CN1858112A - Anti-ultraviolet epoxy composition and preparation method and application thereof - Google Patents
Anti-ultraviolet epoxy composition and preparation method and application thereof Download PDFInfo
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- CN1858112A CN1858112A CNA200510068028XA CN200510068028A CN1858112A CN 1858112 A CN1858112 A CN 1858112A CN A200510068028X A CNA200510068028X A CN A200510068028XA CN 200510068028 A CN200510068028 A CN 200510068028A CN 1858112 A CN1858112 A CN 1858112A
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- epoxy
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 7
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- -1 glyoxaline compound Chemical class 0.000 claims description 20
- 239000006096 absorbing agent Substances 0.000 claims description 15
- 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 15
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 5
- FIAHSBPKJFNWDB-UHFFFAOYSA-N (6,6-dihydroxy-4,4-dimethoxycyclohex-2-en-1-yl)-phenylmethanone Chemical compound C1=CC(OC)(OC)CC(O)(O)C1C(=O)C1=CC=CC=C1 FIAHSBPKJFNWDB-UHFFFAOYSA-N 0.000 claims description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000852 hydrogen donor Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000008065 acid anhydrides Chemical group 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- VMNKHSPZIGIPLL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OCC(CO)(CO)COP(O)O VMNKHSPZIGIPLL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract 3
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- 238000005538 encapsulation Methods 0.000 description 7
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004844 aliphatic epoxy resin Substances 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 3
- 238000007539 photo-oxidation reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004078 cryogenic material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Led Device Packages (AREA)
Abstract
The invention relates to an anti-ultraviolet epoxy composition, a preparation method and application thereof. The curing agent is prepared by heating a mixture of 50-150 parts by weight of a curing agent, 0.1-5.0 parts by weight of a curing accelerator, 0.001-5.0 parts by weight of an ultraviolet stabilizer and 0.001-1 part by weight of a light scattering agent to 80-100 ℃ until the mixture is completely dissolved, cooling the mixture, and uniformly mixing the mixture with 100 parts by weight of epoxy resin. The ultraviolet-resistant epoxy composition can also comprise 0.1-3.0 parts by weight of antioxidant. The epoxy composition has excellent ultraviolet aging resistance and excellent heat resistance, and the glass transition temperature is higher than 130 ℃. It is colorless transparent liquid, and has light transmittance of 800nm higher than 91% and light transmittance of 450nm higher than 87%; the LED packaging structure is suitable for being used as a packaging of a white LED. When the LED is used for packaging white light LEDs based on ultraviolet light, the leakage of the ultraviolet light can be prevented, and the phenomenon of uneven luminous intensity of the LEDs can be improved.
Description
Technical field
The present invention relates to a kind of uvioresistant epoxy composition and its production and use.
Background technology
The semiconductor lighting device is one of the high-tech sector of tool development prospect of 21 century, since the nineties, along with gan is the semi-conductive rise of the third generation of representative, succeeding in developing of blue and white luminous diode, it is as new and effective solid light source, remarkable advantage with long, energy-conservation, environmental protection of life-span becomes the another leap after incandescent light, luminescent lamp on the human illumination history, and its economy and social effect are huge.
At present mainly adopt Resins, epoxy to come the encapsulated semiconductor illuminating device, for example, prior art uses bisphenol A type epoxy resin to encapsulate white light emitting diode (LED) based on UV-light usually.Because Resins, epoxy contains and can absorb ultraviolet aromatic series, bisphenol A type epoxy resin absorbs after the ultraviolet ray, and the meeting oxidation produces carbonyl and forms chromophoric group and causes the resin variable color, and its mechanism is shown in equation 1; In addition, meet after the heat also can variable color for Resins, epoxy; Resin variable color meeting and then cause the transmitance in short wavelength field to descend, this phenomenon is very big to the luminous luminosity influence of blue light and white light LEDs.Thereby the ultraviolet aging resistance performance to Resins, epoxy has very high requirement when adopting Resins, epoxy to come the encapsulated semiconductor illuminating device.
Equation 1
In general,, can adopt to allow ultraviolet ray see through fully, convert ultraviolet ray to heat energy discharge dual mode with utilizing UV light absorber in order to prevent ultraviolet ray ageing.Generally adopt the lower material of aliphatic epoxy resin and the ultraviolet radiation absorption amounts such as dihydroxyphenyl propane of adding hydrogen as main composition for the former people, lower with the ultraviolet radiation absorption amount again hardening accelerator combination reduces the ultraviolet radiation absorption amount of resin itself.But the thermostability of aliphatic epoxy resin is low than the thermostability of aromatic epoxy resin, the second-order transition temperature of aliphatic epoxy resin approximately is about 100 ℃, thereby the stability of the resin that is unfavorable for guaranteeing sealing semiconductor when using to possess welding with action the time, can produce reliability problems, even also thermo-color can take place.Therefore or cause a large amount of ultraviolet leakages and for utilizing UV light absorber to convert ultraviolet ray to method that heat energy is discharged, prior art also is difficult to realize the conversion fully of UV-light,, thereby human body is caused bad influence.
Summary of the invention
The objective of the invention is to overcome prior art and use bisphenol A type epoxy resin to come packaged LED, can cause the resin variable color, and then cause the transmitance in short wavelength field to descend, greatly the luminous luminosity influence of device; When adopting aliphatic epoxy resin as the main composition of packaged material, thermostability is low, stability when the resin that is unfavorable for guaranteeing sealing semiconductor can possess welding with action, can produce reliability problems, also the defective of thermo-color can take place, thereby provide that a kind of anti-ultraviolet aging performance is good, resistance toheat is high, can prevent ultraviolet leakage, can also improve the uvioresistant epoxy composition of LED luminous intensity inequality simultaneously.
Uvioresistant epoxy composition provided by the invention comprises following component:
Resins, epoxy 100 weight parts
Solidifying agent 50～150 weight parts
Curing catalyst 0.1～5.0 weight part
Ultra-violet stabilizer 0.001～5.0 weight part
Light scattering agent 0.001～1 weight part
Described Resins, epoxy is bisphenol A type epoxy resin (DGEBA), and its structure is suc as formula shown in the I:
Described solidifying agent is an acid anhydride type curing agent, for example: methyl hexahydrophthalic anhydride (MeHHPA), its structure is suc as formula shown in the II; Or HHPA (HHPA), its structure is shown in formula III; Preferable methyl HHPA (MeHHPA) wherein.
Described curing catalyst is amine or glyoxaline compound, as: four butyl bromation amine (TBAB), tetraethyl-amine bromide (TEAB), imidazoles (MZ), glyoxal ethyline (MMZ) etc., wherein preferred four butyl bromation amine (TBAB).
Described ultra-violet stabilizer is uv-absorbing agent, cancellation or radical scavenger.
Described uv-absorbing agent comprises organic uv absorbers and inorganic uv-absorbing agent; Described organic uv absorbers is benzophenone or benzotriazole compound; Wherein, the preferred 2,4 dihydroxyl benzophenone of benzophenone compound (BP-1), 2,2-dihydroxyl-4,4-dimethoxy-benzophenone (BP-2) or 2-hydroxyl-4-methoxy benzophenone (BP-3); The preferred 2-of benzotriazole compound (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole (BT-1) or 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole (BT-2); Described inorganic uv-absorbing agent is ZnO or TiO
2
Described cancellation or radical scavenger are hindered amine (HALS) class, as sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester (HS-1), poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) ester (HS-2), 1-(methyl)-8-(1,2,2,6,6-pentamethyl--4-piperidines) sebate (HS-3).
Described light scattering agent is TiO
2, BaTiO
3, ZnO, Al
2O
3, or SiO
2, wherein preferred TiO
2Or ZnO.
Above-mentioned uvioresistant epoxy composition provided by the invention also comprises: the oxidation inhibitor of 0.1～3.0 weight part.
Described oxidation inhibitor is hydrogen donor compound or hydrogen peroxide decomposition agent; Described hydrogen donor compound is the fortified phenol compounds, as 2,2 methylene radical-two (4-methyl-6-tert butyl phenol) (MBMBP); Described hydrogen peroxide decomposition agent is phosphite, phosphoric acid ester, thioether, dialkyl dithio amino formate or phosphorodithioate, preferred three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (TBP), alkyl alcohol pentaerythritol phosphite (618).
Above-mentioned uvioresistant epoxy composition provided by the invention is that above-mentioned each component except that Resins, epoxy is heated to 80～100 ℃ to all dissolvings, with this mixture and Resins, epoxy uniform mixing, can obtain the uvioresistant epoxy composition that is used for encapsulated semiconductor device of the present invention after the cooling.
The invention provides the application of a kind of above-mentioned uvioresistant epoxy composition on the encapsulated semiconductor illuminating device.Ordinary method according to the prior art encapsulation LED, uvioresistant epoxy composition provided by the invention is handled under vacuum condition to remove bubble wherein, inject the mould that LED is housed then, solidify 2h down in 130 ℃, take out LED behind the naturally cooling, be heated to 130 ℃ once more and keep 2h, to remove unrelieved stress and easy volatile component, the photodiode that can obtain encapsulating.
Compare with epoxy with existing LED encapsulation, uvioresistant epoxy composition provided by the invention has following advantage:
1, this epoxy composite has excellent anti-ultraviolet aging performance.
2, this epoxy composite has good resistance toheat, and second-order transition temperature is greater than 130 ℃.
3, this epoxy composite is a colourless transparent liquid, transmittance 800nm＞91%, 450nm＞87%; Suitable to white light LEDs, particularly based on the encapsulation of the white light LEDs of UV-light.
Can prevent ultraviolet leakage when 4, this epoxy composite is used for encapsulation based on the white light LEDs of UV-light.
Can improve the phenomenon of LED luminous intensity inequality when 5, this epoxy composite is used for the LED encapsulation.
Embodiment
Embodiment 1,
In the Erlenmeyer flask of 200ml, the HHPA (solidifying agent), the tetraethyl-amine bromide (curing catalyst) of 0.15 weight part, 1 weight part 2 that add 50 weight parts, 2 methylene radical-two (4-methyl-6-tert butyl phenol) (oxidation inhibitor), 0.001 weight part 2,4 dihydroxyl benzophenone (uv-absorbing agent), 0.001 weight part BaTiO
2(absorption agent and scattering diluent) is heated to 80 ℃ under the magnetic agitation, thing to be mixed all dissolves, and is cooled to room temperature.Add the bisphenol A type epoxy resin DGEBA of 100 weight parts, stir, promptly obtain uvioresistant epoxy composition I of the present invention.
Comparative example 1#,
In the Erlenmeyer flask of 200ml, add the methyl hexahydrophthalic anhydride (solidifying agent) of 77 weight parts, the four butyl bromation amine (curing catalyst) of 1 weight part, be heated to 100 ℃ under the magnetic agitation, thing to be mixed all dissolves, and is cooled to room temperature.Add the bisphenol A type epoxy resin DGEBA of 100 weight parts, stir, obtain uvioresistant epoxy composition I#.
Embodiment 2～10
According to the different uvioresistant epoxy composition II～X that form of method preparation of embodiment 1, it is formed and content is listed in table 1.
The composition of table 1, uvioresistant epoxy composition and content (all in weight part)
| Embodiment | Resins, epoxy DGEBA | Solidifying agent | Curing catalyst | Ultra-violet stabilizer | Light scattering agent | Oxidation inhibitor | |||||
| Kind | Content | Kind | Content | Kind | Content | Kind | Content | Kind | Content | ||
| 1 | 100 | HHPA | 50 | TEAB | 0.15 | BP-1 | 0.001 | BaTiO 3 | 0.001 | MBMBP | 1 |
| 2 | 100 | MeHHPA | 150 | TBAB | 4.5 | BP-2 BT-1 | 0.5 0.5 | Al 2O 3 | 0.1 | 168 | 0.1 |
| 3 | 100 | MeHHPA | 77 | TBAB | 1 | BP-3 BT-2 | 2 0.5 | SiO 2 | 1 | TBP | 0.1 |
| 4 | 100 | MeHHPA | 77 | MZ | 1 | BP-2 BT-1 HS-1 | 2 0.05 0.5 | TiO 2 ZnO | 0.005 0.1 | MBMBP | 1.5 |
| 5 | 100 | MeHHPA | 77 | MMZ | 1 | BP-1 BP-2 BP-3 HS-1 | 1 2 1.9 0.1 | TiO 2 ZnO | 0.05 0.1 | TBP | 1.5 |
| 6 | 100 | MeHHPA | 77 | TBAB | 1 | BP-1 HS-2 | 1 0.1 | TiO 2 ZnO | 0.05 0.1 | MBMBP TBP | 1.5 1.5 |
| 7 | 100 | MeHHPA | 77 | TBAB | 0.1 | BP-2 HS-1 | 1 0.05 | TiO 2 | 0.001 | TBP | 0.5 |
| 8 | 100 | MeHHPA | 77 | TBAB | 5 | BP-3 HS-2 | 1 0.05 | ZnO | 0.1 | MBMBP | 0.5 |
| 9 | 100 | MeHHPA | 77 | TBAB | 1 | BT-1 HS-3 | 0.05 0.01 | ZnO | 0.15 | MBMBP | 1 |
| 10 | 100 | MeHHPA | 77 | TBAB | 1 | BT-2 HS-3 | 0.05 0.05 | ZnO TiO 2 | 0.1 0.005 | MBMBP TBP | 0.5 0.5 |
| 1 # | 100 | MeHHPA | 77 | TBAB | 1 | ||||||
Embodiment 11,
With embodiment 1～10 and comparative example 1
#Uvioresistant epoxy composition I～the X and the I of preparation
#After vacuum defoamation, 130 ℃ solidify 2h in baking oven, take out sample behind the furnace cooling.And then be heated to 130 ℃ of maintenance 2h, to remove unrelieved stress and easy volatile component.Then sample is carried out photooxidation aging property, mechanical property, thermal performance test respectively, the data that obtain are listed in table 2.
1, photooxidation aging property: the employing wavelength is that the luminescent lamp Q-UV Tester of 340nm carries out the irradiation of 1000h, and sample is used the transmitance of Agilengt 8453UV-visible Spectroscopy System ultraviolet-visible pectrophotometer working sample respectively behind pre-irradiation.
2, mechanical property: the anti-reflecting bending strength test of sample is measured according to ATSM D638-01 standard on the breadboard RGT-20A trier of physics and chemistry institute of Chinese Academy of Sciences cryogenic material.
3, thermal characteristics: heat analysis is carried out on SP43320 structural synthesis thermal analyzer.
The photooxidation aging property of table 2, uvioresistant epoxy composition, mechanical property and thermal characteristics
| Physical properties | Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1# | ||
| Initial transmission (%) | 450nm | 88 | 88 | 88 | 86 | 87 | 87 | 87 | 87 | 88 | 87 | 88 |
| 800nm | 92 | 92 | 92 | 91 | 91 | 91 | 91 | 90 | 92 | 92 | 92 | |
| 380nm | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 78 | |
| After the UV-irradiation (%) | 450nm | 65 | 73 | 70 | 74 | 70 | 74 | 76 | 78 | 80 | 81 | 60 |
| 800nm | 69 | 78 | 74 | 80 | 75 | 79 | 81 | 84 | 85 | 88 | 66 | |
| Second-order transition temperature (℃) | 130 | 133 | 136 | 129 | 133 | 137 | 138 | 135 | 134 | 138 | 135 | |
| Bending strength (MPa) | 100 | 98 | 108 | 101 | 102 | 109 | 106 | 105 | 108 | 107 | 106 | |
The epoxy composite of the present invention's preparation is a colourless transparent liquid, as can be seen from Table 2, and its transmittance 800nm＞91%, 450nm＞87%; Suitable to white light LEDs, particularly based on the encapsulation of the white light LEDs of UV-light.Compare with the common bisphenol A-type resin of comparative example, its ultraviolet aging resistance performance is significantly improved, and the transmitance of uvioresistant epoxy composition at the 380nm place of the present invention preparation be 0, has prevented ultraviolet leakage problem fully.This epoxy composite has good resistance toheat, and the adding of anti ultraviolet agent and light scattering agent does not influence the thermal characteristics of epoxy itself, and its second-order transition temperature is greater than 130 ℃.
Through LED encapsulation actual measurement, the uvioresistant epoxy composition of the present invention's preparation can also improve the unequal phenomenon of white light LEDs luminous intensity.
Claims (10)
1, a kind of uvioresistant epoxy composition comprises following component:
Resins, epoxy 100 weight parts
Solidifying agent 50～150 weight parts
Curing catalyst 0.1～5.0 weight part
Ultra-violet stabilizer 0.001～5.0 weight part
Light scattering agent 0.001～1 weight part
Described Resins, epoxy is bisphenol A type epoxy resin:
Described solidifying agent is an acid anhydride type curing agent;
Described curing catalyst is amine or glyoxaline compound;
Described ultra-violet stabilizer is uv-absorbing agent, cancellation or radical scavenger; Wherein, described uv-absorbing agent comprises organic uv absorbers and inorganic uv-absorbing agent; Described organic uv absorbers is benzophenone or benzotriazole compound; Described inorganic uv-absorbing agent is ZnO or TiO
2Described cancellation or radical scavenger are hindered amine compound;
Described light scattering agent is TiO
2, BaTiO
3, ZnO, Al
2O
3, or SiO
2
2, uvioresistant epoxy composition as claimed in claim 1 is characterized in that: described acid anhydride type curing agent is methyl hexahydrophthalic anhydride or HHPA.
3, uvioresistant epoxy composition as claimed in claim 1 is characterized in that: described aminated compounds is four butyl bromation amine or tetraethyl-amine bromide; Described glyoxaline compound is imidazoles or glyoxal ethyline.
4, uvioresistant epoxy composition as claimed in claim 1 is characterized in that: described benzophenone compound is a 2,4 dihydroxyl benzophenone, 2,2-dihydroxyl-4,4-dimethoxy-benzophenone or 2-hydroxyl-4-methoxy benzophenone; Described benzotriazole compound is 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole or 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole.
5, uvioresistant epoxy composition as claimed in claim 1 is characterized in that: described hindered amine compound is a sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester, poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) ester, 1-(methyl)-8-(1,2,2,6,6-pentamethyl--4-piperidines) sebate.
6, uvioresistant epoxy composition as claimed in claim 1 is characterized in that: also comprise the oxidation inhibitor of 0.1～3.0 weight part, described oxidation inhibitor is hydrogen donor compound or hydrogen peroxide decomposition agent.
7, uvioresistant epoxy composition as claimed in claim 6 is characterized in that: described hydrogen donor compound is the fortified phenol compounds; Described hydrogen peroxide decomposition agent is phosphite, phosphoric acid ester, thioether, dialkyl dithio amino formate or phosphorodithioate.
8, uvioresistant epoxy composition as claimed in claim 7 is characterized in that: described fortified phenol compounds is 2,2 methylene radical-two (4-methyl-6-tert butyl phenol); Described phosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester or alkyl alcohol pentaerythritol phosphite.
9, a kind of method for preparing the described uvioresistant epoxy composition of one of claim 1～8, mixture heating up to 80～100 ℃ extremely all dissolvings with above-mentioned each component except that Resins, epoxy, with this mixture and Resins, epoxy uniform mixing, obtain uvioresistant epoxy composition of the present invention after the cooling.
10, the application of the described uvioresistant epoxy composition of one of a kind of claim 1～8 on the encapsulated semiconductor illuminating device.
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Assignee: GUANGDONG ZHONGKE SHUNWEI NEW MATERIAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Assignor: Technical Institute of Physics and Chemistry Chinese Academy of Sciences Contract record no.: 2012440000370 Denomination of invention: Uvioresistant epoxy composition and its preparing method and use Granted publication date: 20071205 License type: Exclusive License Open date: 20061108 Record date: 20120706 |
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