CN103555251A - High-heat-conductivity high-reliability ultraviolet-curing LED (light-emitting diode) electrically-conductive silver adhesive and preparation method thereof - Google Patents
High-heat-conductivity high-reliability ultraviolet-curing LED (light-emitting diode) electrically-conductive silver adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-heat-conductivity high-reliability ultraviolet-curing LED (light-emitting diode) electrically-conductive silver adhesive and a preparation method thereof. The LED electrically-conductive silver adhesive is composed of the following components in parts by weight: 10-30 parts of silica sol blended modified epoxy acrylate prepolymer, 5-20 parts of reactive diluent, 1-5 parts of photoinitiator, 50-90 parts of electrically-conductive silver powder and 0-6 parts of assistant. The prepared LED electrically-conductive silver adhesive has the advantages of favorable bonding property, favorable heat conductivity, favorable electric conductivity and favorable mechanical properties; after being subjected to construction and curing at one time, the heat conductivity can reach 30 W/m.K above, and the volume resistivity can be down two 5*10<-4>ohm.cm below; and the preparation method is simple and low in cost.
Description
[technical field]
The present invention relates to a kind of filled-type LED conductive silver glue and preparation method thereof, particularly a kind of high heat conduction high reliability ultraviolet curing type conductive silver glue that is applicable to high-power and high-luminance LED encapsulation use and preparation method thereof.
[background technology]
Photodiode (LED, Lighting Emitting Diode) be a kind of special semi-conductor solid luminescence device, there is the plurality of advantages such as energy-saving and environmental protection, volume is little, all solid state, the life-span is long, easy to control, be widely used in the industries such as various indoor and outdoor display screens, automobile and backlight, and become emerging following light source the most promising in illuminating product.LED, as a kind of novel green light source product, is following development trend, so government of China both the central and local governments is all encouraging, supporting and helping LED industry development energetically.According to statistics, China 2010 NianLED manufacturing enterprises are family more than 1200 nearly, and employee reaches more than 100,000 people, and output reaches more than 2,000 hundred million, and the output value is over more than 300 hundred million yuan.
Wherein, conductive resin is composition extremely important and crucial in LED encapsulation process.LED conductive resin is the tackiness agent with certain conductive capability, and major function is bonding, conduction and heat conduction; It can bond together LED chip and substrate securely, and makes the new part connecting form electric path.Follow the fast development of the emerging LED industry of strategy in China, LED conductive resin also becomes one of study hotspot of current academia and industrial community.
According to the difference of structure, LED conductive resin is divided into two types of structure-type and filled-types.Filled-type LED conductive resin main component comprises resin, solvent, solidifying agent, color stuffing, coupling agent etc., and wherein each composition all plays not same-action.Owing to being subject to the impact of the factors such as cost, price, it is mainly filled-type that China produces with the LED conductive resin using, and in traditional tackiness agent, adds the filler that can conduct electricity, such as bronze, silver powder, copper powder, electrically conductive graphite powder etc.Wherein, because bronze price is extremely expensive, and the electroconductibility of the conductive filler materials such as copper powder and electrically conductive graphite powder is short of to some extent, so China LED conductive resin overwhelming majority used has used the filled-type conductive silver glue of silver powder.
According to the statistics made by the departments concerned, the market share of China LED conductive silver glue in 2011 is up to 1.1 hundred million yuan, wherein the market share of 90% left and right is occupied by U.S. Ablestik company and SUMITOMO CHEMICAL company, the 8% left and right market share is occupied by imported products such as Britain, France, Korea S, and domestic LED conductive silver glue only occupies 2% left and right.
LED conductive silver glue is according to the difference of solidifying drying mode, and it can mainly be divided into two types of thermofixation and photocurings.Wherein, according to the difference of solidifying drying temperature, it is dry that thermofixation can be divided into room temperature, middle temperature and hot setting.The dry LED conductive silver glue of room temperature and middle temperature curable is very easy to use, but its inconvenience is that dry required time is longer, and storage and execution conditions require stricter; And although the curing rate of drying of hot setting type LED conductive silver glue is fast.But high temperature can produce very large negative impact to other device.Light-cured type LED conductive silver glue be mainly rely on the irradiation of UV-light (UV) and cause that resin prepolymer generation curing cross-linked is sent out should, not only solidify rate of drying fast, and storage and execution conditions require not sternly, therefore become the main flow curing mode of current high-end LED conductive silver glue.
Correlative study shows, along with LED chip temperature raises, the optical throughput of LED can decline rapidly, thereby causes that LED light decay is very fast to be increased and sharply shorten work-ing life.Therefore, the heat conductivility of LED conductive resin becomes very crucial technical problem in LED encapsulation.In the current LED conductive silver glue of China, resin used mostly is epoxy resin, and this is mainly because epoxy resin has the performances such as good cementability, mechanical property, water tolerance, chemical-resistant.But, the resistance toheat of epoxy resin and heat conductivility are all short of to some extent, cause the heat conductivility of the most LED conductive silver glues of China cannot meet international manufacturing science center (NCMS) completely about the technological standard of commercial surface mounting conductive resin, especially along with the development of high-power and high-luminance LED in recent years, to the heat conductivility of conductive resin, require more and more higher.
Meanwhile, except also there are other many shortcomings and deficiencies in the existing LED conductive resin of heat conductivility Cha， China, such as specific conductivity is low, bonding strength is little, contact resistance is unstable, shock resistance is poor etc.Therefore, develop there is high thermal conductivity more, more high conductivity, more excellent reliability and use LED conductive silver glue more easily to become China LED industry to be badly in need of at present solution.
[summary of the invention]
The object of the invention is, in order to overcome the defect of prior art and product, provides a kind of specific conductivity high, and bonding strength is large, and contact resistance is stable, the high heat conduction high reliability ultraviolet curing type LED conductive silver glue that shock resistance is good.
Another object of the present invention is to provide a kind of preparation method of this conductive silver glue.
To achieve these goals, the present invention is by the following technical solutions:
A heat conduction high reliability ultraviolet curing type LED conductive silver glue, is characterized in that being comprised of following parts by weight of component:
Silicon sol blending and modifying epoxy acrylic ester prepolymer in the present invention is prepared by the following method:
A, take appropriate epoxy glyceride, after system being warmed up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip a certain amount of acrylate monomer, be controlled in 0.5～3h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 4～8mgKOH/g, be cooled to room temperature discharging, make epoxy acrylic ester prepolymer;
Under b, room temperature, in the presoma silicon source taking in proportion, add 0.1～3.5moLL
-1hydrochloric acid soln is until system pH is between 3～4, then stirs 10～48h until system is evenly clarified with 600～1000rpm rotating speed, makes silicon sol;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Wherein the consumption of each raw material be take epoxy glyceride as benchmark, presoma silicon source: the mol ratio of epoxy glyceride is 0.1～1, acrylate monomer: the mol ratio of epoxy glyceride is 0.5～2.
Epoxy glyceride in the present invention is one or more the mixture in o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester and trimellitic acid three-glycidyl ester.
In the present invention acrylate monomer be one or both in vinylformic acid and methacrylic acid.
Presoma silicon source in the present invention is one or more the mixture in methyl silicate, tetraethoxy, Union carbide A-162, vinyltriethoxysilane, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and gamma-mercaptopropyltriethoxysilane.
Because LED in use can constantly give out heat always, so LED conductive silver glue has larger requirement to its resistance toheat.Therefore, LED conductive silver glue major function, except conducting function is provided, also needs to possess good heat conduction function.In addition, bonding strength is another important performance indexes of conductive resin.Epoxy resin composition in the present invention is mainly to give bonding and the adhesion property that LED conductive silver glue is good, because LED conductive silver glue needs to play effective cohesive action to LED matrix, and effectively fixed L ED with raising product the resistivity to external impact and vibrations.But, the poor-performings such as the toughness after epoxy resin cure, thermotolerance, thermal conductivity, so the present invention utilizes acrylate resin and silica gel to carry out modification to epoxy resin.
Epoxy acrylic ester prepolymer is to transport one of photosensitive prepolymer with the most use in ultraviolet-curing paint product, its preparating mechanism be generally epoxide group in epoxy resin under the effect of catalyzer open loop and with Acrylic Acid Monomer in-there is esterification in COOH.Epoxy acrylic ester prepolymer and other resin compatible are good, not only many grounds are had to better sticking power, and laser curing velocity is fast, after solidifying, coating gloss and chemical resistance are good, are therefore widely used in coating, ink and adhesive industry.But the water tolerance of Epocryl, thermotolerance, snappiness, thermal conductivity are still short of to some extent, so the present invention carries out silica gel modification to improve these deficiencies to it.
Silicon sol composition in the present invention is mainly to give the protection effect that LED conductive silver glue is good, improves its heat conductivility simultaneously.Silica gel possesses good water tolerance, mechanical property, weather, ageing resistance owing to having 3 D cross-linked Si-O structure; especially excellent high thermal resistance and lower temperature resistance; the related defects of Epocryl be can make up, thereby provide protection and the heat conduction function of LED conductive silver glue increased substantially.
Reactive thinner in the present invention is vinylbenzene, vinyl pyrrolidone, n-butyl acrylate, isobutyl acrylate, senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, iso-bornyl acrylate, β-propyloic acrylic ester, 2-phenoxyethyl acrylate, 1, 6-hexylene glycol double methacrylate, two contracting propylene glycol double methacrylates, tripropylene glycol double methacrylate, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, two contracting trimethylolpropane tetra-acrylate, the mixture of one or more in double pentaerythritol C5 methacrylate and double pentaerythritol methacrylate.
Light trigger in the present invention is st-yrax, α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone and 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl) mixture of one or more in-1-butanone.
Conductive silver powder in the present invention is one or both or three kinds in the flake silver powder of crossing through alkyd mixing solutions immersion treatment respectively, spherical silver powder and unformed silver powder, and the alkyd mixing solutions in the present invention is the solution that alcohol and acid mix by weight 1～30:1.
In the present invention, alcohol is one or more the mixture in ethanol, methyl alcohol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, and described acid is one or more the mixture in hydrochloric acid, sulfuric acid, nitric acid.
Auxiliary agent in the present invention is one or more the mixture in flow agent, defoamer, wetting dispersing agent.
Wherein flow agent can be selected one or more in BYK-306, BYK-333 that German BYK company produces, BYK-323, BYK-358N, BYK-354, also can select Glide410, the Glide435 that German TEGO company produces, one or more in Glide450, Glide432.
Wherein defoamer can be selected one or more in BYK-141, BYK-052 that German BYK company produces, BYK-066N, BYK-055, BYK-023, also can select one or more in Foamex N, Foamex815N, Foamex825, Foamex840, Foamex842, Airex900, Airex910, Airex920 and the Airex931 that German TEGO company produces.
Wherein wetting dispersing agent can be selected BYK-110, the BYK-104S that German BYK company produces, one or more in BYK-163, also can select one or more in Dispers610S, Dispers610, Dispers610S, Dispers700, Dispers710 and the Dispers740W that German TEGO company produces.
A preparation method for above-mentioned high heat conduction high reliability ultraviolet curing type LED conductive silver glue, is characterized in that comprising the following steps:
First silicon sol blending and modifying epoxy acrylic ester prepolymer, reactive thinner, light trigger, auxiliary agent are added respectively and disperse in cylinder with the pre-dispersed 10～30min of 600～1200rpm rotating speed; Then slowly add conductive silver powder, and with rotating speed dispersed with stirring 20～30min of 2000～5000rpm; Pass into again three-roller and grind, until test its fineness not higher than 20 μ m with Hegman grind gage; Last vacuumizing and defoaming makes conductive silver glue finished product.
The present invention compared with prior art, has the following advantages:
By the reasonable selection to the selection of prepolymer, reactive thinner, light trigger, conductive silver powder and multiple auxiliary agent, LED conductive silver glue not only can be bonded together LED chip and substrate securely, and heat conductivility, mechanical property and conductivity are excellent, use simultaneously more convenient, curing speed very fast (with solidify machine solidify dryly only need tens of seconds); It can replace many related productss in the market, and application prospect and potentiality are boundless.
After LED conductive silver glue one-off construction of the present invention solidifies, more than its thermal conductivity can reach 30W/mk, volume specific resistance can be low to moderate 5 * 10
-4below Ω cm, and its preparation method is fairly simple, and cost compare is cheap.
[embodiment]
Below in conjunction with specific embodiment, the present invention is described further, it should be noted that, embodiment does not form the restriction to the claimed scope of the present invention.
Embodiment 1:
A heat conduction high reliability ultraviolet curing type LED conductive silver glue, it is comprised of following parts by weight of component:
The preparation method of silicon sol blending and modifying epoxy acrylic ester prepolymer is wherein:
A, by the required appropriate tetrahydrophthalic acid 2-glycidyl ester (TADE) that takes of said components proportioning, while system being warming up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip vinylformic acid (AA), the consumption of AA is pressed n(AA): n(TADE)=0.8 adds, be controlled in 1h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 5mgKOH/g, is cooled to room temperature discharging, makes epoxy acrylic ester prepolymer;
Under b, room temperature, in the presoma silicon source tetraethoxy (TEOS) taking in proportion, add 2moLL
-1hydrochloric acid soln is until system pH is between 3～4, then stirs 10～48h until system is evenly clarified with 800rpm rotating speed, makes silicon sol, and wherein the consumption of TEOS is by n(TEOS): n(TADE)=0.2 takes;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Reactive thinner is wherein 2-phenoxyethyl acrylate, and light trigger is st-yrax, and conductive silver powder is through m(ethanol): the flake silver powder that the alkyd mixing solutions immersion treatment of m(sulfuric acid)=10:1 is crossed, flow agent is Glide432.
The preparation method of above-mentioned conductive silver glue is: first silicon sol blending and modifying epoxy acrylic ester prepolymer, reactive thinner, light trigger, flow agent, defoamer and wetting dispersing agent are added respectively and disperse in cylinder with the pre-dispersed 10～30min of 1000rpm rotating speed; Then slowly add conductive silver powder, and with rotating speed dispersed with stirring 20～30min of 3000rpm; Pass into again three-roller and grind, until test its fineness not higher than 20 μ m with Hegman grind gage; Last vacuumizing and defoaming.
Embodiment 2:
A heat conduction high reliability ultraviolet curing type LED conductive silver glue, it is comprised of following parts by weight of component:
The preparation method of silicon sol blending and modifying epoxy acrylic ester prepolymer is wherein:
A, by the required mixture that takes appropriate o-phthalic acid diglycidyl ester and Diglycidyl M-phthalate of said components proportioning, while system being warming up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip methacrylic acid (MAA), the consumption of MAA is pressed n(MAA): n(o-phthalic acid diglycidyl ester+Diglycidyl M-phthalate)=1.5 add, be controlled in 2h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 6mgKOH/g, be cooled to room temperature discharging, make epoxy acrylic ester prepolymer,
Under b, room temperature, in the mixture of the presoma silicon source Union carbide A-162 taking in proportion and vinyltriethoxysilane, add 1moLL
-1hydrochloric acid soln is until system pH is between 3～4, with 600rpm rotating speed, stir 10～48h until system is evenly clarified again, make silicon sol, wherein the consumption in presoma silicon source is by n(Union carbide A-162+vinyltriethoxysilane): n(o-phthalic acid diglycidyl ester+Diglycidyl M-phthalate)=0.5 takes;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Reactive thinner is wherein the mixture of senecioate-hydroxyl ethyl ester and methacrylic acid-beta-hydroxy ethyl ester, light trigger is st-yrax, conductive silver powder is through m(Virahol+propyl alcohol): the spherical silver powder that the alkyd mixing solutions immersion treatment of m(sulfuric acid+hydrochloric acid)=20:1 is crossed, flow agent is BYK-323, and defoamer is BYK-066N.
The preparation method of above-mentioned conductive silver glue is identical with the preparation method of embodiment 1, and just adding the rate of dispersion before conductive silver powder is 800rpm, and adding the rate of dispersion after conductive silver powder is 4000rpm.
Embodiment 3:
A heat conduction high reliability ultraviolet curing type LED conductive silver glue, it is comprised of following parts by weight of component:
The preparation method of silicon sol blending and modifying epoxy acrylic ester prepolymer is wherein:
A, by said components proportioning is required, take appropriate hexahydrophthalic acid 2-glycidyl ester, while system being warming up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip AA, the consumption of AA is pressed n(AA): n(hexahydrophthalic acid 2-glycidyl ester)=0.5 add, be controlled in 0.5h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 4mgKOH/g, is cooled to room temperature discharging, makes epoxy acrylic ester prepolymer;
Under b, room temperature, in the presoma silicon source methyl silicate taking in proportion, add 0.1moLL
-1hydrochloric acid soln is until system pH is between 3～4, with 700rpm rotating speed, stir 10～48h until system is evenly clarified again, make silicon sol, wherein the consumption in presoma silicon source is by n(methyl silicate): n(hexahydrophthalic acid 2-glycidyl ester)=0.5 takes;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Reactive thinner is wherein the mixture of vinylbenzene, vinyl pyrrolidone and n-butyl acrylate, light trigger is 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone, and conductive silver powder is respectively through m(propyl carbinol): the unformed silver powder that the alkyd mixing solutions immersion treatment of m(nitric acid)=1:1 is crossed and the mixture of flake silver powder.
The preparation method of above-mentioned conductive silver glue is identical with the preparation method of embodiment 1, and just adding the rate of dispersion before conductive silver powder is 600rpm, and adding the rate of dispersion after conductive silver powder is 2000rpm, there is no adding of auxiliary agent simultaneously.
Embodiment 4:
A heat conduction high reliability ultraviolet curing type LED conductive silver glue, it is comprised of following parts by weight of component:
The preparation method of silicon sol blending and modifying epoxy acrylic ester prepolymer is wherein:
A, by said components proportioning is required, take appropriate terephthalic acid diglycidyl ester, the mixture of trimellitic acid three-glycidyl ester and Diglycidyl M-phthalate, while system being warming up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip the mixture of AA and MAA, the consumption of AA and MAA is pressed n(AA+MAA): n(terephthalic acid diglycidyl ester+trimellitic acid three-glycidyl ester+Diglycidyl M-phthalate)=2 add, be controlled in 3h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 8mgKOH/g, be cooled to room temperature discharging, make epoxy acrylic ester prepolymer,
Under b, room temperature, in the mixture of the presoma silicon source γ-aminopropyl triethoxysilane taking in proportion, γ-methacryloxypropyl trimethoxy silane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and gamma-mercaptopropyltriethoxysilane, add 3.5moLL
-1hydrochloric acid soln is until system pH is between 3～4, with 1000rpm rotating speed, stir 10～48h until system is evenly clarified again, make silicon sol, wherein the consumption in presoma silicon source is by n(presoma silicon source): n(terephthalic acid diglycidyl ester+trimellitic acid three-glycidyl ester+Diglycidyl M-phthalate)=1 takes;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Reactive thinner is wherein the mixture of isobutyl acrylate, β-propyloic acrylic ester, two contracting propylene glycol double methacrylates and double pentaerythritol C5 methacrylate, light trigger is α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone, conductive silver powder is respectively through m(propyl carbinol+sec-butyl alcohol+trimethyl carbinol): the flake silver powder that the alkyd mixing solutions immersion treatment of m(hydrochloric acid+sulphuric acid+nitric acid)=1:1 is crossed and the mixture of spherical silver powder, flow agent is BYK-354, defoamer is Airex910, and wetting dispersing agent is BYK-104S.
The preparation method of above-mentioned conductive silver glue is identical with the preparation method of embodiment 1, and just adding the rate of dispersion before conductive silver powder is 1200rpm, and adding the rate of dispersion after conductive silver powder is 5000rpm.
When LED conductive silver glue is prepared film and tested, slowly add conductive silver glue finished product in watch-glass, control thickness is 1 ± 0.2mm, and then with UV, solidifies machine (IntelliRay600w Xing， U.S. Uvitron) and solidify 20s, makes LED conductive silver glue film.Taken off, carried out various tests.
The test result of conductive silver glue prepared by embodiment of the present invention 1-4 is as shown in table 1:
Table 1: the technological standard according to NCMS about commercial surface mounting conductive resin, the test condition in the present invention is: aging 500h in hot and humid environment (85 ℃, 85%RH).
Note: imported product A and imported product B are respectively the 84-1LMISR4LED conductive resin commodity of U.S. Ablestik company production and the T-3007-20LED conductive resin commodity that SUMITOMO CHEMICAL company produces.
As shown in Table 1, ultraviolet curing type LED conductive silver glue heat conductivility of the present invention and resistance toheat are better, and contact resistance variation rate and change of sheer strength rate are all less than 20%, its related application performance index be better than being abroad correlated with level of like product, not only can meet LED encapsulation use completely, and be particularly suitable for the requirement of the LED chip encapsulation of high-power and high-luminance.Ultraviolet curing type LED conductive silver glue properties of the present invention is all more satisfactory, and easy to use, and curing rate of drying is very fast, is beneficial to very much the raising of production efficiency.
The above-mentioned object with reference to embodiment is to describe the present invention, and is illustrative rather than determinate.For a person skilled in the art, do not deviating under the prerequisite of scope of the present invention and general plotting, it is apparent according to method of the present invention, making different modifications and variations, within should belonging to protection scope of the present invention.
Claims (11)
1. a high heat conduction high reliability ultraviolet curing type LED conductive silver glue, is characterized in that being comprised of following parts by weight of component:
2. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 1, is characterized in that described silicon sol blending and modifying epoxy acrylic ester prepolymer prepared by the following method:
A, take appropriate epoxy glyceride, while system being warming up to 60～80 ℃ under the condition that constantly passes into nitrogen, slowly drip a certain amount of acrylate monomer, be controlled in 0.5～3h and dropwise, after dropwising, be warming up to 90～120 ℃, isothermal reaction finishes reaction when system acid number drops to 4～8mgKOH/g, be cooled to room temperature discharging, make epoxy acrylic ester prepolymer;
Under b, room temperature, in the presoma silicon source taking in proportion, add 0.1～3.5moLL
-1hydrochloric acid soln is until system pH is between 3～4, then stirs 10～48h until system is evenly clarified with 600～1000rpm rotating speed, makes silicon sol;
C, the prepared epoxy acrylic ester prepolymer of a step and the prepared silicon sol of b step are stirred under room temperature, obtain silicon sol blending and modifying epoxy acrylic ester prepolymer;
Wherein the consumption of each raw material be take epoxy glyceride as benchmark, presoma silicon source: the mol ratio of epoxy glyceride is 0.1～1, acrylate monomer: the mol ratio of epoxy glyceride is 0.5～2.
3. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, is characterized in that described epoxy glyceride is one or more the mixture in o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate, terephthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester and trimellitic acid three-glycidyl ester.
4. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, is characterized in that described acrylate monomer is one or both in vinylformic acid and methacrylic acid.
5. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, it is characterized in that described presoma silicon source is one or more the mixture in methyl silicate, tetraethoxy, Union carbide A-162, vinyltriethoxysilane, γ-aminopropyl triethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and gamma-mercaptopropyltriethoxysilane.
6. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, it is characterized in that described reactive thinner is vinylbenzene, vinyl pyrrolidone, n-butyl acrylate, isobutyl acrylate, senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, iso-bornyl acrylate, β-propyloic acrylic ester, 2-phenoxyethyl acrylate, 1, 6-hexylene glycol double methacrylate, two contracting propylene glycol double methacrylates, tripropylene glycol double methacrylate, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, two contracting trimethylolpropane tetra-acrylate, the mixture of one or more in double pentaerythritol C5 methacrylate and double pentaerythritol methacrylate.
7. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, it is characterized in that described light trigger is st-yrax, α, alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-methyl isophthalic acid-(4-first sulfydryl phenyl)-2-morpholine-1-acetone and 2-phenyl-2,2-dimethylamino-1-(4-morpholinyl phenyl) mixture of one or more in-1-butanone.
8. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 2, it is characterized in that described conductive silver powder is one or both or three kinds in the flake silver powder of crossing through alkyd mixing solutions immersion treatment respectively, spherical silver powder and unformed silver powder, described alkyd mixing solutions is the solution that alcohol and acid mix by weight 1～30:1.
9. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 8, it is characterized in that described alcohol is one or more the mixture in ethanol, methyl alcohol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, described acid is one or more the mixture in hydrochloric acid, sulfuric acid, nitric acid.
10. a kind of high heat conduction high reliability ultraviolet curing type LED conductive silver glue according to claim 1, is characterized in that described auxiliary agent is one or more the mixture in flow agent, defoamer, wetting dispersing agent.
The preparation method of the high heat conduction high reliability ultraviolet curing type LED conductive silver glue in 11. 1 kinds of claims 1～10 described in any one, is characterized in that comprising the following steps:
First silicon sol blending and modifying epoxy acrylic ester prepolymer, reactive thinner, light trigger, auxiliary agent are added respectively and disperse in cylinder with the pre-dispersed 10～30min of 600～1200rpm rotating speed; Then slowly add conductive silver powder, and with rotating speed dispersed with stirring 20～30min of 2000～5000rpm; Pass into again three-roller and grind, until test its fineness not higher than 20 μ m with Hegman grind gage; Last vacuumizing and defoaming makes conductive silver glue finished product.
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| CN201310492711.0A CN103555251B (en) | 2013-10-18 | 2013-10-18 | High-heat-conductivity high-reliability ultraviolet-curing LED (light-emitting diode) electrically-conductive silver adhesive and preparation method thereof |
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| CN201310492711.0A CN103555251B (en) | 2013-10-18 | 2013-10-18 | High-heat-conductivity high-reliability ultraviolet-curing LED (light-emitting diode) electrically-conductive silver adhesive and preparation method thereof |
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| CN103555251B CN103555251B (en) | 2015-03-11 |
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| CN104152060A (en) * | 2014-08-18 | 2014-11-19 | 东莞保明亮环保科技有限公司 | UV-curable conductive adhesive |
| CN104312516A (en) * | 2014-10-28 | 2015-01-28 | 成都纳硕科技有限公司 | High-cohesiveness ultraviolet-curing adhesive and preparation method thereof |
| CN104558444A (en) * | 2015-01-14 | 2015-04-29 | 平湖阿莱德实业有限公司 | Photo-cured heat-conductive film and production method thereof |
| CN105161221A (en) * | 2015-10-20 | 2015-12-16 | 西安创联光电新材料有限公司 | Preparation method of copper electronic paste for piezoelectric ceramics |
| CN105936816A (en) * | 2016-06-21 | 2016-09-14 | 阜阳市光普照明科技有限公司 | Siloxane hybridization modified epoxy resin adhesive for encapsulating chips of LED plant growth lamps |
| CN106681070A (en) * | 2017-03-14 | 2017-05-17 | 惠科股份有限公司 | Method for bonding array substrate and flexible circuit board, liquid crystal panel and liquid crystal display |
| CN108084367A (en) * | 2017-12-29 | 2018-05-29 | 安徽科邦树脂科技有限公司 | A kind of antibiotic property acrylic resin |
| CN108752875A (en) * | 2018-06-27 | 2018-11-06 | 刘青 | A kind of preparation method of silica-epoxy acrylate |
| CN112054322A (en) * | 2020-09-04 | 2020-12-08 | 立讯精密工业股份有限公司 | Connecting structure of cable and PCB, plug assembly adopting connecting structure and preparation method of plug assembly |
| CN112510137A (en) * | 2020-12-10 | 2021-03-16 | 广东聚科照明股份有限公司 | Production method of integrated lamp bead |
| CN112951953A (en) * | 2019-12-11 | 2021-06-11 | 深圳市聚飞光电股份有限公司 | LED printing method |
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| CN104152060A (en) * | 2014-08-18 | 2014-11-19 | 东莞保明亮环保科技有限公司 | UV-curable conductive adhesive |
| CN104312516A (en) * | 2014-10-28 | 2015-01-28 | 成都纳硕科技有限公司 | High-cohesiveness ultraviolet-curing adhesive and preparation method thereof |
| CN104312516B (en) * | 2014-10-28 | 2015-12-30 | 成都纳硕科技有限公司 | A kind of high agglutinating value(of coal) ultraviolet photo-curing cementing agent and preparation method thereof |
| CN104558444A (en) * | 2015-01-14 | 2015-04-29 | 平湖阿莱德实业有限公司 | Photo-cured heat-conductive film and production method thereof |
| CN105161221B (en) * | 2015-10-20 | 2017-05-24 | 西安创联光电新材料有限公司 | Preparation method of copper electronic paste for piezoelectric ceramics |
| CN105161221A (en) * | 2015-10-20 | 2015-12-16 | 西安创联光电新材料有限公司 | Preparation method of copper electronic paste for piezoelectric ceramics |
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| CN106681070A (en) * | 2017-03-14 | 2017-05-17 | 惠科股份有限公司 | Method for bonding array substrate and flexible circuit board, liquid crystal panel and liquid crystal display |
| CN106681070B (en) * | 2017-03-14 | 2019-09-03 | 惠科股份有限公司 | The adhesive bonding method of array substrate and flexible circuit board, liquid crystal display panel and liquid crystal display |
| CN108084367A (en) * | 2017-12-29 | 2018-05-29 | 安徽科邦树脂科技有限公司 | A kind of antibiotic property acrylic resin |
| CN108752875A (en) * | 2018-06-27 | 2018-11-06 | 刘青 | A kind of preparation method of silica-epoxy acrylate |
| CN112951953A (en) * | 2019-12-11 | 2021-06-11 | 深圳市聚飞光电股份有限公司 | LED printing method |
| CN112054322A (en) * | 2020-09-04 | 2020-12-08 | 立讯精密工业股份有限公司 | Connecting structure of cable and PCB, plug assembly adopting connecting structure and preparation method of plug assembly |
| CN112510137A (en) * | 2020-12-10 | 2021-03-16 | 广东聚科照明股份有限公司 | Production method of integrated lamp bead |
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