CN103059573B - The LED material of inorganic/organic hybrid nanocomposite and preparation thereof - Google Patents

The LED material of inorganic/organic hybrid nanocomposite and preparation thereof Download PDF

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CN103059573B
CN103059573B CN201210557400.3A CN201210557400A CN103059573B CN 103059573 B CN103059573 B CN 103059573B CN 201210557400 A CN201210557400 A CN 201210557400A CN 103059573 B CN103059573 B CN 103059573B
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CN103059573A (en
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刘伟区
高南
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Guangzhou Chemical Co Ltd of CAS
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Abstract

The invention belongs to optical semiconductor device packaged material field, disclose a kind of inorganic/organic hybrid nanocomposite and the LED material prepared with it.This inorganic/organic hybrid nanocomposite carries out composite hybridization preparation by epoxy and phenyl oligosiloxane and inorganic nano material.With inorganic/organic hybrid nanocomposite for LED material prepared by raw material, preparation process is: 100 parts of inorganic/organic hybrid nanocomposites, 0.1 ~ 40 part of solidifying agent, 0 ~ 1.0 part of curing catalyst, 0 ~ 2.0 part of light scattering agent and 0 ~ 2.0 part of oxidation inhibitor are mixed by weight, 60 ~ 90 DEG C of vacuum Procuring 1 ~ 3h, 120 ~ 140 DEG C of solidification 2 ~ 4h again, last 160 ~ 180 DEG C of solidification 2 ~ 6h, obtain LED material.

Description

The LED material of inorganic/organic hybrid nanocomposite and preparation thereof
Technical field
The invention belongs to optical semiconductor device packaged material field, be specifically related to a kind of containing inorganic nanometer oxide, organic phenyl groups functional group and epoxy functionality inorganic/the LED material of organic hybrid nanocomposite and preparation thereof.
Technical background
Photodiode (LED) is the forth generation light source after incandescent light, fluorescent lamp, high pressure gas lamp, is one of promising high-tech area of 21 century most.In the LED illumination device of current widespread use; packaged material is its indispensable part; it not only has sealing and the function such as protect IC, heat radiation and transmission of signal, also can play simultaneously protection LED component be not subject to ambient temperature and humidity impact, reduce refringence between chip and air thus effective effect improving light output rate.Therefore, to a great extent, packaged material determines light efficiency and the work-ing life of LED component, also directly affects energy-saving efficiency and the life-span of LED illumination material.For LED material, especially high power type LED material, the cohesiveness of high specific refractory power, transmittance and excellence, stopping property, mechanical property, heat-resisting and anti-ultraviolet ageing performance are that material is required, are the important development directions of packaged material in following universal power-type LED illumination.
At present, LED material mainly contains the epoxy resin and the large class of organosilicon material two with high transparent.But along with the development of power-type LED, excellent in mechanical performance but easily the epoxy resin of xanthochromia can not meet the requirement of packaged material completely.Thus, current high power LED package material substantially had high transmission rate, excellent heat-resisting/organosilicon material of the contour performance of ultraviolet occupied by.But as power type LED encapsulation material, organosilicon material also exists some very important problems, as low in refractive index, bonding force is poor, mechanical strength is not high.
For the specific refractory power improving LED material makes the refractive index of itself and chip match, the people such as G.Basin introduce the TiO of high refractive index in LED organosilicon material 2, ZrO 2particle, addition is 2.5% ~ 5% specific refractory power that effectively can improve packaged material, and the luminous efficiency of its LED improves 5%, and brightness is also improved accordingly.The method adding the nanoparticle of high refractive index except above-mentioned points improves outside system refractive index, also high refractive index organic group is introduced by molecular designing, as aromatic groups such as phenyl, naphthyl and anthryls, realize the target of the high refractive index of system, wherein, J.S.Kim etc., by introducing the organic group phenyl with high refractive index in organosilicon systems, effectively improve the refractive index to 1.58 of material.2.0 ~ 5.0) or high refractive index organic group but up to the present, reporting according to existing document, is all adopt a kind of method wherein to improve system specific refractory power, the inorganic nano material (specific refractory power: of high refractive index is namely introduced separately into.For a kind of front method, although easily realize the high refractive index of system, also there is unsurmountable shortcoming simultaneously, when the particle diameter as inorganic nano-particle is excessive or consumption is too much, light transmission and the mechanical property of material can be had a strong impact on.And for a kind of rear method, on the one hand because the specific refractory power of organic group is lower and variation range is narrower relative to inorganic nano-particle, not high to the specific refractory power degree improving material, on the other hand, organic materials surface hardness is low, poor heat resistance, is often difficult to the over-all properties of the system that realizes.Thus, a kind of method is wherein adopted separately cannot to take into account the high refractive index of material, excellent bonding force and mechanical property etc.
Summary of the invention
In order to overcome the deficiencies in the prior art, primary and foremost purpose of the present invention be to provide a kind of inorganic/organic hybrid nanocomposite, this resin have high refractive index, high transmission rate and excellence heat-resisting/ultraviolet performance, had the feature of inorganic materials and organic materials concurrently simultaneously, as light weight, shock resistance, easily process, optical property is homogeneous, wear resistance good, specific refractory power is high and continuously adjustabe.
Another object of the present invention be to provide above-mentioned inorganic/preparation method of organic hybrid nanocomposite.This preparation method carries out composite hybridization with epoxy and phenyl oligosiloxane and inorganic nano material and prepares.
Further object of the present invention be to provide a kind of by above-mentioned inorganic/organic hybrid nanocomposite is LED material prepared by raw material.
A further object of the invention is the preparation method providing above-mentioned LED material.
Object of the present invention is achieved through the following technical solutions:
A preparation method for inorganic/organic hybrid nanocomposite, comprises the following steps:
The preparation of nano-oxide colloidal sol: 5 ~ 100g inorganic salts presoma is dissolved in 50 ~ 500mL alcoholic solvent, stirs, obtain presoma alcoholic solution; 0.5 ~ 10g catalyst A, 1 ~ 200g deionized water and 20 ~ 100mL alcoholic solvent are mixed, and be added drop-wise in presoma alcoholic solution, 20 ~ 80 DEG C of reaction 2 ~ 24h, namely obtain nano-oxide colloidal sol;
(2) preparation of epoxy and phenyl oligosiloxane: by 10 ~ 50g epoxyhydrocarbyl silane, 100g phenyl silane, 10 ~ 50g alkyl silane, 1 ~ 50g deionized water, 1 ~ 5g catalyst B and 80 ~ 400g solvent, stir, 60 ~ 100 DEG C of reaction 4 ~ 24h, by reaction soln vacuum rotary steam 1 ~ 2h, obtain epoxy and phenyl oligosiloxane;
(3) preparation of inorganic/organic hybrid nanocomposite: it is in the colloidal sol of 10 ~ 100g that 10 ~ 100g step (2) gained epoxy and phenyl oligosiloxane is joined the nano oxidized amount of step (1) gained, add 0.1 ~ 3g catalyzer C, 70 ~ 120 DEG C of reaction 4 ~ 16h, except desolventizing and by product, obtain inorganic/organic hybrid nanocomposite.
Inorganic salts presoma described in step (1) is four methyl alcohol titaniums, titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, isocaprylic acid titanium, pungent certain herbaceous plants with big flowers acid titanium, four methyl alcohol zirconiums, tetraethoxide zirconium, four zirconium iso-propoxides, four butanols zirconiums, zirconium iso-octoate, pungent certain herbaceous plants with big flowers acid zirconium, tetraethoxide hafnium, four Virahol hafniums, four trimethyl carbinol hafniums, dimethanol zinc, di-alcohol zinc, diisopropanol zinc, two butanols zinc, isocaprylic acid zinc or pungent certain herbaceous plants with big flowers acid zinc, tetraethoxide silicon, three methyl alcohol silicon, three aluminum ethylates, three Tripropoxyaluminums, more than one in three aluminium butoxides and methyl cellosolve cerium, preferred inorganic salts presoma is more than one in titanium isopropylate, ethanol silicon, butanols zirconium and zinc acetate,
Described alcoholic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol, and preferred alcoholic solvent is ethanol, Virahol or butanols;
Described catalyst A is formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoromethanesulfonic acid, three hexafluorophosphoric acid, oxalic acid, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide; Preferred catalyst A is acetic acid, propionic acid, oxalic acid, ammoniacal liquor or sodium hydroxide;
The particle diameter of described nano-oxide colloidal sol is 10 ~ 100nm.
The general structure of the epoxyhydrocarbyl silane described in step (2) is:
Wherein R to be carbon number be 2 ~ 10 saturated hydrocarbyl or the straight chain that is combined to form of carbon atom and Sauerstoffatom; R 1for methyl, ethyl, n-propyl, sec.-propyl or butyl; R 2for methyl or ethyl; N is 2 or 3;
Described epoxyhydrocarbyl silane is OC 6h 9cH 2cH 2si (OCH 3) 3, OCH 2cHCH 2oC 3h 6si (OCH 3) 3, OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2, OCH 2cHCH 2oC 3h 6si (OCH 2cH 3) 3, OCH 2cHCH 2oC 3h 6siCH 3(OCH 2cH 3) 2, OCH 2cHCH 2oC 8h 16si (OCH 3) 3and OCH 2cHCH 2oC 4h 8si (OCH 3) 3in one or more mixture; Preferred epoxyhydrocarbyl silane is OCH 2cHCH 2oC 8h 16si (OCH 3) 3, OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2, OCH 2cHCH 2oC 3h 6si (OCH 3) 3or OC 6h 9cH 2cH 2si (OCH 3) 3;
Described phenyl silane general structure is:
(R 3) x(R 4) y(R 5) zSi(OR 6) (4-x-y-z)
Wherein, R 3for phenyl, benzyl or styroyl; R 4for methyl, ethyl, n-propyl, sec.-propyl or butyl; R 5for methyl, ethyl, n-propyl, sec.-propyl or butyl; R 6for methyl or ethyl; X is 1,2 or 3, y, z is 0,1 or 2, and x+y+z<4;
Described phenyl silane is C 6h 5si (OCH 2cH 3) 3, CH 3(C 6h 5) Si (OCH 2cH 3) 2, CH 3(C 6h 5) 2siOCH 2cH 3, (C 6h 5) 2si (OCH 2cH 3) 2, C 6h 5si (OCH 3) 3, (C 6h 5) 3siOCH 3, (C 6h 5) 3siOCH 2cH 3cH 3(C 6h 5) Si (OCH 3) 2, CH 3(C 6h 5) 2siOCH 3, (C 6h 5) 2si (OCH 3) 2, C 6h 5cH 2si (OCH 2cH 3) 3, C 6h 5cH 2cH 2si (OCH 3) 3(CH 3) 2c 6h 5siOCH 2cH 3in one or more mixture; Preferred phenyl silane is CH 3(C 6h 5) Si (OCH 3) 2, (C 6h 5) 2si (OCH 3) 2, (C 6h 5) 2si (OCH 2cH 3) 2, C 6h 5si (OCH 3) 3or (C 6h 5) 3siOCH 3;
Described alkyl silane structure general formula is:
(R 7) a(R 8) bSi(OR 9) 4-a-b
Wherein R 7, R 8for the alkyl of C1 ~ C6; R 9for methyl or ethyl; A, b be 0,1 or 2 and a, b are different time be 0;
Described alkyl silane is (CH 3) 2si (OCH 3) 2, (CH 3cH 2) 2si (OCH 3) 2, (CH 3cH 2cH 2) 2si (OCH 3) 2, ((CH 3) 2cH) 2si (OCH 3) 2, (CH 3cH 2cH 2cH 2) 2si (OCH 3) 2, (CH 3) (C 2h 5) Si (OCH 3) 2, CH 3(CH 3cH 2cH 2) Si (OCH 3) 2, (CH 3) 2si (OC 2h 5) 2, (CH 3cH 2) 2si (OC 2h 5) 2, (CH 3cH 2cH 2) 2si (OC 2h 5) 2, ((CH 3) 2cH) 2si (OC 2h 5) 2, (CH 3cH 2cH 2cH 2) 2si (OC 2h 5) 2, (CH 3) (C 2h 5) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2cH 2) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2cH 2cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2cH 2cH 2) Si (OC 2h 5) 2, CH 3si (OCH 3) 3, CH 3cH 2si (OCH 3) 3, CH 3cH 2cH 2si (OCH 3) 3, (CH 3) 2cHSi (OCH 3) 3, CH 3cH 2cH 2cH 2si (OCH 3) 3, C 6h 13si (OCH 3) 3, CH 3si (OC 2h 5) 3, CH 3cH 2si (OC 2h 5) 3, CH 3cH 2cH 2si (OC 2h 5) 3, (CH 3) 2cHSi (OC 2h 5) 3, CH 3cH 2cH 2cH 2si (OC 2h 5) 3and C 6h 13si (OC 2h 5) 3in one or more mixture; Preferred alkyl silane is (CH 3) 2si (OCH 3) 2, (CH 3cH 2cH 2cH 2) 2si (OCH 3) 2, C 6h 13si (OC 2h 5) 3, (CH 3cH 2) 2si (OC 2h 5) 2or CH 3si (OC 2h 5) 3;
Described catalyst B is dibutyl tin laurate, stannous octoate or dibutyl tin acetate;
Described solvent is tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxy six alkane, ethanol, hexanaphthene, butanone, Virahol, butanols or glycol dimethyl ether; Preferred solvent is Isosorbide-5-Nitrae-dioxy six alkane, tetrahydrofuran (THF), glycol dimethyl ether, ethanol or butanone.
Catalyzer C described in step (3) is dibutyl tin laurate, dibutyl tin acetate or stannous octoate;
Described except desolventizing and by product be vacuum rotary steam 0.5 ~ 2h at 60 ~ 100 DEG C.
A kind of by preparation method described above prepare inorganic/specific refractory power of organic hybrid nanocomposite is 1.58 ~ 1.90.
By described above inorganic/the LED material prepared of organic hybrid nanocomposite, this LED material is prepared from by the raw material of following parts by weight:
The compound solidifying agent that described solidifying agent is acid anhydride type curing agent or is made up of methyl ethyl diketone lanthanide series compound and silanol.Wherein, the solidifying agent of anhydrides is one or more the mixture in cyclohexanetricarboxylic acid's acid anhydride, carbic anhydride, methylnadic anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride or 4-methyl tetrahydro phthalic anhydride; Methyl ethyl diketone lanthanide series compound is acetylacetone cobalt, methyl ethyl diketone zirconium, methyl ethyl diketone rhodium, chromium acetylacetonate, ferric acetyl acetonade, acetylacetonate nickel, aluminium acetylacetonate or methyl ethyl diketone neodymium; Silanol is dimethyl phonyl silanol, diethyl phenyl silanol, trimethyl silanol, triethyl silanol, triphenyl silanol, aminomethyl phenyl silicon diol, ethylphenyl silicon diol, Diphenylsilanediol or a phenyl silanetriol.
Preferred solidifying agent is methyl hexahydrophthalic anhydride, HHPA, methylhexahydrophthalic anhydride or aluminium acetylacetonate and diphenyl silanol;
Described curing catalyst is one or more the mixture in tetrabutyl ammonium acetate, Tetrabutyl amonium bromide, four hexyl brometo de amonios, Trimethyllaurylammonium bromide and cetyl trimethylammonium bromide, and preferred curing catalyst is cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide or 4 bromide;
Described light scattering agent is organic light scattering agent polymethylmethacrylate or inorganic light scattering agent TiO 2, BaTiO 3, ZnO, Al 2o 3and SiO 2in one or more mixture, preferred light scattering agent is polymethylmethacrylate;
Described oxidation inhibitor is phosphorous acid esters or Hinered phenols; Wherein phosphorous acid esters are V72-P, V75-P, V76-P or V78-P; Hinered phenols is V84-P or V85-P;
Preferred oxidation inhibitor is V85-P or V72-P.
The transmittance of described LED material at 800nm place is more than 91%, transmittance at 400nm place is more than 87%, and solid residue amount during thermal weight loss 800 DEG C is 12.4% ~ 87.5%, and specific refractory power is more than 1.58, shore hardness is more than 42A, and surface adhesion power is 4B ~ 5B.
By a preparation method for LED material described above, comprise the following steps:
By weight 100 parts of inorganic/organic hybrid nanocomposites, 0.1 ~ 40 part of solidifying agent, 0 ~ 1.0 part of curing catalyst, 0 ~ 2.0 part of light scattering agent and 0 ~ 2.0 part of oxidation inhibitor are mixed, in 60 ~ 90 DEG C of vacuum Procuring 1 ~ 3h, 120 ~ 140 DEG C of solidification 2 ~ 4h again, last 160 ~ 180 DEG C of solidification 2 ~ 6h, obtain LED material.
Principle of the present invention is: on the one hand, adopts sol-gel method to prepare nano-oxide colloidal sol, by the control to synthesis condition, prepares the high refractive index nano oxide sol that size is controlled, and be dispersed in organic solvent; On the other hand, be hydrolyzed epoxyhydrocarbyl silane, phenyl silane and alkyl silane condensation reaction, prepares the high refractive index oligosiloxane containing epoxy group(ing), phenyl.The condensation reaction of the recycling hydroxyl on nano-oxide surface and the hydroxyl of oligosiloxane, carries out compound by the nano-oxide colloidal sol of synthesis and polysiloxane, thus prepares inorganic/organic hybrid nanocomposite.Owing to introducing inorganic nanometer oxide and the organic phenyl groups of high refractive index in system simultaneously, the refractive index effectively by improving inorganic and organic two-phase realizes the high refractive index of this hybrid systems; Meanwhile, by the control to nano-oxide size, obtain the hybrid compound resin that optics is homogeneous.With prepared compound resin for matrix, utilize the solidification of epoxy-functional in resin can prepare LED high-index material, simultaneously by regulating the ratio of epoxyhydrocarbyl silane, alkyl silane in reaction raw materials, the LED high-index material with the mechanical property such as excellent flexibility, hardness can be obtained.
Compared with prior art, there is following advantage and beneficial effect in the present invention:
(1) with tradition separately through compared with the method improving inorganic phase or organic phase specific refractory power, the present invention is the specific refractory power by improving inorganic phase and organic phase simultaneously, more effectively can realize the high refractive index of system.
(2) prepared by the present invention inorganic/organic hybrid nanocomposite, has had the feature of inorganic materials and organic materials concurrently, as high in easy machine-shaping, good heat resistance, specific refractory power and continuously adjustabe etc.
(3) the LED high-index material in the present invention, utilize the epoxy-functional in inorganic/organic hybrid nanocomposite matrix to be cured preparation, prepared encapsulation material had both had organosilicon material high transmission rate, excellent heat/ultraviolet stability, had again the features such as the cementability of epoxy resin excellence and mechanical property.
(4) by regulating the ratio of epoxyhydrocarbyl silane, phenyl silane and alkyl silane in reaction raw materials, and control the size of nano-oxide colloidal sol, the LED material with high transmission rate, high refractive index, excellent resistance to ultraviolet/heat aging and mechanical property can be prepared.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of nano-oxide colloidal sol: be dissolved in 50mL dehydrated alcohol by 5.0g anhydrous zinc acetate, induction stirring is even.0.5g sodium hydroxide, 2.0g deionized water and 20mL dehydrated alcohol are mixed, and is added drop-wise in the ethanolic soln of zinc acetate, after 20 DEG C of reaction 3h, obtain the zinc oxide colloidal sol that median size is 10nm.
(2) preparation of epoxy and phenyl oligosiloxane: by 10g epoxyhydrocarbyl silane OC 6h 9cH 2cH 2si (OCH 3) 3, 100g phenyl silane (C 6h 5) 2si (OCH 2cH 3) 2, 30g alkyl silane (CH 3) 2si (OCH 3) 2, 10g deionized water, 1g catalyst dibutyltin dilaurylate and 80g 1,4-dioxy six alkane is placed in there-necked flask, stir, in 80 DEG C of reaction 6h, after reaction terminates, by reaction soln in 70 DEG C of vacuum rotary steam 1h except anhydrating, solvent and by product, obtain water white epoxy and phenyl oligosiloxane.
(3) preparation of inorganic/organic hybrid nanocomposite: the epoxy and phenyl oligosiloxane 100g nano zine oxide quality joined prepared by step (1) step (2) prepared is in the colloidal sol of 10g, add 0.8g catalyst dibutyltin dilaurylate again, 70 DEG C of reaction 16h, reaction terminates rear removing etoh solvent and by product, 70 DEG C of vacuum rotary steam 1.0h remove etoh solvents and by product, obtain refractive index be 1.58 inorganic/organic hybrid nanocomposite.
(4) preparation of LED material: by above-mentioned prepared inorganic/organic hybrid nanocomposite 100g, solidifying agent methyl hexahydrophthalic anhydride 5g, curing catalyst 4 bromide 0.1g mix, at 90 DEG C of vacuum Procuring 2h, again in 120 DEG C of solidification 2h, finally in 160 DEG C of solidification 6h, obtained LED material; Material is respectively 92.1% and 87.6% at the transmittance of 800nm and 400nm, and solid residue amount during thermal weight loss 800 DEG C is 12.4%, and specific refractory power is 1.58, and shore hardness is 42A, and surface bonding power is 5B.
Embodiment 2
(1) preparation of nano-oxide colloidal sol: 13.5g titanium isopropylate and 16.5g butanols zirconium are dissolved in 120mL Virahol, induction stirring mixes.3.0g propionic acid, 1.0g deionized water and 100mL Virahol are mixed, and is added drop-wise in the aqueous isopropanol of titanium isopropylate and butanols zirconium, at 80 DEG C, react 4h, obtain the titania-zirconia colloidal sol that median size is 72nm.
(2) preparation of epoxy and phenyl oligosiloxane: by 30g epoxyhydrocarbyl silane OC 6h 9cH 2cH 2si (OCH 3) 3, 100g phenyl silane (C 6h 5) 2si (OCH 3) 2, 10g alkyl silane (CH 3cH 2cH 2cH 2) 2si (OCH 3) 2, 20g deionized water, 1.8g catalyzer dibutyl tin acetate and 100g tetrahydrofuran (THF) be placed in there-necked flask, stir, in 70 DEG C of reaction 16h, after reaction terminates, by reaction soln in 50 DEG C of vacuum rotary steam 2h except anhydrating, solvent and by product, obtain water white epoxy and phenyl oligosiloxane.
(3) preparation of inorganic/organic hybrid nanocomposite: nano-titanium oxide-zirconic quality that epoxy and phenyl oligosiloxane 40g step (2) prepared joins prepared by step (1) is in the colloidal sol of 10g, add 0.1g catalyzer dibutyl tin acetate again, 80 DEG C of reaction 12h, except desolventizing Virahol and by product after reaction terminates, 100 DEG C of vacuum rotary steam 0.5h except desolventizing Virahol and by product, obtain refractive index be 1.72 inorganic/organic hybrid nanocomposite.
(4) preparation of LED material: by above-mentioned prepared inorganic/organic hybrid nanocomposite 100g, solidifying agent (0.05g aluminium acetylacetonate and 0.05g diphenyl silanol), oxidation inhibitor V72-P0.8g(Guangzhou will one Chemical Co., Ltd.) and light scattering agent polymethylmethacrylate 1.0g mix, at 60 DEG C of vacuum Procuring 1h, again in 120 DEG C of solidification 2h, finally in 180 DEG C of solidification 3h, obtained LED material; Material is respectively 91.7% and 87.2% at the transmittance of 800nm and 400nm, and the solid residue amount of thermal weight loss 800 DEG C is 28.7%, and specific refractory power is 1.72, and shore hardness is 65A, and surface bonding power is 5B.
Embodiment 3
(1) preparation of nano-oxide colloidal sol: be dissolved in 300mL butanols by 50g butanols zirconium, induction stirring mixes.10g acetic acid, 100g deionized water and 50mL butanols are mixed, and be added drop-wise in butanols zirconium solution, 60 DEG C of reaction 8h, obtain the zirconia sol that median size is 25nm.
(2) preparation of epoxy and phenyl oligosiloxane: by 20g epoxyhydrocarbyl silane OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2, 100g phenyl silane CH 3(C 6h 5) Si (OCH 3) 2, 20g alkyl silane CH 3si (OC 2h 5) 3, 1g deionized water, the sub-tin of 5.0g octoate catalyst and 400g glycol dimethyl ether be placed in there-necked flask, stir, in 100 DEG C of reaction 24h, after reaction terminates, by reaction soln in 100 DEG C of vacuum rotary steam 0.5h except anhydrating, solvent and by product, obtain water white epoxy and phenyl oligosiloxane.
(3) preparation of inorganic/organic hybrid nanocomposite: getting the epoxy and phenyl polysiloxane 50g nano zircite quality joined prepared by step (1) prepared by step (2) is in the colloidal sol of 30g, add the sub-tin of 0.3g octoate catalyst again, 120 DEG C of reaction 4h, except desolventizing butanols and by product after reaction terminates, 90 DEG C of vacuum rotary steam 1.0h except desolventizing butanols and by product, obtain refractive index be 1.79 inorganic/organic hybrid nanocomposite.
(4) preparation of LED material: by above-mentioned prepared inorganic/organic hybrid nanocomposite 100g, solidifying agent HHPA 20g, curing catalyst Trimethyllaurylammonium bromide 0.1g, oxidation inhibitor V85-P(Guangzhou will one Chemical Co., Ltd.) 2.0g mixes, at 80 DEG C of vacuum Procuring 2h, again in 120 DEG C of solidification 4h, finally in 160 DEG C of solidification 4h, obtained LED material; Material is respectively 92.2% and 87.9% at the transmittance of 800nm and 400nm, and the solid residue amount of thermal weight loss 800 DEG C is 61.3%, and specific refractory power is 1.77, and shore hardness is 74A, and surface bonding power is 5B.
Embodiment 4
(1) preparation of nano-oxide colloidal sol: 30g titanium isopropylate, 40g butanols zirconium and 30g ethanol silicon are dissolved in 500mL dehydrated alcohol, induction stirring mixes.5.0g oxalic acid, 200g deionized water and 100mL dehydrated alcohol are mixed, and is added dropwise in above-mentioned mixing solutions, after 60 DEG C of reaction 24h, obtain titania-zirconia-silica sol that median size is 100nm.
(2) preparation of epoxy and phenyl oligosiloxane: by 30g epoxyhydrocarbyl silane OCH 2cHCH 2oC 3h 6si (OCH 3) 3, 100g phenyl silane C 6h 5si (OCH 3) 3, 20g alkyl silane (CH 3cH 2) 2si (OC 2h 5) 2, 30g deionized water, 3.0g catalyst dibutyltin dilaurylate and 200g ethanol is placed in there-necked flask, stir, in 60 DEG C of reaction 24h, after reaction terminates, by reaction soln in 60 DEG C of vacuum rotary steam 1h except anhydrating, solvent and by product, obtain water white epoxy and phenyl oligosiloxane.
(3) preparation of inorganic/organic hybrid nanocomposite: nano-titanium oxide-zirconia-silica quality that epoxy and phenyl polysiloxane 10g step (2) prepared joins prepared by step (1) is in the colloidal sol of 100g, add 3.0g catalyst dibutyltin dilaurylate again, 80 DEG C of reaction 12h, reaction terminates rear removing etoh solvent and by product, 60 DEG C of vacuum rotary steam 2.0h remove etoh solvents and by product, obtain refractive index be 1.90 inorganic/organic hybrid nanocomposite.
(4) preparation of LED material: by above-mentioned prepared inorganic/organic hybrid nanocomposite 100g, solidifying agent methylhexahydrophthalic anhydride 25g, curing catalyst cetyl trimethylammonium bromide 0.2g mix, at 90 DEG C of vacuum Procuring 3h, again in 140 DEG C of solidification 3h, finally in 180 DEG C of solidification 2h, obtained LED material; Material is respectively 91% and 87% at the transmittance of 800nm and 400nm, and the solid residue amount of thermal weight loss 800 DEG C is 87.5%, and specific refractory power is 1.87, and shore hardness is > 100A, and surface bonding power is 4B.
Embodiment 5
(1) preparation of nano-oxide colloidal sol: 20g titanium isopropylate and 10g ethanol silicon are dissolved in 200mL ethanol, induction stirring mixes.1.0g acetic acid, 20g deionized water are mixed with 40mL dehydrated alcohol, and is added dropwise in titanium isopropoxide solution, after 70 DEG C of reaction 2h, obtain the titania-silica colloidal sol that median size is 40nm.
(2) preparation of epoxy and phenyl oligosiloxane: by 50g epoxyhydrocarbyl silane OCH 2cHCH 2oC 8h 16si (OCH 3) 3, 100g phenyl silane (C 6h 5) 3siOCH 3, 50g alkyl silane C 6h 13si (OC 2h 5) 3, 50g deionized water, 1.7g catalyst dibutyltin dilaurylate and 200g butanone be placed in there-necked flask, stir, in 80 DEG C of reaction 4h, after reaction terminates, by reaction soln in 80 DEG C of vacuum rotary steam 1h except anhydrating, solvent and by product, obtain water white epoxy and phenyl oligosiloxane;
(3) preparation of inorganic/organic hybrid nanocomposite: nano-titanium oxide-zirconium white quality that epoxy and phenyl oligosiloxane 70g step (2) prepared joins prepared by step (1) is in the colloidal sol of 21g, add 1.0g catalyst dibutyltin dilaurylate again, 80 DEG C of reaction 8h, reaction terminates rear removing etoh solvent and by product etc., 70 DEG C of vacuum rotary steam 1.0h remove etoh solvents and by product, obtain refractive index be 1.75 inorganic/organic hybrid nanocomposite.
(4) preparation of LED material: by above-mentioned prepared inorganic/organic hybrid nanocomposite 100g, solidifying agent methylhexahydrophthalic anhydride 40g, curing catalyst cetyl trimethylammonium bromide 1.0g, light scattering agent polymethylmethacrylate 2.0g mix, at 80 DEG C of vacuum Procuring 3h, again in 130 DEG C of solidification 4h, finally in 180 DEG C of solidification 4h, obtained LED material; Material is 91.9% and 87.1% at the transmittance of 800nm and 400nm, and solid residue amount during thermal weight loss 800 DEG C is 26.3%, and specific refractory power is 1.71, and shore hardness is 56A, and surface bonding power is 5B.
In the test of material correlated performance, wherein, transmittance adopts the UV8000 ultraviolet-visible pectrophotometer of Shanghai Yuan Xi Instrument Ltd. to test, and thickness of sample is 3mm, the scope of scanning wavelength is 280 ~ 800nm, and the absorbancy wherein choosing 800nm and 400nm place compares;
The particle diameter of nano-oxide colloidal sol adopts the JL-1177 type particle size analyzer of the new powder testing apparatus Instrument Ltd. of Chengdu essence to test;
Thermotolerance adopts TG209F3 (NETZSCH) thermogravimetric analyzer, and under nitrogen atmosphere, useful range is 50 DEG C ~ 800 DEG C, and temperature rise rate is 10 DEG C/min;
Specific refractory power adopts the ZWA type Abbe refractometer of Shanghai optical instrument factory to test;
Surface bonding power records according to the testing method of standard A STM C3359-B;
Hardness reference standard JB 6148-92 adopts Shore durometer A to test.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a preparation method for inorganic/organic hybrid nanocomposite, is characterized in that: comprise the following steps:
(1) preparation of nano-oxide colloidal sol: be dissolved in 50 ~ 500mL alcoholic solvent by 5 ~ 100g presoma, stir, obtains presoma alcoholic solution, 0.5 ~ 10g catalyst A, 1 ~ 200g deionized water and 20 ~ 100mL alcoholic solvent are mixed, and be added drop-wise in presoma alcoholic solution, 20 ~ 80 DEG C of reaction 2 ~ 24h, namely obtain nano-oxide colloidal sol, the particle diameter of described nano-oxide colloidal sol is 10 ~ 100nm, described presoma is four methyl alcohol titaniums, titanium tetraethoxide, titanium tetraisopropylate, four butanols titaniums, isocaprylic acid titanium, pungent capric acid titanium, four methyl alcohol zirconiums, tetraethoxide zirconium, four zirconium iso-propoxides, four butanols zirconiums, zirconium iso-octoate, pungent capric acid zirconium, tetraethoxide hafnium, four Virahol hafniums, four trimethyl carbinol hafniums, dimethanol zinc, di-alcohol zinc, diisopropanol zinc, two butanols zinc, isocaprylic acid zinc, pungent capric acid zinc, zinc acetate, tetraethoxide silicon, three methyl alcohol silicon, three aluminum ethylates, three Tripropoxyaluminums, three aluminium butoxides, more than one in ethanol tin and methyl cellosolve cerium,
(2) preparation of epoxy and phenyl oligosiloxane: by 10 ~ 50g epoxyhydrocarbyl silane, 100g phenyl silane, 10 ~ 50g alkyl silane, 1 ~ 50g deionized water, 1 ~ 5g catalyst B and 80 ~ 400g solvent, stir, 60 ~ 100 DEG C of reaction 4 ~ 24h, by reaction soln vacuum rotary steam 1 ~ 2h, obtain epoxy and phenyl oligosiloxane;
(3) preparation of inorganic/organic hybrid nanocomposite: 10 ~ 100g step (2) gained epoxy and phenyl oligosiloxane is joined in 10 ~ 100g step (1) gained nano-oxide colloidal sol, add 0.1 ~ 3g catalyzer C, 70 ~ 120 DEG C of reaction 4 ~ 16h, except desolventizing and by product, obtain inorganic/organic hybrid nanocomposite; Described inorganic/specific refractory power of organic hybrid nanocomposite is 1.58 ~ 1.90;
Described catalyst A is formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoromethanesulfonic acid, three hexafluorophosphoric acid, oxalic acid, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide;
Described catalyst B is dibutyl tin laurate, stannous octoate or dibutyl tin acetate;
Described catalyzer C is dibutyl tin laurate, dibutyl tin acetate or stannous octoate.
2. preparation method according to claim 1, is characterized in that: the alcoholic solvent described in step (1) is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol;
The general structure of the epoxyhydrocarbyl silane described in step (2) is: wherein R to be carbon number be 2 ~ 10 saturated hydrocarbyl or the straight chain that is combined to form of carbon atom and Sauerstoffatom; R 1for methyl, ethyl, n-propyl, sec.-propyl, phenyl or butyl; R 2for methyl or ethyl; N is 2 or 3; Work as R 1during for phenyl, described epoxyhydrocarbyl silane is OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2;
Described phenyl silane general structure is:
(R 3) x(R 4) y(R 5) zSi(OR 6) (4-x-y-z)
Wherein, R 3for phenyl, benzyl or styroyl; R 4for methyl, ethyl, n-propyl, sec.-propyl or butyl; R 5for methyl, ethyl, n-propyl, sec.-propyl or butyl; R 6for methyl or ethyl; X is 1,2 or 3, y, z is 0,1 or 2, and x+y+z<4;
Described alkyl silane structure general formula is:
(R 7) a(R 8) bSi(OR 9) 4-a-b
Wherein R 7, R 8for the alkyl of C1 ~ C6; R 9for methyl or ethyl; A, b be 0,1 or 2 and a, b are different time be 0;
Described solvent is tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxy six alkane, ethanol, hexanaphthene, butanone, Virahol, butanols or glycol dimethyl ether;
Described in step (3) except desolventizing and by product be vacuum rotary steam 0.5 ~ 2h at 60 ~ 100 DEG C.
3. preparation method according to claim 2, is characterized in that:
Described alcoholic solvent is ethanol, Virahol or butanols;
Described catalyst A is acetic acid, propionic acid, oxalic acid or sodium hydroxide;
Described epoxyhydrocarbyl silane is OC 6h 9cH 2cH 2si (OCH 3) 3, OCH 2cHCH 2oC 3h 6si (OCH 3) 3, OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2, OCH 2cHCH 2oC 3h 6si (OCH 2cH 3) 3, OCH 2cHCH 2oC 3h 6siCH 3(OCH 2cH 3) 2, OCH 2cHCH 2oC 8h 16si (OCH 3) 3and OCH 2cHCH 2oC 4h 8si (OCH 3) 3in one or more mixture;
Described phenyl silane is C 6h 5si (OCH 2cH 3) 3, CH 3(C 6h 5) Si (OCH 2cH 3) 2, CH 3(C 6h 5) 2siOCH 2cH 3, (C 6h 5) 2si (OCH 2cH 3) 2, C 6h 5si (OCH 3) 3, (C 6h 5) 3siOCH 3, (C 6h 5) 3siOCH 2cH 3cH 3(C 6h 5) Si (OCH 3) 2, CH 3(C 6h 5) 2siOCH 3, (C 6h 5) 2si (OCH 3) 2, C 6h 5cH 2si (OCH 2cH 3) 3, C 6h 5cH 2cH 2si (OCH 3) 3or (CH 3) 2c 6h 5siOCH 2cH 3in one or more mixture;
Described alkyl silane is (CH 3) 2si (OCH 3) 2, (CH 3cH 2) 2si (OCH 3) 2, (CH 3cH 2cH 2) 2si (OCH 3) 2, ((CH 3) 2cH) 2si (OCH 3) 2, (CH 3cH 2cH 2cH 2) 2si (OCH 3) 2, (CH 3) (C 2h 5) Si (OCH 3) 2, CH 3(CH 3cH 2cH 2) Si (OCH 3) 2, (CH 3) 2si (OC 2h 5) 2, (CH 3cH 2) 2si (OC 2h 5) 2, (CH 3cH 2cH 2) 2si (OC 2h 5) 2, ((CH 3) 2cH) 2si (OC 2h 5) 2, (CH 3cH 2cH 2cH 2) 2si (OC 2h 5) 2, (CH 3) (C 2h 5) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2cH 2) Si (OC 2h 5) 2, (CH 3) (CH 3cH 2cH 2cH 2) Si (OCH 3) 2, (CH 3) (CH 3cH 2cH 2cH 2) Si (OC 2h 5) 2, CH 3si (OCH 3) 3, CH 3cH 2si (OCH 3) 3, CH 3cH 2cH 2si (OCH 3) 3, (CH 3) 2cHSi (OCH 3) 3, CH 3cH 2cH 2cH 2si (OCH 3) 3, C 6h 13si (OCH 3) 3, CH 3si (OC 2h 5) 3, CH 3cH 2si (OC 2h 5) 3, CH 3cH 2cH 2si (OC 2h 5) 3, (CH 3) 2cHSi (OC 2h 5) 3, CH 3cH 2cH 2cH 2si (OC 2h 5) 3and C 6h 13si (OC 2h 5) 3in one or more mixture;
Described solvent is Isosorbide-5-Nitrae-dioxy six alkane, tetrahydrofuran (THF), glycol dimethyl ether, ethanol or butanone.
4. preparation method according to claim 3, is characterized in that:
Described epoxyhydrocarbyl silane is OCH 2cHCH 2oC 8h 16si (OCH 3) 3, OCH 2cHCH 2oC 3h 6siPh (OCH 2cH 3) 2, OCH 2cHCH 2oC 3h 6si (OCH 3) 3or OC 6h 9cH 2cH 2si (OCH 3) 3;
Described phenyl silane is CH 3(C 6h 5) Si (OCH 3) 2, (C 6h 5) 2si (OCH 3) 2, (C 6h 5) 2si (OCH 2cH 3) 2, C 6h 5si (OCH 3) 3or (C 6h 5) 3siOCH 3;
Described alkyl silane is: (CH 3) 2si (OCH 3) 2, (CH 3cH 2cH 2cH 2) 2si (OCH 3) 2, C 6h 13si (OC 2h 5) 3, (CH 3cH 2) 2si (OC 2h 5) 2or CH 3si (OC 2h 5) 3.
5. one kind by the preparation method described in any one of Claims 1 to 4 prepare inorganic/organic hybrid nanocomposite.
6. by according to claim 5 inorganic/the LED material that is prepared from of organic hybrid nanocomposite, it is characterized in that: this LED material is prepared from by the raw material of following parts by weight:
The transmittance of described LED material at 800nm place is more than 91%, transmittance at 400nm place is more than 87%, and solid residue amount during thermal weight loss 800 DEG C is 12.4% ~ 87.5%, and specific refractory power is more than 1.58, shore hardness is more than 42A, and surface adhesion power is 4B ~ 5B.
7. LED material according to claim 6, is characterized in that:
The compound solidifying agent that described solidifying agent is acid anhydride type curing agent or is made up of methyl ethyl diketone lanthanide series compound and silanol; Described curing catalyst is quaternary ammonium salt;
Described light scattering agent is one or more the mixture in organic light scattering agent and inorganic light scattering agent;
Described oxidation inhibitor is phosphorous acid esters or Hinered phenols.
8. LED material according to claim 7, is characterized in that:
Described acid anhydride type curing agent is one or more the mixture in cyclohexanetricarboxylic acid's acid anhydride, carbic anhydride, methylnadic anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride and 4-methyl tetrahydro phthalic anhydride;
Described methyl ethyl diketone lanthanide series compound is acetylacetone cobalt, methyl ethyl diketone zirconium, methyl ethyl diketone rhodium, chromium acetylacetonate, ferric acetyl acetonade, acetylacetonate nickel, aluminium acetylacetonate or methyl ethyl diketone neodymium;
Described silanol is dimethyl phonyl silanol, diethyl phenyl silanol, trimethyl silanol, triethyl silanol, triphenyl silanol, aminomethyl phenyl silicon diol, ethylphenyl silicon diol, Diphenylsilanediol or a phenyl silanetriol; Described curing catalyst is one or more the mixture in tetrabutyl ammonium acetate, Tetrabutyl amonium bromide, four hexyl brometo de amonios, Trimethyllaurylammonium bromide and cetyl trimethylammonium bromide;
Described organic light scattering agent is polymethylmethacrylate;
Described inorganic light scattering agent is TiO 2, BaTiO 3, ZnO, Al 2o 3or SiO 2;
Described phosphorous acid esters are V72-P, V75-P, V76-P or V78-P;
Described Hinered phenols is V84-P or V85-P.
9. LED material according to claim 6, is characterized in that:
Described solidifying agent is methyl hexahydrophthalic anhydride, HHPA, methylhexahydrophthalic anhydride or aluminium acetylacetonate and diphenyl silanol;
Described curing catalyst is cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide or 4 bromide;
Described oxidation inhibitor is V85-P or V72-P.
10. the preparation method of the LED material according to any one of claim 6 ~ 9, is characterized in that: comprise the following steps:
By weight 100 parts of inorganic/organic hybrid nanocomposites, 0.1 ~ 40 part of solidifying agent, 0 ~ 1.0 part of curing catalyst, 0 ~ 2.0 part of light scattering agent and 0 ~ 2.0 part of oxidation inhibitor are mixed, 60 ~ 90 DEG C of vacuum Procuring 1 ~ 3h, 120 ~ 140 DEG C of solidification 2 ~ 4h again, last 160 ~ 180 DEG C of solidification 2 ~ 6h, obtain LED material.
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