN103068884B (en) | Photosensitive silicone resin composition | |
| CN102875811B (en) | Preparation method for phenyl vinyl MQ silicone resin | |
| CN102391529A (en) | Preparation method of silicone resin type organic/inorganic hybrid material for packaging | |
| CN102898648B (en) | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof | |
| EP2439225B1 (en) | Organic silicon compound, thermosetting composition containing said organic silicon compound, and sealing material for optical semiconductor | |
| CN102585228B (en) | Organic silicon electronic-pouring sealant with high refractive index and high transparency, as well as preparation and application thereof | |
| WO2010138221A1 (en) | Silicone composition for producing transparent silicone materials and optical devices | |
| CN105802532A (en) | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel | |
| CN105315675A (en) | Ultraviolet light-curing composition | |
| EP1973963A1 (en) | Thermally stable transparent silicone resin compositions and methods for their preparation and use | |
| KR20130073894A (en) | Novel organosilicon compound and thermosetting resin composition, cured resin, and semiconductor sealing material containing said organosilicon compound | |
| CN102516500A (en) | Organic silicon modified epoxy resin for packaging LED (Light Emitting Diode), and preparation method and application thereof | |
| CN104045831A (en) | Siloxane bridged ladderlike polysiloxane and preparation method thereof | |
| CN102634026B (en) | Hydrogen-based silicone resin containing trifunctional group chain element and preparation method thereof | |
| CN102433005B (en) | Liquid phenyl silica gel for LED and preparation method thereof | |
| CN102898650A (en) | T-chain unit phenyl-containing MTQ silicon resin and preparation method thereof | |
| CN104629057A (en) | Methyl phenyl vinyl borosilicate resin and preparation method and application thereof | |
| CN104788488A (en) | Preparation method of naphthyl alkoxysilane | |
| CN101665572A (en) | Organic silicon resin for encapsulating LED and preparation method thereof | |
| CN104449551A (en) | LED packaging silica gel with high refractive index and yellowing resistance | |
| CN102153865A (en) | Organic silicon material for packaging high-power light-emitting diode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110817 |