CN100556954C - Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing - Google Patents
Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing Download PDFInfo
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- CN100556954C CN100556954C CNB2006100838461A CN200610083846A CN100556954C CN 100556954 C CN100556954 C CN 100556954C CN B2006100838461 A CNB2006100838461 A CN B2006100838461A CN 200610083846 A CN200610083846 A CN 200610083846A CN 100556954 C CN100556954 C CN 100556954C
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Abstract
The invention belongs to the composition epoxy resin field, particularly be suitable for the organic silicon epoxy resin composition of large-power light-emitting diodes encapsulation with anti-ultraviolet and high temperature ageing.The component of said composition and content are: molecular structure contains organosilicon epoxy resin 100 weight parts of at least one Si-H group and (seeing a right formula) group simultaneously, and other Resins, epoxy is greater than 0 smaller or equal to 200 weight parts, catalyzer 0.01～0.1 weight part; Described catalyzer is beta diketone metal complex, β ketone fat metal complex or their mixture.By blend, cast, curing molding.Composition of the present invention has good optical transparence and good uvioresistant, high-temperature aging resisting performance, can be used for the packaged material of luminous or optics or as optical adhesive, is particularly suitable for the packaged material as great power LED.
Description
Technical field
The invention belongs to the composition epoxy resin field, particularly be suitable for the organic silicon epoxy resin composition of large-power light-emitting diodes (LED) encapsulation with anti-ultraviolet and high temperature ageing.
Background technology
Resins, epoxy is owing to have high optical transparence, and excellent mechanical property, adhesiveproperties and processing performance are used as the encapsulation that packaged material is widely used in light emitting diode (LED).But for white light LEDs, owing to be subjected to the ultraviolet irradiation that comes out from blue chip or purple light chip, add the thermal ageing that chip temperature raises and causes, the phenomenon of performance degradation can take place in Resins, epoxy in application, as the resin flavescence, transmittance obviously descends, thereby greatly reduces the work-ing life of device.To white light LEDs high-power, high light efficiency, this problem is especially outstanding.This also is one of key issue of occurring in application of white light LEDs.In order to address this problem, can adopt anti-ultraviolet, better optically transparent material such as the organic silicon materials of high temperature resistant aging resistance on the one hand.But the processing performance of organosilicon material, intensity and adhesiveproperties all are not so good as Resins, epoxy.Can carry out modification to Resins, epoxy on the other hand, when keeping its feature performance benefit, improve its anti-ultraviolet, high temperature resistant aged performance.
From the research of having delivered, by organic-silicon-modified be the main path of preparation anti-ultraviolet, high temperature resistant aging LED epoxy resin encapsulating material.Because the consistency of Resins, epoxy and silicone resin is poor, the method for modification mainly is a chemical modification, just the organosilicon segment is incorporated in the molecular structure of Resins, epoxy, and is disclosed as United States Patent (USP) (USP6632892,2003); The way that physical blending is also arranged, the consistency such as the United States Patent (USP) (USP6800373,2004) that improve organosilicon and Resins, epoxy by the method for adding tensio-active agent are disclosed.The shortcoming of above-mentioned patented method is to need to use anhydride curing agent, and the ultra-violet resistance energy and the high temperature ageing performance of material are reduced.
The previous patent of invention of applying for of the inventor " anti-ultraviolet and high temperature ageing composition epoxy resin " (application number 200510130312.5) has overcome the shortcoming of above-mentioned patented method.Do not need to add acid anhydride type curing agent, and under the effect of little amount of catalyst, making organosilicon epoxy resin be solidified into high material transparent, and having good ultra-violet resistance energy and high temperature resistant aging resistance.Described catalyzer is made up of organosilicon alkylol cpd and beta diketone metal complex.
Another advantage of the curing that above-mentioned patent adopted is that the Si-H group in the organosilicon epoxy resin molecular structure does not influence curing reaction, and when using anhydride-cured, acid anhydrides meeting and Si-H radical reaction releasing hydrogen gas produce bubble thereby make in the last cured article.Therefore adopt above-mentioned curing, by addition reaction of silicon with hydrogen synthesizing organo-silicon Resins, epoxy the time, whether the reaction of Si-H group do not required fully, and if adopt anhydride-cured, the Si-H group must react completely.Because whether the reaction to the Si-H group does not require fully, can the organosilicon content of organosilicon epoxy resin be improved greatly, and can in certain scope, adjust so that the productive rate of reaction improves greatly on the one hand.The inventor finds, in the structure of organic epoxy silicone, contain simultaneously Si-H and
During group, when being the composition curing of organosilicon alkylol cpd and beta diketone metal complex, has higher reactive behavior with the described catalyzer of above-mentioned patent.Studies show that further if remove organic silanol in the above-mentioned catalyst combination, organosilicon epoxy resin equally can curing molding, and has very high reactive behavior.Owing to do not use organic silanol, make the transparency of organosilicon epoxy resin cured article better.The inventor finds simultaneously, contains anti-ultraviolet and high temperature ageing performance that the Si-H group can further improve organosilicon epoxy resin in the molecular structure.This may be because the Si-H group has reductibility, thereby can effectively eliminate free radical or the superoxide that material internal produces under ultraviolet and high temperature ageing.
Summary of the invention
The objective of the invention is to overcome existing epoxy resin encapsulating material ultra-violet resistance energy and the low defective of high temperature ageing performance, the organic silicon epoxy resin composition of a kind of LED package with anti-ultraviolet and high temperature ageing is provided, do not needing to add acid anhydride type curing agent, and under the effect of little amount of catalyst, make organosilicon epoxy resin be solidified into high material transparent, and have good ultra-violet resistance energy and high temperature resistant aging resistance.
Photodiode of the present invention (LED) encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing, and in weight part, the component of said composition and content are:
100 parts of organosilicon epoxy resins,
Other Resins, epoxy is greater than 0 smaller or equal to 200 parts,
0.01～0.1 part of catalyzer.
Preferred ingredient and content are:
100 parts of organosilicon epoxy resins,
Other Resins, epoxy is greater than 0 smaller or equal to 100 parts,
0.025～0.075 part of catalyzer.
Contain at least one Si-H group and one in each molecule of described organosilicon epoxy resin simultaneously
Group, described organosilicon epoxy resin has following structure:
Wherein: R
1Be CH
3Or C
6H
5R
2Be C
aH
2a, a 〉=2; R
3, R
4Be H, CH
3Or C
6H
5Re is CH
3Or
R wherein
2Be C
aH
2a, a 〉=2;
m+n＝4，m＝0～2；m1＝0～500，n1＝0～500。
Above-mentioned organosilicon epoxy resin can carry out addition reaction of silicon with hydrogen with the alkene that contains the epoxy group(ing) cyclohexyl by corresponding hydrogen containing siloxane and prepare.As document Journal of Polymer Science:Part A:Polymer Chemistry, Vol.28,479～503 (1990) report.
Described other Resins, epoxy is selected from cycloaliphatic epoxy resin, bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, the mixture of one or more in the novolac epoxy etc.These resins can the regulating ring epoxy resins solidification rate, cured epoxy resin second-order transition temperature and reduce cost.
Described catalyzer comprises beta diketone metal complex, β ketone fat metal complex or their mixture.
Described beta diketone metal complex or β ketone fat metal complex are that structure is X-CO-CH
2Metal complexs such as the copper of-CO-Y, cobalt, zinc, zirconium, aluminium, manganese, chromium, nickel.Wherein X is CH
3, C
6H
5Perhaps C (CH
3)
3, Y is CH
3, C (CH
3)
3, OC (CH
3)
3Perhaps OC
nH
2n+1, n=1～4 wherein.
In order to operate the convenience with technology, can catalyst component be dissolved in other the Resins, epoxy earlier, as bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, other organosilicon epoxy resin that does not contain the Si-H group, the mixture of one or more in the novolac epoxy, the mass percentage concentration of catalyzer are 0.5～5%.
If catalyst consumption is too low among the present invention, will make that solidification value curing too high or Resins, epoxy is incomplete.If catalyst consumption is too high, might causes the initial coloration of cured epoxy resin, and make anti-ultraviolet, the high temperature ageing degradation of cured epoxy resin.
Characteristics of the present invention are the catalyzer that only need to use minute quantity, do not use solidifying agent such as acid anhydride type curing agent.Therefore initial coloration or anti-ultraviolet and the high temperature ageing performance decrease that solidifying agent and catalyzer bring can be avoided or reduce effectively, also organosilyl content in the cured article can be improved greatly.In addition, owing to contain Si-H group in the structure, the anti-ultraviolet of organosilicon epoxy resin and high temperature resistant aging resistance are further enhanced with reductibility.So the organic silicon epoxy resin composition of anti-ultraviolet of the present invention and high temperature ageing has excellent ultra-violet resistance energy and high temperature ageing performance.The organic silicon epoxy resin composition of anti-ultraviolet of the present invention and high temperature ageing has kept good processing performance, optical clear performance and the mechanical property that Resins, epoxy had simultaneously.
Photodiode of the present invention (LED) encapsulation with the organic silicon epoxy resin composition of anti-ultraviolet and high temperature ageing in use, by blend, cast, curing molding.Concrete preparation process is as follows: at first will contain at least one Si-H and one in the molecular structure simultaneously
The organosilicon epoxy resin of group and other Resins, epoxy mix, and add catalyzer then and mix, and remove bubble under vacuum, are poured in the mould to be cured.Curing can be carried out in a step, and temperature is 110～150 ℃, and according to the difference of temperature, be 10 minutes to 2 hours set time.Also can carry out in two steps, at first carry out Procuring under 60～100 ℃, according to the difference of temperature, be 5 to 30 minutes set time, carries out after fixing then under 110～150 ℃.
Because composition of the present invention has good optical transparence and good uvioresistant, high-temperature aging resisting performance, therefore can be used for the packaged material of luminous or optics or be used as optical adhesive, be particularly suitable for as the packaged material of great power LED or as optical adhesive.
Description of drawings
Fig. 1. the variation of transmittance before and after the embodiment of the invention 4 ultraviolet ageings.
Fig. 2. the variation of transmittance before and after the embodiment of the invention 4 high temperature ageings.
Fig. 3. the variation of transmittance before and after the embodiment of the invention 5 ultraviolet ageings.
Fig. 4. the variation of transmittance before and after the embodiment of the invention 5 high temperature ageings.
Embodiment
Specify the present invention below by specific embodiment, but the present invention is not limited to following embodiment.
Embodiment 1: organosilicon epoxy resin A's is synthetic
In the there-necked flask of 300ml, add 4-vinyl cyclohexyl 1,2 epoxy compounds 24.8 grams (0.2mol), tetramethyl-tetrahydrochysene cyclotetrasiloxane 18.0 grams (0.075mol), toluene 40ml.System is warming up to 70～75 ℃, adds 5～10ppm (in the gross weight of reactant) chloroplatinic acid catalyst, reacted 5 hours.After reaction finished, adding 0.002 gram di-mercaptobenzothiazolby also stirred 10 minutes.Solvent and unreacted reactant are removed under 2mmHg/80 ℃ with Rotary Evaporators then, obtained water white transparency Resins, epoxy A 41.6 grams, productive rate is about 97%.
Embodiment 2: organosilicon epoxy resin B's is synthetic
In the there-necked flask of 300ml, add 4-vinyl cyclohexyl 1,2 epoxy compounds 24.8 grams (0.2mol), tetramethyl-tetrahydrochysene cyclotetrasiloxane 24.0 grams (0.1mol), toluene 50ml.System is warming up to 70～75 ℃, adds 5～10ppm (in the gross weight of reactant) chloroplatinic acid catalyst, reacted 5 hours.After reaction finished, adding 0.002 gram di-mercaptobenzothiazolby also stirred 10 minutes.Solvent and unreacted reactant are removed under 2mmHg/80 ℃ with Rotary Evaporators then, obtained water white transparency Resins, epoxy B 46.5 grams, productive rate is about 95%.
Embodiment 3: the configuration of catalyzer
In the 20ml beaker, add 2g bisphenol A epoxide resin and 0.04g aluminium acetylacetonate.Beaker is put into 120 ℃ of baking ovens, treat that aluminium acetylacetonate is dissolved in after the Resins, epoxy to take out, be cooled to after the room temperature standby.
Embodiment 4: organic silicon epoxy resin composition
Organosilicon epoxy resin A that adding 2g obtains in embodiment 1 in beaker and the catalyzer that in embodiment 3, obtains 0.01 gram.The final vacuum deaeration stirs.Be poured into then in the mould of polycarbonate or silicon rubber.The baking oven of putting into 90 ℃ solidifies taking-up after 10 minutes.Solidified 30 minutes down at 130 ℃ then, obtain water white epoxy resin cured product sample, thickness of sample is 3mm.Cured article in the transmitance of different wave length and through the thermal ageing of 150 ℃/24hr and the transmitance behind the ultraviolet light and aging as depicted in figs. 1 and 2.The mercury lamp irradiation of 500W is used in the ultraviolet ageing experiment, and its radiating wavelength region is 250～320nm, and sample is 35cm apart from the distance of fluorescent tube, and irradiation time is 12 hours.
Embodiment 5: organic silicon epoxy resin composition
Remove the organosilicon epoxy resin B that Resins, epoxy A changes embodiment 2 into, other condition is with embodiment 4.Cured article in the transmitance of different wave length and through the thermal ageing of 150 ℃/24hr and the transmitance behind the UV-irradiation 12hr as shown in Figure 3 and Figure 4.
Comparative example 1
In beaker, add the 1.6g hexahydrophthalic anhydride respectively, the 0.04g Tetrabutyl amonium bromide.Put into 130 ℃ of baking ovens, treat that Tetrabutyl amonium bromide takes out after being dissolved in hexahydrophthalic anhydride.After temperature is cooled to room temperature, in beaker, adds 2 gram bisphenol A epoxide resins, and stir.Be poured into then in the mould of polycarbonate or silicon rubber, and put into 130 ℃ baking oven and solidify after 30 minutes and take out.Obtain water white epoxy resin cured product.Cured article is in the transmitance of different wave length and through thermal ageing transmitance such as Fig. 2 and shown in Figure 4 of 150 ℃/24hr.
Comparative example 2
Remove Resins, epoxy and change into outside cycloaliphatic epoxy resin ERL4221 (3,4 epoxy-cyclohexane formic acid-3 ', the 4 ' epoxy-cyclohexane methyl esters) Resins, epoxy, other condition is with comparative example 1.Cured article in the transmitance of different wave length and through the transmitance behind the UV-irradiation 12hr as shown in figures 1 and 3.
Claims (4)
1. a LED package is characterized in that in weight part, the component of said composition and content are with the organic silicon epoxy resin composition of anti-ultraviolet and high temperature ageing:
100 parts of organosilicon epoxy resins,
Other Resins, epoxy is greater than 0 smaller or equal to 200 parts,
0.01～0.1 part of catalyzer;
Contain at least one Si-H group and one in each molecule of described organosilicon epoxy resin simultaneously
Group, described organosilicon epoxy resin has following structure:
Wherein: R
1Be CH
3Or C
6H
5R
2Be C
aH
2a, a=2; R
3, R
4Be H, CH
3Or C
6H
5Re is CH
3Or
R wherein
2Be C
aH
2a, a=2;
m+n＝4，m＝0～2；m1＝0～500，n1＝0～500；
Described catalyzer is beta diketone metal complex, β ketone fat metal complex or their mixture.
2. composition according to claim 1 is characterized in that, in weight part, the component of said composition and content are:
100 parts of organosilicon epoxy resins,
Other Resins, epoxy is greater than 0 smaller or equal to 100 parts,
0.025～0.075 part of catalyzer.
3. composition according to claim 1 and 2 is characterized in that: described other Resins, epoxy is selected from cycloaliphatic epoxy resin, bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, the mixture of one or more in the novolac epoxy.
4. composition according to claim 1 is characterized in that: described beta diketone metal complex or β ketone fat metal complex are that structure is X-CO-CH
2The copper of-CO-Y, cobalt, zinc, zirconium, aluminium, manganese, chromium, nickel metal complex; Wherein X is CH
3, C
6H
5Perhaps C (CH
3)
3Y is CH
3, C (CH
3)
3Perhaps OC
nH
2n+1, n=1～4 wherein.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100838461A CN100556954C (en) | 2006-06-05 | 2006-06-05 | Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100838461A CN100556954C (en) | 2006-06-05 | 2006-06-05 | Light emitting diode encapsulates the organic silicon epoxy resin composition with anti-ultraviolet and high temperature ageing |
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| CN100556954C true CN100556954C (en) | 2009-11-04 |
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| CN101921571B (en) * | 2010-08-13 | 2014-11-05 | 王行柱 | High-temperature resistant packaging adhesive for high-power LED lamp and preparation method thereof |
| CN102353883B (en) * | 2011-06-14 | 2013-07-10 | 中国电子科技集团公司第十三研究所 | High temperature aging device for microwave transistor |
| CN102516500B (en) * | 2011-11-30 | 2014-03-26 | 浙江中宙光电股份有限公司 | Organic silicon modified epoxy resin for packaging LED (Light Emitting Diode), and preparation method and application thereof |
| CN110527300B (en) * | 2019-09-17 | 2021-08-27 | 四川大学 | High-strength epoxy-silicone rubber modified material with interpenetrating network structure |
| CN110591375B (en) * | 2019-09-17 | 2021-08-27 | 四川大学 | High-performance epoxy-silicone rubber modified material with interpenetrating network structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112146A (en) * | 1994-03-25 | 1995-11-22 | 信越化学工业株式会社 | Silicone rubber/epoxy resin integral composite and method for making |
| WO1998033645A1 (en) * | 1997-02-04 | 1998-08-06 | Polyset Company, Inc. | Die adhesive or encapsulant of epoxy siloxane and polyepoxy resin |
| EP1010727A2 (en) * | 1998-12-17 | 2000-06-21 | Rhodia Inc. | Release composition |
| CN1432601A (en) * | 2002-01-17 | 2003-07-30 | 佳能株式会社 | Epoxy resin composition, surface treatment method, liquid jetting record head and liquid jeeint recorder |
-
2006
- 2006-06-05 CN CNB2006100838461A patent/CN100556954C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112146A (en) * | 1994-03-25 | 1995-11-22 | 信越化学工业株式会社 | Silicone rubber/epoxy resin integral composite and method for making |
| WO1998033645A1 (en) * | 1997-02-04 | 1998-08-06 | Polyset Company, Inc. | Die adhesive or encapsulant of epoxy siloxane and polyepoxy resin |
| EP1010727A2 (en) * | 1998-12-17 | 2000-06-21 | Rhodia Inc. | Release composition |
| CN1432601A (en) * | 2002-01-17 | 2003-07-30 | 佳能株式会社 | Epoxy resin composition, surface treatment method, liquid jetting record head and liquid jeeint recorder |
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Assignee: Beijing SHOUKEHUA Micro-Electronics Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract record no.: 2011990000641 Denomination of invention: Ultraviolet and high temperature aging resistant organic silicon epoxy resin composition used for luminescent diode encapsulation Granted publication date: 20091104 License type: Exclusive License Open date: 20071212 Record date: 20110714 |
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