CN102321879A - Method for improving appearance and conductive performance of conductive microspheres - Google Patents
Method for improving appearance and conductive performance of conductive microspheres Download PDFInfo
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- CN102321879A CN102321879A CN201110162722A CN201110162722A CN102321879A CN 102321879 A CN102321879 A CN 102321879A CN 201110162722 A CN201110162722 A CN 201110162722A CN 201110162722 A CN201110162722 A CN 201110162722A CN 102321879 A CN102321879 A CN 102321879A
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Abstract
The invention relates to a method for improving appearance and conductive performance of conductive microspheres. The method comprises the following steps of: (1) mixing a monomer, a dispersant, an initiator and a solvent and performing polymerization reaction under the protection of nitrogen to obtain polymer microspheres; (2) dispersing the polymer microspheres in strong acid, then washing to be neutral, and adding into positively charged polyelectrolyte aqueous solution to perform surface modification; (3) dispersing the microspheres which are obtained through the treatment of the step (2) into palladium sol with negatively charged surface; and (4) ultrasonically dispersing the microspheres which are obtained through treatment of the step (3) into rare earth compound-containing chemical plating solution, washing after the reaction is finished, and drying to obtain the microspheres. The preparation method is simple and does not have new equipment requirement; unit cells on the surfaces of the polymer conductive composite microspheres prepared by the method are obviously finned; the surfaces are smoother; the problem of plating layer stripping is improved; metal layers on the surfaces of the microspheres are uniformly distributed; and the conductive performance is improved.
Description
Technical field
The invention belongs to the preparation field of conductive micro-balloons, particularly a kind of method of improving conductive micro-balloons pattern and conductivity.
Background technology
Conducting particles is the core in anisotropic conductive film (ACF) material; According to the performance requriements of ACF with conducting particles; The complex microsphere of organic/inorganic nucleocapsid structure is its main research object; It is compared with the pure metal microballoon, can reduce density, the cost of microballoon, can make its shape more regular again.Conductive particle in the one Chinese patent application 2007100203223.7 and 200580024285.1 all by single dispersion resin spheroidal particle as matrix, behind its surface attachment metal nickel dam, adhere to silver layer again, make it have conductive capability.
Electroless plating method is a kind of method that preparation ACF uses always with conducting particles the most, and the coating that this method obtains relatively evenly, continuously.The metal level at present more common conduction complex microsphere surface has nickel, silver, copper etc.Its preparation process all is to adopt to obtain carrying out chemical liquid deposition after polymer microballoon alligatoring, sensitization, the activation more mostly.This preparation method is fairly simple, can produce in enormous quantities.But use the conductive micro-balloons surface of existing electroless plating method preparation to tend to occur problems such as structure cell is thick, coating comes off, this directly can have influence on the electroconductibility of conductive micro-balloons.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of improving conductive micro-balloons pattern and conductivity, and the preparation method of this method is simple, and operation is cheap, and no new installation requirement can be mass-produced; The prepared obvious refinement of conducting polymer complex microsphere surface cell, the surface is Paint Gloss, and conductivity increases.
A kind of method of improving conductive micro-balloons pattern and conductivity of the present invention comprises:
(1) with monomer, dispersion agent, initiator and solvent add in the reaction vessel mixture, after stirring, nitrogen protection, at 50-80 ℃ of following polyreaction 12-24h, centrifugal, alcohol is washed, vacuum drying, obtains polymer microballoon;
(2) above-mentioned polymer microballoon is dispersed in 20-80 ℃ the strong acid, in ultrasound environments or stir down and handled 10-90 minute, washing is to neutral then, joins in the polyelectrolyte aqueous solution of positively charged to carry out surface-treated again, and is centrifugal at last, wash;
(3) will handle the microballoon that obtains through step (2) and be dispersed in the surperficial electronegative palladium colloidal sol, temperature of reaction is 20-50 ℃, handles 10-90 minute centrifugal then, washing in ultrasound environments or under stirring;
(4) will handle the microballoon ultra-sonic dispersion obtain through step (3) and contain in the chemical plating fluid of rare earth compound, 0-60 ℃ ultrasonic or stir reaction down 10-120 minute, washing is at last dried and is promptly got.
Monomer described in the step (1) is vinylbenzene or TEB 3K; Dispersion agent is Vinylpyrrolidone polymer, polyoxyethylene glycol or ROHM; Initiator is Diisopropyl azodicarboxylate or Lucidol; Solvent is one or more the mixture in ethanol, methyl alcohol, Virahol, the water.
The only described monomer of step (1) accounts for the 10-40% of mixture quality, and dispersion agent accounts for the 5-20% of monomer mass, the 1-5% that initiator accounts for monomer mass, and solvent accounts for the 50-89.4% of mixture quality.
Strong acid described in the step (2) is the vitriol oil, oleum or chlorsulfonic acid.
Polyelectrolyte described in the step (2) is poly diallyldimethylammonium chloride or gathers ethyliminum that the concentration of polyelectrolyte is 0.005-0.05mol/L in the described polyelectrolyte aqueous solution.
The preparation of the palladium colloidal sol described in the step (3) is to be the palladium source with the Palladous chloride; Vinylpyrrolidone polymer is a protective material; Reductive agent is xitix or Peng Qinghuana, and wherein the ratio of Palladous chloride, protective material, reductive agent and water is 0.03-0.08mol: 0.05-0.2g: 0.01-0.1mol: 100mL.
Rare earth compound described in the step (4) is that in vitriol, nitrate salt or the muriate of lanthanum, cerium or yttrium one or more are compound.
The concentration of rare earth compound in chemical plating fluid described in the step (4) is 0.01-0.2g/L.
Chemical plating fluid described in the step (4) is made up of main salt, complexing agent, reductive agent, tensio-active agent; Wherein main salt is single nickel salt, copper sulfate or Silver Nitrate, and concentration is 10-30g/L; Complexing agent is that in ammonium chloride, Trisodium Citrate, sodium-acetate, quadrol, EDTA, Seignette salt, the ammonia one or more are compound, and concentration is 30-70g/L; Reductive agent is a kind of in Peng Qinghuana, inferior sodium phosphate, formaldehyde, the glucose, and concentration is 10-20g/L; Tensio-active agent is that in polyoxyethylene glycol, the cetyl trimethylammonium bromide one or both are compound, and concentration is 1-20g/L.
The invention solves problems such as the structure cell that the conduction complex microsphere surface of existing electroless plating method preparation tends to occur is thick, coating comes off, make up new electroless plating method.
The present invention adds rare-earth elements of lanthanum, cerium or yttrium in plating bath, utilize it that plating bath is carried out modification, improves bath stability, and improves the pattern and the conductivity thereof of conduction complex microsphere.
Be in the REE (like lanthanum, cerium, yttrium etc.) of the 3rd subgroup in the periodictable, show stronger adsorptive power.After they add plating bath with suitable amount, can be preferentially adsorbed on the lattice defect place (like room, end of dislocation, crystal boundary etc.) of matrix surface thereby reduce surface energy, improved the nucleation rate of alloy layer, deposition is accelerated; And when rare earth is adsorbed on the metallic surface, the unsaturated link(age) of surface atom is compensated, and changed the interaction mode between surface atom, surface energy and critical forming core merit are reduced, improved nucleation rate, impel the crystalline refinement.In the process that coating thickens, rare earth can also reduce crystal boundary energy, hinders moving of crystal boundary, thereby has suppressed (rare earth .2007,28 (1): 102) of growing up of crystal grain.
Beneficial effect
(1) preparation method of the present invention is simple, and operation is cheap, and no new installation requirement can be mass-produced;
(2) the obvious refinement of conducting polymer complex microsphere surface cell of the present invention's preparation, the surface is Paint Gloss; The coating problem of coming off improves, microsphere surface metal level uniform distribution, and conductivity increases.
Description of drawings
The sem photograph of polystyrene microsphere behind the chemical nickel plating that does not add rare earth of Fig. 1 Comparative Examples 1.
The sem photograph that contains polystyrene microsphere behind the chemical nickel plating of rare earth in the plating bath of Fig. 2 embodiment 1.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) 6.3g vinylbenzene, 1g Vinylpyrrolidone polymer, 0.075g Diisopropyl azodicarboxylate, 15g ethanol, 1.667g water are added in the four-necked bottle, after stirring, nitrogen protection, at 65 ℃ of following polymerization 24h, centrifugal, alcohol is washed, vacuum drying;
(2) polymer microballoon is dispersed in 80 ℃ the vitriol oil, under agitation handled 30 minutes, washing is to neutral, joins 0.02M and gathers in the aqueous solution of ethyliminum (MW=20000) and carry out surface-treated, washing;
(3) again polymer microballoon being dispersed in the middle priming reaction temperature of surperficial electronegative palladium colloidal sol (0.05mmol Palladous chloride, 0.01g Vinylpyrrolidone polymer, 0.02mmol Peng Qinghuana are dissolved in the 100mL water) is 30 ℃; Ultrasonic 60 minutes; Washing, alcohol is washed, vacuum drying;
(4) at last the polymer microballoon after the activation is dispersed in the chemical nickel-plating liquid (composition of chemical nickel-plating liquid: single nickel salt 10g/L, inferior sodium phosphate 20g/L, Trisodium Citrate 15g/L, sodium-acetate 20g/L, polyoxyethylene glycol 20g/L, lanthanum sulfat 0.1g/L; PH value=5) in; Be reflected under the ultrasound environments and carry out, temperature is 40 ℃, reacts 30 minutes; Washing, vacuum drying.
The SEM of the PS/Ni complex microsphere that this enforcement obtains figure sees accompanying drawing 2, relatively can find out with the SEM figure (Fig. 1) that does not add the PS/Ni complex microsphere that rare earth compound obtains, add rare earth compound after; Coating surface obviously improves; The structure cell refinement, smooth surface, and also its resistivity is from 10
-1～10
-2Ω cm drops to 10
-2～10
-3Ω cm, conductivity obviously improves.
Embodiment 2
(1) 6.3g TEB 3K, 1g polyoxyethylene glycol, 0.075g Diisopropyl azodicarboxylate, 16g ethanol are added in the four-necked bottle, after stirring, nitrogen protection, at 70 ℃ of following polymerization 24h, centrifugal, alcohol is washed, vacuum drying;
(2) polymer microballoon is dispersed in 20 ℃ the chlorsulfonic acid, under agitation handled 80 minutes, washing is to neutral, joins in the aqueous solution of 0.02M poly diallyldimethylammonium chloride (MW=70000) to carry out surface-treated, washing;
(3) again polymer microballoon is dispersed in activation in the surperficial electronegative palladium colloidal sol (0.05mmol Palladous chloride, 0.01g Vinylpyrrolidone polymer, 0.05mmol Peng Qinghuana are dissolved in the 100mL water); Temperature of reaction is 50 ℃, stirs after 50 minutes washing; Alcohol is washed, vacuum drying;
(4) at last the polymer microballoon after the activation is dispersed in the chemical bronze plating liquid (composition of chemical bronze plating liquid: copper sulfate 15g/L, EDTA disodium salt 20g/L, Seignette salt 40g/L, formaldehyde 10ml/L, polyoxyethylene glycol 10-20g/L, Cerium II Chloride 0.01g/L, lanthanum sulfat 0.02g/L; In the pH value=12-13); Be reflected under the ultrasound condition and carry out, temperature is 30 ℃, reacts 30 minutes; Washing, vacuum drying.
Embodiment 3
(1) 5g PS, 0.5g ROHM, 0.005g Lucidol, 19.5g Virahol are added in the four-necked bottle, after stirring, nitrogen protection, at 65 ℃ of following polymerization 20h, centrifugal, alcohol is washed, vacuum drying;
(2) polymer microballoon is dispersed in 50 ℃ the oleum, under agitation handled 60 minutes, washing is to neutral; Joining 0.01M again gathers in the aqueous solution of ethyliminum (MW=20000) and carries out surface-treated, washing;
(3) again polymer microballoon being dispersed in the middle temperature of reaction of surperficial electronegative palladium colloidal sol (0.05mmol Palladous chloride, 0.01g Vinylpyrrolidone polymer, 0.02mmol xitix are dissolved in the 100mL water) is 20 ℃; Stir activation in 90 minutes; Washing, alcohol is washed, vacuum drying;
(4) at last the polymer microballoon after the activation is dispersed in the chemical plating liquid (composition of chemical plating liquid: A liquid: silver ammino solution (the 3g Silver Nitrate is dissolved in the 60ml water, and under agitation dropping ammonia is just dissolved until the deposition of separating out); B liquid: glucose sugar 20g/L, tartrate 5g/L, ethanol (stablizer; Can not add yet) 100ml/L, cetyl trimethylammonium bromide 1g/L, Cerium II Chloride 0.05g, Yttrium trinitrate 0.01g/L, improved chemical plating liquid is an A liquid: B liquid=use at 1: 1), be reflected under the induction stirring and carry out; Temperature is 10 ℃; Reacted washing, vacuum drying 1 hour.
Comparative Examples 1
(1) 6.3g vinylbenzene, 1g Vinylpyrrolidone polymer, 0.075g Diisopropyl azodicarboxylate, 15g ethanol, 1.667g water are added in the four-necked bottle, after stirring, nitrogen protection, at 65 ℃ of following polymerization 24h, centrifugal, alcohol is washed, vacuum drying;
(2) polymer microballoon is dispersed in 80 ℃ the vitriol oil, under agitation handled 30 minutes, washing is to neutral, joins 0.04M and gathers in the aqueous solution of ethyliminum (MW=20000) and carry out surface-treated, washing;
(3) again polymer microballoon being dispersed in the middle priming reaction temperature of surperficial electronegative palladium colloidal sol (0.05mmol Palladous chloride, 0.01g Vinylpyrrolidone polymer, 0.02mmol Peng Qinghuana are dissolved in the 100mL water) is 30 ℃; Ultrasonic 60 minutes; Washing, alcohol is washed, vacuum drying;
(4) at last the polymer microballoon after the activation is dispersed in the chemical nickel-plating liquid (composition of chemical nickel-plating liquid: single nickel salt 10g/L, inferior sodium phosphate 20g/L, Trisodium Citrate 15g/L, sodium-acetate 20g/L, polyoxyethylene glycol 20g/L; PH value=5) in; Be reflected under the ultrasound environments and carry out, temperature is 40 ℃, reacts 30 minutes; Washing, vacuum drying.
The SEM figure of the PS/Ni complex microsphere that this enforcement obtains sees accompanying drawing 1, and from figure, can see: do not add the PS/Ni complex microsphere that rare earth compound obtains, coating surface is coarse; Its resistivity is 10
-1～10
-2Ω cm, conductivity is lower.
Claims (9)
1. method of improving conductive micro-balloons pattern and conductivity comprises:
(1) with monomer, dispersion agent, initiator and solvent add in the reaction vessel mixture, after stirring, nitrogen protection, at 50-80 ℃ of following polyreaction 12-24h, centrifugal, alcohol is washed, vacuum drying, obtains polymer microballoon;
(2) above-mentioned polymer microballoon is dispersed in 20-80 ℃ the strong acid, in ultrasound environments or stir down and handled 10-90 minute, washing is to neutral then, joins in the polyelectrolyte aqueous solution of positively charged to carry out surface-treated again, and is centrifugal at last, wash;
(3) will handle the microballoon that obtains through step (2) and be dispersed in the surperficial electronegative palladium colloidal sol, temperature of reaction is 20-50 ℃, handles 10-90 minute centrifugal then, washing in ultrasound environments or under stirring;
(4) will handle the microballoon ultra-sonic dispersion obtain through step (3) and contain in the chemical plating fluid of rare earth compound, 0-60 ℃ ultrasonic or stir reaction down 10-120 minute, washing is at last dried and is promptly got.
2. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1 is characterized in that: the monomer described in the step (1) is vinylbenzene or TEB 3K; Dispersion agent is Vinylpyrrolidone polymer, polyoxyethylene glycol or ROHM; Initiator is Diisopropyl azodicarboxylate or Lucidol; Solvent is one or more the mixture in ethanol, methyl alcohol, Virahol, the water.
3. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1; It is characterized in that: the only described monomer of step (1) accounts for the 10-40% of mixture quality; Dispersion agent accounts for the 5-20% of monomer mass, the 1-5% that initiator accounts for monomer mass, and solvent accounts for the 50-89.4% of mixture quality.
4. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1 is characterized in that: the strong acid described in the step (2) is the vitriol oil, oleum or chlorsulfonic acid.
5. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1; It is characterized in that: the polyelectrolyte described in the step (2) is poly diallyldimethylammonium chloride or gathers ethyliminum that the concentration of polyelectrolyte is 0.005-0.05mol/L in the described polyelectrolyte aqueous solution.
6. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1; It is characterized in that: the preparation of the palladium colloidal sol described in the step (3) is to be the palladium source with the Palladous chloride; Vinylpyrrolidone polymer is a protective material; Reductive agent is xitix or Peng Qinghuana, and wherein the ratio of Palladous chloride, protective material, reductive agent and water is 0.03-0.08mol: 0.05-0.2g: 0.01-0.1mol: 100mL.
7. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1 is characterized in that: the rare earth compound described in the step (4) is that in vitriol, nitrate salt or the muriate of lanthanum, cerium or yttrium one or more are compound.
8. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1 is characterized in that: the concentration of rare earth compound in chemical plating fluid described in the step (4) is 0.01-0.2g/L.
9. a kind of method of improving conductive micro-balloons pattern and conductivity according to claim 1 is characterized in that: the chemical plating fluid described in the step (4) is made up of main salt, complexing agent, reductive agent, tensio-active agent; Wherein main salt is single nickel salt, copper sulfate or Silver Nitrate, and concentration is 10-25g/L; Complexing agent is that in ammonium chloride, Trisodium Citrate, sodium-acetate, quadrol, EDTA, Seignette salt, the ammonia one or more are compound, and concentration is 30-70g/L; Reductive agent is a kind of in Peng Qinghuana, inferior sodium phosphate, formaldehyde, the glucose, and concentration is 10-20g/L; Tensio-active agent is that in polyoxyethylene glycol, the cetyl trimethylammonium bromide one or both are compound, and concentration is 1-20g/L.
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| CN102658071A (en) * | 2012-05-16 | 2012-09-12 | 东华大学 | Method for preparing conductive golden ball for anisotropism conductive film |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
| CN104342644A (en) * | 2013-07-23 | 2015-02-11 | 比亚迪股份有限公司 | A chemical silvering solution and a silvering method |
| CN104342643A (en) * | 2013-07-23 | 2015-02-11 | 比亚迪股份有限公司 | A chemical silvering solution and a silvering method |
| CN104342645A (en) * | 2013-07-23 | 2015-02-11 | 比亚迪股份有限公司 | A chemical silvering solution and a silvering method |
| TWI504433B (en) * | 2013-10-18 | 2015-10-21 | Nat Inst Chung Shan Science & Technology | Preparation of modified organic carbon - metal shell composite microspheres |
| CN105002585A (en) * | 2015-09-02 | 2015-10-28 | 刘健 | Preparation method for conductive fibers with optimized parameters |
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| CN105088381A (en) * | 2015-09-02 | 2015-11-25 | 刘健 | Method for preparing polyacrylonitrile/yttrium nitrate conductive fibers by adopting chemical silvering |
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| CN104342645A (en) * | 2013-07-23 | 2015-02-11 | 比亚迪股份有限公司 | A chemical silvering solution and a silvering method |
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| CN105063788A (en) * | 2015-09-02 | 2015-11-18 | 刘健 | Preparation method of chemical silver-plated polyacrylonitrile conductive fibers |
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| CN105478752A (en) * | 2015-12-14 | 2016-04-13 | 东华大学 | Preparation method of micron polymer-based composite conductive gold balls |
| CN105478752B (en) * | 2015-12-14 | 2017-10-24 | 东华大学 | A kind of preparation method of micrograde polymer base composite conducting gold goal |
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Application publication date: 20120118 |