CN102311714A - High thermal and electric conducting adhesive filled with nanometer silver and preparation method thereof - Google Patents
High thermal and electric conducting adhesive filled with nanometer silver and preparation method thereof Download PDFInfo
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Abstract
The invention which discloses a high thermal and electric conducting adhesive filled with nanometer silver belongs to the technical field of electronic packaging material preparation. In the invention, nanometer silver powder which has the characteristic of low melting point (melting is realized under a condition of below 250DEG C) is used to prepare the high thermal and electric conducting electronic adhesive, and disadvantages of high viscosity, decreased mechanical property and low thermal conductivity which are caused by the high filling volume in filling traditional single micrometer silver powder are overcome. According to the present invention, the nanometer silver powder is prepared with a chemical process, so the preparative nanometer silver powder has the advantages of small particle size and good monodispersion; and the electric conducting adhesive which is prepared by treating the preparative nanometer powder combined with the micron silver powder which has a sheet shape as a thermal and electric conducting filler of the high thermal and electric conducting adhesive has more excellent performances which comprise characteristics of high thermal conductivity, high electric conductivity, high shear strength, high impact strength, proper viscosity and thixotropy and the like than electric conducting adhesives filled with pure silver powder having a sheet shape, and can be widely applied to the bonding of large power LED chips and electronic packaging which needs good thermal conductivity.
Description
Technical field
The invention belongs to the electronic material preparation field; Refer in particular to a kind of nanometer silver and fill high heat-conductivity conducting glue and preparation method thereof; Its nano-silver conductive particle is synthetic via chemical method, through selecting cooperating between specific micron order silver powder and nano silver particles, prepares the high heat-conductivity conducting glue of excellent performance.
Background technology
Conductive resin is as a kind of novel electron environment-friendly materials, just progressively replaces wiping solder and is widely used in various fields such as LED encapsulation, IC Chip Packaging and PCB.Conductive resin is made up of macromolecule matrix, conductive filler material and auxiliary agent etc. usually, and mostly typical macromolecule matrix is epoxy resin, and conductive filler material comprises silver powder, copper powder, aluminium powder, carbon black etc., and auxiliary agent comprises solidifying agent etc.Silver powder is because its high conductivity and conductivity are the main stuffing of conductive resin.
In recent years along with technological continuous development such as chip design, heat dissipation design; High-power LED encapsulation has obtained considerable progress, and high-power LED chip is lighted for a long time and will be produced great amount of heat, and this requires the electronics sizing agent of adhering chip and led support not only to need high intensity; Suitable viscosity and thixotropy; Also need it to have the favorable conductive thermal conductivity, and higher heat conductivility helps the heat radiation of led chip, can reduce the light decay of LED lamp.
Silver is superior high conduction highly heat-conductive material, and with the metallographic ratio, price has greater advantages.So present silver remains functional stuffing ideal in the conductive resin.The silver powder that present conductive resin uses is size distribution very wide sphere or flake silver powder basically, and these silver powder are processed through traditional chemical method and mechanical mill, and the pattern of particle is quite difficult with size control, and is repeated relatively poor.The performance of conductive resin can only be filled a prescription through experimental groping.USP 7524893 provides a kind of preparation method of conductive resin, and conductive powder body is about 90% commercial silver powder, mixes a small amount of copper powder or zinc powder, improves stability.USP 7262511 utilizes the very wide micron order silver powder of size distribution and a small amount of nano-silver powder to mix, and prepares conductive resin, improves electrical and thermal conductivity.Yet used nano-silver powder particle diameter is all bigger in these methods, all at 50nm even more than the 100nm; For nano-silver powder, there is direct relation between the particle diameter of its melting temperature and nano-silver powder, generally speaking; Particle diameter is below 30nm; The fusing point of nano-silver powder can be low to moderate below 250 ℃, and particle diameter is thin more, and fusing point is low more.In conductive resin, fill particle diameter less than the 30nm nano-silver powder; Its nanometer silver in the heated baking solidification process will produce fusing; In process of cooling; Can directly soak between these nano-silver powders, and no longer be to contact through a contact or face as common micro-silver powder to realize contact, realize the conductive and heat-conductive of conductive filler material.
Summary of the invention
The nanometer silver that technical problem to be solved by this invention provides that a kind of thermal conductivity is high, intensity is high, good conductivity and viscosity and thixotropy are suitable for the some glue in the LED packaging process is filled high heat-conductivity conducting glue.For solving above technical problem, the present invention adopts following technical scheme:
Said conductive resin is the uniform mixture of conducting particles, epoxy resin, solvent and solidifying agent, and said conducting particles comprises micro-silver powder and nano-silver powder, and the weight ratio of said each component is:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
(2) epoxy resin: 4.5-15%;
(3) solvent: 0-2%;
(4) solidifying agent: 3-12%;
More than each component add up and be absolutely.
Preferably, said micro-silver powder, its tap density is greater than 2.0g/ml, and median size is between 3-15 μ m.
Preferably, said nano-silver powder, its diameter is less than 30nm, and tap density is greater than 2.0g/ml.
Preferably, the quality of said micro-silver powder quality (M), nano-silver powder (N) than scope is: M:N=10:1 ~ 2:1.
Preferably, said solvent is the polar solvent that mixes with hexane, is specially ethanol, acetone or N (DMF or two kinds, three kinds or whole mixture between them.
Preferably, said solidifying agent is a kind of of methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride or this both mixing.
Through above technical scheme, not only thermal conductivity is high, intensity is high for the disclosed high heat-conductivity conducting glue of the present invention, good conductivity but also viscosity and thixotropy are suitable for the some glue in the LED packaging process.
The present invention also provides above nanometer silver to fill the preparation method of high heat-conductivity conducting glue, and it may further comprise the steps:
(1) configuration A component: the hexane solution of Silver monoacetate;
Configuration B component: Peng Qinghuana (NaBH
4) aqueous solution;
Configuration C component: the hexane solution of oleyl amine;
The B component and the C component solution of certain volume ratio slowly are added drop-wise in the A component solution, and vigorous stirring waits to drip the continued vigorous stirring simultaneously; Obtain brownish black liquid, after leaving standstill, solution meeting layering; The upper strata is a dark solution, and lower floor is a water or jelly shape light color material, and the water or the jelly shape light color material of lower floor removed; Remove the water of lower floor or the solution that the later solution of jelly shape light color material promptly contains nano particle, after this solution heating, vacuumize; The overwhelming majority's hexane is removed, add the mixed solution of hexane/ethanol/acetone toward the liquid the inside that obtains, ultra-sonic dispersion; Centrifugal then, repeat above-mentioned steps, obtain the nano-silver powder of size at last less than 30nm;
(2), with above-mentioned nano-silver powder, mix with micro-silver powder, epoxy resin, solvent and solidifying agent, weight ratio is during mixing:
1), conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
2), epoxy resin: 4.5-15%;
3), solvent: 0-2%;
4), solidifying agent: 3-12%;
More than each component add up and be absolutely.
Preferably, the mol ratio of the A component in the said step (1), B component, C component is: (1 ~ 5): (3 ~ 12): 5.
Advantage of the present invention is: the nano-silver powder particle diameter through present method obtains is superfine, and the preparation process is simple, and the distribution of particle is quite even.And, can determine the size of prepared nano-silver powder through the mole proportioning of reactant.
The present invention realizes the contact between the silver powder particles through the low-temperature sintering of nano-silver powder, thereby produces higher electrical and thermal conductivity performance.For nano-silver powder, there is direct relation between the particle diameter of its melting temperature and nano-silver powder, generally speaking, particle diameter is below 30nm, and the fusing point of nano-silver powder can be low to moderate below 250 ℃, and particle diameter is thin more, and fusing point is low more.In conductive resin, fill particle diameter less than the 30nm nano-silver powder; Its nanometer silver in the heated baking solidification process will produce fusing; In process of cooling; Can directly soak between these nano-silver powders, and no longer be to contact through a contact or face as common micro-silver powder to realize contact, with conductive and heat-conductive.
Description of drawings
The silver-colored nano powder TEM figure of Fig. 1 particle diameter about 5 nanometers;
The silver-colored nano powder TEM figure of Fig. 2 particle diameter about 30 nanometers;
Fig. 3 nano powder is through pattern contrast synoptic diagram before and after the 150-250 ℃ of sintering;
The performance comparison table of the conductive resin that Fig. 4 embodiment of the invention 4-9 and comparative example 1 are prepared.
Embodiment
The invention discloses a kind of nanometer silver and fill high heat-conductivity conducting glue, belong to the electronic package material preparing technical field.The present invention has combined nano-silver powder to have the characteristics of lower melting point (under the condition below 250 ℃, just can realize fusing); The electronics sizing agent that has prepared high heat-conductivity conducting; Need possess high loading level and cause viscosity higher thereby overcome traditional single micro-silver powder filling, the shortcoming that mechanical property weakens and thermal conductivity is still not high.The present invention has adopted chemical method to prepare silver-colored nano powder, and the prepared nano-silver powder particle diameter that obtains is little, monodispersity good; The conductive resin that combines micron-stage sheet-like silver powder to prepare the nano powder of preparation as the conductive and heat-conductive filler in the high heat-conductivity conducting glue; To have more excellent performance than the conductive resin of filling with pure flake silver powder; Comprise that high thermal conductivity, high conductivity, high shear strength, high impact strength reach characteristics such as more suitable viscosity and thixotropy, but widespread use and high-power LED chip are bonding and need the Electronic Packaging of thermal conductive resin to use.
Specifically, conductive resin according to the invention is the uniform mixture of conducting particles, epoxy resin, solvent and solidifying agent, and said conducting particles comprises micro-silver powder and nano-silver powder, and the weight ratio of said each component is:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
(2) epoxy resin: 4.5-15%;
(3) solvent: 0-2%;
(4) solidifying agent: 3-12%;
More than each component add up and be absolutely.
Said micro-silver powder, its tap density are greater than 2.0g/ml, and median size is between 3-15 μ m.
Said nano-silver powder, its diameter is less than 30nm, and tap density is greater than 2.0g/ml.
The quality of said micro-silver powder quality (M), nano-silver powder (N) than scope is: M:N=10:1 ~ 2:1.
Said solvent is the polar solvent that mixes with hexane, is specially ethanol, acetone or N (DMF or two kinds, three kinds or whole mixture between them.
Said solidifying agent is a kind of of methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride or this both mixing.
Said epoxy resin is a kind of or its mixture among E44, E51, TDE-85, the ERL4221.
The preparation method that a kind of nanometer silver provided by the present invention is filled high heat-conductivity conducting glue can pass through also A component, B component and C component concentrations are confirmed that the mode of recently controlling mol ratio with volume obtains that preparation process just is refined as like this:
(1) A component: configuration concentration is the hexane solution of 0.1mol/L Silver monoacetate;
The B component: configuration concentration is 0.3mol/L Peng Qinghuana (NaBH
4) aqueous solution;
The C component: the volumetric concentration of configuration oleyl amine is 50% hexane solution;
The B component and the C component solution of certain volume ratio slowly are added drop-wise in the A component solution, and vigorous stirring waited to drip the continued vigorous stirring 2 hours simultaneously, obtained brownish black liquid.After leaving standstill 2 hours, solution meeting layering, the upper strata is a dark solution, lower floor is water or jelly shape light color material, removes with the water or the jelly shape light color material of separating funnel with lower floor.Remove the solution that the later solution of water or jelly promptly contains nano particle.This solution is positioned over the vacuum drying oven internal heating after 30-50 ℃, vacuumizes, can the overwhelming majority's hexane be removed, obtain very thick liquid.Add volume inside and be 3-5 times of hexane/ethanol/acetone of A component volume (hexane: ethanol: the mixed solution of acetone=1:1:1), ultra-sonic dispersion 5-15 minute, centrifugal under the 3000-10000rpm rotating speed then, repeat above-mentioned steps 3-5 time.With obtaining the nano-silver powder of size less than 30nm.
(2) with above-mentioned nano-silver powder, mix with micro-silver powder, epoxy resin, solvent and solidifying agent, weight ratio is during mixing:
1), conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
2), epoxy resin: 4.5-15%;
3), solvent: 0-2%;
4), solidifying agent: 3-12%;
More than each component add up and be absolutely.
The volume ratio of the A in the said step (1), B, C three components is: volume weight part of A component, B component, C component is:
A component: 1-5 parts by volume;
B component: 1-4 parts by volume;
C component: 1 parts by volume.
Below set forth in detail through specific embodiment:
Embodiment 1: the uniform silver-colored nano powder of preparation particle diameter:
Dispose following solution:
The A component: concentration is the hexane solution of 0.1mol/L Silver monoacetate;
The B component: concentration is 0.3mol/L Peng Qinghuana (NaBH
4) aqueous solution;
The C component: the volumetric concentration of oleyl amine is 50% hexane solution;
The B component of 1 volume and the C component solution of 1 volume slowly are added drop-wise in the A component solution of 1 volume, and vigorous stirring 2h obtains dark brown solution simultaneously.After leaving standstill 2 hours, solution meeting layering, the upper strata is a dark solution, lower floor is water or jelly shape light color material, removes with the water or the jelly shape light color material of separating funnel with lower floor.Remove the solution that the later solution of water or jelly promptly contains nano particle.After this solution is positioned over vacuum drying oven internal heating to 50 ℃, vacuumize, can the overwhelming majority's hexane be removed, obtain very thick object.Add inside 3 times of A component volumes hexane/ethanol/acetone (hexane: ethanol: the mixed solution of acetone=1:1:1), ultra-sonic dispersion 10 minutes, centrifugal under the 8000rpm rotating speed then, repeat above-mentioned steps 5 times.Fig. 1 is the TEM picture through above process synthetic nano-silver powder; Resultant nano-silver powder is of a size of 5-10nm.
Embodiment 2: the uniform silver-colored nano powder of preparation particle diameter:
Dispose following solution:
The A component: concentration is the hexane solution of 0.1mol/L Silver monoacetate;
The B component: concentration is 0.3mol/L Peng Qinghuana (NaBH
4) aqueous solution;
The C component: the volumetric concentration of oleyl amine is 50% hexane solution;
The B component of 4 volumes and the C component solution of 1 volume slowly are added drop-wise in the A component solution of 5 volumes, and vigorous stirring 2h obtains dark brown solution simultaneously.After leaving standstill 2 hours, solution meeting layering, the upper strata is a dark solution, lower floor is water or jelly shape light color material, removes with the water or the jelly shape light color material of separating funnel with lower floor.Remove the solution that the later solution of water or jelly promptly contains nano particle.After this solution is positioned over vacuum drying oven internal heating to 30 ℃, vacuumize, can the overwhelming majority's hexane be removed, obtain very thick object.Add inside 5 times of A component volumes hexane/ethanol/acetone (hexane: ethanol: the mixed solution of acetone=1:1:1), ultra-sonic dispersion 5 minutes, centrifugal under the 3000rpm rotating speed then, repeat above-mentioned steps 5 times.Fig. 2 is the TEM picture through above process synthetic nano-silver powder; Resultant nano-silver powder is of a size of 25-30nm.
Embodiment 3: the uniform silver-colored nano powder of preparation particle diameter:
Dispose following solution:
The A component: concentration is the hexane solution of 0.1mol/L Silver monoacetate;
The B component: concentration is 0.3mol/L Peng Qinghuana (NaBH
4) aqueous solution;
The C component: the volumetric concentration of oleyl amine is 50% hexane solution;
The C component solution of the B component of 2 volumes and 1 volume slowly is added drop-wise in the A component solution of 3 volumes (dripping off in about 15 minutes), vigorous stirring 2h obtains dark brown solution simultaneously.After leaving standstill 2 hours, solution meeting layering, the upper strata is a dark solution, lower floor is water or jelly shape light color material, removes with the water or the jelly shape light color material of separating funnel with lower floor.Remove the solution that the later solution of water or jelly promptly contains nano particle.After this solution is positioned over vacuum drying oven internal heating to 30 ℃, vacuumize, can the overwhelming majority's hexane be removed, obtain very thick object.Add inside 4 times of A component volumes hexane/ethanol/acetone (hexane: ethanol: the mixed solution of acetone=1:1:1), ultra-sonic dispersion 15 minutes, centrifugal under the 10000rpm rotating speed then, repeat above-mentioned steps 5 times.With the nano-silver powder that obtains being of a size of 10-15nm.
Above embodiment proves that superfine through the nano-silver powder particle diameter that present method obtains, the preparation process is simple, and the distribution of particle is quite even.And, can determine the size of prepared nano-silver powder through the mole proportioning (in above embodiment, being converted into volume ratio) of reactant.
Embodiment 4: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 10 microns,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=5:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 88%;
(2) epoxy resin ERL4221:6.5%;
(3) solvent DMF: 0.5%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 5%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Embodiment 5: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 15 microns,
Embodiment 1 prepared diameter is the 5-10 nano-silver powder,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=10:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 82.5%;
(2) epoxy resin E51:8.5%;
(3) solvent acetone: 0.5%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 8.5%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer
Embodiment 6: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 3 microns,
Embodiment 2 prepared diameters are the 25-30 nano-silver powder,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=2:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 92%;
(2) epoxy resin ERL4221:4.5%;
(3) solvent: 0.5%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 3%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Embodiment 7: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 8 microns,
Embodiment 1 prepared diameter is the 5-10 nano-silver powder,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=6:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 75%;
(2) epoxy resin E44:5%, epoxy resin ERL4221:5%;
(3) etoh solvent: 1%;
(4) solidifying agent methyl tetrahydro phthalic anhydride: 9%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Embodiment 8: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 10 microns,
Embodiment 1 prepared diameter is the 5-10 nano-silver powder,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=3:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 77%;
(2) epoxy resin E51:10%;
(3) solvent DMF: 1%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 6%, methyl tetrahydro phthalic anhydride: 6%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Embodiment 9: the preparation of conductive resin when of micro-silver powder and nano-silver powder particle diameter and quality
The size and the mass ratio of micro-silver powder and nano-silver powder are following:
The median size of micro-silver powder is 5 microns,
The mass ratio of micro-silver powder quality (M), nano-silver powder (N) is M:N=5:1.
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 86%;
(2) epoxy resin TDE85:12%;
(3) etoh solvent: 0%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 12%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Comparative example 1: the preparation of conventional micro-silver powder filled conductive glue
The size of micro-silver powder is following:
The median size of micro-silver powder is 5 microns,
With above-mentioned conducting particles and epoxy resin, solvent, solidifying agent etc. mix and obtain conductive resin.Wherein each material title and quality proportioning are:
(1) conducting particles (being micro-silver powder): 86%;
(2) epoxy resin TDE85:12%;
(3) etoh solvent: 1%;
(4) solidifying agent methyl hexahydrophthalic anhydride: 11%.
Prepared conductive resin behind 90 ℃ of baking 1h again 200 ℃ solidify 1 hour after; Adopt the thermal conductivity of Netzsch LFA457 specimen; Adopting sheet glass is that the base prepares the electroconductibility specimen; Prepare the electric conductivity that adopts the four probe method specimen behind the conductive resin sample according to length, width and the thickness of sheet glass, viscosity and thixotropy data have the test of Brookfield HBDV-II+PCP viscometer.
Prove through above embodiment; The conductive resin that combines micron-stage sheet-like silver powder to prepare the nano powder of preparation as the conductive and heat-conductive filler in the high heat-conductivity conducting glue; To have more excellent performance than the conductive resin of filling with pure flake silver powder; Comprise that high thermal conductivity, high conductivity, high shear strength, high impact strength reach characteristics such as more suitable viscosity and thixotropy, but widespread use and high-power LED chip are bonding and need the Electronic Packaging of thermal conductive resin to use.
For reaching illustration purpose; This patent is narrated as above with preferred embodiments, and so it is not in order to qualification the present invention, and any affiliated technical field is not breaking away from the spirit and scope of the present invention; When can doing a little change and polishing, so protection scope of the present invention is when exceeding with claims.
Claims (8)
1. a nanometer silver is filled high heat-conductivity conducting glue, it is characterized in that said conductive resin is the uniform mixture of conducting particles, epoxy resin, solvent and solidifying agent, and said conducting particles comprises micro-silver powder and nano-silver powder, and the weight ratio of said each component is:
(1) conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
(2) epoxy resin: 4.5-15%;
(3) solvent: 0-2%;
(4) solidifying agent: 3-12%;
More than each component add up and be absolutely.
2. a kind of nanometer silver as claimed in claim 1 is filled high heat-conductivity conducting glue, it is characterized in that said micro-silver powder, and its tap density is greater than 2.0g/ml, and median size is between 3-15 μ m.
3. a kind of nanometer silver as claimed in claim 1 is filled high heat-conductivity conducting glue, it is characterized in that said nano-silver powder, and its diameter is less than 30nm, and tap density is greater than 2.0g/ml.
4. a kind of nanometer silver as claimed in claim 1 is filled high heat-conductivity conducting glue, it is characterized in that the quality of said micro-silver powder quality (M), nano-silver powder (N) than scope is: M:N=10:1 ~ 2:1.
5. a kind of nanometer silver as claimed in claim 1 is filled high heat-conductivity conducting glue, it is characterized in that said solvent is the polar solvent that mixes with hexane, is specially ethanol, acetone or N (DMF) or two kinds, three kinds or whole mixture between them.
6. a kind of nanometer silver as claimed in claim 1 is filled high heat-conductivity conducting glue, it is characterized in that said solidifying agent is the wherein a kind of of methyl tetrahydro phthalic anhydride and methyl hexahydrophthalic anhydride or this both mixing.
7. a kind of nanometer silver as claimed in claim 1 is filled the preparation method of high heat-conductivity conducting glue, it is characterized in that it may further comprise the steps:
(1) configuration A component: the hexane solution of Silver monoacetate;
Configuration B component: Peng Qinghuana (NaBH
4) aqueous solution;
Configuration C component: the hexane solution of oleyl amine;
The B component and the C component solution of certain volume ratio slowly are added drop-wise in the A component solution, and vigorous stirring waits to drip the continued vigorous stirring simultaneously; Obtain brownish black liquid, after leaving standstill, solution meeting layering; The upper strata is a dark solution, and lower floor is a water or jelly shape light color material, and the water or the jelly shape light color material of lower floor removed; Remove the water of lower floor or the solution that the later solution of jelly shape light color material promptly contains nano particle, after this solution heating, vacuumize; The overwhelming majority's hexane is removed, add the mixed solution of hexane/ethanol/acetone toward the liquid the inside that obtains, ultra-sonic dispersion; Centrifugal then, repeat above-mentioned steps, obtain the nano-silver powder of size at last less than 30nm;
(2), with above-mentioned nano-silver powder, mix with micro-silver powder, epoxy resin, solvent and solidifying agent, weight ratio is during mixing:
1), conducting particles (being the quality summation of micro-silver powder, nano-silver powder): 65-95%;
2), epoxy resin: 4.5-15%;
3), solvent: 0-2%;
4), solidifying agent: 3-12%;
More than each component add up and be absolutely.
8. a kind of nanometer silver as claimed in claim 7 is filled the preparation method of high heat-conductivity conducting glue, it is characterized in that A component, the B component in the said step (1), the mol ratio of C component are: (1 ~ 5): (3 ~ 12): 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110247354 CN102311714B (en) | 2011-08-24 | 2011-08-24 | High thermal and electric conducting adhesive filled with nanometer silver and preparation method thereof |
Applications Claiming Priority (1)
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2810310A4 (en) * | 2012-02-01 | 2016-01-20 | Baker Hughes Inc | Thermoelectric devices using sintered bonding |
| CN106854447A (en) * | 2016-12-02 | 2017-06-16 | 天津宝兴威科技股份有限公司 | A kind of preparation method of nano-silver conductive glue |
| CN107011841A (en) * | 2016-01-28 | 2017-08-04 | 光洋应用材料科技股份有限公司 | Conductive silver adhesive and conductive silver layer |
| CN109585488A (en) * | 2019-01-02 | 2019-04-05 | 京东方科技集团股份有限公司 | LED display base plate and preparation method thereof, display device |
| CN110709487A (en) * | 2017-06-07 | 2020-01-17 | 田中贵金属工业株式会社 | Thermally and electrically conductive adhesive composition |
| CN113555166A (en) * | 2021-08-09 | 2021-10-26 | 东莞市松乔电子有限公司 | Method for manufacturing silver powder conductive adhesive tape capable of preventing oil absorption deformation and silver powder conductive adhesive tape |
| CN114262583A (en) * | 2021-12-21 | 2022-04-01 | 深圳市中金岭南有色金属股份有限公司科学技术开发院 | Silver conductive adhesive for high-conductivity interconnection die bonding of high-power LED chips and components |
| CN115124951A (en) * | 2022-05-13 | 2022-09-30 | 上海本诺电子材料有限公司 | Nano conductive adhesive and preparation method thereof |
| CN115678015A (en) * | 2021-07-29 | 2023-02-03 | 华为技术有限公司 | Modified organic silicon resin, conductive adhesive and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008045351A2 (en) * | 2006-10-06 | 2008-04-17 | Momentive Performance Materials Inc. | Composition and associated method |
| CN101629057A (en) * | 2009-08-22 | 2010-01-20 | 漳立冰 | Nano conductive adhesive and preparation method thereof |
-
2011
- 2011-08-24 CN CN 201110247354 patent/CN102311714B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008045351A2 (en) * | 2006-10-06 | 2008-04-17 | Momentive Performance Materials Inc. | Composition and associated method |
| CN101629057A (en) * | 2009-08-22 | 2010-01-20 | 漳立冰 | Nano conductive adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 虞莲莲: "《实用有色金属材料手册》", 31 January 2002, 机械工业出版社 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2810310A4 (en) * | 2012-02-01 | 2016-01-20 | Baker Hughes Inc | Thermoelectric devices using sintered bonding |
| CN107011841A (en) * | 2016-01-28 | 2017-08-04 | 光洋应用材料科技股份有限公司 | Conductive silver adhesive and conductive silver layer |
| CN106854447A (en) * | 2016-12-02 | 2017-06-16 | 天津宝兴威科技股份有限公司 | A kind of preparation method of nano-silver conductive glue |
| CN110709487B (en) * | 2017-06-07 | 2022-01-14 | 田中贵金属工业株式会社 | Thermally and electrically conductive adhesive composition |
| CN110709487A (en) * | 2017-06-07 | 2020-01-17 | 田中贵金属工业株式会社 | Thermally and electrically conductive adhesive composition |
| CN109585488A (en) * | 2019-01-02 | 2019-04-05 | 京东方科技集团股份有限公司 | LED display base plate and preparation method thereof, display device |
| CN115678015A (en) * | 2021-07-29 | 2023-02-03 | 华为技术有限公司 | Modified organic silicon resin, conductive adhesive and preparation method thereof |
| CN113555166A (en) * | 2021-08-09 | 2021-10-26 | 东莞市松乔电子有限公司 | Method for manufacturing silver powder conductive adhesive tape capable of preventing oil absorption deformation and silver powder conductive adhesive tape |
| CN113555166B (en) * | 2021-08-09 | 2022-10-04 | 东莞市松乔电子有限公司 | Method for manufacturing silver powder conductive adhesive tape capable of preventing oil absorption deformation and silver powder conductive adhesive tape |
| CN114262583A (en) * | 2021-12-21 | 2022-04-01 | 深圳市中金岭南有色金属股份有限公司科学技术开发院 | Silver conductive adhesive for high-conductivity interconnection die bonding of high-power LED chips and components |
| CN114262583B (en) * | 2021-12-21 | 2022-12-20 | 深圳市中金岭南有色金属股份有限公司科学技术开发院 | Silver conductive adhesive for high-conductivity interconnection die bonding of high-power LED chips and components |
| CN115124951A (en) * | 2022-05-13 | 2022-09-30 | 上海本诺电子材料有限公司 | Nano conductive adhesive and preparation method thereof |
| CN115124951B (en) * | 2022-05-13 | 2024-03-12 | 上海本诺电子材料有限公司 | Nanometer conductive adhesive and preparation method thereof |
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