CN106928867A - A kind of carbon nanotube conducting glue and its preparation method and application - Google Patents
A kind of carbon nanotube conducting glue and its preparation method and application Download PDFInfo
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- CN106928867A CN106928867A CN201710190725.5A CN201710190725A CN106928867A CN 106928867 A CN106928867 A CN 106928867A CN 201710190725 A CN201710190725 A CN 201710190725A CN 106928867 A CN106928867 A CN 106928867A
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- 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
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- 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
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
The invention provides a kind of carbon nanotube conducting glue, count by weight, including 20~35 parts of metal packing, 15~25 parts of CNT, 30~40 parts of epoxy resin, 1~5 part of diluent, 8~12 parts of curing agent, 1~5 part of coupling agent, the CNT is arranged in parallel in conducting resinl.The conducting resinl that the present invention is provided includes the CNT of high connductivity high heat conduction, and CNT can fill the space between metal packing, improve the contact area between metal packing, increase conductive channel；Simultaneously, CNT is one-dimensional material, with electricity, heat transfer anisotropy, its electronic structure is also in anisotropy, can be aligned in magnetic field or electric field environment, is applied in electronic device, the axial direction of CNT is heat conduction direction, two end faces bonded needed for carbon nanotube conducting glue, preferably using the electric-conductivity heat-conductivity high characteristic of CNT can make conducting resinl have excellent heat conductivility.
Description
Technical field
The present invention relates to conducting resinl technical field, more particularly to a kind of carbon nanotube conducting glue and preparation method thereof and should
With.
Background technology
With the development of science and technology, requirement more and more higher of the electronic system to the actually used performance of electronic device so that
Direction of the electronic device gradually toward miniaturization, high frequency and high-power is developed, the multi-functional ultra-large collection of more high integration
Also it is being continuously developed into circuit.But incident hyperpyrexia metric density turns into the main of influence electronic device life and reliability
Factor, therefore, increase the heat dispersion of electronic device, so that it is quite important to reduce its temperature.
Conducting resinl is a kind of adhesive for solidifying or having certain electric conductivity after drying, generally with matrix resin and conduction
Material is main constituents, and conductive material is combined together by the bonding effect of matrix resin, forms conductive path.Will
Conducting resinl is applied in electronic device, and chip can be made perfect with substrate Nian Jie, realizes the conductive and heat conduction function of electronic device.
But, conducting resinl belongs to the small part of thermal conductivity in electronic device, can be notified by Law of Barrel and have a strong impact on electronic device
Heat transfer.
The content of the invention
It is an object of the invention to provide a kind of carbon nanotube conducting glue and its preparation method and application, the conducting resinl has
Excellent heat conductivility.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of carbon nanotube conducting glue, count by weight, including following components：
The CNT is arranged in parallel in conducting resinl.
Preferably, the material of the metal packing is one or more in silver, copper, gold, silver copper-clad and carbon copper-clad.
Preferably, the metal packing is the mixture of metal nanoparticle and metal microparticle.
Preferably, the particle diameter of the metal nanoparticle is 1~100nm；The particle diameter of the metal microparticle is 1~10
μm。
Preferably, the mass ratio of the metal nanoparticle and metal microparticle is (10~15)：2.
Preferably, the CNT is the one kind in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes
Or it is several.
Preferably, the length of the CNT is 1~30 μm.
The invention provides the preparation method of carbon nanotube conducting glue described in above-mentioned technical proposal, comprise the following steps：
(1) epoxy resin and coupling agent are mixed, obtains substrate mixture；
(2) in magnetic field or electric field environment, the substrate mixture that the step (1) is obtained is filled out with CNT, metal
Material and diluent mixing, obtain carbon nanotube conducting glue precursor；
(3) in magnetic field or electric field environment, the carbon nanotube conducting glue precursor that the step (2) is obtained is mixed with curing agent
Close, obtain carbon nanotube conducting glue.
Preferably, the intensity in the magnetic field is 5~15T；The intensity of the electric field is 1~4V/cm.
The invention provides carbon nanotube conducting glue described in above-mentioned technical proposal or preparation method described in above-mentioned technical proposal
Application of the carbon nanotube conducting glue for obtaining in electronic device, the axial direction of the CNT in the carbon nanotube conducting glue is
Heat conduction direction, two end faces bonded needed for carbon nanotube conducting glue.
The invention provides a kind of carbon nanotube conducting glue, count by weight, including 20~35 parts of metal packing, carbon are received
15~25 parts of mitron, 30~40 parts of epoxy resin, 1~5 part of diluent, 8~12 parts of curing agent, 1~5 part of coupling agent, the carbon
Nanotube is arranged in parallel in conducting resinl.The conducting resinl that the present invention is provided includes the CNT of high connductivity high heat conduction, and carbon is received
Mitron can fill the space between metal packing, improve the contact area between metal packing, increase conductive channel；Meanwhile,
CNT is one-dimensional material, and with electricity, heat transfer anisotropy, its electronic structure is also in anisotropy, can in magnetic field or
Aligned in electric field environment, be applied in electronic device, the axial direction of CNT is heat conduction direction, is led perpendicular to CNT
Two end faces bonded needed for electric glue, preferably using the electric-conductivity heat-conductivity high characteristic of CNT can have conducting resinl excellent
Different heat conductivility.
Brief description of the drawings
Schematic diagrames of the Fig. 1 for the carbon nanotube conducting glue for providing of the invention under magnetic field state；
Schematic diagrames of the Fig. 2 for the carbon nanotube conducting glue for providing of the invention under electric field status.
Specific embodiment
The invention provides a kind of carbon nanotube conducting glue, count by weight, including following components：
The CNT is arranged in parallel in conducting resinl.
The carbon nanotube conducting glue that the present invention is provided includes metal packing；On the basis of the weight of metal packing, the gold
The parts by weight for belonging to filler are 20~35 parts, more preferably preferably 25~33 parts, 28~31 parts.In the present invention, the gold
The material for belonging to filler be preferably in silver, copper, gold, silver copper-clad and carbon copper-clad one or more.
In the present invention, the metal packing is preferably the mixture of metal nanoparticle and metal microparticle.At this
In invention, the particle diameter of the metal nanoparticle be preferably 1~100nm, more preferably 10~80nm, most preferably 20~
60nm；The particle diameter of the metal microparticle is preferably 1~10 μm, most preferably more preferably 2~8 μm, 4~6 μm.In this hair
In bright, the mass ratio of the metal nanoparticle and metal microparticle is preferably (10~15):2, more preferably (11~14):
2, most preferably (12~13):2.The present invention does not have special for the shape of the metal nanoparticle and metal microparticle
Limit, one or more in concretely petal, spherical and sheet.The present invention does not have for the source of the metal packing
Special restriction, it is specific such as commercially available prod using metal packing well known to those skilled in the art.
In the present invention, the space that the metal packing can be between filling carbon nano-pipe, improves between conductive filler
Contact area, increases conductive and heat-conductive passage.Additionally, the tunnel conduction of the metal nanoparticle being dispersed in the middle of metal microparticle
Effect, can make the conductive network in material more perfect, improve conductance.
The present invention provide carbon nanotube conducting glue include 15~25 parts of CNTs, preferably 17~23 parts, more preferably
It is 19~21 parts.In the present invention, the CNT is preferably SWCN, double-walled carbon nano-tube and multi-wall carbon nano-tube
One or more in pipe.In the present invention, the length of the CNT is preferably 1~30 μm, more preferably 5~25 μm.
The present invention originates without special restriction for the CNT, is prepared into using method well known to those skilled in the art
The CNT or commercially available carbon nanotube product for arriving.
The present invention provide carbon nanotube conducting glue include 30~40 parts of epoxy resin, preferably 32~38 parts, more preferably
It is 34~36 parts.In the present invention, the epoxy resin is preferably the epoxy resin containing bis-phenol, o-cresol novolak type epoxy
One or more in resin and cycloaliphatic epoxy resin.
The carbon nanotube conducting glue that the present invention is provided includes 1~5 part of diluent, more preferably preferably 2~4 parts, 3 parts.
In the present invention, the diluent is preferably reactive diluent, more preferably methacrylic acid-beta-hydroxy ethyl ester (HEMA), 1,6-
Hexanediyl ester (HDDA), phenoxy group triethoxy acrylate, iso-bornyl acrylate, acrylate long-chain ester,
Double (methyl) acrylate of tetrahydrofurfuryl (methyl) acrylate, 1,6-HD, propoxylation multi-functional acrylate,
One or more in methoxy poly (ethylene glycol) monomethacrylates and methoxy poly (ethylene glycol) mono acrylic ester.
The carbon nanotube conducting glue that the present invention is provided includes 8~12 parts of curing agent, preferably 9~11 parts, more preferably 10
Part.In the present invention, the curing agent is preferably maleic anhydride, phthalic anhydride, three boron nitride ethylamine complex, double
One or more in cyanamide and aromatic polyamine.
The carbon nanotube conducting glue that the present invention is provided includes 1~5 part of coupling agent, more preferably preferably 2~4 parts, 3 parts.
In the present invention, the coupling agent is preferably epoxy radicals trimethoxy silane, aminopropyltriethoxywerene werene, aminopropyl front three
TMOS, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane
In one or more.
The invention provides a kind of preparation method of carbon nanotube conducting glue described in above-mentioned technical proposal, including following step
Suddenly：
(1) epoxy resin and coupling agent are mixed, obtains substrate mixture；
(2) in magnetic field or electric field environment, the substrate mixture that the step (1) is obtained is filled out with CNT, metal
Material and diluent mixing, obtain carbon nanotube conducting glue precursor；
(3) in magnetic field or electric field environment, the carbon nanotube conducting glue precursor that the step (2) is obtained is mixed with curing agent
Close, obtain carbon nanotube conducting glue.
The present invention mixes epoxy resin and coupling agent, obtains substrate mixture.The present invention is for by the epoxy resin
The mode mixed with coupling agent does not have special restriction, using the technical scheme of mixing well known to those skilled in the art.
The epoxy resin and coupling agent are preferably ground mixing by the present invention.The present invention does not have special for the ground and mixed
Limit, using the technical scheme of the ground and mixed that can be well mixed material well known to those skilled in the art.At this
In invention, the time of the ground and mixed is preferably 25~35min, more preferably 30min.
After obtaining substrate mixture, the present invention in magnetic field or electric field environment, by described matrix mixture and CNT,
Metal packing and diluent mix, and obtain carbon nanotube conducting glue precursor.In the present invention, the intensity in the magnetic field is preferably 5
~15T, more preferably 7~13T, most preferably 9~11T.In the present invention, the electric field preferably uses direct current；The electricity
The intensity of field is preferably 1~4V/cm, most preferably more preferably 1.5~3.5V/cm, 2~3V/cm.
Before the metal packing is mixed with substrate mixture, CNT and diluent, described in preferred pair of the present invention
Metal packing is surface-treated, and the surface treatment preferably includes following steps：
Metal packing is carried out into ultrasonically treated and stir process successively in surface conditioning agent；
Metal packing to obtaining is cleaned and dried, the metal packing after being surface-treated.
Metal packing is carried out ultrasonically treated and stir process by the present invention successively in surface conditioning agent.In the present invention,
The solute of the surface conditioning agent is preferably malonic acid, ethanedioic acid, glutaric acid or adipic acid；The solvent of the surface conditioning agent is excellent
Elect acetone, ethanol or water as.In the present invention, the concentration of the surface conditioning agent is preferably 0.1~2mol/L, more preferably
0.5~1.5mol/L, most preferably 0.8~1.2mol/L.In the present invention, the metal packing is dense in surface conditioning agent
Degree is preferably 0.1~2mol/L, most preferably more preferably 0.5~1.5mol/L, 0.8~1.2mol/L.
In the present invention, the ultrasonically treated time be preferably 80~120min, more preferably 90~110min, it is optimal
Elect 100min as；The ultrasonically treated frequency is preferably 20~35kHz, most preferably more preferably 25~30kHz, 28kHz.
In the present invention, the time of the stir process be preferably 5~15min, more preferably 8~12min, most preferably
10min；The revolution stir speed (S.S.) of the stir process is preferably 1400~1600r/min, more preferably 1500r/min；It is described
The rotation stir speed (S.S.) of stir process is preferably 950~1150r/min, more preferably 1050r/min.
In the present invention, the surface conditioning agent can remove organic lubrication of the fatty acid of metal packing surface remaining
Layer, further to improve the electric conductivity and bonding strength of conducting resinl.
After completing stir process, the material that preferred pair of the present invention is obtained carries out separation of solid and liquid.The present invention is for the solid-liquid
The mode of separation does not have special restriction, using the technical scheme of separation of solid and liquid well known to those skilled in the art.This hair
It is bright preferably to use centrifugation.In the present invention, the time of the centrifugation be preferably 25~35min, more preferably
30min；The centrifugation rate of the centrifugation is preferably 9000~11000r/min, more preferably 10000r/min.
After completing the separation of solid and liquid, the present invention is cleaned and dried to the metal packing for obtaining, and is surface-treated
Metal packing afterwards.In the present invention, the cleaning agent that the cleaning is used is preferably the solvent of the surface conditioning agent.In this hair
In bright, the drying is preferably vacuum drying；The vacuum drying temperature is preferably 65~75 DEG C, more preferably 70 DEG C；Institute
Stating the vacuum drying time is preferably 20~28h, more preferably 24h；The vacuum drying vacuum is preferably 0.04~
0.06MPa, more preferably 0.05MPa.
It is of the invention preferably in magnetic field or electric field environment after being surface-treated to the metal packing, by described matrix
Mixture mixes with the metal packing after CNT, surface treatment and diluent, obtains carbon nanotube conducting glue precursor.This hair
The bright no spy of mode for the metal packing after described matrix mixture, CNT, surface treatment and diluent are mixed
Different restriction, using the technical scheme of mixing well known to those skilled in the art.The present invention preferably mixes described matrix
Metal packing and diluent after thing, CNT, surface treatment are ground mixing.The present invention does not have for the ground and mixed
There is special restriction, the technical scheme using the ground and mixed that can be well mixed material well known to those skilled in the art is
Can.In the present invention, the time of the ground and mixed be preferably 1.5~2.5h, more preferably 2h.
After metal packing after described matrix mixture, CNT, surface treatment and diluent are mixed, the present invention is excellent
Select the material to being obtained after mixing to disperse, obtain nanotube conductive glue precursor.The present invention is not special for the dispersion
Restriction, using scattered technical scheme well known to those skilled in the art.Present invention preferably employs dispersed with stirring；It is described
The time of dispersed with stirring is preferably 50~70min, most preferably more preferably 55~65min, 60min；The dispersed with stirring
Revolution stir speed (S.S.) is preferably 1400~1600r/min, more preferably 1500r/min；The rotation stirring speed of the dispersed with stirring
Rate is preferably 950~1150r/min, more preferably 1050r/min.
After obtaining the nanotube conductive glue precursor, the present invention leads the CNT in magnetic field or electric field environment
Electric glue precursor mixes with curing agent, obtains carbon nanotube conducting glue.In the present invention, the intensity in the magnetic field be preferably 5~
15T, more preferably 7~13T, most preferably 9~11T.In the present invention, the electric field preferably uses direct current；The electric field
Intensity be preferably 1~4V/cm, most preferably more preferably 1.5~3.5V/cm, 2~3V/cm.The present invention is for by the carbon
The mode that nanotube conductive glue precursor mixes with curing agent does not have special restriction, using mixing well known to those skilled in the art
Technical scheme.Preferably with curing agent be ground the carbon nanotube conducting glue precursor and mix by the present invention.The present invention
There is no special restriction for the ground and mixed, using it is well known to those skilled in the art can by material be well mixed grind
Grind the technical scheme of mixing.In the present invention, the time of the ground and mixed be preferably 0.5~1.5h, more preferably 1h.
After the carbon nanotube conducting glue precursor is mixed with curing agent, the material obtained after preferred pair of the present invention mixing according to
It is secondary to be disperseed and stood, obtain carbon nanotube conducting glue.The present invention disperses without special restriction for described, using ability
Scattered technical scheme known to field technique personnel.Present invention preferably employs ultrasonic disperse；The time of the ultrasonic disperse
Preferably 50~70min, more preferably 55~65min, most preferably 60min；The frequency of the ultrasonic disperse is preferably 20~
35kHz, more preferably 25~30kHz, most preferably 28kHz.In the present invention, the time of the standing preferably with dispersion after
Environment residing for material is relevant, specifically, material after by dispersion is placed in magnetic field environment, the time of the standing is preferably
2~4 days, more preferably 3 days；Material after by dispersion is placed in electric field environment, and time of the standing is preferably 20~
40min, more preferably 30min.
In the present invention, the CNT in carbon nanotube conducting glue can be aligned in magnetic field or electric field environment,
Its schematic diagram is as illustrated in fig. 1 and 2.CNT is magnetic anisotropy, is symmetrical magnetic along the direction of pipe axle.Magnetic field takes
To CNT electricity, heat transfer anisotropy, and along the electricity of magnetic direction, thermal conduction characteristic is better than perpendicular to magnetic
Field direction is a lot, therefore CNT is placed in magnetic field, CNT is arranged along magnetic direction, can preferably utilize carbon
The electric-conductivity heat-conductivity high characteristic of nanotube, makes conducting resinl have excellent heat conductivility.Meanwhile, the electronic structure of CNT is also in
Anisotropy, the dipole of pipe axial direction is significantly larger than radially, and the power of electric field orientation CNT just comes from its high polarization,
Under DC Electric Field, the high polarization can make CNT produce orientation to reverse and induction force in direction of an electric field, therefore will
CNT is placed in electric field, CNT is arranged along direction of an electric field, preferably can be led using the high connductivity of CNT
Thermal characteristics, makes conducting resinl have excellent heat conductivility.
The invention provides carbon nanotube conducting glue described in above-mentioned technical proposal or preparation method described in above-mentioned technical proposal
Application of the carbon nanotube conducting glue for obtaining in electronic device, the axial direction of the CNT in the carbon nanotube conducting glue is
Heat conduction direction, two end faces bonded needed for carbon nanotube conducting glue.
The present invention leads the CNT when carbon nanotube conducting glue obtained above is applied in electronic device
Electric glue is coated on electronic device surface.The present invention does not have special limit to the thickness of carbon nanotube conducting gel coating
It is fixed, it is configured according to actual technical requirements.Carbon nanotube conducting gel coating is heated described in preferred pair of the present invention
Solidification.In the present invention, the temperature being heating and curing is preferably 140~160 DEG C, more preferably 145~155 DEG C, most preferably
It is 150 DEG C；The time being heating and curing be preferably 60~120min, more preferably 70~110min, most preferably 80~
100min。
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) count by weight, 35 parts of bisphenol A epoxide resins and 3 parts of epoxy radicals trimethoxy silanes are mixed, grinding
30min, obtains substrate mixture；
(2) Argent grain is mixed with surface conditioning agent, the ultrasound 100min under 28kHz, then in revolution 1500r/min,
10min is stirred under the stir speed (S.S.) of rotation 1050r/min, in 30min is centrifuged under 10000r/min, using ethanol to the silver that obtains
Particle is cleaned, then in being vacuum dried 24h under 70 DEG C, 0.05MPa, the Argent grain after being surface-treated；Wherein, it is described
Silver nano-grain and the mass ratio of silver-colored micron particles are 12 in Argent grain:2, the surface conditioning agent is molten for the ethanol of malonic acid
Liquid, concentration is 1mol/L, and concentration of the Argent grain in surface conditioning agent is 1mol/L；
In magnetic field intensity in the environment of 10T, substrate mixture that the step (1) is obtained and 20 parts of length for 5~
Argent grain and 3 parts of methacrylic acid-beta-hydroxy ethyl ester mixing after 25 μm of multi-walled carbon nano-tubes, 29 parts of surface treatments, grind 2h,
Then in revolution 1500r/min, dispersed with stirring 60min under the stir speed (S.S.) of rotation 1050r/min, carbon nanotube conducting glue is obtained
Precursor；
(3) in the environment that magnetic field intensity is 10T, the carbon nanotube conducting glue precursor and 10 that the step (2) is obtained
Part maleic anhydride mixing, grinds 1h, then in ultrasonic disperse 60min under 28kHz, stands 3 days, obtains carbon nanotube conducting
Glue.
Embodiment 2
(1) count by weight, by 40 parts of cycloaliphatic epoxy resins and 5 parts of γ-glycidyl ether oxygen propyl trimethoxies
Silane mixture, grinds 25min, obtains substrate mixture；
(2) copper particle is mixed with surface conditioning agent, the ultrasound 120min under 25kHz, then in revolution 1600r/min,
5min is stirred under the stir speed (S.S.) of rotation 950r/min, in 25min is centrifuged under 11000r/min, using water to the copper particle that obtains
Cleaned, then in being vacuum dried 20h under 75 DEG C, 0.04MPa, the copper particle after being surface-treated；Wherein, the copper
Copper nano particles and the mass ratio of copper micron particles are 15 in grain:2, the surface conditioning agent is the aqueous solution of glutaric acid, concentration
It is 1.5mol/L, concentration of the copper particle in surface conditioning agent is 0.5mol/L；
In magnetic field intensity in the environment of 15T, substrate mixture that the step (1) is obtained and 25 parts of length for 3~
Copper particle and 5 parts of phenoxy group triethoxy crylic acid ester mixtures after 20 μm of double-walled carbon nano-tube, 35 parts of surface treatments, grinding
1.5h, then in revolution 1400r/min, dispersed with stirring 70min, obtains CNT under the stir speed (S.S.) of rotation 1150r/min
Conducting resinl precursor；
(3) in the environment that magnetic field intensity is 15T, the carbon nanotube conducting glue precursor and 12 that the step (2) is obtained
Part three boron nitride ethylamine complex mixing, grinds 1.5h, then in ultrasonic disperse 50min under 30kHz, stands 2 days, obtains carbon and receives
Mitron conducting resinl.
Embodiment 3
(1) count by weight, by 30 parts of o-cresol phenolic resin varnish and 1 part of aminopropyl trimethoxysilane
Mixing, grinds 30min, obtains substrate mixture；
(2) gold grain is mixed with surface conditioning agent, the ultrasound 80min under 28kHz, then in revolution 1500r/min, from
15min is stirred under the stir speed (S.S.) for turning 1050r/min, in 30min is centrifuged under 10000r/min, using acetone to the gold that obtains
Grain is cleaned, then in being vacuum dried 24h under 70 DEG C, 0.05MPa, the gold grain after being surface-treated；Wherein, the gold
Gold nano grain and the mass ratio of golden micron particles are 10 in particle:2, the surface conditioning agent is the acetone soln of ethanedioic acid,
Concentration is 0.5mol/L, and concentration of the gold grain in surface conditioning agent is 1.5mol/L；
In electric-field intensity in the DC electric field environment of 3V/cm, the substrate mixture that the step (1) is obtained and 15 parts
Length is that gold grain and 1 part of 1,6 hexanediol diacrylate after 1~30 μm of SWCN, 20 parts of surface treatments are mixed
Close, grind 2h, then in revolution 1500r/min, dispersed with stirring 50min under the stir speed (S.S.) of rotation 1050r/min, obtain carbon and receive
Mitron conducting resinl precursor；
(3) in the DC electric field environment that electric-field intensity is 3V/cm, the carbon nanotube conducting that the step (2) is obtained
Glue precursor mixes with 8 parts of phthalic anhydrides, grinds 1h, then in ultrasonic disperse 70min under 28kHz, stands 30min, obtains
Carbon nanotube conducting glue.
Embodiment 4
(1) count by weight, by 28 parts of bisphenol A epoxide resins and 2 parts of γ-methacryloxypropyl trimethoxies
Silane mixture, grinds 35min, obtains substrate mixture；
(2) silver-colored copper-clad particle is mixed with surface conditioning agent, the ultrasound 80min under 35kHz, then in revolution 1600r/
Min, 10min is stirred under the stir speed (S.S.) of rotation 1150r/min, in 35min is centrifuged under 9000r/min, using acetone to obtaining
Silver-colored copper-clad particle cleaned, then in being vacuum dried 28h under 65 DEG C, 0.06MPa, the silver-colored copper-clad after being surface-treated
Grain；Wherein, silver-colored copper-clad nano particle and the mass ratio of silver-colored copper-clad micron particles are 13 in the silver-colored copper-clad particle:2, the surface
Inorganic agent is the acetone soln of adipic acid, and concentration is 2mol/L, and concentration of the silver-colored copper-clad particle in surface conditioning agent is
2mol/L；
In electric-field intensity in the DC electric field environment of 4V/cm, the substrate mixture that the step (1) is obtained and 22 parts
Length is the silver-colored copper-clad particle and 2 parts of methoxy poly (ethylene glycol) lists third after 5~25 μm of multi-walled carbon nano-tubes, 32 parts of surface treatments
Olefin(e) acid ester mixes, and grinds 2.5h, then in revolution 1400r/min, dispersed with stirring under the stir speed (S.S.) of rotation 950r/min
55min, obtains carbon nanotube conducting glue precursor；
(3) in the DC electric field environment that electric-field intensity is 4V/cm, the carbon nanotube conducting that the step (2) is obtained
Glue precursor mixes with 11 parts of dicyandiamides, grinds 0.5h, then in ultrasonic disperse 65min under 20kHz, stands 20min, obtains carbon and receives
Mitron conducting resinl.
As seen from the above embodiment, the conducting resinl that the present invention is provided includes the CNT of high connductivity high heat conduction, and carbon is received
Mitron can fill the space between metal packing, improve the contact area between metal packing, increase conductive channel；Meanwhile,
CNT is one-dimensional material, and with electricity, heat transfer anisotropy, its electronic structure is also in anisotropy, can in magnetic field or
Aligned in electric field environment, be applied in electronic device, the axial direction of CNT is heat conduction direction, is led perpendicular to CNT
Two end faces bonded needed for electric glue, preferably using the electric-conductivity heat-conductivity high characteristic of CNT can have conducting resinl excellent
Different heat conductivility.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of carbon nanotube conducting glue, counts by weight, including following components：
The CNT is arranged in parallel in conducting resinl.
2. carbon nanotube conducting glue according to claim 1, it is characterised in that the material of the metal packing be silver, copper,
One or more in gold, silver copper-clad and carbon copper-clad.
3. carbon nanotube conducting glue according to claim 1 and 2, it is characterised in that the metal packing is metal nano
The mixture of particle and metal microparticle.
4. carbon nanotube conducting glue according to claim 3, it is characterised in that the particle diameter of the metal nanoparticle is 1
~100nm；The particle diameter of the metal microparticle is 1~10 μm.
5. carbon nanotube conducting glue according to claim 4, it is characterised in that the metal nanoparticle and metal micro
The mass ratio of particle is (10~15)：2.
6. carbon nanotube conducting glue according to claim 1, it is characterised in that the CNT is single
One or more in pipe, double-walled carbon nano-tube and multi-walled carbon nano-tubes.
7. the carbon nanotube conducting glue according to claim 1 or 6, it is characterised in that the length of the CNT is 1~
30μm。
8. the preparation method of the carbon nanotube conducting glue described in claim 1~7 any one, comprises the following steps：
(1) epoxy resin and coupling agent are mixed, obtains substrate mixture；
(2) in magnetic field or electric field environment, substrate mixture that the step (1) is obtained and CNT, metal packing and
Diluent mixes, and obtains carbon nanotube conducting glue precursor；
(3) in magnetic field or electric field environment, the carbon nanotube conducting glue precursor that the step (2) is obtained mixes with curing agent,
Obtain carbon nanotube conducting glue.
9. preparation method according to claim 8, it is characterised in that the intensity in the magnetic field is 5~15T；The electric field
Intensity be 1~4V/cm.
10. the carbon nanotube conducting glue described in claim 1~7 any one or preparation method described in claim 8 or 9 are obtained
Application of the carbon nanotube conducting glue in electronic device, it is characterised in that the CNT in the carbon nanotube conducting glue
Axial direction be heat conduction direction, needed for carbon nanotube conducting glue bond two end faces.
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| CN107828344A (en) * | 2017-11-21 | 2018-03-23 | 桂林电子科技大学 | A kind of one-dimensional micro-nanometer particle/epoxy resin compound cutan arranged along Z-direction and preparation method thereof |
| CN108165192A (en) * | 2017-12-28 | 2018-06-15 | 张家港康得新光电材料有限公司 | Heat-conducting glue band and preparation method thereof |
| CN108949041A (en) * | 2018-07-24 | 2018-12-07 | 原晋波 | A kind of conductive adhesive for LED encapsulation and preparation method thereof based on wicker copper nano powder |
| CN109097002A (en) * | 2018-08-10 | 2018-12-28 | 平湖阿莱德实业有限公司 | The preparation method of the interface sealant of heat filling orientation displacement arrangement |
| CN109929235A (en) * | 2019-03-03 | 2019-06-25 | 姜丽丽 | A kind of electric-conductivity heat-conductivity high carbon nano-complex and preparation method thereof |
| CN110564327A (en) * | 2019-09-16 | 2019-12-13 | 常州斯威克光伏新材料有限公司 | Epoxy resin conductive adhesive film |
| CN112432589A (en) * | 2020-11-30 | 2021-03-02 | 中南大学 | Parallel flexible strain sensor and preparation method thereof |
| CN113278388A (en) * | 2021-04-26 | 2021-08-20 | 青岛歌尔微电子研究院有限公司 | Conductive silver adhesive and preparation method thereof |
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| CN107828344A (en) * | 2017-11-21 | 2018-03-23 | 桂林电子科技大学 | A kind of one-dimensional micro-nanometer particle/epoxy resin compound cutan arranged along Z-direction and preparation method thereof |
| CN107828344B (en) * | 2017-11-21 | 2020-11-03 | 桂林电子科技大学 | One-dimensional micro-nano particle/epoxy resin composite adhesive film arranged along Z direction and preparation method thereof |
| CN108165192A (en) * | 2017-12-28 | 2018-06-15 | 张家港康得新光电材料有限公司 | Heat-conducting glue band and preparation method thereof |
| CN108949041A (en) * | 2018-07-24 | 2018-12-07 | 原晋波 | A kind of conductive adhesive for LED encapsulation and preparation method thereof based on wicker copper nano powder |
| CN109097002A (en) * | 2018-08-10 | 2018-12-28 | 平湖阿莱德实业有限公司 | The preparation method of the interface sealant of heat filling orientation displacement arrangement |
| CN109929235A (en) * | 2019-03-03 | 2019-06-25 | 姜丽丽 | A kind of electric-conductivity heat-conductivity high carbon nano-complex and preparation method thereof |
| CN110564327A (en) * | 2019-09-16 | 2019-12-13 | 常州斯威克光伏新材料有限公司 | Epoxy resin conductive adhesive film |
| CN112432589A (en) * | 2020-11-30 | 2021-03-02 | 中南大学 | Parallel flexible strain sensor and preparation method thereof |
| CN113278388A (en) * | 2021-04-26 | 2021-08-20 | 青岛歌尔微电子研究院有限公司 | Conductive silver adhesive and preparation method thereof |
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