CN103937445A - Preparation method of transparent organic silica gel with high refractive index for high brightness and large power COB-LED encapsulation - Google Patents

Abstract

The invention relates to a preparation method of a transparent organic silica gel with a high refractive index for high brightness and large power COB-LED encapsulation, and belongs to the technical field of photoelectrical device encapsulation materials. The key points of the preparation method are that: phenyl vinyl resin (component A) and phenyl hydrogen-containing silicone oil (component B), which both have a high refractive index and are transparent, are synthesized firstly, then chloroplatinic acid or platinum complex is used as the catalyst, and finally the mixture of the component A and the component B is cured under a certain condition so as to obtain the transparent and high temperature resistant organic silicone encapsulating gel; wherein the mass ratio of the component A to the component B is (1-5):1. The preparation method comprises the following steps: mixing the component A and the component B, then adding a little amount of catalyst, or mixing the component B and the catalyst firstly, then adding a certain ratio of component A; fully mixing and blending the mixture, and curing under a certain condition so as to obtain the organic silicone encapsulation gel. The refractive index of the prepared organic silicone encapsulation gel is 1.5167 to 1.5577, the light transmittance at 450 nm is 95% or more, the thermal decomposition temperature at a nitrogen gas atmosphere can reach 404.63 DEG C, the hardness is 58 to 65, and the adhesive strength is 56.8 MPa.

Description

Transparent organic silicon glue is rolled in high brightness, high-power COB-LED encapsulation preparation method with height

Technical field

The present invention relates to a kind of high brightness, high-power COB-LED(Chip on Board, chip on board encapsulation) encapsulate the preparation method with high folding transparent organic silicon glue, belong to the packaged material technical field of photoelectric device.

Background technology

The chemical structure of organosilicon material uniqueness makes it have inorganics and organic characteristic concurrently, there is the performances such as excellent heat-resisting, weather-proof, durable, low temperature flexibility, UV stable, high water vapor transmittance, be a kind of novel material that is being related to that technical renovation, the modernization of national defense, the national economic development and living standards of the people improve, be widely used in electric, semiconductor electronic, high light large power LED encapsulation etc.Organosilicon product is because having electric insulation, fire-retardant, radiation hardness, corrosion-resistant, high-low temperature resistant, and the good characteristic such as good biocompatibility, have a wide range of applications in fields such as space flight and aviation, military project apparatus, electric, health care, automobile, building, household chemicalss.In recent years, China's power-type and great power LED have reached international industry bleeding edge, and researching and producing in quick propelling of the epitaxial wafer in LED field and chip, has but ignored the research to packaged material relatively.China's high brightness, high-power COB-LED encapsulation at present needs by import with organic silica gel is most of, and expensive, this has greatly limited further developing of LED industry.Because of the shortage of domestic funds and technology, there is the problems such as specific refractory power is lower, the transparency is not enough, thermotolerance is not good, poor mechanical property in product.

In order to address the above problem, first the present invention designs transparent phenyl vinyl resin (A component) and the phenyl hydrogen-containing silicon oil (B component) of synthetic high folding, between adjustment monomer, ratio can realize the Modulatory character of refractive index, changes the component that synthetic catalyst, control reaction conditions etc. can synthesize suitable molecular weight and molecular weight distribution, then utilize Platinic chloride or platinum complex to make curing catalysts, under gentle condition, 25 ~ 120oC is curable, A, the refractive index of B component is all more than 1.50, the consistency of two kinds of components is fine, catalyst levels is few, curing reaction transformation efficiency is high, no coupling product generates, inner and surperficial all energy completion of cure, shrinking percentage low (0 ~ 0.5%), resistance to elevated temperatures is excellent especially, heat decomposition temperature reaches 404.63oC, can life-time service at 150 ~ 200oC, it is high that this packaging plastic has refractive index, condition of cure gentleness, solidification rate is fast, the transparency is good, hardness is suitable, cohesive strength is high, high temperature resistant, the advantage such as ageing-resistant.

Summary of the invention

The object of this invention is to provide the preparation method of a kind of high brightness, high-power COB-LED encapsulation organic silica gel.Another object of the present invention is to prepare a kind of novel organosilicon high-temperature plastic, to improve the resistance toheat of current organic silicon packaging glue, realizes the Modulatory character of organic silicon packaging glue refractive index simultaneously.

The preparation method who the present invention relates to a kind of high brightness, the high folding transparent organic silicon glue of high-power COB-LED encapsulation, is characterized in that having following technological process and step:

A. one of synthetic (A component) method of phenyl vinyl resin: take 8.6 ~ 10.9g 1,3,5,7-tetramethyl--1,3,5,7-tetraphenyl tetrasiloxane ring body (D ₄), 2.64 ~ 5.28g methyl ethylene dimethoxy silane, 0.5～2.0g γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) is placed in three-necked bottle, add xylene solvent, be warming up to 90oC, add appropriate basic catalyst, it is: Tetramethylammonium hydroxide (Me ₄or potassium hydroxide (KOH) or eight hydration barium sulfate (Ba (OH) NOH) ₂8H ₂o); Temperature remains on 90oC ~ 110oC/4h; Underpressure distillation, removes solvent and small-molecule substance in system; Obtain phenyl vinyl resin;

Two of synthetic (A component) method of phenyl vinyl resin: take 8.6 ~ 10.9g 1,3,5,7-tetramethyl--1,3,5,7-tetraphenyl tetrasiloxane ring body (D ₄), 2.64 ~ 5.28g methyl ethylene dimethoxy silane, 0.5～2.0g γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) is placed in three-necked bottle, adds and heavily steams in right amount dimethylbenzene as reaction solvent, then passes into N ₂and heat up, in the time that temperature rises to 80 ~ 90oC, splash into 0.1 ~ 1.0g DMF (DMF) as promotor, and then splash into 0.1 ~ 1.5g Me ₄the silicon alkoxide solution catalyst of NOH; Temperature remains on 85 ~ 95oC/2h, 96 ~ 105oC/2h, and 106 ~ 115oC/2h, is then directly warming up to 150 ~ 180oC, and maintains 1 ~ 2h and make catalyzer Me ₄nOH is decomposed; Then at this temperature, carry out underpressure distillation 3 ~ 5h, remove the solvent in reaction system and decompose rear small-molecule substance; Finally obtain phenyl vinyl resin;

B. synthetic (the B component) of phenyl hydrogen-containing silicon oil: add 3.85 ~ 5.45g D in three-necked bottle ₄, 2.4 ~ 6.4g 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane (hydrogeneous ring body), using dimethylbenzene and Virahol as mixed solvent, is uniformly mixed the dense H of rear dropping 0.1 ~ 2g ₂sO ₄catalyzer, is warming up to 50 ~ 60oC, back flow reaction 2 ~ 4h; Add the tetramethyl-dihydro base sily oxide (hydrogeneous double-seal head) of 0.2 ~ 1.5g, balanced reaction 3 ~ 5h; Through dehydration, underpressure distillation, cooling, filter after, obtain phenyl hydrogen-containing silicon oil;

C. the curing process of high folding transparent organic silicon packaging plastic: above-mentioned two kinds of materials are fully uniformly mixed, the mass ratio of A, B component is (1 ~ 5): 1, then add a certain amount of catalyzer Platinic chloride or platinum complex, A, B constituent mass summation with the ratio of catalyzer are: (3 ~ 10): (0.003 ~ 0.01); Or after first being mixed with catalyzer, B component adds again a certain proportion of A component; After being fully uniformly mixed, underpressure distillation exhaust bubble; After row finishes, self-vulcanizing 1 ~ 4h; Or heating 80 ~ 120oC solidifies 1min ~ 120min; Finally obtain curing high brightness, high-power COB-LED encapsulation height folding transparent organic silicon glue.

Mechanism and the feature of the inventive method are as described below:

The present invention utilizes 1,3,5,7-tetramethyl--1,3, the open loop of 5,7-tetraphenyl tetrasiloxane ring body and the open loop of methyl ethylene dimethoxy silane, copolymerization are introduced phenyl ring in organosilicon matrix, vinyl has higher specific refractory power and can carry out addition reaction with containing hydrogen silicone oil to ensure prepared packaging plastic, transparent, the resistant to elevated temperatures phenyl organic silicon packaging glue of the high folding of preparation.The organosilicon solidification value that the present invention adopts is fast compared with low rate, between 25 ~ 120oC.Present device is fairly simple, and cost is lower, and operational condition is easy to control.Philosophy and technique of the present invention is different from common organic silica gel curing.

Adopt height folding transparent organic silicon packaging plastic prepared by the inventive method through Abbe refractometer, non-isothermal DSC test, ISOTHERMAL DSC test, ultraviolet spectrophotometer, durometer, electronic tension tester, TGA test, 180oC/1000h characterizes its refractive index, condition of cure, solidification rate, the transparency, hardness, cohesive strength, thermotolerance, the performance such as ageing-resistant respectively.Its refractive index is 1.5167 ~ 1.5577; Can start to solidify at 36.35oC; Be 2min ~ 1min in 100oC ~ 120oC isothermal curing time; At the transmittance at 450nm place higher than 95%; Under room temperature condition, hardness is 58 ~ 65; Cohesive strength is 56.8MPa; Heat decomposition temperature under nitrogen atmosphere reaches 404.63oC; 180oC under air atmosphere, the burn-in test of 1000h.

Advantage of the present invention is: not only can realize the regulation and control of organic silicon packaging glue refractive index, can also realize the raising of resistance toheat, light transmission, cohesive strength etc., prepare the packaging plastic that a kind of over-all properties is superior.

Embodiment

After now specific embodiments of the invention being specified in.

Embodiment mono-

Take 8.6g D ₄, 2.64g methyl ethylene dimethoxy silane, 0.85g KH-560 is placed in three-necked bottle, add 30mL xylene solvent, be warming up to 90oC, add 0.2g Tetramethylammonium hydroxide catalyzer, temperature remains on 90oC ~ 110oC/4h, underpressure distillation, removes solvent and small-molecule substance etc. in system, obtains phenyl vinyl resin.

In three-necked bottle, add 3.85gD ₄, 2.5g 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane, 5mL dimethylbenzene and 20mL Virahol, as mixed solvent, are uniformly mixed the dense H of rear dropping 0.4g ₂sO ₄catalyzer, is warming up to 50 ~ 60oC, back flow reaction 2 ~ 4h.Add the hydrogeneous double-seal head of 0.3g, balanced reaction 4h.Through dehydration, underpressure distillation, cooling, filter after, obtain phenyl hydrogen-containing silicon oil.

The 2g phenyl vinyl resin of synthesized is mixed with 1g phenyl hydrogen-containing silicon oil, taking 0.003g Platinic chloride as curing catalysts, after mixing, under vacuum condition, get rid of bubble; Or even with phenyl vinyl mixed with resin again after solidifying agent and phenyl hydrogen-containing silicon oil are mixed, vacuumize eliminating bubble.Under 80oC condition, solidify 0.5h, under 100 ° of C conditions, solidify 1h, obtain phenyl resin organic silica gel.

Organic silicon packaging glue refractive index prepared by the present embodiment is 1.5167, reaches 95% at the transmittance at 450nm place.

Embodiment bis-

First in 250mL three-necked bottle, add 10.9gD ₄, 5.28g methyl ethylene dimethoxy silane, 1.18g KH-560, and add 0.018g Ba (OH) ₂8H ₂o, as catalyzer, then measures the solvent of 20mL toluene as reaction with graduated cylinder, is uniformly mixed; Warming-in-water is to 80oC, backflow 4h, then add the end-capping reagent of 0.28g vinyl double-seal head as reaction, backflow 2h.After reaction end is cooling, be washed till neutrality with deionized water, underpressure distillation obtains colorless transparent viscous liquid after removing solvent and water, splash into micro-dilute sulphuric acid, by centrifugal method by after salt and organism layering, remove supernatant liquid, finally use the tetrafluoroethylene membrane filtration of 0.45um, be phenyl vinyl resin.

In three-necked bottle, add 5.45gD ₄, 4.8g 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane, 5mL heavily steams dimethylbenzene, 20mL Virahol as solvent, is uniformly mixed, and drips 0.59g dense H ₂sO ₄, be warming up to 50oC, and at this temperature stirring reaction 2 ~ 3h.Add the hydrogeneous double-seal head of 0.46g as end-capping reagent, balanced reaction 3h, add again 10%(massfraction) water continue stir 0.5h with decompose sulfuric ester, stratification, disacidify water layer, oil-reservoir water is washed till to neutrality, reheat decompression and pull out low refuse, cooling, filter and obtain object product phenyl hydrogen-containing silicon oil.

The 3.5g phenyl vinyl resin of synthesized is mixed with 1.5g phenyl hydrogen-containing silicon oil, taking 0.005g Platinic chloride as curing catalysts, after mixing, under vacuum condition, get rid of bubble; Or even with phenyl vinyl mixed with resin again after solidifying agent and phenyl hydrogen-containing silicon oil are mixed, vacuumize eliminating bubble.Under 80oC condition, solidify 2h, obtain phenyl resin organic silica gel.

Organic silicon packaging glue refractive index prepared by the present embodiment is 1.5412, reaches 95.5% at the transmittance at 450nm place.

Embodiment tri-

Get 8.8g D ₄, 4.35g methyl ethylene dimethoxy silane, 0.98g KH-560 is placed in there-necked flask, adds 20mL heavily to steam dimethylbenzene as reaction solvent, then passes into N ₂and heat up, in the time that temperature rises to 90oC, splash into 0.2gDMF as promotor, and then splash into 0.3g Me ₄the silicon alkoxide solution of NOH is as polymerisation catalysts, and temperature remains on 90oC/2h, 100oC/2h, and 110oC/2h, is then directly warming up to 165 oC and maintains 1.5h and make catalyzer Me ₄nOH is decomposed, and then at this temperature, carries out underpressure distillation 5h, removes the solvent in reaction system and decomposes rear small-molecule substance etc., finally obtains phenyl vinyl resin.

In three-necked bottle, add 8.75g D ₄, 4.8g 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane, 10mL heavily steams dimethylbenzene, 40mL Virahol as solvent, is uniformly mixed, and drips 0.59g dense H ₂sO ₄, be warming up to 50oC, and at this temperature stirring reaction 2 ~ 3 h.Add the hydrogeneous double-seal head of 0.80g as end-capping reagent, balanced reaction 3h, stratification, disacidify water layer, be washed till neutrality by oil-reservoir water, reheats decompression and pull out low refuse, cooling, filters and obtain object product phenyl hydrogen-containing silicon oil.

The 7g phenyl vinyl resin of synthesized is mixed with 3g phenyl hydrogen-containing silicon oil, taking 0.01g platinum complex as curing catalysts, after mixing, under vacuum condition, get rid of bubble; Or even with phenyl vinyl mixed with resin again after solidifying agent and phenyl hydrogen-containing silicon oil are mixed, vacuumize eliminating bubble.Under 80oC condition, solidify 1h, under 100 ° of C conditions, solidify 1h, obtain phenyl resin organic silica gel.

Organic silicon packaging glue refractive index prepared by the present embodiment is 1.5577, reaches 96% at the transmittance at 450nm place.

Claims (1)

1. the preparation method that transparent organic silicon glue is rolled in high brightness, high-power COB-LED encapsulation with height, is characterized in that the concrete steps of the method are as follows:

A. one of synthetic (A component) method of phenyl vinyl resin: take 8.6 ~ 10.9g 1,3,5,7-tetramethyl--1,3,5,7-tetraphenyl tetrasiloxane ring body (D ₄), 2.64 ~ 5.28g methyl ethylene dimethoxy silane, 0.5～2.0g γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) is placed in three-necked bottle, add xylene solvent, be warming up to 90oC, add appropriate basic catalyst, it is: Tetramethylammonium hydroxide (Me ₄or potassium hydroxide (KOH) or eight hydration barium sulfate (Ba (OH) NOH) ₂8H ₂o); Temperature remains on 90oC ~ 110oC/4h; Underpressure distillation, removes solvent and small-molecule substance in system; Obtain phenyl vinyl resin;

Two of synthetic (A component) method of phenyl vinyl resin: take 8.6 ~ 10.9g 1,3,5,7-tetramethyl--1,3,5,7-tetraphenyl tetrasiloxane ring body (D ₄), 2.64 ~ 5.28g methyl ethylene dimethoxy silane, 0.5～2.0g γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) is placed in three-necked bottle, adds and heavily steams in right amount dimethylbenzene as reaction solvent, then passes into N ₂and heat up, in the time that temperature rises to 80 ~ 90oC, splash into 0.1 ~ 1.0g DMF (DMF) as promotor, and then splash into 0.1 ~ 1.5g Me ₄the silicon alkoxide solution catalyst of NOH; Temperature remains on 85 ~ 95oC/2h, 96 ~ 105oC/2h, and 106 ~ 115oC/2h, is then directly warming up to 150 ~ 180oC, and maintains 1 ~ 2h and make catalyzer Me ₄nOH is decomposed; Then at this temperature, carry out underpressure distillation 3 ~ 5h, remove the solvent in reaction system and decompose rear small-molecule substance; Finally obtain phenyl vinyl resin;

B. synthetic (the B component) of phenyl hydrogen-containing silicon oil: add 3.85 ~ 5.45g D in three-necked bottle ₄, 2.4 ~ 6.4g 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane (hydrogeneous ring body), using dimethylbenzene and Virahol as mixed solvent, is uniformly mixed the dense H of rear dropping 0.1 ~ 2g ₂sO ₄catalyzer, is warming up to 50 ~ 60oC, back flow reaction 2 ~ 4h; Add the tetramethyl-dihydro base sily oxide (hydrogeneous double-seal head) of 0.2 ~ 1.5g, balanced reaction 3 ~ 5h; Through dehydration, underpressure distillation, cooling, filter after, obtain phenyl hydrogen-containing silicon oil;

C. the curing process of high folding transparent organic silicon packaging plastic: above-mentioned two kinds of materials are fully uniformly mixed, the mass ratio of A, B component is (1 ~ 5): 1, then add a certain amount of catalyzer Platinic chloride or platinum complex, A, B constituent mass summation with the ratio of catalyzer are: (3 ~ 10): (0.003 ~ 0.01); Or after first being mixed with catalyzer, B component adds again a certain proportion of A component; After being fully uniformly mixed, underpressure distillation exhaust bubble; After row finishes, self-vulcanizing 1 ~ 4h; Or heating 80 ~ 120oC solidifies 1min ~ 120min; Finally obtain curing high brightness, high-power COB-LED encapsulation height folding transparent organic silicon glue.