CN100509952C - Transparent epoxy nano composite material and preparation method and application thereof - Google Patents
Transparent epoxy nano composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN100509952C CN100509952C CNB2006100809666A CN200610080966A CN100509952C CN 100509952 C CN100509952 C CN 100509952C CN B2006100809666 A CNB2006100809666 A CN B2006100809666A CN 200610080966 A CN200610080966 A CN 200610080966A CN 100509952 C CN100509952 C CN 100509952C
- Authority
- CN
- China
- Prior art keywords
- nano
- epoxy
- composite material
- particle
- transparent epoxy
- 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.)
- Expired - Fee Related
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000011256 inorganic filler Substances 0.000 claims abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 60
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 33
- 239000004408 titanium dioxide Substances 0.000 claims description 23
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 239000004848 polyfunctional curative Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229960001866 silicon dioxide Drugs 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 150000001412 amines Chemical group 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005538 encapsulation Methods 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012764 mineral filler Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 21
- 239000002105 nanoparticle Substances 0.000 abstract description 17
- 230000032683 aging Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 23
- 239000011257 shell material Substances 0.000 description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000002834 transmittance Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011246 composite particle Substances 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 silicon-dioxide-titanium dioxide-gold Chemical compound 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a transparent epoxy nano composite material and a preparation method and application thereof, wherein the filler of the transparent epoxy nano composite material is a composite nano inorganic filler; the composite nano inorganic filler comprises: a silica nanoparticle as a core, titania as a shell coated outside the silica nanoparticle, and a silica outer layer coated outside the titania shell; the transparent epoxy nano composite material has good transparency, has excellent ultraviolet shielding effect compared with common pure transparent epoxy, and greatly improves the ultraviolet aging resistance; the transparent epoxy nano composite material also has the advantages of low thermal expansion coefficient, high thermal conductivity and the like; the invention is suitable for packaging light-emitting semiconductor devices such as LEDs.
Description
Technical field
The present invention relates to a kind of transparent epoxy nano composite material and its production and use, more particularly, the present invention relates to the transparent epoxy nano composite material and its production and use of a kind of filler for composite nanometer particle with nuclear-shell structure.
Background technology
Present photodiode (Light emitting diode, LED) waiting used for electronic packaging Resins, epoxy mainly is the bisphenol A-type transparent epoxy resin, it is very ripe that transparent epoxy resin is used for the charactron encapsulation.But the encapsulation of LED solid state lighting device is different with common charactron encapsulation, and particularly the white light LEDs based on UV-light is higher to the various performance demands of Resins, epoxy.For example: be difficult to realize the conversion fully of UV-light for the white light LEDs of burst of ultraviolel, a large amount of ultraviolet leakages can not be ignored people's influence, so Resins, epoxy must be able to absorb ultraviolet ray and prevents its leakage; Bisphenol A type epoxy resin contains can absorb ultraviolet aromatic series, absorb after the ultraviolet ray, the meeting oxidation produces carbonyl and forms chromophoric group and causes the resin variable color, and then causes the transmittance in shortwave field to descend, and this phenomenon is very big to blue light and the luminous luminosity influence of white light LEDs.Also there are shortcomings such as thermal expansivity height, thermal conductivity be low in the normal transparent epoxy in addition, and these have all limited the use of Resins, epoxy.
Since high molecule nano composite material can each component of bond material performance, form the matrix material of excellent combination properties such as heat, electricity, light, become the focus in investigation of materials field in recent years.For example can improve the ultraviolet shielded effect of epoxy, the ultraviolet ageing performance of raising material by adding fillers such as nano titanium oxide, zinc oxide, cerium oxide; Reduce thermal expansivity, the thermal conductivity of epoxy by Nano fillings such as adding silicon-dioxide.If prepare epoxy nano composite material, then can improve shortcomings such as the ultraviolet shielded efficient of Resins, epoxy is low, ultraviolet aging resistance poor performance, thermal expansivity height.But because the specific refractory power and the macromolecule matrix of above-mentioned various inorganic nano-fillers differ many, for example: most of high molecular specific refractory power is about 1.5, and the specific refractory power of Nano fillings such as titanium dioxide, zinc oxide, cerium oxide is all greater than 2, thereby so the affiliation that adds of mineral filler inevitably cause scattering of light and cause the transmittance of matrix material to descend.
To prepare in general the specific refractory power that the transparent polymer matrix material must guarantee filler (Refractive Index, RI) identical with macromolecule matrix.But the specific refractory power of mineral filler in most cases and epoxy matrix and unequal, if prepared nano composite material is a film like, the caused scattering of light that do not match of the specific refractory power of filler and matrix can obtain part by the particle diameter that reduces filler and compensates.For example: people (Journal of AppliedPolymer Science such as Mingna Xiong, Vol.90,1923-1931 (2003)), prepared polystyrene butyl acrylate latex/ZnO nano composite film by direct blending, its thickness is between 64-68um, the visible region transmittance descends above 10% when ZnO (60nm) content 3wt%, and content is that 5% o'clock visible region transmitance descends above 20%.But this compensation is limited when prepared material is bigger block of thickness, can not prepare the nano composite material of high filler content, for example we had once prepared transparent epoxy/ZnO nano composite material (Polymer, 47 (2006) 2127-2132), the adding of filler is little to the influence of the visible region transmittance of matrix material when ZnO content is lower than 0.07%, and the transmitance of visible region sharply descends when ZnO content surpasses 0.07%.When packing material size is too small in addition (as less than 20nm), packing specific area sharply increases, also aggravation thereupon of agglomeration, add the viscosity that can cause mixture behind the epoxy prepolymer and become between big, filler and basal body interface negative effects such as reactive force increase, thereby cause Nano filling to reunite serious and can not in epoxy matrix, effectively disperse.These agglomerating particless can cause scattering of light again in matrix material, thereby cause the decline of material transmittance.Therefore, the particle diameter that only reduces filler when the preparation transparent epoxy nano composite material is not enough, must guarantee that the specific refractory power and the epoxy matrix of filler are complementary.
Summary of the invention
The purpose of this invention is to provide a kind of visible light transmittance rate height, ultraviolet shielded effective, and have the low thermal expansivity and the transparent epoxy nano composite material of high thermal.
Another object of the present invention provides a kind of method for preparing above-mentioned transparent epoxy nano composite material.
A further object of the present invention provides a kind of purposes of above-mentioned transparent epoxy nano composite material.
Technical scheme of the present invention is as follows:
Transparent epoxy nano composite material provided by the invention comprises:
Epoxy resin-base material and the nanometer inorganic filler that is dispersed in this epoxy resin-base material is characterized in that described nanometer inorganic filler is the composite Nano mineral filler; Described composite Nano mineral filler comprises:
As the nano SiO 2 particle nuclear of nuclear, be coated on the titanium dioxide shell outside the nano SiO 2 particle nuclear and be coated on silica outer layer outside the titanium dioxide shell as shell;
The particle diameter of described nano SiO 2 particle nuclear is 10-1000nm;
Described nano SiO 2 particle nuclear is 76-64:23-31:1-5 with the weight part proportioning of titanium dioxide shell and silica outer layer;
The weight part proportioning of described composite Nano mineral filler and epoxy resin-base material is 0.1-30: 99.9-70;
The epoxy resin-base material that described epoxy resin-base material is its specific refractory power between the specific refractory power of the specific refractory power of silicon-dioxide and titanium dioxide.
Described epoxy resin-base material is made up of Resins, epoxy and epoxy hardener; The weight part proportioning of described Resins, epoxy and epoxy hardener is 0.8:1～1.2:1.
Described Resins, epoxy is bisphenol A type epoxy resin and is the bisphenol A type epoxy resin behind the process hydrogenation.
The preparation method of transparent epoxy nano composite material provided by the invention may further comprise the steps:
(1) preparation has the nano-complex particle of core/shell structure
The silica dioxide granule that with particle diameter is 10-1000nm is distributed in the polar organic solvent with ultrasonic or stirring means, and described polar solvent is methyl alcohol, dehydrated alcohol or ethylene glycol; The concentration of described silica dioxide granule in polar organic solvent is to be dispersed with 5-20 gram silica dioxide granules in every liter of polar organic solvent;
In the time at 1-10 hours under the stirring state, at the uniform velocity add 0.0189-0.121mol butyl (tetra) titanate (TBOT) again and react, constantly add entry in the time of reaction, make that the concentration of water remains on 0.2-0.4mol/L in the solution;
Continued stirring reaction 2-10 hours after adding butyl (tetra) titanate, just obtain containing the solution of nano-complex particle with nuclear-shell structure; Described have the nano-complex particle of core/shell structure by forming as the nano SiO 2 particle nuclear of nuclear with as the titanium dioxide skin outside the described nano SiO 2 particle nuclear of being coated on of shell;
(2) three layers of nano-complex particle of preparation
In above-mentioned solution, add entry and ammoniacal liquor, the concentration that makes water in the solution is 2-10mol/L, and the concentration of ammoniacal liquor is 0.05～0.2mol/L, after stirring, in 1-5 hours, add the 0.0011-0.026mol tetraethoxy, nano-complex particle is carried out finishing;
Continue to stir after 2-10 hours, centrifugation obtains white precipitate;
The gained white precipitate is carried out drying treatment, and 500-900 ℃ of down calcinings 0.5-2 hours, obtain coating the outer field three layers of nano-complex particle of layer of silicon dioxide again on the surface of the nano-complex particle of described core/shell structure;
In described three layers of nano-complex particle, be 76-64:23-31:1-5 as the described nano SiO 2 particle nuclear of nuclear and as the titanium dioxide shell of shell and the weight part proportioning of silica outer layer;
(3) three layers of nano-complex particle that step (2) is made evenly spread in the epoxy hardener, and then add Resins, epoxy and mix, and afterwards, solidify 0.5-15 hours down at 90-150 ℃, promptly obtain transparent epoxy nano composite material of the present invention; The weight part proportioning of described three layers of nano-complex particle and described epoxy hardener is 0.00022:1～0.78:1; The weight part proportioning of described Resins, epoxy and epoxy hardener is 0.8:1～1.2:1;
The particle diameter of described nano SiO 2 particle is 10-200nm.Described Resins, epoxy is the bisphenol A type epoxy resin behind bisphenol A type epoxy resin or the process hydrogenation.Described epoxy hardener is the acid anhydride type curing agent that contains the curing catalyst of 0.1～5.0wt%; Described curing catalyst is amine curing catalyst or imidazoles curing catalyst.Described acid anhydride type curing agent is methyl hexahydrophthalic anhydride or HHPA; Described amine curing catalyst is four butyl bromation amine or tetraethyl-amine bromide; Described imidazoles curing catalyst is imidazoles or glyoxal ethyline.
Transparent epoxy nano composite material of the present invention can be used for the encapsulation of photoelectric device or LED solid state lighting device.
In order to reduce the photocatalysis of titanium dioxide, strengthen the ultraviolet-resistant aging performance of transparent epoxy nano composite material, the present invention coats the layer of silicon dioxide skin at the outermost of the nano-complex particle S-T with core/shell structure, thus formation silicon-dioxide-titanium dioxide-gold/silicon dioxide nano complex particle (abbreviation S-T-S).
Specific refractory power is as a kind of inwardness of material itself, and the specific refractory power of control material is unrealistic arbitrarily.But Bohren and Huffman (Absorption and Scattering of Light by Small Particles, JohnWiley﹠amp; Sons, if Inc.1983) pointed out once that the particle with nucleocapsid structure can satisfy following relation, particle was then invisible when it was joined macromolecule matrix:
ε wherein
1, ε
2And ε
mBe respectively the specific inductivity of stratum nucleare, shell and macromolecule matrix material, a
1And a
2It is respectively the radius of nuclear and whole composite particles.Because ε=n
2So the specific refractory power of composite particles equals the specific refractory power of macromolecule matrix at this moment, that is:
N wherein
C-s, n
c, n
sBe respectively the specific refractory power of composite particles, nuclear, shell each several part, v
sIt is the volume fraction of shell.Because the volume fraction and the massfraction of material are corresponding, therefore when the specific refractory power of macromolecule matrix material between examine and the specific refractory power of shell material between the time, the stratum nucleare that then can be by regulating composite particles and the mass ratio of shell are regulated and control the specific refractory power of composite particles, make the specific refractory power of composite particles equal the specific refractory power of macromolecule matrix material, thereby prepare transparent composite.The present invention uses the nano SiO 2 particle of low-refraction as kernel, at the titanium dioxide of skin coating high refractive index, so the specific refractory power of epoxy resin-base material should be between between the two.
Compared with prior art, the present invention has following advantage:
1, the method for preparing transparent epoxy nano composite material provided by the invention, have the specific refractory power that the nano-complex particle of nucleocapsid structure is regulated Nano filling by preparation, overcome the light scattering phenomenon that existing nano composite material causes because of specific refractory power does not match.
2, the transparent epoxy nano composite material of method provided by the invention preparation at the visible region transmittance greater than 80%.
3, the epoxy nano composite material of method provided by the invention preparation has good ultraviolet shielded effect, can prevent ultraviolet leakage when being used for the encapsulation based on the white light LEDs of UV-light.
4, method provided by the invention has coated layer of silicon dioxide at the Nano filling skin, has reduced the photocatalysis of titanium dioxide; The epoxy composite material of preparation has good ultraviolet-resistant aging performance, is applicable to the outdoor environment under sunshine.
5, the transparent epoxy nano composite material of method preparation provided by the invention has good thermal characteristics, as lower thermal expansivity and high thermal.
Description of drawings
Fig. 1 prepares the technological line figure of transparent epoxy nano composite material
The optical photograph of Fig. 2 sample segment
Embodiment
Transparent epoxy nano composite material of the present invention is to realize by technological line as shown in Figure 1:
At first use low refractive index silica nano particle 1 as kernel, coat the titanium dioxide shell 2 of high refractive index, the specific refractory power 3 of recently regulating composite particles by the quality of control nuclear/shell at skin; Then the surface of nano-complex particle (S-T) with core/shell structure is handled 4, three layers of nano-complex particle that obtain having specific refractive index (are called for short S-T-S); Again it is distributed to the polymerization of epoxy resin-base material, can prepares transparent nano matrix material 5.
Further specify the present invention below by specific embodiment and Comparative Examples:
With the 5g particle diameter be 10nm spherical ultra-sonic dispersion in the 1L methanol solution, add 3.6g (0.2mol) H then
2It is 0.2mol/L that O makes the concentration of water in the solution.Under the stirring state, in above-mentioned solution, add 6.43g (0.0189mol) butyl (tetra) titanate (TBOT) in the 1h, add 1.36g (0.0756mol) H simultaneously
2O makes that the concentration of water remains on 0.2mol/L in the solution, continues stirred solution 2h and makes the butyl (tetra) titanate hydrolysis reaction complete, forms the composite nanoparticle (S-T) of coated by titanium dioxide silicon-dioxide.
In above-mentioned solution, add entry and ammoniacal liquor, make that the concentration of water and ammoniacal liquor reaches 2mol/L and 0.05mol/L respectively in the solution.After stirring, in 1h, add 0.23g (0.0011mol) tetraethoxy (TEOS), S-T composite nano-granule sub-surface is carried out coated with silica.After continuing to stir 2h, centrifugation obtains white precipitate, the dry back of gained precipitation is calcined 2h down at 500 ℃, obtains silica-titania-silicon-dioxide (S-T-S) composite nanoparticle (content of titanium dioxide is about 23wt%, and outer dioxide-containing silica is about 1wt%).
Prepared S-T-S composite nanoparticle 4.3g is joined (HHPA in the 5.5g epoxy hardener, comprising 0.5wt% tetraethyl-amine bromide) back adding 4.5g bisphenol A type epoxy resin is uniformly dispersed, after mixing, inject led die, curing molding can obtain transparent epoxy/S-T-S nano composite material (filler content is 30wt%) encapsulated LED.Concrete condition of cure is 150 ℃ and solidifies 0.5h down, solidifies 6h down at 110 ℃ then.Adopt the transparent epoxy nano composite material encapsulated LED of present embodiment preparation, have good transmitance at visible region, ultraviolet shielding effect is good, and the ultraviolet-resistant aging performance is good.
With the 10g particle diameter be 100nm spherical ultra-sonic dispersion in the 1L ethanolic soln, add 5.4g (0.3mol) H then
2It is 0.3mol/L that O makes the concentration of water in the solution.Under the stirring state, in above-mentioned solution, add 16.16g (0.0475mol) butyl (tetra) titanate (TBOT) in the 5h, add 3.42g (0.19mol) H simultaneously
2O makes that the concentration of water remains on 0.3mol/L in the solution, continues stirred solution 5h and makes the butyl (tetra) titanate hydrolysis reaction complete, forms the composite nanoparticle (S-T) of coated by titanium dioxide silicon-dioxide.
In above-mentioned solution, add entry and ammoniacal liquor, make that the concentration of water and ammoniacal liquor reaches 5mol/L and 0.1mol/L respectively in the solution.After stirring, in 2h, add 0.98g (0.0047mol) TEOS, S-T composite nano-granule sub-surface is carried out coated with silica.After continuing to stir 5h, centrifugation obtains white precipitate, the dry back of gained precipitation is calcined 1h down at 700 ℃, obtains silica-titania-silicon-dioxide (S-T-S) composite nanoparticle (content of titanium dioxide is about 27wt%, and outer dioxide-containing silica is about 2wt%).
Prepared S-T-S composite nanoparticle 1g is joined in the 25g epoxy hardener (methyl hexahydrophthalic anhydride the comprises the 2wt% four butyl bromation amine) back that is uniformly dispersed add the 25g bisphenol A epoxide resin.After mixing, inject led die, curing molding can obtain transparent epoxy/S-T-S nano composite material (filler content is 2wt%) encapsulated LED.Concrete condition of cure is 135 ℃ and solidifies 1h down that 100 ℃ solidify 10h down then.Adopt the transparent epoxy nano composite material encapsulated LED of present embodiment preparation, have good transmitance at visible region, ultraviolet shielding effect is good, and the ultraviolet-resistant aging performance is good.
With the 20g particle diameter be 1000nm spherical ultra-sonic dispersion in the 1L ethylene glycol solution, add 7.2g (0.4mol) H then
2It is 0.4mol/L that O makes the concentration of water in the solution.Under the stirring state, in above-mentioned solution, add 41.17g (0.121mol) butyl (tetra) titanate (TBOT) in the 10h, add 8.71g (0.484mol) H simultaneously
2O makes that the concentration of water remains on 0.4mol/L in the solution, continues stirred solution 10h and makes the butyl (tetra) titanate hydrolysis reaction complete, forms the composite nanoparticle (S-T) of coated by titanium dioxide silicon-dioxide.
In above-mentioned solution, add entry and ammoniacal liquor, make that the concentration of water and ammoniacal liquor reaches 10mol/L and 0.2mol/L respectively in the solution.After stirring, in 5h, add 5.43g (0.026mol) TEOS, S-T composite nano-granule sub-surface is carried out coated with silica.After continuing to stir 10h, centrifugation obtains white precipitate, the dry back of gained precipitation is calcined 0.5h down at 900 ℃, obtains silica-titania-silicon-dioxide (S-T-S) composite nanoparticle (content of titanium dioxide is about 31wt%, and outer dioxide-containing silica is about 5wt%).
Prepared S-T-S composite nanoparticle 0.1g is joined (methyl hexahydrophthalic anhydride comprises the 5wt% imidazoles, also can replace imidazoles with the 5wt%2-Methylimidazole) in the 45g epoxy hardener, and the back that is uniformly dispersed adds the bisphenol A epoxide resin behind the 55g hydrogenation.After mixing, inject led die, curing molding can obtain transparent epoxy/S-T-S nano composite material (filler content is 0.1wt%) encapsulated LED.Concrete condition of cure is 120 ℃ and solidifies 3h down, solidifies 12h down at 90 ℃ then.Adopt the transparent epoxy nano composite material encapsulated LED of present embodiment preparation, have good transmitance, have certain ultraviolet shielding effect, and the ultraviolet-resistant aging performance is good at visible region.
Comparative Examples 1
(methyl hexahydrophthalic anhydride comprises the 2wt% four butyl bromation amine) and 50g bisphenol A type epoxy resin mix in the 50g epoxy hardener, inject led die, and curing molding can obtain the transparent epoxy encapsulated LED of non-modified.Concrete condition of cure is 135 ℃ and solidifies 1h down that 100 ℃ solidify 10h down then.Adopt the transparent epoxy matrix material encapsulated LED of this Comparative Examples preparation, have good transmitance at visible region, but do not have ultraviolet shielding effect.
Comparative Examples 2
The spherical nanoparticle of 1g silicon-dioxide (the about 100nm of particle diameter) is joined in the 25g epoxy hardener (methyl hexahydrophthalic anhydride comprises the 2wt% four butyl bromation amine) the back adding 25g bisphenol A type epoxy resin that is uniformly dispersed.After mixing, under 135 ℃, solidify 1h, solidify 10h down at 100 ℃ then, obtain opaque epoxy/silicon dioxide nano composite material.Can not be used for the LED encapsulation.
Comparative Examples 3
With the 10g particle diameter be 100nm spherical ultra-sonic dispersion in the 1L ethanolic soln, add 5.4g (0.3mol) H then
2It is 0.3mol/L that O makes the concentration of water in the solution.In above-mentioned solution, add 25.5g (0.0075mol) butyl (tetra) titanate (TBOT) under the stirring state in the 5h, add 5.4g (0.0 3mol) H simultaneously
2O, make that the concentration of water remains on 0.3mol/L in the solution, continuing stirred solution 5h makes the butyl (tetra) titanate hydrolysis reaction complete, centrifugation obtains white precipitate, the dry back of gained precipitation is calcined 1h down at 700 ℃, obtain the composite nanoparticle (S-T) (silica core content is about 62.5wt%, and content of titanium dioxide is about 37.5wt%) of coated by titanium dioxide silicon-dioxide.
Prepared S-T composite nanoparticle 1g is joined in the 25g epoxy hardener (methyl hexahydrophthalic anhydride the comprises the 2wt% four butyl bromation amine) back that is uniformly dispersed add the 25g bisphenol A epoxide resin.After mixing, solidify down 1h in 135 ℃, solidify 10h down at 100 ℃ then, get final product epoxy/S-T nano composite material (filler content is 2wt%).Gained material visible-light district transmittance is very poor, can not be used for the encapsulation of LED.
Comparative Examples 4
With the 10g particle diameter be 100nm spherical ultra-sonic dispersion in the 1L ethanolic soln, add 5.4g (0.3mol) H then
2It is 0.3mol/L that O makes the concentration of water in the solution.In above-mentioned solution, add 16.15g (0.0475mol) butyl (tetra) titanate (TBOT) under the stirring state in the 5h, add 3.42g (0.19mol) H simultaneously
2O, make that the concentration of water remains on 0.3mol/L in the solution, continuing stirred solution 5h makes the butyl (tetra) titanate hydrolysis reaction complete, centrifugation obtains white precipitate, the dry back of gained precipitation is calcined the composite nanoparticle (S-T) (silica core content is about 72.5wt%, and content of titanium dioxide is about 27.5wt%) that 2h forms coated by titanium dioxide silicon-dioxide down at 500 ℃.
Prepared S-T composite nanoparticle 1g is joined in the 25g epoxy hardener (methyl hexahydrophthalic anhydride the comprises the 2wt% four butyl bromation amine) back that is uniformly dispersed add the 25g bisphenol A epoxide resin.After mixing, inject led die, curing molding can obtain transparent epoxy/S-T nano composite material (filler content is 2wt%) encapsulated LED.Concrete condition of cure is 135 ℃ and solidifies 1h down that 100 ℃ solidify 10h down then.Adopt the transparent epoxy matrix material encapsulated LED of this Comparative Examples preparation, have good transmitance at visible region, ultraviolet shielding effect is good, but the ultraviolet-resistant aging poor-performing.
Fig. 2 is the optical photograph of sample segment.
1, transmittance: adopt the Lambda900 ultraviolet-visible spectrophotometer that the optical property of embodiment 1～3 and Comparative Examples 1～4 resultant sample is tested, sweep limit is 250nm～850nm, and resolving power is 1nm.
2, light aging resisting property: the sample that employing embodiment 1, Comparative Examples 1 and Comparative Examples 4 obtain is to encapsulating the LED life-span after the test package based on the UV-light white light LEDs.
3, thermal expansivity: adopt elevated temperature heat to continue analyser RJY-2P, the sample that embodiment 1～3 and Comparative Examples 1 obtain is tested with the heat-up rate of 5 ℃/min.
The data that obtain are listed in table 1 respectively, in table 1, light transmission with transmittance (%) expression sample, in optical wavelength 400～800nm scope, be the visible region, this regional transmittance numerical value is high more, illustrate that light transmission is good more, be the UV-light zone below optical wavelength 400nm, this regional transmittance numerical value is low more, illustrates that ultraviolet screener efficient is high more; With the light aging resisting property of LED photoaging life-span (h) expression sample, this numerical value is high more, illustrates that light aging resisting property is good more; With the hot expansibility of thermal expansivity (um/m ℃) expression sample, the low more requirement that meets the photoelectric device encapsulation with material more of this numerical value.
As can be seen from Table 1, the transparent epoxy nano composite material of the present invention's preparation has good visible region light transmission, can compare favourably with common pure epoxy resin; The matrix material transmittance of doing filler with respect to pure silicon dioxide or titanium dioxide has obtained tangible improvement, thereby and this preparation method can obtain transparent composite material according to the specific refractory power that the specific refractory power of epoxy matrix is regulated filler.Compare with pure epoxy, the prepared matrix material of the present invention has good ultraviolet screener effect, can reach more than 99.5% for the ultraviolet screener efficient below the 350nm; The transparent epoxy nano composite material of the present invention preparation has good ultraviolet-resistant aging performance in addition, has improved 77% with respect to the common pure epoxy encapsulated LED life-span; Because filler outside coats layer of silicon dioxide, its light caloytic action is also weakened greatly, and with respect to the prepared matrix material of the outer field filler of coated silica not, the ultraviolet-resistant aging performance has improved 36%.It can also be seen that from table 1 that in addition with respect to common pure epoxy, the thermal expansivity of transparent epoxy nano composite material also greatly reduces.
Table 1
Claims (9)
1, a kind of transparent epoxy nano composite material comprises:
Epoxy resin-base material and the nanometer inorganic filler that is dispersed in this epoxy resin-base material is characterized in that described nanometer inorganic filler is the composite Nano mineral filler; Described composite Nano mineral filler comprises:
As the nano SiO 2 particle nuclear of nuclear, be coated on the titanium dioxide shell outside the nano SiO 2 particle nuclear and be coated on silica outer layer outside the titanium dioxide shell as shell;
The particle diameter of described nano SiO 2 particle nuclear is 10-1000nm;
Described nano SiO 2 particle nuclear is 76-64:23-31:1-5 with the weight part proportioning of titanium dioxide shell and silica outer layer;
The weight part proportioning of described composite Nano mineral filler and epoxy resin-base material is 0.1-30:99.9-70;
The epoxy resin-base material that described epoxy resin-base material is its specific refractory power between the specific refractory power of the specific refractory power of silicon-dioxide and titanium dioxide.
2, by the described transparent epoxy nano composite material of claim 1, it is characterized in that described epoxy resin-base material is made up of Resins, epoxy and epoxy hardener; The weight part proportioning of described Resins, epoxy and epoxy hardener is 0.8:1～1.2:1.
By the described transparent epoxy nano composite material of claim 2, it is characterized in that 3, described Resins, epoxy is bisphenol A type epoxy resin or is the bisphenol A type epoxy resin behind the process hydrogenation.
4, the preparation method of the described transparent epoxy nano composite material of a kind of claim 1 may further comprise the steps:
(1) preparation has the nano-complex particle of core/shell structure
The silica dioxide granule that with particle diameter is 10-1000nm is distributed in the polar organic solvent with ultrasonic or stirring means, and described polar solvent is methyl alcohol, dehydrated alcohol or ethylene glycol; The concentration of described silica dioxide granule in polar organic solvent is to be dispersed with 5-20 gram silica dioxide granules in every liter of polar organic solvent;
In the time at 1-10 hours under the stirring state, at the uniform velocity add the 0.0189-0.121mol butyl (tetra) titanate again and react, constantly add entry in the time of reaction, make that the concentration of water remains on 0.2-0.4mol/L in the solution;
Continued stirring reaction 2-10 hours after adding butyl (tetra) titanate, just obtain containing the solution of nano-complex particle with nuclear-shell structure; Described have the nano-complex particle of core/shell structure by forming as the nano SiO 2 particle nuclear of nuclear with as the titanium dioxide skin outside the described nano SiO 2 particle nuclear of being coated on of shell;
(2) three layers of nano-complex particle of preparation
In above-mentioned solution, add entry and ammoniacal liquor, the concentration that makes water in the solution is 2-10mol/L, and the concentration of ammoniacal liquor is 0.05～0.2mol/L, after stirring, in 1-5 hours, add the 0.0011-0.026mol tetraethoxy, nano-complex particle is carried out finishing;
Continue to stir after 2-10 hours, centrifugation obtains white precipitate;
The gained white precipitate is carried out drying treatment, and 500-900 ℃ of down calcinings 0.5-2 hours, obtain coating the outer field three layers of nano-complex particle of layer of silicon dioxide again on the surface of the nano-complex particle of described core/shell structure;
In described three layers of nano-complex particle, be 76-64:23-31:1-5 as the described nano SiO 2 particle nuclear of nuclear and as the titanium dioxide shell of shell and the weight part proportioning of silica outer layer;
(3) three layers of nano-complex particle that step (2) is made evenly spread in the epoxy hardener, and then add Resins, epoxy and mix, and afterwards, solidify 0.5-15 hours down at 90-150 ℃, promptly obtain transparent epoxy nano composite material of the present invention; The weight part proportioning of described three layers of nano-complex particle and described epoxy hardener is 0.00022:1～0.78:1; The weight part proportioning of described Resins, epoxy and epoxy hardener is 0.8:1～1.2:1;
5, by the preparation method of the described transparent epoxy nano composite material of claim 4, it is characterized in that the particle diameter of described nano SiO 2 particle is 10-200nm.
By the preparation method of claim 4 or 5 described transparent epoxy nano composite materials, it is characterized in that 6, described Resins, epoxy is the bisphenol A type epoxy resin behind bisphenol A type epoxy resin or the process hydrogenation.
7, by the preparation method of the described transparent epoxy nano composite material of claim 4, it is characterized in that described epoxy hardener is the acid anhydride type curing agent that contains the curing catalyst of 0.1～5.0wt%; Described curing catalyst is amine curing catalyst or imidazoles curing catalyst.
8, by the preparation method of the described transparent epoxy nano composite material of claim 7, it is characterized in that described acid anhydride type curing agent is methyl hexahydrophthalic anhydride or HHPA;
Described amine curing catalyst is four butyl bromation amine or tetraethyl-amine bromide;
Described imidazoles curing catalyst is imidazoles or glyoxal ethyline.
9, the purposes of the described transparent epoxy nano composite material of a kind of claim 1 is characterized in that, this transparent epoxy nano composite material is used for the encapsulation of photoelectric device or LED solid state lighting device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100809666A CN100509952C (en) | 2006-05-26 | 2006-05-26 | Transparent epoxy nano composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100809666A CN100509952C (en) | 2006-05-26 | 2006-05-26 | Transparent epoxy nano composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077923A CN101077923A (en) | 2007-11-28 |
| CN100509952C true CN100509952C (en) | 2009-07-08 |
Family
ID=38905603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100809666A Expired - Fee Related CN100509952C (en) | 2006-05-26 | 2006-05-26 | Transparent epoxy nano composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509952C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2009069429A1 (en) * | 2007-11-29 | 2011-04-07 | 日産化学工業株式会社 | Silica-containing epoxy curing agent and epoxy resin cured product |
| CN101661983B (en) * | 2008-08-26 | 2012-03-14 | 富准精密工业(深圳)有限公司 | Light emitting diode (LED) and preparation method thereof |
| CN101974245B (en) * | 2010-09-29 | 2013-07-03 | 北京化工大学 | High-transparent ultraviolet-blocking energy-saving membrane and solution phase transfer preparation method |
| CN102816402B (en) * | 2011-06-09 | 2015-08-05 | 北京化工大学 | A kind of highly-transparent ultraviolet-resistant imitates ceramic flexible nano composite film material and preparation method thereof |
| CN102286260A (en) * | 2011-06-28 | 2011-12-21 | 上海景涵实业有限公司 | Non-yellowing high-transmittance insulated epoxy adhesive for light emitting diode (LED) and preparation method and use thereof |
| CN102408681B (en) * | 2011-09-10 | 2014-07-23 | 广东东阳光铝业股份有限公司 | Composite material for packaging and preparation method thereof |
| JP5756054B2 (en) * | 2012-04-16 | 2015-07-29 | 信越化学工業株式会社 | Thermosetting resin composition for LED reflector, LED reflector and optical semiconductor device using the same |
| CN102926273B (en) * | 2012-10-26 | 2014-12-31 | 方少彬 | Nanoparticle-reinforced wallpaper paste and preparation method thereof |
| CN104118066B (en) * | 2014-08-29 | 2016-07-27 | 河南易成新能源股份有限公司 | The manufacture method of nano hybridization resin-diamond line |
| CN105694362B (en) * | 2014-11-27 | 2018-01-02 | 中国科学院化学研究所 | Light-shielding polymer nano composite material |
| CN104559422B (en) * | 2014-12-18 | 2016-08-17 | 益阳市资阳区明乐士涂料厂 | A kind of similar immiscible particle for ornament materials and preparation method thereof |
| CN106876145A (en) * | 2017-03-24 | 2017-06-20 | 湖北大学 | A kind of solar cell TiO2/SiO2Core shell structure light anode and preparation method thereof |
| CN108047499A (en) * | 2017-12-18 | 2018-05-18 | 苏州亿沃光电科技有限公司 | LED encapsulation nucleocapsid particles, epoxy composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189459A (en) * | 1998-01-09 | 1998-08-05 | 中国科学院固体物理研究所 | Nanometre titanium dioxide/silicon dioxide mesic hole compound and prepn. thereof |
| CN1244516A (en) * | 1999-08-10 | 2000-02-16 | 复旦大学 | Preparation of composite nanometer titania-silica material |
| US20020197475A1 (en) * | 2001-03-30 | 2002-12-26 | Degussa Ag | Organosilicon nano/microhybrid or microhybrid system composition for scratch and abrasion resistant coatings |
| CN1631995A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Spherical zinc oxide and titanium dioxide composite particles with particle structures on surfaces, and preparation method and application thereof |
| CN1663388A (en) * | 2004-03-03 | 2005-09-07 | 中国科学院理化技术研究所 | Tourmaline and titanium dioxide particle composite coated with micro mesoporous silicon dioxide on surface and preparation method and application thereof |
-
2006
- 2006-05-26 CN CNB2006100809666A patent/CN100509952C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189459A (en) * | 1998-01-09 | 1998-08-05 | 中国科学院固体物理研究所 | Nanometre titanium dioxide/silicon dioxide mesic hole compound and prepn. thereof |
| CN1244516A (en) * | 1999-08-10 | 2000-02-16 | 复旦大学 | Preparation of composite nanometer titania-silica material |
| US20020197475A1 (en) * | 2001-03-30 | 2002-12-26 | Degussa Ag | Organosilicon nano/microhybrid or microhybrid system composition for scratch and abrasion resistant coatings |
| CN1631995A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Spherical zinc oxide and titanium dioxide composite particles with particle structures on surfaces, and preparation method and application thereof |
| CN1663388A (en) * | 2004-03-03 | 2005-09-07 | 中国科学院理化技术研究所 | Tourmaline and titanium dioxide particle composite coated with micro mesoporous silicon dioxide on surface and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101077923A (en) | 2007-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509952C (en) | Transparent epoxy nano composite material and preparation method and application thereof | |
| CN101338066B (en) | Transparent epoxy nano composite material and preparation method and application thereof | |
| CN105765736B (en) | Ultraviolet-shielding type silicone adhesives piece used for encapsulation of solar battery and use its solar cell module | |
| CN106674852A (en) | Blue-ray-proof lens and resin raw material thereof | |
| CN108938450A (en) | A kind of lignin modification titanium dioxide granule and the preparation method and application thereof | |
| EP1817161A2 (en) | Optically reliable nanoparticle based nanocomposite hri encapsulant and photonic waveguiding material | |
| CN102690658A (en) | Quantum dot-embedded porous silicon dioxide composite material, and preparation method and application thereof | |
| CN101955728A (en) | Organic-inorganic hybrid wear-resistant transparent coating for reinforcing surface of optical plastics | |
| CN110408214B (en) | Preparation method of super-amphiphobic fluorescent micro-nano spheres | |
| CN104164209A (en) | Transparent addable curable LED filament packaging silicone | |
| CN105219100A (en) | A kind of organic silicon resin encapsulant for LED and preparation method thereof | |
| CN103554503A (en) | Preparation method of nanometer TiO2/silicon resin hybrid transparent composite material | |
| CN102079877A (en) | Preparation method for high-performance LED encapsulation material | |
| CN102516501A (en) | Photo-curing material for manufacturing light-emitting diode (LED) lens | |
| CN106047276A (en) | High-hardness high-adhesion modified high-heat conduction LED organosilicon package glue and preparation method thereof | |
| CN109844571A (en) | Antireflection material | |
| CN109651789A (en) | A kind of transparent polyester material and preparation method thereof with light absorption and solvent resistant cracking | |
| CN102876281A (en) | Preparation method for nano TiO2 modified high-refractive index organic silica gel for chip on board-light emitting diode (COB-LED) pressing strip | |
| CN100556954C (en) | Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing | |
| CN107177318A (en) | A kind of photovoltaic EVA adhesive film and preparation method thereof | |
| CN107573507A (en) | A kind of preparation method of big particle diameter polysiloxanes microballoon | |
| CN104610897B (en) | A kind of preparation method of the acrylic acid modified epoxy resin for LED encapsulation | |
| CN106098915A (en) | A kind of nano-perovskite modified silica-gel being applied to LED plant growth lamp chip package | |
| CN109957209B (en) | Epoxy resin composition, resin product, preparation method thereof and resin product | |
| CN103555250A (en) | High-transparency ultraviolet aging-resistant non-conductive chip adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: GUANGDONG ZHONGKE SHUNWEI NEW MATERIAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Assignor: Technical Institute of Physics and Chemistry Chinese Academy of Sciences Contract record no.: 2012440000368 Denomination of invention: Transparent epoxy nano composite material and its preparation method and use Granted publication date: 20090708 License type: Exclusive License Open date: 20071128 Record date: 20120706 |
|
| ASS | Succession or assignment of patent right |
Owner name: GUANGDONG CAS.SUNWILL NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: TECHNICAL INSTITUTE OF PHYSICS AND CHEMISTRY, CAS Effective date: 20121126 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100080 HAIDIAN, BEIJING TO: 523000 FOSHAN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121126 Address after: 523000 Guangdong city of Foshan province Shunde high tech Development Zone (Ronggui) Keyuan Road No. six of Patentee after: GUANGDONG ZHONGKE SHUNWEI NEW MATERIAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 100080 No. 2, north of Haidian District, Beijing, Zhongguancun Patentee before: Technical Institute of Physics and Chemistry Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 Termination date: 20170526 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |