CN104347192A - Method for preparing electronic conductive micro-sphere for producing anisotropic conductive film by simply absorbing metal palladium ions - Google Patents
Method for preparing electronic conductive micro-sphere for producing anisotropic conductive film by simply absorbing metal palladium ions Download PDFInfo
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Abstract
The invention discloses a method for preparing electronic conductive micro-spheres for producing an anisotropic conductive film by simply absorbing metal palladium ions. The method comprises the following steps of step I, preparing polymer seed balls; step II, preparing seed ball dispersion liquid; step III, preparing emulsion; step IV, adding the emulsion into the seed ball dispersion liquid for swelling to obtain a swelling solution; step V, performing polymerization, centrifuging, cleaning and vacuum drying on the swelling solution, water and surfactant to obtain monodisperse cross-linked polymer micro-spheres; step VI, dispersing the cross-linked polymer micro-spheres in strong oxidizing acid containing palladium chloride, wherein the concentration of the strong oxidizing acid is 0.1-3g/L; performing ultrasonic mixing, centrifuging and washing until the PH value is neutral, and adding a reducing agent for reducing to obtain polymer micro-spheres with high-catalytic-activity palladium; step VII, adding the polymer micro-spheres into electroless plating solution for plating. Compared with the traditional adsorption method for colloid palladium, the method disclosed by the invention has the advantages of fewer steps, high adsorption capacity, good effect and uneasiness for analyzing; the intrusion of tin ions is reduced, and the risk that activating and sensitizing liquid is easy to deteriorate is eliminated.
Description
Technical field
The present invention relates to anisotropic conductive film (being called for short ACF) field, particularly relate to the method that one prepares conductive micro-balloons (nickel plating microballoon, plating palladium microballoon, silver-coated microspheres, gold-plated microballoon and alloy microballoon) more easily.
Background technology
The development that information, communication industry are advanced by leaps and bounds, drives electronic circuit to become more meticulous with integrated, and increasing integrated circuit needs to assemble with wiring board, and traditional tin lead welding connects and can not meet the demands.Anisotropic conductive film simplifies technique, improves reliability, greatly facilitates electronic equipment to light, thin, little future development.Anisotropic conductive film (being called for short ACF) is mainly used in the connection of the microcircuit such as display pannel, flexible PCB of electronic calculator, liquid crystal, plasma and various semiconductor.Feature respectively to anisotropic conductive film (ACF) is longitudinal conducting, lateral isolation, and wherein core is the preparation of conductive micro-balloons.
When tradition colloid palladium absorbing process prepares conductive micro-balloons, first want multiple steps such as alligatoring, absorption, activation, sensitization, dispergation.Conventional process is many, complex process, and absorption palladium ion amount is few, and easily resolves, and can introduce tin ion, the risk that existence activates, sensitizing solution is perishable.Often occur that when preparing conductive micro-balloons conductive micro-balloons is rough, loosely, coating such as easily to come off at the problem metal level adhesion.
Have Chinese Patent Application No. 200510019313.2 in the similar patent of polymer microsphere surface plating, but adopt traditional adsorption method plating, complex steps, technique is unstable.
Directly adsorb gold-plated patent at polymer microsphere surface and have Chinese Patent Application No. 201210154648.5,201110162698.3, take direct ADSORPTION OF GOLD ion reduction and chemical deposition, it is inadequate that the method plates out gold goal packing, rough, and needing that gold plate thickness is thicker could meet low resistance requirement, cost is higher.If microsphere surface plating alloy conductive metal layer, can by layer gold THICKNESS CONTROL 10
-30nm.Use uncrosslinked polymer microsphere in above-mentioned patent in addition, this microballoon is not ageing-resistant, should not for the preparation of ACF.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of monodisperse high-performance conductive microballoon, this preparation method comparatively conventional method is simple, does not use stannous chloride, simplifies the steps such as absorption, activation, sensitization, obtained conductive micro-balloons surface layer gold is smooth, fine and close.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: the method for the conductive micro-balloons that a kind of simple and easy adsorbing metal palladium ion is produced for the preparation of anisotropic conductive film, comprises the steps:
Step one: monomer, dispersant, initator and solvent are added in reaction vessel and mixes, under inert gas shielding, be polymerized 2-24h at constant temperature 50-80 DEG C, centrifugal, washing, drying obtain polymerization species ball, and planting ball particle size is 400nm-8 μm;
Step 2: kind ball step one obtained is distributed in the aqueous solution containing surfactant, dispersant, ultrasonic agitation is even, prepares kind of a ball dispersion liquid;
Step 3: initator is dissolved in mass ratio example mix crosslinking agent, activated monomer, chain-transferring agent oil-based liquid in, the aqueous solution of the surfactant of certain mass ratio, dispersant, ethanol is added in this oil-based liquid, ultrasonic emulsification 5-60min, obtains emulsion;
Step 4: emulsion described in step 3 is added to plant in ball dispersion liquid described in step 2 and carry out swelling 24-48h, obtain swelling solution;
Step 5: swelling solution described in step 4 is carried out polymerization reaction with certain mixing speed at 70-98 DEG C, reaction time is 2-24h, through centrifugal, clean, vacuumize, obtained adsorbable Metal Palladium also can for the preparation of the monodisperse cross-linked polymer microsphere of conductive micro-balloons in anisotropic conductive film, and the particle diameter of described mono-disperse polymer microspheres is 1-50 μm;
Step 6: the monodisperse cross-linked polymer microsphere described in step 5 is dispersed in containing palladium bichloride concentration be 0.1-3g/L, mass percent concentration is in the acid with strong oxidizing property of 30%-80%, ultrasonic agitation 1-60min in 25-80 DEG C of water-bath, then centrifugal, be washed to pH value for neutral, add the polymer microsphere that reducing agent reduction obtains having high catalytic activity palladium;
Step 7: step 6 gained polymer microsphere is added in chemical plating fluid and carries out plating, obtain the conductive micro-balloons that can be used for preparing anisotropic conductive film;
Monomer described in step one is one or more the mixture in following material: styrene, methyl methacrylate, hydroxyethyl methacrylate;
Dispersant described in step one, step 2, step 3 is one or more the mixture in following material: polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol;
Initator described in step one is one or more the mixture in following material: azodiisobutyronitrile, benzoyl peroxide;
Solvent described in step one is one or more the mixture in following material: ethanol, methyl alcohol, isopropyl alcohol, water;
In step 3, initator is one or more the mixture in following material: benzoyl peroxide, azodiisobutyronitrile;
In step 3, crosslinking agent is one or more the mixture in following material: Ethylene glycol dimethacrylate, methacrylic acid butanediol ester, 1,6-hexanediyl ester, TEGDMA, trimethylol-propane trimethacrylate, divinylbenzene;
In step 3, activated monomer is one or more the mixture in following material: methyl methacrylate, styrene, acetoacetoxyethyl methacrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate, isobornyl acrylate;
Step 3 Chain transfer agent is that one or more the mixture in following material: 3-dredges the different monooctyl ester of base propionic acid, mercaptoethanol, TGA, lauryl mercaptan;
In step 2, step 3 and step 5, surfactant is one or more the mixture in following material: lauryl sodium sulfate, neopelex, dodecyltriethanolamine sulfate;
In step 6, acid with strong oxidizing property is one or more the mixture in following material: sulfuric acid, nitric acid;
Reducing agent described in step 6 is one or more the mixture in following material: hydrazine, dimethyamine borane, sodium hypophosphite.
The further restriction of technique scheme is, the mass ratio of the monomer described in step one, dispersant, initator, solvent is 100:(10-50): (0.5-10): (100-1000).
The further restriction of technique scheme is, plants in ball dispersion liquid described in step 2, and water, surfactant, dispersant mass ratio are 100:(0.25-5): (1-5).
The further restriction of technique scheme is, in oil-based liquid described in step 3, initator, crosslinking agent, activated monomer, chain-transferring agent mass ratio are (0.1-8): (3-95): (5-90): (0-30); In emulsion described in step 3, the mass ratio of oil-based liquid, water, surfactant, ethanol is 100:(100-1000): (3-10): (1-30).
The further restriction of technique scheme is, in step 6, the concentration being made into acid with strong oxidizing property Chlorine in Solution palladium used is 0.1-3g/L, and the mass ratio of acid with strong oxidizing property and water is 1:(0.5-3), this strong oxidizing property acid concentration is 30%-80%.
The further restriction of technique scheme is, chemical plating fluid described in step 7 is the one in following material: chemical nickel plating, chemical silvering, chemical palladium-plating, chemical gilding plating solution.
Compared with prior art, the present invention has following beneficial effect: preparation method of the present invention comparatively conventional method is more simple, does not use stannous chloride, simplifies the steps such as absorption, activation, sensitization, and obtained conductive micro-balloons surface layer gold is smooth, fine and close.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of 1.6 μm of kind balls in the embodiment of the present invention 1.
Fig. 2 is the electromicroscopic photograph of 3. 9 μm of polymer microspheres in the embodiment of the present invention 1.
Fig. 3 is the electromicroscopic photograph of 4.5 μm of compound nickel balls in the embodiment of the present invention 1.
Fig. 4 is the electromicroscopic photograph of 9.3 μm of polymer microspheres in the embodiment of the present invention 2.
Fig. 5 is the electromicroscopic photograph of 9.9 μm of compound nickel balls in the embodiment of the present invention 2.
Fig. 6 is the electromicroscopic photograph of 10.0 μm of nickel gold complex microspheres in the embodiment of the present invention 2.
Fig. 7 is the electromicroscopic photograph of 8.8 μm of compound nickel balls in the embodiment of the present invention 3.
Fig. 8 is the electromicroscopic photograph of 4 μm of kind balls in the embodiment of the present invention 4.
Fig. 9 is the electromicroscopic photograph of 20 μm of compound nickel balls in the embodiment of the present invention 4.
Figure 10 is the electromicroscopic photograph of 20 μm of compound nickel balls in comparative example of the present invention.
Embodiment
The present invention proposes a kind of preparation method of conductive micro-balloons, and described conductive micro-balloons produces for anisotropic conductive film the conductive micro-balloons used.
The preparation method of this conductive micro-balloons, comprises the steps:
Step one: monomer, dispersant, initator and solvent are added in reaction vessel and mixes, under inert gas shielding, be polymerized 2-24h at constant temperature 50-80 DEG C, centrifugal, washing, drying obtain polymerization species ball, and planting ball particle size is 400nm-8 μm;
Step 2: kind ball step one obtained is distributed in the aqueous solution containing surfactant, dispersant, ultrasonic agitation is even, prepares kind of a ball dispersion liquid;
Step 3: initator is dissolved in mass ratio example mix crosslinking agent, activated monomer, chain-transferring agent oil-based liquid in, the aqueous solution of the surfactant of certain mass ratio, dispersant, ethanol is added in this oil-based liquid, ultrasonic emulsification 5-60min, obtains emulsion;
Step 4: emulsion described in step 3 is added to plant in ball dispersion liquid described in step 2 and carry out swelling 24-48h, obtain swelling solution;
Step 5: swelling solution described in step 4 is carried out polymerization reaction with certain mixing speed at 70-98 DEG C, reaction time is 2-24h, through centrifugal, clean, vacuumize, obtained adsorbable Metal Palladium also can for the preparation of the monodisperse cross-linked polymer microsphere of conductive micro-balloons in anisotropic conductive film, and the particle diameter of described mono-disperse polymer microspheres is 1-50 μm;
Step 6: the monodisperse cross-linked polymer microsphere described in step 5 is dispersed in containing palladium bichloride concentration be 0.1-3g/L, mass percent concentration is in the acid with strong oxidizing property of 30%-80%, ultrasonic agitation 1-60min in 25-80 DEG C of water-bath, then centrifugal, be washed to pH value for neutral, add the polymer microsphere that reducing agent reduction obtains having high catalytic activity palladium;
Step 7: step 6 gained polymer microsphere is added in chemical plating fluid and carries out plating, obtain the conductive micro-balloons that can be used for preparing anisotropic conductive film.
Monomer described in step one is one or more the mixture in following material: the Monofunctional monomers such as styrene, methyl methacrylate, hydroxyethyl methacrylate.
Dispersant described in step one, step 2, step 3 is one or more the mixture in following material: polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG) etc.
Initator described in step one is one or more the mixture in following material: azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO).
Solvent described in step one is one or more the mixture in following material: ethanol, methyl alcohol, isopropyl alcohol, water.
The mass ratio of the monomer described in step one, dispersant, initator, solvent is 100:(10-50): (0.5-10): (100-1000).
Plant in ball dispersion liquid described in step 2, water, surfactant, dispersant mass ratio are 100:(0.25-5): (1-5).
In oil-based liquid described in step 3, initator, crosslinking agent, activated monomer, chain-transferring agent mass ratio are (0.1-8): (3-95): (5-90): (0-30).
In emulsion described in step 3, the mass ratio of oil-based liquid, water, surfactant, ethanol is 100:(100-1000): (3-10): (1-30).
In step 3, initator is one or more the mixture in following material: the oil-soluble initiators such as benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN);
In step 3, crosslinking agent is one or more the mixture in following material: Ethylene glycol dimethacrylate (EGDMA), methacrylic acid butanediol ester (BDDMA), 1,6-hexanediyl ester (HDDA), TEGDMA (TEGDMA), trimethylol-propane trimethacrylate (TMPTMA), divinylbenzene (DVB).
In step 3, activated monomer is one or more the mixture in following material: methyl methacrylate (MMA), styrene (ST), acetoacetoxyethyl methacrylate (AAEM), ethoxyethoxyethyl acrylate (EOEOEA), glycidyl methacrylate (GMA), isobornyl acrylate (IBOA).
Step 3 Chain transfer agent is that one or more the mixture in following material: 3-dredges the aliphat mercaptan such as the different monooctyl ester of base propionic acid (IOMP), mercaptoethanol (ME), TGA (TGA), lauryl mercaptan (NDM).
In step 2, step 3 and step 5, surfactant is one or more the mixture in following material: lauryl sodium sulfate (SDS), neopelex (SDBS), dodecyltriethanolamine sulfate (TLS).
In step 6, the concentration being made into acid with strong oxidizing property Chlorine in Solution palladium used is 0.1-3g/L.Acid with strong oxidizing property is one or more the mixture in following material: the inorganic acid such as sulfuric acid, nitric acid.The mass ratio of acid with strong oxidizing property and water is 1:(0.5-3).This strong oxidizing property acid concentration is 30%-80%.
Reducing agent described in step 6 is one or more the mixture in following material: hydrazine, dimethyamine borane (DMAB), sodium hypophosphite.
Chemical plating fluid described in step 7 is the one in following material: chemical nickel plating, chemical silvering, chemical palladium-plating, chemical gilding plating solution.Can a kind of metal of plating during plating, or plating various metals in different plating solutions several times.
preparationembodiment 1
| Material name | Producer | Specification |
| MMA | Molecular material Co., Ltd of beautiful Yanggao County of Huizhou Mitsubishi | Analyze pure |
| PVP | Traditional Chinese medicines chemical reagent Co., Ltd | Analyze pure K30 |
| AIBN | Shishewei Chemical Co., Ltd., Shanghai | Chemical pure (after refining) |
| Methyl alcohol | Guangdong, Taishan City emigrant century plastics Co., Ltd | Chemical pure |
| SDS | Kingsoft, Chengdu chemical reagent Co., Ltd | Analyze pure |
| EGDMA | Korea S TBK(Guangzhou San Wang chemical materials Co., Ltd is acted on behalf of) | Chemical pure |
| AAEM | Dragon husky (Guangzhou San Wang chemical materials Co., Ltd agency) | Chemical pure |
| ME | Traditional Chinese medicines chemical reagent Co., Ltd | Analyze pure |
| Ethanol | East, Guangzhou reddening factory | Chemical pure |
| Sulfuric acid | East, Guangzhou reddening factory | Analyze pure |
| Palladium bichloride | Traditional Chinese medicines chemical reagent Co., Ltd | Chemical pure |
Plant ball preparation: add in four-hole bottle by 15g MMA, 2g PVP, 0.2g AIBN, 50g methyl alcohol, 50g water, under nitrogen protection, stir, at constant temperature 60 DEG C, react 4h, centrifugal clean, vacuumize, obtained polymerization species ball, its particle diameter is about 1.6 μm.
Monodisperse cross-linked polymer microsphere preparation: get 1.0g above-mentioned polymerization species ball and be dispersed in 100g water, add 0.5g SDS, 1g PVP ultrasonic evenly after add uniform stirring in there-necked flask, obtain kind of a ball dispersion liquid.Get 1g AIBN and be dissolved in 9g EGDMA, 6gAAEM, 1g ME, then add 40g water, 2g ethanol, 1.2g SDS, ultrasonic agitation 30min obtains emulsion.Emulsion is added in kind of ball dispersion liquid and carry out swelling 24h, obtain swelling solution.After swelling solution being placed in 90 DEG C of water-bath constant temperature polymerization 5h, centrifugal clean, vacuumize, obtain white monodisperse cross-linked polymer microsphere, microballoon size is about 3.9 μm.
Get the monodisperse cross-linked polymer microsphere of the above-mentioned white of 1g and be dispersed in the solution 10mL that h 2 so 4 concentration is 60%, adding palladium bichloride makes its concentration be 3.0g/L, ultrasonic agitation 40min in constant temperature 70 DEG C of water-baths, then centrifugal, with deionized water, microballoon is washed till neutrality, obtains the polymer microsphere of yellow absorption palladium ion.Collect above-mentioned centrifuged supernatant and microballoon cleaning solution, be evaporated to dry, then add 2% dilute nitric acid dissolution, constant volume is to 1L.After being diluted 1000 times again, measure palladium concentration with atomic absorption spectrophotometer, its result is 1.4ppm.
The yellow microballoon of above-mentioned absorption palladium ion is scattered in reducing solution, palladium ion is reduced into the Metal Palladium with catalytic activity, now yellow microballoon becomes grey black microballoon, and this ball is carried out chemical nickel plating at chemical nickel-plating liquid, obtains the compound nickel ball that particle diameter is 4.5 μm.
preparationembodiment 2
Get in preparation embodiment 1 and be polymerized species ball 0.2g and be dispersed in 100g water, add 1g SDS, 3g PVP ultrasonic evenly after add in there-necked flask and stir, obtain kind of a ball dispersion liquid.
Get 3g AIBN and be dissolved in 30g TMPTMA, 15gAAEM, 5g mercaptoethanol, then add 120g water, 6g ethanol, 2.0g SDS, ultrasonic agitation 30min obtains emulsion.
Emulsion is added in kind of ball dispersion liquid and carry out swelling 24h, obtain swelling solution.
After swelling solution being placed in 90 DEG C of water-bath constant temperature polymerization 5h, centrifugal clean, vacuumize.Obtain white monodisperse cross-linked polymer microsphere, microballoon size is about 9.3 μm.
Get that 1g is above-mentioned to be obtained white monodisperse cross-linked polymer microsphere and be dispersed in the solution 10mL that h 2 so 4 concentration is 60%, add palladium bichloride and make its concentration be 1.4g/L.Ultrasonic agitation 40min in constant temperature 70 DEG C of water-baths, then centrifugal, with deionized water, microballoon is washed till neutrality, obtains the polymer microsphere of yellow absorption palladium ion.Collect above-mentioned centrifuged supernatant and microballoon cleaning solution, be evaporated to dry, then add 2% dilute nitric acid dissolution, constant volume is to 1L.After being diluted 1000 times again, measure palladium concentration with atomic absorption spectrophotometer, its result is 1.3ppm.
The yellow microballoon of above-mentioned absorption palladium ion is scattered in reducing solution, palladium ion is reduced into the Metal Palladium with catalytic activity, now yellow microballoon becomes grey black microballoon, and this ball is carried out chemical nickel plating at chemical nickel-plating liquid, obtains the compound nickel ball that particle diameter is 9.9 μm.
Above-mentioned compound nickel ball is carried out chemical gilding at chemical gold plating liquid, obtains the nickel gold composite conductive micro-balloons that particle diameter is 10.0 μm.
preparationembodiment 3
Get in preparation embodiment 1 and be polymerized species ball 0.2g and be dispersed in 300g water, add 3g SDS, 9g PVP ultrasonic evenly after add in there-necked flask and stir, obtain kind of a ball dispersion liquid.
Get 3g AIBN and be dissolved in 30g EGDMA, 10gAAEM, 5g ST, 5g mercaptoethanol, then add 600g water, 20g ethanol, 4.5g SDS, ultrasonic agitation 30min obtains emulsion.
Emulsion is added uniform stirring 24h in kind of ball dispersion liquid, obtain swelling solution.
After swelling solution being placed in 90 DEG C of water-bath constant temperature polymerization 5h, centrifugal clean, vacuumize.Obtain white monodisperse cross-linked polymer microsphere, microballoon size is about 8.3 μm.
Get the monodisperse cross-linked polymer microsphere of the above-mentioned white of 1g and be dispersed in the solution 10mL that h 2 so 4 concentration is 60%, add palladium bichloride and make its concentration be 1.6g/L.Ultrasonic agitation 40min in constant temperature 70 DEG C of water-baths, then centrifugal, with deionized water, microballoon is washed till neutrality, obtains the polymer microsphere of yellow absorption palladium ion.Collect above-mentioned centrifuged supernatant and microballoon cleaning solution, be evaporated to dry, then add 2% dilute nitric acid dissolution, constant volume is to 1L.After being diluted 1000 times again, measure palladium concentration with atomic absorption spectrophotometer, its result is 2.4ppm.
The yellow microballoon of above-mentioned absorption palladium ion is scattered in reducing solution, palladium ion is reduced into the Metal Palladium with catalytic activity, now yellow microballoon becomes grey black microballoon, and this ball is carried out chemical nickel plating at chemical nickel-plating liquid, obtains the compound nickel ball that particle diameter is 8.8 μm.
preparationembodiment 4
Polymerization species ball preparation: 9.5g MMA, 0.9g PVP, 0.15g AIBN, 63g methyl alcohol, 19g water are added in four-hole bottle, under nitrogen protection, stirs; 3h is reacted at constant temperature 60 DEG C, centrifugal clean, vacuumize; obtained polymerization species ball, its particle diameter is about 4.1 μm.
Get above-mentioned cenospecies ball 0.35g to be dispersed in 100g water, add 1g SDS, 3g PVP ultrasonic evenly after add in there-necked flask and stir, obtain kind of a ball dispersion liquid.
Get 3g AIBN and be dissolved in 40g EGDMA, 5g ST, then add 120g water, 6g ethanol, 2.0g SDS, ultrasonic agitation 30min obtains emulsion.
Emulsion is added uniform stirring 24h in kind of ball dispersion liquid, obtain swelling solution.
After swelling solution being placed in 90 DEG C of water-bath constant temperature polymerization 5h, centrifugal clean, vacuumize.Obtain white monodisperse cross-linked polymer microsphere, microballoon size is about 20.0 μm.
Get the monodisperse cross-linked polymer microsphere of the above-mentioned white of 1g and be dispersed in the solution 10mL that h 2 so 4 concentration is 60%, add palladium bichloride and make its concentration be 0.7g/L.Ultrasonic agitation 40min in constant temperature 70 DEG C of water-baths, then centrifugal, with deionized water, microballoon is washed till neutrality, obtains the polymer microsphere of yellow absorption palladium ion.Collect above-mentioned centrifuged supernatant and microballoon cleaning solution, be evaporated to dry, then add 2% dilute nitric acid dissolution, constant volume is to 1L.After being diluted 1000 times again, measure palladium concentration with atomic absorption spectrophotometer, its result is 1.2ppm.
The yellow microballoon of above-mentioned absorption palladium ion is scattered in reducing solution, palladium ion is reduced into the Metal Palladium with catalytic activity, now yellow microballoon becomes grey black microballoon, and this ball is carried out chemical nickel plating at chemical nickel-plating liquid, obtains the compound nickel ball that particle diameter is 20.6 μm.
Palladium constituent content according to above four examples measure can illustrate, palladium constituent content has obvious minimizing before absorption and after absorption, according to the change of palladium constituent content and microballoon quantity and surface area, can show that the amount of the adsorbable palladium of microballoon is directly proportional according to microsphere surface is long-pending.Number content of monomer and chain-transferring agent added by microballoon of microballoon specific area adsorbance is directly proportional.
Microballoon absorption palladium principle of the present invention is, microsphere surface has a lot of side chain, carboxylate radical can be oxidized under heating acid with strong oxidizing property condition, carboxylate radical can adsorb into palladium salt with palladium ion, secondly there is linear molecule segment uncrosslinked in a large number on crosslinked microsphere top layer, packing is not high, and its mesopore can a large amount of palladium ion of physical absorption.The invention reside in the degree regulating monomer and chain-transferring agent; First, increase or reduce the degree of Monofunctional monomers and chain-transferring agent, increase or reduce oxidized side chain to adjust palladium ion chemisorbed amount; Secondly the degree increasing or reduce Monofunctional monomers and chain-transferring agent regulates microballoon packing to regulate palladium ion physical absorption amount.Chemisorbed and physical absorption are that synergy improves the adsorbance of palladium ion mutually.
Claims (6)
1. the simple and easy adsorbing metal palladium ion method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, is characterized in that, comprise the steps:
Step one: monomer, dispersant, initator and solvent are added in reaction vessel and mixes, under inert gas shielding, be polymerized 2-24h at constant temperature 50-80 DEG C, centrifugal, washing, drying obtain polymerization species ball, and planting ball particle size is 400nm-8 μm;
Step 2: kind ball step one obtained is distributed in the aqueous solution containing surfactant, dispersant, ultrasonic agitation is even, prepares kind of a ball dispersion liquid;
Step 3: initator is dissolved in mass ratio example mix crosslinking agent, activated monomer, chain-transferring agent oil-based liquid in, the aqueous solution of the surfactant of certain mass ratio, dispersant, ethanol is added in this oil-based liquid, ultrasonic emulsification 5-60min, obtains emulsion;
Step 4: emulsion described in step 3 is added to plant in ball dispersion liquid described in step 2 and carry out swelling 24-48h, obtain swelling solution;
Step 5: swelling solution described in step 4 is carried out polymerization reaction with certain mixing speed at 70-98 DEG C, reaction time is 2-24h, through centrifugal, clean, vacuumize, obtained adsorbable Metal Palladium also can for the preparation of the monodisperse cross-linked polymer microsphere of conductive micro-balloons in anisotropic conductive film, and the particle diameter of described mono-disperse polymer microspheres is 1-50 μm;
Step 6: the monodisperse cross-linked polymer microsphere described in step 5 is dispersed in containing palladium bichloride concentration be 0.1-3g/L, mass percent concentration is in the acid with strong oxidizing property of 30%-80%, ultrasonic agitation 1-60min in 25-80 DEG C of water-bath, then centrifugal, be washed to pH value for neutral, add the polymer microsphere that reducing agent reduction obtains having high catalytic activity palladium;
Step 7: step 6 gained polymer microsphere is added in chemical plating fluid and carries out plating, obtain the conductive micro-balloons that can be used for preparing anisotropic conductive film;
Monomer described in step one is one or more the mixture in following material: styrene, methyl methacrylate, hydroxyethyl methacrylate;
Dispersant described in step one, step 2, step 3 is one or more the mixture in following material: polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol;
Initator described in step one is one or more the mixture in following material: azodiisobutyronitrile, benzoyl peroxide;
Solvent described in step one is one or more the mixture in following material: ethanol, methyl alcohol, isopropyl alcohol, water;
In step 3, initator is one or more the mixture in following material: benzoyl peroxide, azodiisobutyronitrile;
In step 3, crosslinking agent is one or more the mixture in following material: Ethylene glycol dimethacrylate, methacrylic acid butanediol ester, 1,6-hexanediyl ester, TEGDMA, trimethylol-propane trimethacrylate, divinylbenzene;
In step 3, activated monomer is one or more the mixture in following material: methyl methacrylate, styrene, acetoacetoxyethyl methacrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate, isobornyl acrylate;
Step 3 Chain transfer agent is that one or more the mixture in following material: 3-dredges the different monooctyl ester of base propionic acid, mercaptoethanol, TGA, lauryl mercaptan;
In step 2, step 3 and step 5, surfactant is one or more the mixture in following material: lauryl sodium sulfate, neopelex, dodecyltriethanolamine sulfate;
In step 6, acid with strong oxidizing property is one or more the mixture in following material: sulfuric acid, nitric acid;
Reducing agent described in step 6 is one or more the mixture in following material: hydrazine, dimethyamine borane, sodium hypophosphite.
2. the simple and easy adsorbing metal palladium ion as claimed in claim 1 method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, it is characterized in that, the mass ratio of the monomer described in step one, dispersant, initator, solvent is 100:(10-50): (0.5-10): (100-1000).
3. the simple and easy adsorbing metal palladium ion as claimed in claim 1 method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, it is characterized in that, plant in ball dispersion liquid described in step 2, water, surfactant, dispersant mass ratio are 100:(0.25-5): (1-5).
4. the simple and easy adsorbing metal palladium ion as claimed in claim 1 method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, is characterized in that,
In oil-based liquid described in step 3, initator, crosslinking agent, activated monomer, chain-transferring agent mass ratio are (0.1-8): (3-95): (5-90): (0-30);
In emulsion described in step 3, the mass ratio of oil-based liquid, water, surfactant, ethanol is 100:(100-1000): (3-10): (1-30).
5. the simple and easy adsorbing metal palladium ion as claimed in claim 1 method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, it is characterized in that, in step 6, the concentration being made into acid with strong oxidizing property Chlorine in Solution palladium used is 0.1-3g/L, the mass ratio of acid with strong oxidizing property and water is 1:(0.5-3), this strong oxidizing property acid concentration is 30%-80%.
6. the simple and easy adsorbing metal palladium ion as claimed in claim 1 method of conductive micro-balloons of producing for the preparation of anisotropic conductive film, it is characterized in that, chemical plating fluid described in step 7 is the one in following material: chemical nickel plating, chemical silvering, chemical palladium-plating, chemical gilding plating solution.
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| CN201410553289.XA CN104347192B (en) | 2014-10-17 | 2014-10-17 | A kind of method that simple adsorbing metal palladium ion prepares the conductive micro-balloons producing for anisotropic conductive film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106866875A (en) * | 2017-03-01 | 2017-06-20 | 深圳飞世尔新材料股份有限公司 | It is a kind of to can be used for toughness reinforcing microballoon of anisotropic conductive and preparation method thereof |
| CN108084314A (en) * | 2017-04-21 | 2018-05-29 | 安徽理工大学 | The heart-shaped nanoparticle palladium composite material of P (AAEM-St) claddings |
| CN109735257A (en) * | 2019-01-11 | 2019-05-10 | 成都其其小数科技有限公司 | A kind of heat-resisting conductive micro-balloons and preparation method for anisotropic conductive film |
| CN110878131A (en) * | 2019-09-03 | 2020-03-13 | 中山大学 | Method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization |
| CN113089152A (en) * | 2021-04-06 | 2021-07-09 | 军事科学院系统工程研究院军需工程技术研究所 | High-quality and high-efficiency production method of in-situ polymerization flame-retardant chinlon 66 fully drawn yarn |
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| JP2000315426A (en) * | 1999-05-06 | 2000-11-14 | Sekisui Chem Co Ltd | Transparent conductive particulate, transparent anisotropic conductive adhesive, conductive connection structure, and press-input type display device |
| CN102658071A (en) * | 2012-05-16 | 2012-09-12 | 东华大学 | Method for preparing conductive golden ball for anisotropism conductive film |
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| JP2000315426A (en) * | 1999-05-06 | 2000-11-14 | Sekisui Chem Co Ltd | Transparent conductive particulate, transparent anisotropic conductive adhesive, conductive connection structure, and press-input type display device |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866875A (en) * | 2017-03-01 | 2017-06-20 | 深圳飞世尔新材料股份有限公司 | It is a kind of to can be used for toughness reinforcing microballoon of anisotropic conductive and preparation method thereof |
| CN108084314A (en) * | 2017-04-21 | 2018-05-29 | 安徽理工大学 | The heart-shaped nanoparticle palladium composite material of P (AAEM-St) claddings |
| CN108084314B (en) * | 2017-04-21 | 2021-03-30 | 安徽理工大学 | P (AAEM-St) coated heart-shaped nano palladium particle composite material |
| CN109735257A (en) * | 2019-01-11 | 2019-05-10 | 成都其其小数科技有限公司 | A kind of heat-resisting conductive micro-balloons and preparation method for anisotropic conductive film |
| CN109735257B (en) * | 2019-01-11 | 2021-04-02 | 无锡亚星新材料科技有限公司 | Heat-resistant conductive microsphere for anisotropic conductive adhesive film and preparation method |
| CN110878131A (en) * | 2019-09-03 | 2020-03-13 | 中山大学 | Method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization |
| CN110878131B (en) * | 2019-09-03 | 2021-04-02 | 中山大学 | Method for preparing monodisperse polymer microspheres by redox-initiated dispersion polymerization |
| CN113089152A (en) * | 2021-04-06 | 2021-07-09 | 军事科学院系统工程研究院军需工程技术研究所 | High-quality and high-efficiency production method of in-situ polymerization flame-retardant chinlon 66 fully drawn yarn |
| CN113089152B (en) * | 2021-04-06 | 2022-11-22 | 军事科学院系统工程研究院军需工程技术研究所 | High-quality and high-efficiency production method of in-situ polymerization flame-retardant chinlon 66 fully drawn yarn |
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