CN113412321A - Organic silicon resin conductive adhesive and preparation method and application thereof - Google Patents
Organic silicon resin conductive adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN113412321A CN113412321A CN202080000045.2A CN202080000045A CN113412321A CN 113412321 A CN113412321 A CN 113412321A CN 202080000045 A CN202080000045 A CN 202080000045A CN 113412321 A CN113412321 A CN 113412321A
- Authority
- CN
- China
- Prior art keywords
- particles
- silver
- conductive
- dimensional dendritic
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 87
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 331
- 229920002545 silicone oil Polymers 0.000 claims abstract description 70
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 171
- 229910052709 silver Inorganic materials 0.000 claims description 171
- 239000004332 silver Substances 0.000 claims description 171
- -1 polysiloxane Polymers 0.000 claims description 91
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 68
- 229910052802 copper Inorganic materials 0.000 claims description 68
- 239000010949 copper Substances 0.000 claims description 68
- 229920001296 polysiloxane Polymers 0.000 claims description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229920002050 silicone resin Polymers 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 14
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 14
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001723 curing Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses an organic silicon resin conductive adhesive which comprises the following components in parts by weight based on 100 parts by weight: 40-84 parts of conductive particles, 10-25 parts of organic silicon resin, 5.5-20 parts of silicone oil, 0.2-3.0 parts of silane coupling agent, 0.01-1 part of catalyst and 0.005-0.05 part of inhibitor; the conductive particles are conductive particles having a three-dimensional dendritic microstructure. The invention also provides a preparation method of the organic silicon resin conductive adhesive and application of the organic silicon resin conductive adhesive in a semiconductor element. According to the invention, the conductive particles with the three-dimensional dendritic microstructure are applied, so that the contact among the conductive particles is multipoint contact, a conductive network is formed, the contact resistance of the conductive network is greatly reduced, and the conductivity is greatly improved; meanwhile, the conductive adhesive obtained by the invention has the advantages of rapid curing, long-time operation and use in a room temperature environment, simple preparation method, mild conditions and suitability for industrial production.
Description
The invention belongs to the technical field of semiconductor materials, and particularly relates to an organic silicon resin conductive adhesive as well as a preparation method and application thereof.
The conductive adhesive is widely used in the manufacture and assembly of electronic equipment, integrated circuits, semiconductor devices, passive elements, solar cells, solar modules and/or light emitting diodes as an adhesive having a certain conductivity after drying or curing. Conductive adhesives provide mechanical bonding and electrical conduction between two surface elements, so they must have good mechanical properties and low resistance electrical conduction properties. Typically, the conductive paste formulation consists of conductive particles and a polymeric resin and additives, where the resin typically provides a mechanical bond between the two components and the conductive particles typically provide the desired electrical continuity.
Firstly, the traditional conductive adhesive uses spherical, spheroidal and flaky silver particles or spherical, spheroidal and flaky silver-coated copper particles, and the contact between two conductive particles is a point contact no matter two spherical conductive particles or two flaky conductive particles, so that the conductive performance is low; therefore, in order to improve the conductive performance of the conductive paste, the amount or amount of the conductive particles must be increased to improve the conductive performance, which leads to an increase in cost. Secondly, the conventional conductive adhesive is easy to dry during the dispensing or printing operation, and is generally exposed for no more than 8 hours at room temperature, and if the exposure time exceeds 8 hours, the unused conductive adhesive becomes difficult to use, which causes inconvenience and waste during the use. Thirdly, the traditional conductive adhesive has long curing time, generally requiring 30min or more, resulting in increased production cycle and reduced production capacity.
Disclosure of Invention
In order to solve the problems, the invention provides the organic silicon resin conductive adhesive, which has high conductive performance, good adhesive force, short curing time and long operability time by using the conductive particles with the three-dimensional dendritic microstructure and adjusting the formula of the conductive adhesive, and solves the problems that the cost is increased, the operation time is short, the curing time is long and the production period is increased in order to improve the conductivity of the conventional conductive adhesive.
The invention also aims to provide a preparation method of the organic silicon resin conductive adhesive, which is simple to operate, mild in condition and easy to implement.
The invention also provides application of the organic silicon resin conductive adhesive in a semiconductor element.
The technical scheme adopted by the invention is as follows:
the organic silicon resin conductive adhesive comprises the following components in parts by weight, based on 100 parts by weight of the total weight;
40-84 parts of conductive particles, 10-25 parts of organic silicon resin, 5.5-20 parts of silicone oil, 0.2-3.0 parts of silane coupling agent, 0.01-1 part of catalyst and 0.005-0.05 part of inhibitor;
wherein the conductive particles are conductive particles having a three-dimensional dendritic microstructure.
Therefore, the contact among the conductive particles is multipoint contact to form a conductive network, which is different from the point contact among the conventional spherical conductive particles, flaky conductive particles or similar spherical conductive particles when the conventional spherical conductive particles, flaky conductive particles or similar spherical conductive particles are mixed, so that the contact resistance is greatly reduced, and the conductive performance is greatly improved; in addition, through multipoint contact, the conductive effect can be achieved when fewer conductive particles are used, so that the using amount of the conductive particles is reduced, the cost is reduced, and the using performance of the conductive adhesive is improved.
Preferably, the specific surface area of the conductive particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2/g。
Thus, the specific surface area of the conductive particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The printing performance of the conductive particles with the three-dimensional dendritic microstructure is ensured while the conductivity of the conductive particles is ensured; when in useThe specific surface area exceeds 3.5m2In the case of the/g, the conductive paste obtained is difficult to print and difficult to use on a large scale.
Preferably, the conductive particles having a three-dimensional dendritic microstructure are silver particles having a three-dimensional dendritic microstructure or silver-coated copper particles having a three-dimensional dendritic microstructure.
As such, in particular embodiments, the conductive particles of the present invention may include silver particles having a three-dimensional dendritic microstructure, and one or more of spherical silver particles, flake silver particles, or spheroidal silver particles;
in particular embodiments, the conductive particles of the present invention may include silver particles having a three-dimensional dendritic microstructure, and one or more of spherical silver particles, flake silver particles, or spheroidal silver particles;
in particular embodiments, the conductive particles of the present invention may include silver-coated copper particles having a three-dimensional dendritic microstructure, and one or more of spherical silver particles, flake silver particles, or spheroidal silver particles;
in particular embodiments, the conductive particles of the present invention may include silver-coated copper particles having a three-dimensional dendritic microstructure, and one or more of spherical silver-coated copper particles, flake-shaped silver-coated copper particles, or spheroidal silver-coated copper particles.
Preferably, the conductive particles are a mixture of spherical silver particles and silver particles having a three-dimensional dendritic microstructure, and the mass ratio of the silver particles having the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver particles is 0.1-50 mu m.
Preferably, the conductive particles are a mixture of spherical silver particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver particles is 0.1-50 mu m.
Preferably, the conductive particles are a mixture of flake-like silver particles and silver particles having a three-dimensional dendritic microstructure, and the mass ratio of the silver particles having the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver particles is 0.1-50 mu m.
Preferably, the conductive particles are a mixture of flake silver particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver particles is 0.1-50 mu m.
Preferably, the conductive particles are a mixture of flaky silver-coated copper particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver-coated copper particles is 0.1-50 mu m.
Preferably, the conductive particles are a mixture of spherical silver-coated copper particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver-coated copper particles is 0.1-50 mu m.
Preferably, the silver particles having a three-dimensional dendritic microstructure have a size of 0.1 to 50 μm.
Preferably, the silver-coated copper particles with the three-dimensional dendritic microstructure have a size of 0.1-50 μm.
Therefore, the printing ink permeability of the pure conductive particles with the three-dimensional dendritic microstructure is weaker than that of spherical particles, flaky particles or spheroidal particles, and when the conductive particles with the three-dimensional dendritic microstructure are mixed with the morphology particles, the advantages of the two parts can be kept, namely the conductivity of the conductive particles is improved, and the problem of poor printing ink permeability of the pure conductive particles with the three-dimensional dendritic microstructure is solved.
Specific embodiments of the present invention are not limited to the specific mixture ratio of the silver particles having the three-dimensional dendritic microstructure or the silver-coated copper particles having the three-dimensional dendritic microstructure to the spherical silver particles, flaky silver particles, spherical silver-coated copper particles, or flaky silver-coated copper particles. The specific embodiment of the present invention may be one or more of silver particles and spherical silver particles having a three-dimensional dendritic microstructure, flake silver particles, spheroidal silver particles, spherical silver-coated copper particles, flake silver-coated copper particles, and spheroidal silver-coated copper particles, and may also be one or more of silver-coated copper particles and spherical silver particles having a three-dimensional dendritic microstructure, flake silver particles, spheroidal silver particles, spherical silver-coated copper particles, flake silver-coated copper particles, and spheroidal silver-coated copper particles.
Wherein the mass ratio of the particles having a three-dimensional dendritic microstructure to the total of the conductive particles is (0.05 to 0.95): 1.
thus, the conductive particles are particles with a three-dimensional dendritic microstructure or a mixture of the particles with other conductive particles, the mass of the particles with the three-dimensional dendritic microstructure accounts for 5-100% of the total mass of the conductive particles, more preferably 5-95%, and the sizes of the conductive particles, spherical particles, flaky particles or spheroidal particles with the three-dimensional dendritic microstructure are all 0.1-50 μm. Therefore, when the conductive particles with the three-dimensional dendritic microstructure are mixed with the conventional flaky, spherical or spheroidal conductive particles, the conductive particles are also in multipoint contact, and the conductivity is good.
Preferably, the conductive particles are silver particles or silver-coated copper particles, wherein the coating weight of silver in the copper-coated particles with the three-dimensional dendritic microstructure is 5-40%.
Preferably, the silicone resin is at least one of methylpolysiloxane, methylhydrogenpolysiloxane, and methylvinylpolysiloxane.
Preferably, the silicone oil is at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methylphenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil and hydroxy hydrogen-containing silicone oil.
Preferably, the silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane and isobutyltriethoxysilane.
Thus, the silane coupling agent bridges a "molecular bridge" between the conductive adhesive and the semiconductor component, such as a chip, to be bonded, i.e., connects two materials having very different properties together to increase the bonding strength.
Preferably, the catalyst is a platinum catalyst.
Preferably, the inhibitor is at least one of 3-methyl-1-butyn-3-ol, 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, pyridine, acrylonitrile, 2-vinyl isopropanol, benzotriazole, an organic phosphine compound and diallyl maleate.
Thus, the conductive adhesive is composed of conductive particles, organic silicon resin, a silane coupling agent, silicone oil, an inhibitor and a catalyst, and the obtained conductive adhesive is a thermosetting conductive adhesive and can be subjected to one-time thermosetting or two-time thermosetting. The one-time thermal curing of the conductive adhesive can be preferably performed within 15-300 s at the temperature of 50-170 ℃, and the one-time curing operation is suitable for products with low repair rate; the twice curing operation is suitable for products with high repair rate, the first curing can be pre-cured within 15-20 s at 50-170 ℃, the cured conductive adhesive and the base material have enough adhesive force to test the performance of the semiconductor element, but the repairing is easy, and the second curing can be cured within 15-300 s at 50-170 ℃.
No matter one-time curing or two-time curing is selected, the conductive adhesive has the characteristics of good adhesion and low resistivity after curing; meanwhile, the conductive adhesive can be operated and used for more than 48 hours at room temperature of 22-25 ℃, which is enough for long-term use under various electronic assembly and solar photovoltaic assembly operation conditions, the viscosity of the conductive adhesive does not rise by more than 20% after being exposed for 24hrs under the room temperature environment, and the viscosity of the conductive adhesive does not rise by more than 50% after being exposed for 48hrs under the room temperature environment; the conductive adhesive is suitable for being used in a dispensing mode, and the conductive adhesive is also suitable for being used in a printing mode. The conductive adhesive can form conductive keys between two substrates or between components and the substrates, and can be used for manufacturing and assembling electronic equipment, integrated circuits, semiconductor devices, passive elements and solar photovoltaic components.
The invention also provides a preparation method of the organic silicon resin conductive adhesive, which comprises the following steps:
s1, weighing the following components in parts by weight: 40-84 parts of conductive particles, 10-25 parts of organic silicon resin, 5.5-20 parts of silicone oil, 0.2-3.0 parts of silane coupling agent, 0.01-1 part of catalyst and 0.005-0.05 part of inhibitor, wherein the conductive particles comprise conductive particles with a three-dimensional dendritic microstructure for later use;
s2, placing the organic silicon resin, the silicone oil, the silane coupling agent, the catalyst and the initiator weighed in the S1 into a reactor, uniformly stirring, adding the conductive particles, and uniformly stirring to obtain a mixture; the agitation mixing process may be mechanical agitation mixing, milling mixing, or a combination of both.
And S3, grinding the mixture to obtain the organic silicon resin conductive adhesive.
The invention also protects the application of the organic silicon resin conductive agent in a semiconductor element.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the conductive particles with the three-dimensional dendritic microstructure are applied, so that the contact among the conductive particles is multipoint contact, a conductive network is formed, the contact resistance of the conductive network is greatly reduced, and the conductivity is greatly improved; meanwhile, the consumption of the conductive particles is reduced, and the cost is effectively reduced;
2. according to the invention, the conductive particles with the three-dimensional dendritic microstructure and the flaky, spherical or spheroidal conductive particles are mixed for use, so that the advantage of high conductivity of the conductive particles with the three-dimensional dendritic microstructure is maintained, and the defect of poor ink permeability of the conductive particles with the three-dimensional dendritic microstructure printed by only using the flaky, spherical or spheroidal conductive particles is overcome by utilizing the good ink permeability of the flaky, spherical or spheroidal conductive particles;
3. the conductive adhesive has the advantages that the conductive adhesive can be quickly cured and can be operated and used for a long time in a room temperature environment by adopting an organic system which is composed of methyl polysiloxane, methyl hydrogen polysiloxane, methyl vinyl polysiloxane, methyl silicone oil, methyl hydrogen silicone oil, methyl vinyl silicone oil, vinyl triethoxysilane, vinyl trimethoxy silicon, 3-methyl-1-butyn-3-ol, 2-vinyl isopropanol and platinum catalyst according to a specific ratio;
4. the preparation method is simple, mild in condition and suitable for industrial production.
FIG. 1 is a schematic view of a contact between two spherical conductive particles of the prior art; wherein 001 represents a spherical conductive particle, and 0011a represents a contact point between two spherical conductive particles;
fig. 2 is an SEM image of one viewing angle of silver particles having a three-dimensional dendritic microstructure;
fig. 3 is an SEM image of another angle of view of silver particles having a three-dimensional dendritic microstructure;
FIG. 4 is a schematic view of the contact of conductive particles having a three-dimensional dendritic microstructure with spherical conductive particles; wherein 002 represents a conductive particle having a three-dimensional dendritic microstructure, and 001 represents a spherical conductive particle; 0012a is a contact point;
FIG. 5 is a schematic view of the contact of a conductive particle having a three-dimensional dendritic microstructure with a conductive particle having a three-dimensional dendritic microstructure; wherein 002a and 002b each represent a conductive particle having a three-dimensional dendritic microstructure, and 002ab represents a contact point;
fig. 6 is a tensile schematic diagram of the adhesion strength test.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The silver particles having a three-dimensional dendritic microstructure, the silver-coated copper particles having a three-dimensional dendritic microstructure, the spherical silver particles, the flaky silver particles, the spheroidal silver particles, the spherical silver-coated copper particles, the flaky silver-coated copper particles, and the spheroidal silver-coated copper particles used in the following examples were all obtained by purchase.
Example 1
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles comprise 20 parts of spherical silver particles and 52 parts of silver particles with a three-dimensional dendritic microstructure; size of spherical silver particles, i.e. particle diameter D501.5 μm, a specific surface area of 0.3m2(g) particle diameter D of silver particles having a three-dimensional dendritic microstructure50Is 4.0 μm and has a specific surface area of 0.69m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The embodiment also provides a preparation method of the conductive adhesive, which comprises the following steps:
s1, weighing the following components in parts by weight: 52 parts of silver particles with a three-dimensional dendritic microstructure, 20 parts of spherical silver particles, 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane, 1.0 part of methyl vinyl polysiloxane, 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen silicone oil, 0.90 part of methyl vinyl silicone oil, 0.55 part of vinyl triethoxysilane, 0.30 part of vinyl trimethoxy silane, 0.01 part of platinum catalyst, 0.04 part of 3-methyl-1-butyn-3-ol and 0.03 part of 2-vinyl isopropanol for later use;
s2, sequentially putting the methyl polysiloxane, the methyl hydrogen polysiloxane, the methyl vinyl polysiloxane, the methyl silicone oil, the methyl hydrogen silicone oil, the methyl vinyl silicone oil, the vinyl triethoxysilane, the vinyl trimethoxysilane, the platinum catalyst, the 3-methyl-1-butyn-3-ol and the 2-vinyl isopropanol weighed in the S1 into a stainless steel container, stirring and mixing, and then adding the silver particles with the three-dimensional dendritic microstructure and the spherical silver particles to obtain a mixture;
and S3, further grinding and mixing the mixture on a three-roll grinder to obtain 200g of the organic silicon resin conductive adhesive.
Example 2
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles comprise 20 parts of flaky silver particles and 52 parts of silver particles with a three-dimensional dendritic microstructure; size of flaky silver particles, i.e., particle diameter D501.5 μm, a specific surface area of 0.3m2(g) particle diameter D of silver particles having a three-dimensional dendritic microstructure50Is 4.0 μm and has a specific surface area of 0.69m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 3
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
The conductive particles comprise 20 parts of flaky silver particles and 52 parts of silver-coated copper particles with three-dimensional dendritic microstructures; size of flaky silver particles, i.e., particle diameter D501.5 μm, a specific surface area of 0.35m2(g) particle diameter D of silver-coated copper particles having three-dimensional dendritic microstructure506.5 μm, a specific surface area of 0.49m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 4
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles are 72 parts of silver particles with three-dimensional dendritic microstructures, and the particle diameter D of the silver particles with the three-dimensional dendritic microstructures50Is 4.0 μm and has a specific surface area of 0.69m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 5
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
65 parts of conductive particles, 22 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles are 65 parts of silver particles with a three-dimensional dendritic microstructure, and the particle diameter D of the silver particles with the three-dimensional dendritic microstructure50Is 4.0 μm and has a specific surface area of 0.69m2/g；
The organic silicon resin comprises 18.5 parts of methyl polysiloxane, 2.5 parts of methylhydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 6
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles are 72 parts of silver-coated copper particles with a three-dimensional dendritic microstructure, and the particle diameter D of the silver-coated copper particles with the three-dimensional dendritic microstructure506.5 μm, a specific surface area of 0.49m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 7
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
65 parts of conductive particles, 22 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles are three-dimensional65 parts of silver-coated copper particles with dendritic microstructure, and the particle diameter D of silver-coated copper particles with three-dimensional dendritic microstructure506.5 μm, a specific surface area of 0.49m2/g；
The organic silicon resin comprises 18.5 parts of methyl polysiloxane, 2.5 parts of methylhydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Example 8
The embodiment provides a silicone resin conductive adhesive, which comprises the following raw materials in parts by weight, based on 100 parts by weight:
72 parts of conductive particles, 15 parts of organic silicon resin, 12.07 parts of silicone oil, 0.85 part of silane coupling agent, 0.07 part of inhibitor and 0.01 part of platinum catalyst.
Wherein the conductive particles are 72 parts of silver particles with three-dimensional dendritic microstructures, and the particle diameter D of the silver particles with the three-dimensional dendritic microstructures502.0 μm and a specific surface area of 3.5m2/g；
The organic silicon resin comprises 10.5 parts of methyl polysiloxane, 3.5 parts of methyl hydrogen polysiloxane and 1.0 part of methyl vinyl polysiloxane;
the silicone oil comprises 9.4 parts of methyl silicone oil, 1.77 parts of methyl hydrogen-containing silicone oil and 0.90 part of methyl vinyl silicone oil;
the silane coupling agent comprises 0.55 part of vinyl triethoxysilane and 0.30 part of vinyl trimethoxysilane;
the inhibitor comprises 0.04 part of 3-methyl-1-butyne-3-ol and 0.03 part of 2-vinyl isopropanol.
The preparation method of this example is the same as that of example 1.
Comparative example 1
The same formulation and preparation as in example 4 was carried out, except that the silver particles having a three-dimensional dendritic microstructure had a particle diameter D501.7 μm, a specific surface area of 4.19m2/g。
Comparative example 2
The same formulation and preparation as in example 1, except that the conductive particles were 72 parts of spherical silver particles having a particle diameter D501.5 μm and a specific surface area of 0.3m2/g。
Comparative example 3
The same formulation and preparation as in example 1, except that the conductive particles were 72 parts of flaky silver particles, and the particle diameter D of the spherical silver particles501.5 μm and a specific surface area of 0.3m2/g。
The conductive adhesive of the embodiment 1 to the embodiment 8 of the present invention has better performance, and the conductive adhesive samples of the embodiment 1 to the embodiment 8 and the conductive adhesive samples of the comparative example 1 to the comparative example 3 are subjected to performance tests, including a viscosity performance test, a thermal expansion coefficient test, a glass transition temperature test, a curing temperature and time test, a volume resistivity test, a shear strength test, a viscosity change test, and the like.
Wherein the viscosity of the conductive adhesive is measured by using a viscometer at 25 ℃ and the coefficient of thermal expansion is measured by the TMA method; glass transition temperature was measured by DSC method; curing time temperature and time were tested in a chain oven;
the volume resistivity test process of the conductive adhesive comprises the following steps: printing a conductive adhesive sample on a glass sheet, and then curing at 1500 ℃ for 15 s; the width of the cured conductive adhesive is 5mm, the height is 42um, and the length is 70 mm; then testing the resistance of the conductive adhesive and calculating the volume resistivity of the conductive adhesive according to the following formula:
in the formula: l, b and d are respectively the length, width and thickness (cm) of the conductive adhesive sample, R is the resistance (omega) of the conductive adhesive sample, and rho is the volume resistivity (omega cm) of the conductive adhesive sample.
The process of testing the shear strength of the conductive adhesive comprises the following steps: measuring the bonding strength of the conductive adhesive sample by a method for measuring the tensile shear strength of the conductive adhesive sample by referring to the national standard GB/T7124-2008 adhesive (rigid material to rigid material); FIG. 6 is a schematic view showing the measurement in which a tensile machine pulls two aluminum sheets in a direction of 180 degrees at a speed of 200mm/min until the conductive adhesive layer is broken, the breaking load on the dial of the testing machine is noted, 6 tensile samples are taken for testing, and the shear strength (W) is calculated according to the following formula:
W＝P/S
in the formula: w is the shear strength, P is the breaking load, and S is the lap area.
The viscosity change test process of the conductive adhesive comprises the following steps: a sample of conductive gel was tested for viscosity using a viscometer Brookfield HBT at 10rpm SC4-14/6R 25 deg.C, then the conductive gel was exposed to 25 deg.C room temperature environment for 48hrs and tested for viscosity change according to the following equation:
table 1 table of performance data for conductive adhesive samples
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Volume resistivity (omega. cm) | 2.3x10 -3 | 2.3x10 -3 | 2.4x10 -3 | 2.0x10 -3 | 2.3x10 -3 | 2.1x10 -3 | 2.3x10 -3 | 2.5x10 -3 | 8.9x10 -3 | 8.5x10 -3 | 8.4x10 -3 |
| Shear strength (MPa) | 2.2 | 2.1 | 2.2 | 1.9 | 1.8 | 1.9 | 1.7 | 1.9 | 1.9 | 2.3 | 2.3 |
| Printing performance | Good printing | Good printing | Good printing | Can accept | Can accept | Can accept | Can accept | Can accept | Difficulty in printing | Good printing | Good printing |
| Viscosity @26 ℃ C., Pa.s | 40±15 | 40±15 | 40±15 | 40±15 | 40±15 | 40±15 | 40±15 | 49±15 | 69±15 | 36±15 | 38±15 |
| 48hrs Exposure viscosity change (%) | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ | ＜50％ |
| Coefficient of thermal expansion (ppm) | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 | 156±20 |
| Glass transition temperature (. degree. C.) | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 | -35±10 |
Table 1 is a table of performance data for the conductive paste samples of examples 1-8 and comparative examples 1-3, as can be seen from table 1:
(1) the bulk resistivity of the samples of examples 1-8 is significantly lower than the samples of comparative examples 1-3;
the conductive pastes of examples 1 to 3 respectively used conductive particles in which spherical silver particles or flake silver particles were mixed with silver particles having a three-dimensional dendritic microstructure and silver-coated copper particles having a three-dimensional dendritic microstructure, and the results showed that the bulk resistivity of examples 1 to 3 was lower by 45% or more than the comparative example;
the bulk resistivity of the conductive paste of examples 4 and 5, which used 100% of silver particles having a three-dimensional dendritic microstructure, was significantly lower than that of comparative examples 1 to 2, and particularly, the amount of the conductive particles of example 7 was reduced to 65%, which was still significantly lower than that of comparative examples 1 to 2; meanwhile, the results show that the volume resistivity of the conductive adhesive using the silver-coated copper particles with the three-dimensional dendritic microstructure is also obviously lower than that of comparative examples 1 to 3.
Since the conductive particles in comparative examples 2 and 3 are spherical silver particles or flaky silver particles, as shown in fig. 1, the contact between two spherical silver particles is a point contact, and the contact area is small; and the conductive particles in the conductive paste sample of the embodiment are conductive particles with a three-dimensional dendritic structure or a mixture of conductive particles with a three-dimensional dendritic structure and spherical, flaky or spheroidal particles, wherein fig. 2 and 3 are SEM images of silver particles with a three-dimensional dendritic microstructure at two visual angles, namely, typical morphologies of silver particles with a three-dimensional dendritic microstructure used in the present invention. When the conductive particles with the three-dimensional dendritic structures are mixed or the conductive particles with the three-dimensional dendritic structures are mixed with spherical, flaky or spheroidal particles, as shown in fig. 4 and 5, the contact between the two conductive particles is multi-point contact, and the network-shaped electric conduction is established, so that the contact resistance between the conductive particles is effectively reduced, and the electric conductivity is greatly improved.
(2) The bulk resistivity of comparative example 1 was greatly increased and the printing performance was greatly decreased as compared with the samples of comparative examples 2 to 3, indicating that the conductive particles having a three-dimensional dendritic microstructure could increase the bulk resistivity of the conductive paste sample, but the specific surface area of the silver particles having a three-dimensional dendritic microstructure used in comparative example 1 was 4.19m2A specific surface area (0.69 m) higher than that of example 42G), indicating that the specific surface area of the silver particles with a three-dimensional dendritic microstructure cannot be too high, otherwise the printing performance is reduced and large-scale mass use is difficult.
(3) The printing performance of the samples of the examples 4 to 8 is lower than that of the samples of the comparative examples 2 and 3, the printing performance of the samples of the examples 1 to 3 is better than that of the samples of the examples 4 to 8, because the printing ink penetration performance of the samples of the examples 1 to 3 is inferior to that of the spherical silver particles or the flaky silver particles due to the unique three-dimensional dendritic microstructure of the conductive particles, the spherical silver particles or the flaky silver particles have the advantage of good printing ink penetration performance, but the conductive performance of the samples is inferior to that of the silver particles or the silver-coated copper particles with the three-dimensional dendritic microstructure, the spherical silver particles or the flaky silver particles and the silver particles or the silver-coated copper particles with the three-dimensional dendritic microstructure are mixed for use, the advantage of high conductive performance of the three-dimensional dendritic microstructure is maintained, the defect of poor printing ink penetration performance is overcome, and the manufactured conductive adhesive has good conductive performance, the printing ink permeability is superior.
(4) The samples of examples 1 to 8 are equivalent to the samples of comparative examples 1 to 3 in terms of viscosity change after exposure for 48hrs, because the organic systems adopted by the samples of examples and comparative examples are methyl polysiloxane, methylhydrogen polysiloxane, methyl vinyl polysiloxane, methyl silicone oil, methyl hydrogen silicone oil, methyl vinyl silicone oil, vinyl triethoxysilane, vinyl trimethoxy silicon, 3-methyl-1-butyn-3-ol, 2-vinyl isopropanol and platinum catalyst which are combined according to specific proportions, and the specific organic material composition makes the conductive adhesive prepared by the method have the advantages of being capable of being rapidly cured and being operated and used for a long time under a room temperature environment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (18)
- The organic silicon resin conductive adhesive is characterized by comprising the following components in parts by weight, based on 100 parts by weight of the total weight;40-84 parts of conductive particles, 10-25 parts of organic silicon resin, 5.5-20 parts of silicone oil, 0.2-3.0 parts of silane coupling agent, 0.01-1 part of catalyst and 0.005-0.05 part of inhibitor;wherein the conductive particles comprise conductive particles having a three-dimensional dendritic microstructure.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles having a three-dimensional dendritic microstructure have a specific surface area of 0.2 to 3.5m2/g。
- The silicone resin conductive adhesive according to claim 2, wherein the conductive particles having a three-dimensional dendritic microstructure are silver particles having a three-dimensional dendritic microstructure or silver-clad copper particles having a three-dimensional dendritic microstructure.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles are spherical silver particles and silver particles having a three-dimensional dendritic microstructureMixing particles, wherein the mass ratio of the silver particles with the three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles are a mixture of spherical silver particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles are a mixture of flake-like silver particles and silver particles having a three-dimensional dendritic microstructure, and the mass ratio of the silver particles having a three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles are a mixture of flake silver particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 1The conductive particles are a mixture of flaky silver-coated copper particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the flaky silver-coated copper particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 1, wherein the conductive particles are a mixture of spherical silver-coated copper particles and silver-coated copper particles with a three-dimensional dendritic microstructure, and the mass ratio of the silver-coated copper particles with the three-dimensional dendritic microstructure to the total conductive particles is (0.05-0.95): 1, the specific surface area of the silver-coated copper particles with the three-dimensional dendritic microstructure is 0.2-3.5 m2The size of the spherical silver-coated copper particles is 0.1-50 mu m.
- The silicone resin conductive adhesive according to claim 2, 4 or 6, wherein the silver particles having a three-dimensional dendritic microstructure have a size of 0.1 to 50 μm.
- The silicone resin conductive adhesive according to claim 3,5, 7 or 8, wherein the silver-coated copper particles with the three-dimensional dendritic microstructure have a size of 0.1 to 50 μm.
- The silicone resin conductive paste according to claim 1, wherein the silicone resin is at least one of methyl polysiloxane, methylhydrogen polysiloxane, and methylvinyl polysiloxane.
- The silicone resin conductive paste according to claim 1, wherein the silicone oil is at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, and hydroxy hydrogen-containing silicone oil.
- The conductive silicone resin adhesive according to claim 1, wherein the silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane and isobutyltriethoxysilane.
- The silicone resin conductive adhesive according to claim 1, wherein the catalyst is a platinum catalyst.
- The silicone resin conductive adhesive according to claim 1, wherein the inhibitor is at least one of 3-methyl-1-butyn-3-ol, 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, pyridine, acrylonitrile, 2-vinyl isopropanol, benzotriazole, an organic phosphine compound, and diallyl maleate.
- The preparation method of the silicone resin conductive adhesive according to any one of claims 1 to 16, characterized by comprising the following steps:s1, weighing the following components in parts by weight: 40-84 parts of conductive particles, 10-25 parts of organic silicon resin, 5.5-20 parts of silicone oil, 0.2-3.0 parts of silane coupling agent, 0.01-1 part of catalyst and 0.005-0.05 part of inhibitor; wherein the conductive particles comprise conductive particles having a three-dimensional dendritic microstructure for use;s2, placing the organic silicon resin, the silicone oil, the silane coupling agent, the catalyst and the initiator weighed in the S1 into a reactor, stirring uniformly, adding the conductive particles, and stirring uniformly to obtain a mixture;and S3, grinding the mixture to obtain the organic silicon resin conductive adhesive.
- Use of a silicone resin conductive paste according to any one of claims 1 to 16 in a semiconductor device.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/072639 WO2021142752A1 (en) | 2020-01-17 | 2020-01-17 | Organic silicon resin conductive adhesive, and preparation method therefor and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113412321A true CN113412321A (en) | 2021-09-17 |
Family
ID=76864494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080000045.2A Pending CN113412321A (en) | 2020-01-17 | 2020-01-17 | Organic silicon resin conductive adhesive and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113412321A (en) |
| WO (1) | WO2021142752A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015410A (en) * | 2021-11-12 | 2022-02-08 | 凯仁精密材料(江苏)有限公司 | Premixing method of conductive glue, conductive adhesive tape and preparation method of conductive adhesive tape |
| CN114937518A (en) * | 2022-06-07 | 2022-08-23 | 无锡帝科电子材料股份有限公司 | Low-temperature curing conductive silver paste for HJT efficient battery and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116218460A (en) * | 2022-12-20 | 2023-06-06 | 广州市儒兴科技股份有限公司 | Organic silicon conductive adhesive and preparation method and application thereof |
| CN116082845A (en) * | 2023-01-05 | 2023-05-09 | 厦门牛转乾坤新材料有限公司 | Conductive silica gel and preparation method thereof |
| WO2024149457A1 (en) * | 2023-01-11 | 2024-07-18 | Wacker Chemie Ag | Silicone based resin composition, and semiconductor device comprising the same |
| CN116218411A (en) * | 2023-04-03 | 2023-06-06 | 北京中石伟业科技无锡有限公司 | Conductive filler, preparation method thereof, conductive adhesive and application |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003375A (en) * | 2010-07-30 | 2013-03-27 | 太阳控股株式会社 | Conductive paste for offset printing |
| CN103400637A (en) * | 2013-08-05 | 2013-11-20 | 清华大学深圳研究生院 | Electroconductive slurry and preparation method thereof, and printed circuit material |
| WO2015184597A1 (en) * | 2014-06-04 | 2015-12-10 | Dow Global Technologies Llc | Solid polymer electrolyte and compound used for thereof |
| JP2016139597A (en) * | 2015-01-26 | 2016-08-04 | 住友金属鉱山株式会社 | Manufacturing method of dendritic silver coated copper powder |
| WO2016151859A1 (en) * | 2015-03-26 | 2016-09-29 | 住友金属鉱山株式会社 | Silver-coated copper powder and conductive paste, conductive material, and conductive sheet using same |
| CN106573303A (en) * | 2014-08-26 | 2017-04-19 | 住友金属矿山株式会社 | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet each of which uses same |
| EP3162466A1 (en) * | 2014-06-25 | 2017-05-03 | Sumitomo Metal Mining Co., Ltd. | Copper powder, and copper paste, electrically conductive coating material and electrically conductive sheet each produced using said copper powder |
| EP3192597A1 (en) * | 2014-09-12 | 2017-07-19 | Sumitomo Metal Mining Co., Ltd. | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet, each of which uses said silver-coated copper powder |
| US20190359842A1 (en) * | 2017-01-26 | 2019-11-28 | The Yokohama Rubber Co., Ltd. | Electrically Conductive Composition |
| JP2019218590A (en) * | 2018-06-18 | 2019-12-26 | 住友金属鉱山株式会社 | Manufacturing method of copper powder and copper powder |
-
2020
- 2020-01-17 CN CN202080000045.2A patent/CN113412321A/en active Pending
- 2020-01-17 WO PCT/CN2020/072639 patent/WO2021142752A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103003375A (en) * | 2010-07-30 | 2013-03-27 | 太阳控股株式会社 | Conductive paste for offset printing |
| CN103400637A (en) * | 2013-08-05 | 2013-11-20 | 清华大学深圳研究生院 | Electroconductive slurry and preparation method thereof, and printed circuit material |
| WO2015184597A1 (en) * | 2014-06-04 | 2015-12-10 | Dow Global Technologies Llc | Solid polymer electrolyte and compound used for thereof |
| EP3162466A1 (en) * | 2014-06-25 | 2017-05-03 | Sumitomo Metal Mining Co., Ltd. | Copper powder, and copper paste, electrically conductive coating material and electrically conductive sheet each produced using said copper powder |
| CN106573303A (en) * | 2014-08-26 | 2017-04-19 | 住友金属矿山株式会社 | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet each of which uses same |
| EP3192597A1 (en) * | 2014-09-12 | 2017-07-19 | Sumitomo Metal Mining Co., Ltd. | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet, each of which uses said silver-coated copper powder |
| JP2016139597A (en) * | 2015-01-26 | 2016-08-04 | 住友金属鉱山株式会社 | Manufacturing method of dendritic silver coated copper powder |
| WO2016151859A1 (en) * | 2015-03-26 | 2016-09-29 | 住友金属鉱山株式会社 | Silver-coated copper powder and conductive paste, conductive material, and conductive sheet using same |
| US20190359842A1 (en) * | 2017-01-26 | 2019-11-28 | The Yokohama Rubber Co., Ltd. | Electrically Conductive Composition |
| JP2019218590A (en) * | 2018-06-18 | 2019-12-26 | 住友金属鉱山株式会社 | Manufacturing method of copper powder and copper powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015410A (en) * | 2021-11-12 | 2022-02-08 | 凯仁精密材料(江苏)有限公司 | Premixing method of conductive glue, conductive adhesive tape and preparation method of conductive adhesive tape |
| CN114937518A (en) * | 2022-06-07 | 2022-08-23 | 无锡帝科电子材料股份有限公司 | Low-temperature curing conductive silver paste for HJT efficient battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021142752A1 (en) | 2021-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113412321A (en) | Organic silicon resin conductive adhesive and preparation method and application thereof | |
| EP2451881B1 (en) | Electrically conductive adhesives | |
| CN101669258B (en) | The method of attachment of electric conductor, conductor connection member, syndeton and solar module | |
| US9123835B2 (en) | Connected structure and method for manufacture thereof | |
| CN111480206B (en) | Conductive paste | |
| CN105315677B (en) | A kind of high-performance silicon-based shielding Heat Conduction Material and preparation method thereof | |
| WO2019111623A1 (en) | Electrically conductive paste | |
| CN113808779B (en) | Low-temperature curing insulating medium slurry for chip resistor | |
| CN110982463A (en) | Conductive adhesive and solar cell | |
| EP3369781B1 (en) | Resin composition, bonded body and semiconductor device | |
| CN113412319B (en) | Epoxy resin conductive adhesive and preparation method and application thereof | |
| CN113412320A (en) | Modified epoxy acrylic resin conductive adhesive and preparation method and application thereof | |
| JP5353163B2 (en) | Conductive ink composition and solar cell in which collector electrode is formed using the composition | |
| KR20140035993A (en) | Circuit-connecting material and connected circuit board structure | |
| WO2021142751A1 (en) | Acrylic conductive adhesive and preparation method and application thereof | |
| CN114068064A (en) | Conductive paste, preparation method and preparation method of conductive film | |
| TW202233734A (en) | Aqueous dispersion | |
| JP2023028091A (en) | Composition and method for producing laminate | |
| KR20180031531A (en) | Paste composition and its manufacturing method with a conductive , thermally conductive , corrosion-resistant properties | |
| CN109627473B (en) | Preparation process of enhanced organic silicon composite sheet with surface tack removal function | |
| JP6053567B2 (en) | Conductive adhesive film for connecting ribbon wire to solar cell surface electrode | |
| JP5692295B2 (en) | Method for forming solar cell collector electrode and solar cell module provided with the solar cell | |
| CN110023446A (en) | The conductive silicone adhesive composition of condensation curable | |
| WO2023276946A1 (en) | Composition | |
| TW202344599A (en) | Composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210917 |