CN107964382A - A kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive - Google Patents
A kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive Download PDFInfo
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- CN107964382A CN107964382A CN201711443673.4A CN201711443673A CN107964382A CN 107964382 A CN107964382 A CN 107964382A CN 201711443673 A CN201711443673 A CN 201711443673A CN 107964382 A CN107964382 A CN 107964382A
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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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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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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Abstract
A kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive of the present invention, by monomer, initiator, dispersant and solvent are prepared into polymer microsphere, and prepare sulfhydryl modified carbon nanotubes, coated using low temperature plasma enhancing chemical vapour deposition technique in processed polymer microsphere surface, grow sulfhydryl modified carbon nanotubes, sulfhydryl modified carbon nanotubes microballoon is made, sulfhydryl modified carbon nanotubes microballoon is dispersed in by acrylic resin again, curing agent, the acrylic size system of surfactant and coupling agent composition, finally carry out deaeration processing, obtain sulfhydryl modified carbon nanotubes microsphere conductive adhesive.The present invention by being grafted sulfydryl on the carbon nanotubes, stronger make a concerted effort can be produced with many metals using sulfydryl, the conducting resinl caking property thus prepared is increased substantially, while overcomes the too high levels of conductive filler in conventional conductive glue, the shortcomings of expensive, preparation process is complicated, environmental pollution is high.
Description
Technical field
The present invention relates to conducting resinl field, and in particular to a kind of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive
Preparation method.
Background technology
With world information, the fast development of communication industry, its is important as interactive critical component for display device
Higher and higher, the Thin Film Transistor-LCD of property（Thin film transistor-liquid crystal display,
TFT-LCD）The technology that microelectronics retrofit is carried out on monocrystalline, it is transplanted in large-area glass and carries out thin film transistor (TFT)
（TFT）The processing of array, then by the array base palte and another substrate with color filter film, using with the mature liquid crystal of industry
Display（LCD）Technology, forms a liquid crystal cell, then process such as polaroid such as pastes at the process after passing through, and eventually forms liquid crystal
Show device.Using FPD (flat panel display) industry that TFT-LCD is technology mainstream in global information with communicating
Occupy epochmaking status in technical industry.
Conducting resinl is a kind of adhesive for being provided simultaneously with electric conductivity and adhesive property, it can connect a variety of conductive materials
It is connected together, makes to be connected storeroom formation conductive path.It is by the way that conductive filler is filled in organic polymer matrix,
So as to make it have with metal similar in electric conductivity.Unlike common conductive polymer, conducting resinl requires system storing up
There is mobility under the conditions of depositing, can be cured by heating or other modes, so as to form the connection with some strength.
Conductive filler is the excellent metallic of electric conductivity, and polymeric matrix is generally promoted by performed polymer, curing agent, toughener, curing
It is formulated into agent and other auxiliary agents, the mechanical property and adhesive property of conducting resinl are mainly determined by polymeric matrix.It is common
Performed polymer includes epoxy resin, polyurethane, phenolic resin etc..
Liquid crystal panel is in colored filter substrate module and pixel driver substrate module the two up/down glass substrate groups
Layer of liquid crystal molecule is enclosed among part, in order to drive liquid crystal to deflect, TFT-LCD turns on up/down glass base using conductive gold size
Plate component.Conductive gold size is into conductive micro-balloons are polymer microballoon surface claddings by conductive gold spacer and frame glue hybrid modulation
W metal conductive layer, reuses electroless plating method and plates Au layers, form conducting particles.After substrate is bonded, the gold of conductive gold spacer outer layer/
Nickel wrapping layer can transmit electronics, and the flexible resin balls of conductive gold spacer kernel can buffer the pressure after fitting.
The production of conventional conductive gold goal is to carry out gold/nickel using resin ball surface of the electroless plating method at a diameter of 5-8 μm
Parcel, the energy consumption of this method is big, complex process, and the gold salt used in gold plating process is cyanide mostly, and toxicity is very big, during easily
Heavy metal pollution is produced, and gold is expensive, adds cost.
Chinese invention patent application number 201510845618.2 discloses a kind of side of carbon nanotubes coated polymer microballoon
Method：Carbon nano tube dispersion liquid is prepared using surfactant, polymer microballoon and dispersion liquid are sufficiently mixed, centrifugation removes
Upper strata carbon nano tube dispersion liquid, cleaning removes surfactant, dry, the polymer microballoon of carbon nanotubes cladding is obtained, with generation
It is used for the electrically conductive particles of anisotropic conductive adhesive paste for the polymer microballoon of metal (nickel and/or gold) cladding.
Chinese invention patent application number 201510230420.3 discloses the preparation method and conduction of graphene-based resin balls
The preparation method of frame glue, common conductive gold in conductive frame glue at present is replaced using graphene-based resin balls as conducting particles
Ball, the preparation process of the graphene-based resin balls is environmentally protective, can avoid the huge sum of money produced in conductive gold spacer production process
Belong to pollution.
Using carbon material coated polymer microballoon with its abundant raw material, electric conductivity and excellent in mechanical performance in such scheme
Advantage, the plating metal Type of Collective thing microballoon of fictitious hosts costliness, possesses bright prospects in microelectronics Packaging field.However,
Power deficiency is combined in bonding process, between carbon material and metal interface, hole and bubble are also easy to produce, with carbon material conductive filler
Dosage increase, electric conductivity but causes the reduction of conducting resinl caking property while optimization, and then causes the adhesion strength of composite construction
Reduce, when load easily produces bonding failure.
The content of the invention
For power deficiency is combined between carbon material and metal interface, hole and bubble are also easy to produce, when triggering composite construction load
The defects of easily producing bonding failure, the present invention are produced by being grafted sulfydryl on the carbon nanotubes using sulfydryl and metal surface
It is stronger to make a concerted effort, thus the conducting resinl caking property prepared is increased substantially, while overcome conductive in conventional conductive glue
The too high levels of filler, the shortcomings of expensive, preparation process is complicated, environmental pollution is high.
To solve the above problems, the present invention uses following technical scheme：
（1）Using styrene monomer, azodiisobutyronitrile initiator, dispersant and etoh solvent, by 60-90 DEG C of reaction 5-18
Hour, polymer microsphere is prepared into, the particle diameter of the polymer microsphere is 1-8 μm；
（2）Use carbon nanotubes that original carbon nanotubes are added in nitration mixture for raw material, the quality of the carbon nanotubes and nitration mixture
Than for 1:180-220,30 min of ultrasonic disperse, is placed in constant temperature blender with magnetic force at 80 DEG C and is refluxed 30 min；Then
Carbon nanotubes after processing is added in a large amount of deionized waters and is cooled down, is centrifuged, and is filtered repeatedly to neutrality, vacuum drying, system
Oxide/carbon nanometer tube is obtained, the oxide/carbon nanometer tube is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptos third
Base trimethoxy silane, 75 DEG C of reflux, unnecessary 3- mercaptopropyl trimethoxysilanes are washed away with dichloromethane, are filtered, and vacuum is dried
It is dry, sulfhydryl modified carbon nanotubes is made, grinding is spare；
（3）The polymer microsphere is subjected to heating activating surface, strengthens chemical vapor deposition side with low temperature plasma
The polymer microsphere surface cladding or grow sulfhydryl modified carbon nanotubes that method is crossed in activation process, are made sulfhydryl modified carbon and receive
Mitron microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 2-20 mass parts is dispersed with stirring by 45-60 parts third
The acrylic size system of olefin(e) acid resin, 20-30 part curing agent, 3-5 parts of surfactants and 3-8 parts of coupling agent compositions, most
Deaeration processing is carried out afterwards, obtains sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
Preferably, the styrene monomer, azodiisobutyronitrile initiator, dispersant and etoh solvent press quality parts ratio
Example is 5-30: 0.01-3 : 0.05-3 :100, the dispersant is one kind in chloroform, mercaptoethanol and thioacetic acid.
Preferably, the carbon nanotubes is the mixing of one or both in single-walled carbon nanotube and multi-walled carbon nanotube, institute
A diameter of 1-40 nm of carbon nanotubes are stated, purity is more than 97%.
Preferably, the nitration mixture is volume ratio H2SO4:HNO3=3:1, the oxide/carbon nanometer tube, 3- mercapto propyl group trimethoxies
The mass ratio of base silane and dichloromethane is 1-5:4-8:100.
Preferably, activating treatment temperature is stated as 140-190 DEG C.
Preferably, low temperature plasma enhancing chemical vapor deposition method be under high vacuum environment, control etc. from
Daughter density is 3 × 1012-9 × 1012, vacuum 0.001-0.1Pa, is passed through the sulfhydryl modified carbon nanotube powder,
Assistant depositing is oriented in polymer microsphere surface using plasma at room temperature.
Preferably, step（3）In be made the sulfydryl carbon nanotubes microspherulite diameter be 2-10 μm.
Preferably, the curing agent is one or both of isocyanates, pyridine, amino resins and tetraisopropoxy titanium
Combination of the above, the surfactant are lauryl sodium sulfate, neopelex, lauryl sodium sulfate, 12
Combination more than one or both of sodium alkyl sulfonate, ammonium lauryl sulfate and sodium tetradecyl sulfate, the coupling agent
For silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, boric acid ester coupler
In one kind.
Preferably, the defoaming method is that conducting resinl is evacuated to 0.1-10Pa or so using vacuum pump, and it is small to stand 2-8
When, then be passed through nitrogen and recover to normal pressure.
In addition a kind of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive is provided, be prepared by the above method.
It is to carry out the parcel of gold/nickel in resin ball surface using electroless plating method to overcome the production of conventional conductive gold goal,
Energy consumption is big, complex process, and the gold salt used in gold plating process is cyanide mostly, and toxicity is very big, during be also easy to produce a huge sum of money
Belong to pollution, and gold expensive, the problem of adding cost, existing scheme is using carbon material coated polymer microballoon with it
The advantage of abundant raw material, electric conductivity and excellent in mechanical performance, the plating metal Type of Collective thing microballoon of fictitious hosts costliness, however,
Power deficiency is combined in bonding process, between carbon material and metal interface, hole and bubble are also easy to produce, with carbon material conductive filler
Dosage increase, electric conductivity but causes the reduction of conducting resinl caking property, and then causes the bonding of composite construction strong while optimization
Degree reduces, and when load easily produces bonding failure.A kind of in consideration of it, liquid crystal display circuit sulfydryl carbon nanotubes microballoon of the present invention
The preparation method of conducting resinl, carbon nanotubes is carried out it is sulfhydryl modified, processed polymer microsphere surface cladding, growth sulfydryl
Modified carbon nanotubes, is made sulfhydryl modified carbon nanotubes microballoon, is finally dispersed in by acrylic resin, curing agent, surface
The acrylic size system of activating agent and coupling agent composition, obtains conducting resinl.The present invention by being grafted mercapto on the carbon nanotubes
Base, can be stronger with joint efforts with the generation of various material surface using sulfydryl, has excellent conductive bond for liquid crystal display circuit
Property, at the same overcome the too high levels of conductive filler in conventional conductive glue, expensive, preparation process is complicated, environmental pollution
The shortcomings of property is high.
By the liquid crystal display circuit for preparing of the present invention with sulfydryl carbon nanotubes microsphere conductive adhesive and conductive gold spacer conducting resinl into
Row test comparison, the present invention has a clear superiority as shown in table 1 under the conditions of identical contact resistance.
Table 1：
The present invention provides a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive, with prior art phase
Than, its protrude the characteristics of and excellent effect be：
1st, the present invention utilizes mercapto functional group and the rapid complex coordination of metal ion, energy by being grafted sulfydryl on the carbon nanotubes
It is stronger with joint efforts with the generation of various metals surface, it can overcome and power deficiency is combined between carbon material and metal interface, be also easy to produce hole
And bubble, the defects of easily producing bonding failure when triggering composite construction load, thus the conducting resinl caking property prepared obtains
Increase substantially.
2nd, the liquid crystal display circuit that prepared by the present invention is excellent with sulfydryl carbon nanotubes microsphere conductive adhesive electric conductivity, so as to
The shortcomings that enough avoiding the too high levels of conductive filler in conventional conductive glue, reduces application amount, is effectively reduced production cost.
3rd, sulfhydryl modified carbon nanotubes microballoon is dispersed in by acrylic resin, curing agent, surfactant by the present invention
With the acrylic size system of coupling agent composition, technique is simple and easy to control, safe and non-toxic, environmentally protective.
Embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Scope be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）It is 5 in mass fraction ratio: 0.01: 0.05 :100, take styrene monomer, azodiisobutyronitrile triggers
Agent, chloroform and etoh solvent, by 90 DEG C reaction 5 it is small when, be prepared into polymer microsphere, the particle diameter of the polymer microsphere is 6 μ
m；
（2）Using a diameter of 40 nm, single-walled carbon nanotube of the purity more than 97% is raw material, and original carbon nanotubes are added to
H2SO4:HNO3=3:In 1 nitration mixture, the mass ratio of the carbon nanotubes and nitration mixture is 1:180,30 min of ultrasonic disperse, is placed in perseverance
30 min are refluxed on warm magnetic stirring apparatus at 80 DEG C；Then the carbon nanotubes after processing is added to a large amount of deionizations
Cool down, centrifuge in water, and filter repeatedly to neutrality, vacuum drying, oxide/carbon nanometer tube is made.By oxide/carbon nanometer tube, 3- mercaptos
The mass ratio of propyl trimethoxy silicane and dichloromethane is 1:4:100 weigh raw material, and the oxide/carbon nanometer tube of preparation is added
Into dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptopropyl trimethoxysilanes, 75 DEG C of reflux, are washed with dichloromethane
Unnecessary 3- mercaptopropyl trimethoxysilanes are removed, are filtered, vacuum drying, sulfhydryl modified carbon nanotubes is made, grinding is spare；
（3）The polymer microsphere is subjected to heating activating surface, activating treatment temperature is 140 DEG C, uses low-temperature plasma
Body strengthens the polymer microsphere surface cladding that chemical vapor deposition method crossed in activation process, grows sulfhydryl modified carbon nanometer
Pipe, it is 3 × 10 to control plasma density12, vacuum 0.001Pa, is passed through the sulfhydryl modified carbon nanotube powder, in room
Temperature it is lower using plasma orientation assistant depositing in polymer microsphere surface, it is 2 μm of sulfhydryl modified carbon nanotubes that particle diameter, which is made,
Microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 10 mass parts is dispersed with stirring by 60 parts of acrylic acid trees
The acrylic resin that fat, 25 parts of pyridines, 3 parts of lauryl sodium sulfate, dodecyl sodium sulfate and 2 parts of titanate coupling agents form
Colloid system, finally carries out deaeration processing, obtains sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
Sulfhydryl modified carbon nanotubes microsphere conductive adhesive in embodiment 1 is used to bond LCD display and thin film circuit,
Carry out room temperature condition and in 150 DEG C of temperature, pressure 15Kg/cm2 ,Hot pressing time 20 seconds, adhesive property and conducting performance test such as table
Shown in 2.
Embodiment 2
（1）It is 30 in mass fraction ratio: 0.2 : 0.15 :100, take styrene monomer, azodiisobutyronitrile triggers
Agent, mercaptoethanol and etoh solvent, by 65 DEG C reaction 18 it is small when, be prepared into polymer microsphere, the grain of the polymer microsphere
Footpath is 4 μm；
（2）Using a diameter of 10 nm, multi-walled carbon nanotube of the purity more than 97% is raw material, and original carbon nanotubes are added to
H2SO4:HNO3=3:In 1 nitration mixture, the mass ratio of the carbon nanotubes and nitration mixture is 1:190,30 min of ultrasonic disperse, is placed in
30 min are refluxed in constant temperature blender with magnetic force at 80 DEG C；Then by the carbon nanotubes after processing be added to it is a large amount of go from
Cool down, centrifuge in sub- water, and filter repeatedly to neutrality, vacuum drying, oxide/carbon nanometer tube is made.By oxidation multi-wall carbon nano-tube
The mass ratio of pipe, 3- mercaptopropyl trimethoxysilanes and dichloromethane is 5:5:100 weigh raw material, by the carbonoxide nanometer of preparation
Pipe is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptopropyl trimethoxysilanes, 75 DEG C of reflux, use dichloro
Methane washes away unnecessary 3- mercaptopropyl trimethoxysilanes, filters, vacuum drying, and sulfhydryl modified carbon nanotubes is made, and grinding is standby
With；
（3）The polymer microsphere is subjected to heating activating surface, activating treatment temperature is 180 DEG C, uses low-temperature plasma
Body strengthens the polymer microsphere surface cladding that chemical vapor deposition method crossed in activation process, grows sulfhydryl modified carbon nanometer
Pipe, it is 5 × 1012, vacuum 0.01Pa to control plasma density, the sulfhydryl modified carbon nanotube powder is passed through, in room
Temperature it is lower using plasma orientation assistant depositing in polymer microsphere surface, it is 4 μm of sulfhydryl modified carbon nanotubes that particle diameter, which is made,
Microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 8 mass parts is dispersed with stirring by 45-60 parts of acrylic acid
Resin, 35 parts of curing agent are combination, 5 parts of dodecyl sodium sulfates and 3 parts of Aluminate idols in amino resins and tetraisopropoxy titanium
Join the acrylic size system of agent composition, finally carry out deaeration processing, obtain sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
Sulfhydryl modified carbon nanotubes microsphere conductive adhesive in embodiment 2 is used to bond LCD display and thin film circuit,
Carry out room temperature condition and in 150 DEG C of temperature, pressure 15Kg/cm2 ,Hot pressing time 20 seconds, adhesive property and conducting performance test such as table
Shown in 2.
Embodiment 3
（1）It is 15 in mass fraction ratio: 0.5 : 3 :100, take styrene monomer, azodiisobutyronitrile initiator,
Thioacetic acid and etoh solvent, by 70 DEG C reaction 12 it is small when, be prepared into polymer microsphere, the particle diameter of the polymer microsphere is
5μm；
（2）Using a diameter of 30 nm, single-walled carbon nanotube of the purity more than 97% and multi-walled carbon nanotube are raw material, will be original
Carbon nanotubes is added to H2SO4:HNO3=3:In 1 nitration mixture, the mass ratio of the carbon nanotubes and nitration mixture is 1:190, ultrasound point
30 min are dissipated, is placed in constant temperature blender with magnetic force at 80 DEG C and is refluxed 30 min；Then the carbon nanotubes after processing is added
Enter into a large amount of deionized waters and cool down, centrifuge, and filter repeatedly to neutrality, vacuum drying, oxide/carbon nanometer tube is made.By oxidation
The mass ratio of multi-walled carbon nanotube, 3- mercaptopropyl trimethoxysilanes and dichloromethane is 4:4:100 weigh raw material, by preparation
Oxide/carbon nanometer tube is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptopropyl trimethoxysilanes, and 75 DEG C are returned
Stream, unnecessary 3- mercaptopropyl trimethoxysilanes are washed away with dichloromethane, are filtered, vacuum drying, and sulfhydryl modified carbon nanometer is made
Pipe, grinding are spare；
（3）The polymer microsphere is subjected to heating activating surface, activating treatment temperature is 190 DEG C, uses low-temperature plasma
Body strengthens the polymer microsphere surface cladding that chemical vapor deposition method crossed in activation process, grows sulfhydryl modified carbon nanometer
Pipe, it is 7 × 1012, vacuum 0.05Pa to control plasma density, the sulfhydryl modified carbon nanotube powder is passed through, in room
Temperature it is lower using plasma orientation assistant depositing in polymer microsphere surface, it is 5 μm of sulfhydryl modified carbon nanotubes that particle diameter, which is made,
Microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 15 mass parts is dispersed with stirring by 55 parts of acrylic acid trees
Fat, 20 parts of curing agent amino resins, 3 parts of lauryl sodium sulfate, neopelex and 7 parts of boric acid ester coupler compositions
Acrylic size system, finally carry out deaeration processing, obtain sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
Sulfhydryl modified carbon nanotubes microsphere conductive adhesive in embodiment 3 is used to bond LCD display and thin film circuit,
Carry out room temperature condition and in 150 DEG C, pressure 15Kg/cm2 of temperature, hot pressing time 20 seconds, adhesive property and conducting performance test are such as
Shown in table 2.
Embodiment 4
（1）It is 16 in mass fraction ratio: 0.2 : 2.5 :100, take styrene monomer, azodiisobutyronitrile triggers
Agent, mercaptoethanol and etoh solvent, by 85 DEG C reaction 10 it is small when, be prepared into polymer microsphere, the grain of the polymer microsphere
Footpath is 6 μm；
（2）Using a diameter of 5 nm, single-walled carbon nanotube of the purity more than 97% and multi-walled carbon nanotube are raw material, by original carbon
Nanotube is added to H2SO4:HNO3=3:In 1 nitration mixture, the mass ratio of the carbon nanotubes and nitration mixture is 1:190, ultrasonic disperse
30 min, are placed in constant temperature blender with magnetic force at 80 DEG C and are refluxed 30 min；Then the carbon nanotubes after processing is added
Cool down, centrifuge into a large amount of deionized waters, and filter repeatedly to neutrality, vacuum drying, oxide/carbon nanometer tube is made.It is more by aoxidizing
The mass ratio of wall carbon nano tube, 3- mercaptopropyl trimethoxysilanes and dichloromethane is 2:6:100 weigh raw material, by the oxygen of preparation
Carbon nano tube is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptopropyl trimethoxysilanes, and 75 DEG C are returned
Stream, unnecessary 3- mercaptopropyl trimethoxysilanes are washed away with dichloromethane, are filtered, vacuum drying, and sulfhydryl modified carbon nanometer is made
Pipe, grinding are spare；
（3）The polymer microsphere is subjected to heating activating surface, activating treatment temperature is 170 DEG C, uses low-temperature plasma
Body strengthens the polymer microsphere surface cladding that chemical vapor deposition method crossed in activation process, grows sulfhydryl modified carbon nanometer
Pipe, it is 3 × 1012, vacuum 0.06Pa to control plasma density, the sulfhydryl modified carbon nanotube powder is passed through, in room
Temperature it is lower using plasma orientation assistant depositing in polymer microsphere surface, it is 6 μm of sulfhydryl modified carbon nanotubes that particle diameter, which is made,
Microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 2 mass parts is dispersed with stirring by 60 parts of acrylic acid trees
The acrylic acid tree that fat, 30 parts of pyridines, 5 parts of lauryl sodium sulfate, neopelex and 3 parts of phosphate coupling agents form
Fat colloid system, finally carries out deaeration processing, obtains sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
The sulfhydryl modified carbon nanotubes microsphere conductive adhesive of embodiment 4 is used to bond LCD display and thin film circuit, into
Row room temperature condition and in 150 DEG C, pressure 15Kg/cm2 of temperature, hot pressing time 20 seconds, adhesive property and conducting performance test such as table 2
It is shown.
Embodiment 5
（1）It is 20 in mass fraction ratio: 1.5 : 2.5 :100, take styrene monomer, azodiisobutyronitrile triggers
Agent, chloroform and etoh solvent, by 90 DEG C reaction 5 it is small when, be prepared into polymer microsphere, the particle diameter of the polymer microsphere is 8 μ
m；
（2）Using a diameter of 30 nm, multi-walled carbon nanotube of the purity more than 97% is raw material, and original carbon nanotubes are added to
H2SO4:HNO3=3:In 1 nitration mixture, the mass ratio of the carbon nanotubes and nitration mixture is 1:200,30 min of ultrasonic disperse, is placed in
30 min are refluxed in constant temperature blender with magnetic force at 80 DEG C；Then by the carbon nanotubes after processing be added to it is a large amount of go from
Cool down, centrifuge in sub- water, and filter repeatedly to neutrality, vacuum drying, oxide/carbon nanometer tube is made.By oxidation multi-wall carbon nano-tube
The mass ratio of pipe, 3- mercaptopropyl trimethoxysilanes and dichloromethane is 5:5:100 weigh raw material, by the carbonoxide nanometer of preparation
Pipe is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptopropyl trimethoxysilanes, 75 DEG C of reflux, use dichloro
Methane washes away unnecessary 3- mercaptopropyl trimethoxysilanes, filters, vacuum drying, and sulfhydryl modified carbon nanotubes is made, and grinding is standby
With；
（3）The polymer microsphere is subjected to heating activating surface, activating treatment temperature is 170 DEG C, uses low-temperature plasma
Body strengthens the polymer microsphere surface cladding that chemical vapor deposition method crossed in activation process, grows sulfhydryl modified carbon nanometer
Pipe, it is 3 × 10 to control plasma density12, vacuum 0.1Pa, is passed through the sulfhydryl modified carbon nanotube powder, in room temperature
It is lower micro- for 8 μm of sulfhydryl modified carbon nanotubes in polymer microsphere surface, obtained particle diameter using plasma orientation assistant depositing
Ball；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 20 mass parts is dispersed with stirring by 50 parts of acrylic acid trees
The acrylic size system that fat, 25 parts of tetraisopropoxy titaniums, 5 parts of lauryl sodium sulfate and 5 parts of bimetallic coupling agents form,
Deaeration processing is finally carried out, obtains sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
Sulfhydryl modified carbon nanotubes microsphere conductive adhesive in embodiment 5 is used to bond LCD display and thin film circuit,
Carry out room temperature condition and in 150 DEG C of temperature, pressure 15Kg/cm2 ,Hot pressing time 20 seconds, adhesive property and conducting performance test such as table
Shown in 2.
Comparative example 1
The conductive gold spacer of the parcel of gold/nickel is carried out in a diameter of 8 μm of resin ball surface with electroless plating method.
Comparative example 2
（1）Styrene monomer, azodiisobutyronitrile initiator, dispersant and etoh solvent will be used, it is small by 60 DEG C of reactions 5
When, polymer microsphere is prepared into, the particle diameter of the polymer microsphere is 8 μm；
（2）Carbon nanotubes is disperseed in deionized water, polymer microsphere to be added in dispersion liquid and is uniformly mixed, after centrifugal treating
The microballoon of carbon nanotubes cladding is made；
（3）Calculate according to the mass fraction by 10 mass parts carbon nanotubes microballoons be dispersed with stirring by 60 parts of acrylic resins, 20 parts it is different
The acrylic size system of cyanate, 3 parts of lauryl sodium sulfate and 7 parts of silane coupling agent compositions, finally carries out at deaeration
Reason, obtains the resin-coated microsphere conductive adhesive of carbon nanotubes.
Conducting resinl prepared by comparative example 1 and 2 is used to bond LCD display and thin film circuit, carry out room temperature condition and
150 DEG C of temperature, pressure 15Kg/cm2 ,Hot pressing time 20 seconds, adhesive property and conducting performance test are as shown in table 2.
Table 2
Claims (10)
1. a kind of liquid crystal display circuit preparation method of sulfydryl carbon nanotubes microsphere conductive adhesive, it is characterised in that specifically include
Following steps：
（1）Using styrene monomer, azodiisobutyronitrile initiator, dispersant and etoh solvent, by 60-90 DEG C of reaction 5-18
Hour, polymer microsphere is prepared into, the particle diameter of the polymer microsphere is 1-8 μm；
（2）Use carbon nanotubes that original carbon nanotubes are added in nitration mixture for raw material, the quality of the carbon nanotubes and nitration mixture
Than for 1:180-220,30 min of ultrasonic disperse, is placed in constant temperature blender with magnetic force at 80 DEG C and is refluxed 30 min；Then
Carbon nanotubes after processing is added in a large amount of deionized waters and is cooled down, is centrifuged, and is filtered repeatedly to neutrality, vacuum drying, system
Oxide/carbon nanometer tube is obtained, the oxide/carbon nanometer tube is added in dichloromethane, 10 min of ultrasonic disperse, adds 3- mercaptos third
Base trimethoxy silane, 75 DEG C of reflux, unnecessary 3- mercaptopropyl trimethoxysilanes are washed away with dichloromethane, are filtered, and vacuum is dried
It is dry, sulfhydryl modified carbon nanotubes is made, grinding is spare；
（3）The polymer microsphere is subjected to heating activating surface, strengthens chemical vapor deposition side with low temperature plasma
Polymer microsphere surface cladding that method is crossed in activation process, grow sulfhydryl modified carbon nanotubes, and sulfhydryl modified carbon is made and receives
Mitron microballoon；
（4）Calculate according to the mass fraction and the sulfhydryl modified carbon nanotubes microballoon of 2-20 mass parts is dispersed with stirring by 45-60 parts third
The acrylic size system of olefin(e) acid resin, 20-30 part curing agent, 3-5 parts of surfactants and 3-8 parts of coupling agent compositions, most
Deaeration processing is carried out afterwards, obtains sulfhydryl modified carbon nanotubes microsphere conductive adhesive.
2. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the styrene monomer, azodiisobutyronitrile initiator, dispersant and etoh solvent are in mass fraction ratio
5-30 : 0.01-3 : 0.05-3 :100, the dispersant is one kind in chloroform, mercaptoethanol and thioacetic acid.
3. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, mixing of the carbon nanotubes for one or both in single-walled carbon nanotube and multi-walled carbon nanotube, the carbon
A diameter of 1-40 nm of nanotube, purity are more than 97%.
4. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the nitration mixture is H2SO4:HNO3Volume ratio is 3:1, the oxide/carbon nanometer tube, 3- mercapto propyl trimethoxy silicon
The mass ratio of alkane and dichloromethane is 1-5:4-8:100.
5. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the activating treatment temperature is 140-190 DEG C.
6. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the low temperature plasma enhancing chemical vapor deposition method is under high vacuum environment, plasma is controlled
Density is 3 × 1012 - 9×1012, vacuum 0.001-0.1Pa, is passed through the sulfhydryl modified carbon nanotube powder, in room temperature
It is lower to orient assistant depositing in polymer microsphere surface using plasma.
7. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, step（3）In be made the sulfydryl carbon nanotubes microspherulite diameter be 2-10 μm.
8. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the curing agent is more than one or both of isocyanates, pyridine, amino resins and tetraisopropoxy titanium
Combination, the surfactant is lauryl sodium sulfate, neopelex, lauryl sodium sulfate, dodecyl
Combination more than one or both of sodium sulfonate, ammonium lauryl sulfate and sodium tetradecyl sulfate, the coupling agent is silicon
In alkane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, boric acid ester coupler
It is a kind of.
9. a kind of preparation method of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive according to claim 1,
It is characterized in that, the defoaming method is that conducting resinl is evacuated to 0.1-10Pa or so using vacuum pump, when standing 2-8 is small,
Nitrogen is passed through again to recover to normal pressure.
10. a kind of liquid crystal display circuit sulfydryl carbon nanotubes microsphere conductive adhesive, it is characterised in that any by claim 1-9
Method described in claim is prepared.
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