CN104559060A - Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition - Google Patents
Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition Download PDFInfo
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- CN104559060A CN104559060A CN201410847932.XA CN201410847932A CN104559060A CN 104559060 A CN104559060 A CN 104559060A CN 201410847932 A CN201410847932 A CN 201410847932A CN 104559060 A CN104559060 A CN 104559060A
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Abstract
The invention discloses halogen-free flame-retardant epoxy resin composition for LED encapsulation. The halogen-free flame-retardant epoxy resin composition comprises the following raw materials by mass percent: 30-50% of epoxy resin, 10-20% of DOPO, 0.1-1% of an addition accelerator, 30-50% of methylhexahydrophthalic anhydride, 0.5-2% of a curing accelerator and 0.1-0.5% of a defoaming agent. The invention further discloses a preparation method for the composition. The preparation method is simple in process step and easy to realize, and can be used for quickly preparing a halogen-free flame-retardant epoxy resin composition product for LED encapsulation. The halogen-free flame-retardant epoxy resin composition for LED encapsulation provided by the invention is reasonable in formula, very low in halogen content (not more than 900 ppm) and excellent in flame resistance, and adopts a phosphorus flame retardant technology. An encapsulated LED lamp is good in light transmittance and high in hardness, has small influence on TG (glass transition temperature) and is particularly suitable for LED encapsulation protection.
Description
Technical field
The present invention relates to LED composition epoxy resin technical field, be specifically related to a kind of halogen-free flameproof LED composition epoxy resin and preparation method thereof.
Background technology
The encapsulating epoxy resin major part of existing LED does not have flame retardant properties, even very easily burns, and when LED continues to light, the temperature of lamp body can sharply raise, thus the possibility causing lamp body burning is very high.Although and also have the encapsulating epoxy resin of flame retardant type in the market, but what adopt due to it is halogen flame retardant, colloid content of halogen is very high, and it is this concerning content of halogen requires very strict electronic product for LED etc., this is a serious defect, and the LED particularly exported to foreign countries is stricter to the requirement of content of halogen, how outstanding regardless of other performances by the LED of this epoxy encapsulation, all can directly be denied.
Therefore, more need a Halogen in the market and have the LED composition epoxy resin of flame retardant properties concurrently.
Summary of the invention
For above-mentioned deficiency, an object of the present invention is, provides a kind of formula rationally, content of halogen low (≤900ppm), and the halogen-free flameproof LED composition epoxy resin having flame retardant properties concurrently.
Two of object of the present invention is, for above-mentioned deficiency, provides a kind of energy quick Fabrication to go out the preparation method of above-mentioned halogen-free flameproof LED composition epoxy resin.
For achieving the above object, technical scheme provided by the present invention is: a kind of halogen-free flameproof LED composition epoxy resin, and it is made up of the raw material of following mass percent:
Epoxy resin 30 ~ 50%,
DOPO 10～20%，
Addition promotor 0.1 ~ 1%,
Methyl hexahydrophthalic anhydride 30 ~ 50%,
Curing catalyst 0.5 ~ 2%,
Defoamer 0.1 ~ 0.5%.
As a modification of the present invention, described epoxy resin is the compound of the epoxy group(ing) containing two or more.
As a modification of the present invention, described epoxy resin is at least one in bisphenol A-type diglycidylether, alicyclic diepoxide, bisphenol-f type diglycidylether.
As a modification of the present invention, described DOPO is the assorted-10-phosphorus of 9,10-dihydro-9-oxy-assorted luxuriant and rich with fragrance-10 oxide compounds.
As a modification of the present invention, described addition promotor be triphenyl phosphorus, 4,4-diaminobenzene sulfones, at least one in benzene diketone.
As a modification of the present invention, described curing catalyst is Halogen quaternary ammonium salt promotor.
A preparation method for above-mentioned halogen-free flameproof LED composition epoxy resin, it comprises the following steps:
(1) epoxy resin, DOPO and addition promotor are joined in flask, then 115 ~ 135 DEG C are heated to while stirring, then insulated and stirred to whole system become as clear as crystal after, continue insulated and stirred discharging while hot after 4 ~ 6 hours, obtained phosphorous epoxy resin, then add after defoamer is stirred to and mixes completely, obtain A mixture, stand-by;
(2) methyl hexahydrophthalic anhydride is joined in flask, vacuumize while stir, slowly drip curing catalyst simultaneously, wait discharging after continuing to vacuumize 1 ~ 2 hour while stirring after dripping curing catalyst, obtain B mixture, stand-by;
(3) A mixture mixed mutually with B mixture and stir, then heat to 120 ~ 140 DEG C, obtaining halogen-free flameproof LED composition epoxy resin goods after cured.
As a modification of the present invention, described flask is four-hole boiling flask.
As a modification of the present invention, described step (1) adopts oil bath type of heating to heat.
Beneficial effect of the present invention is: the formula of halogen-free flameproof LED composition epoxy resin provided by the invention is reasonable; what adopt is phosphorus flame-retarded technology; the content of halogen of whole system is very low (≤900ppm); and have excellent flame retardant properties concurrently; packaged LED transmittance is good; hardness is high, little on the impact of TG temperature, is specially adapted to the packaging protection of LED.Preparation method provided by the invention can make halogen-free flameproof LED composition epoxy resin goods fast, and processing step is succinct, and be easy to realize, productivity is high.
Below in conjunction with embodiment, the present invention is further described.
Embodiment
Embodiment 1, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides, it is made up of the raw material of following mass percent: epoxy resin 44.2%, DOPO10%, addition promotor 0.3%, methyl hexahydrophthalic anhydride 44%, curing catalyst 1%, defoamer 0.5%.
Preferably, described epoxy resin is the compound of the epoxy group(ing) containing two or more.Concrete, described epoxy resin is at least one in bisphenol A-type diglycidylether, alicyclic diepoxide, bisphenol-f type diglycidylether.Described DOPO is the assorted-10-phosphorus of 9,10-dihydro-9-oxy-assorted luxuriant and rich with fragrance-10 oxide compounds.Described addition promotor be triphenyl phosphorus, 4,4-diaminobenzene sulfones, at least one in benzene diketone.Described curing catalyst is Halogen quaternary ammonium salt promotor.
A preparation method for above-mentioned halogen-free flameproof LED composition epoxy resin, it comprises the following steps:
(1) epoxy resin, DOPO and addition promotor are joined in flask, this flask is preferably four-hole boiling flask, oil bath type of heating is adopted to heat this flask, then be heated to 115 ~ 135 DEG C while stirring, then insulated and stirred to whole system become as clear as crystal after, continue insulated and stirred discharging while hot after 4 ~ 6 hours, obtained phosphorous epoxy resin, then add after defoamer is stirred to and mixes completely, obtain A mixture, stand-by;
(2) methyl hexahydrophthalic anhydride is joined in flask, vacuumize while stir, slowly drip curing catalyst simultaneously, wait discharging after continuing to vacuumize 1 ~ 2 hour while stirring after dripping curing catalyst, obtain B mixture, stand-by;
(3) A mixture mixed mutually with B mixture and stir, then heat to 120 ~ 140 DEG C, after 1 ~ 2 hour to be solidified, obtaining halogen-free flameproof LED composition epoxy resin goods.
Embodiment 2, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, distinctive points is, it is made up of the raw material of following mass percent: epoxy resin 39.5%, DOPO15%, addition promotor 0.15%, methyl hexahydrophthalic anhydride 44%, curing catalyst 1%, defoamer 0.35%.
Embodiment 3, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, distinctive points is, it is made up of the raw material of following mass percent: epoxy resin 34.3%, DOPO20%, addition promotor 0.35%, methyl hexahydrophthalic anhydride 44%, curing catalyst 1%, defoamer 0.35%.
Embodiment 4, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, distinctive points is, it is made up of the raw material of following mass percent: epoxy resin 50%, DOPO18%, addition promotor 1%, methyl hexahydrophthalic anhydride 30%, curing catalyst 0.9%, defoamer 0.4%.
Embodiment 5, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides and preparation method thereof, it is made up of the raw material of following mass percent: epoxy resin 30%, DOPO19%, addition promotor 0.1%, methyl hexahydrophthalic anhydride 50%, curing catalyst 0.5%, defoamer 0.4%.
Embodiment 6, a kind of halogen-free flameproof LED composition epoxy resin that the present embodiment provides and preparation method thereof, it is substantially the same manner as Example 1, distinctive points is, epoxy resin 42%, DOPO13%, addition promotor 0.5%, methyl hexahydrophthalic anhydride 43.4%, curing catalyst 0.8%, defoamer 0.3%.
Above-described embodiment is only the good embodiment of the present invention, and the present invention can not enumerate out whole embodiments, the technical scheme of one of all employing above-described embodiments, or according to the equivalent variations that above-described embodiment does, all in scope.
Comparative example 1: the fire-retardant epoxy resin being applied to LED choosing certain company on market, test event and method:
Content of halogen: high performance liquid chromatography (HPLC)
Flame retardant properties: UL method of testing (by V0, V1, V2...... grade separation)
Hardness: shore D sclerometer.
Second-order transition temperature (TG): DSC tester.
The impact of the physicals after composition being solidified after wherein hardness and second-order transition temperature can reflect DOPO and epoxy resin addition, thus determine its encapsulation that whether can be used for LED and can available protecting be played.Be example with regard to only carrying out quantitative measurement to the halogen-free flameproof LED composition epoxy resin goods of embodiment 1-3 below, test result is specifically see table 1.
| Content of halogen | Flame retardant properties | Hardness | Second-order transition temperature | |
| Embodiment 1 | 438ppm | V1 | 90 | 122℃ |
| Embodiment 2 | 376ppm | V0 | 81 | 110℃ |
| Embodiment 3 | 351ppm | V0 | 74 | 101℃ |
| Comparative example 1 | 51% | V0 | 88 | 136℃ |
By table 1, can learn, compared with comparative example 1, halogen-free flameproof LED composition epoxy resin content of halogen of the present invention meets Halogen standard (<900ppm), hardness and second-order transition temperature also meet the demand of LED, particularly embodiment 2 is ideal schemes, content of halogen meets Halogen standard, flame retardant properties reaches UL-94V0 level, package requirements can be met, TG point is on the low side, from the angle of balance various aspects of performance, the halogen-free flameproof encapsulation of LED can be met preferably, and the finished product transmittance of encapsulation is good, internal stress is little, the more important thing is that there is outstanding halogen-free flameproof performance.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.As described in the above embodiment the present invention, adopt method same or similar with it and component and other composition and method of making the same of obtaining all in scope.
Claims (10)
1. a halogen-free flameproof LED composition epoxy resin, is characterized in that, it is made up of the raw material of following mass percent:
Epoxy resin 30 ~ 50%,
DOPO 10～20%，
Addition promotor 0.1 ~ 1%,
Methyl hexahydrophthalic anhydride 30 ~ 50%,
Curing catalyst 0.5 ~ 2%,
Defoamer 0.1 ~ 0.5%.
2. halogen-free flameproof LED composition epoxy resin according to claim 1, is characterized in that: it is made up of the raw material of following mass percent: epoxy resin 39.5%, DOPO15%, addition promotor 0.15%, methyl hexahydrophthalic anhydride 44%, curing catalyst 1%, defoamer 0.35%.
3. halogen-free flameproof LED composition epoxy resin according to claim 1 and 2, is characterized in that: described epoxy resin is the compound of the epoxy group(ing) containing two or more.
4. halogen-free flameproof LED composition epoxy resin according to claim 1 and 2, is characterized in that: described epoxy resin is at least one in bisphenol A-type diglycidylether, alicyclic diepoxide, bisphenol-f type diglycidylether.
5. halogen-free flameproof LED composition epoxy resin according to claim 1 and 2, is characterized in that: described DOPO is the assorted-10-phosphorus of 9,10-dihydro-9-oxy-assorted luxuriant and rich with fragrance-10 oxide compounds.
6. halogen-free flameproof LED composition epoxy resin according to claim 1 and 2, is characterized in that: described addition promotor be triphenyl phosphorus, 4,4-diaminobenzene sulfones, at least one in benzene diketone.
7. halogen-free flameproof LED composition epoxy resin according to claim 1 and 2, is characterized in that: described curing catalyst is Halogen quaternary ammonium salt promotor.
8. the preparation method of arbitrary described halogen-free flameproof LED composition epoxy resin in claim 1 ~ 7, is characterized in that: it comprises the following steps:
(1) epoxy resin, DOPO and addition promotor are joined in flask, then 115 ~ 135 DEG C are heated to while stirring, then insulated and stirred to whole system become as clear as crystal after, continue insulated and stirred discharging while hot after 4 ~ 6 hours, obtained phosphorous epoxy resin, then add after defoamer is stirred to and mixes completely, obtain A mixture, stand-by;
(2) methyl hexahydrophthalic anhydride is joined in flask, vacuumize while stir, slowly drip curing catalyst simultaneously, wait discharging after continuing to vacuumize 1 ~ 2 hour while stirring after dripping curing catalyst, obtain B mixture, stand-by;
(3) A mixture mixed mutually with B mixture and stir, then heat to 120 ~ 140 DEG C, obtaining halogen-free flameproof LED composition epoxy resin goods after cured.
9. halogen-free flameproof LED composition epoxy resin according to claim 8, is characterized in that: described flask is four-hole boiling flask.
10. halogen-free flameproof LED composition epoxy resin according to claim 8, is characterized in that: described step (1) adopts oil bath type of heating to heat.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410847932.XA CN104559060A (en) | 2014-12-31 | 2014-12-31 | Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition |
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| CN201410847932.XA CN104559060A (en) | 2014-12-31 | 2014-12-31 | Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556458A (en) * | 2017-09-08 | 2018-01-09 | 江苏扬农锦湖化工有限公司 | A kind of phosphor-containing halogen-free type epoxy resin and preparation method thereof and composite flame-proof material |
| CN111117165A (en) * | 2020-01-21 | 2020-05-08 | 汕头市骏码凯撒有限公司 | Halogen-free flame-retardant transparent epoxy molding compound and preparation method thereof |
| CN113621217A (en) * | 2021-08-31 | 2021-11-09 | 固德电材系统（苏州）股份有限公司 | Halogen-free flame-retardant epoxy resin and preparation method, use method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04370113A (en) * | 1991-06-18 | 1992-12-22 | Sanko Kagaku Kk | Epoxy resin composition |
| JP2009013263A (en) * | 2007-07-03 | 2009-01-22 | Nitto Denko Corp | Epoxy resin composition for sealing optical semiconductor element and optical semiconductor device using the same |
| CN101942073A (en) * | 2009-07-07 | 2011-01-12 | 日本化药株式会社 | Optical semiconductor sealing curable resin composition and cured article thereof |
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2014
- 2014-12-31 CN CN201410847932.XA patent/CN104559060A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04370113A (en) * | 1991-06-18 | 1992-12-22 | Sanko Kagaku Kk | Epoxy resin composition |
| JP2009013263A (en) * | 2007-07-03 | 2009-01-22 | Nitto Denko Corp | Epoxy resin composition for sealing optical semiconductor element and optical semiconductor device using the same |
| CN101942073A (en) * | 2009-07-07 | 2011-01-12 | 日本化药株式会社 | Optical semiconductor sealing curable resin composition and cured article thereof |
Non-Patent Citations (1)
| Title |
|---|
| 梁静等: "DOPO与环氧树脂反应特性的研究", 《绝缘材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556458A (en) * | 2017-09-08 | 2018-01-09 | 江苏扬农锦湖化工有限公司 | A kind of phosphor-containing halogen-free type epoxy resin and preparation method thereof and composite flame-proof material |
| CN107556458B (en) * | 2017-09-08 | 2019-08-02 | 江苏扬农锦湖化工有限公司 | A kind of phosphor-containing halogen-free type epoxy resin and preparation method thereof and composite flame-proof material |
| CN111117165A (en) * | 2020-01-21 | 2020-05-08 | 汕头市骏码凯撒有限公司 | Halogen-free flame-retardant transparent epoxy molding compound and preparation method thereof |
| CN113621217A (en) * | 2021-08-31 | 2021-11-09 | 固德电材系统（苏州）股份有限公司 | Halogen-free flame-retardant epoxy resin and preparation method, use method and application thereof |
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Application publication date: 20150429 |