CN105070351A - Flexible conductive microballoon and applications thereof - Google Patents
Flexible conductive microballoon and applications thereof Download PDFInfo
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- CN105070351A CN105070351A CN201510381262.1A CN201510381262A CN105070351A CN 105070351 A CN105070351 A CN 105070351A CN 201510381262 A CN201510381262 A CN 201510381262A CN 105070351 A CN105070351 A CN 105070351A
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Abstract
The invention discloses a flexible conductive microballoon, an anisotropic conductive material employing the same, an anisotropic conductive film employing the flexible conductive microballoon, and a current connection structure employing the flexible conductive microballoon. The flexible conductive microballoon comprises high-molecular polymer resin and at least one metal conducive layer. The flexible conductive microballoon has special mechanical performances, thereby enabling the flexible conductive microballoon to be very soft. When the center of a connection microelectrode is pressed, the flexible conductive microballoon cannot be broken into pieces but deforms with the geometrical shape of a contact pressure environment, thereby enabling the contact area of the conductive metal layer of the flexible conductive microballoon with the microelectrode to be increased. Meanwhile, the flexible conductive microballoon has a function of proper rebounding, thereby enabling the flexible conductive microballoon to still maintain the close contact with the microelectrode in a thermal expansion environment. The flexible conductive microballoon is high in adhesive force, is not liable to be separated, is not liable to cause poor contact, enables the service life of the microelectrode to be longer, enables the microelectrode to be more reliable, and can meet the finer application requirements.
Description
Technical field
The present invention relates to Electronic products manufacturing field, be specifically related to a kind of pliable and tough conductive micro-balloons and application thereof.
Background technology
The electrical connection field extensive use of anisotropic conductive material between the microelectrode of electronic equipment, it is formed primarily of insulating resin binding agent and the conductive composite microsphere be dispersed in insulating resin binding agent, and the performance of conductive composite microsphere is most important for the quality and performance of anisotropic conductive material.Conductive micro-balloons is generally composited by the resin balls insulated and conducting metal skin, in the heat pressing process carrying out microelectrode electrical connection, require that complex microsphere is out of shape to increase the contact area with electrode, but because resin balls is different from the hardness of metal outer, thus complex microsphere very easily broken fly into pieces during pressurized, cause microelectrodes bad, make Joint failure., there is soft ball or between hard sphere and metal, set up the design of soft formation in the problem of conductive micro-balloons distortion during in order to solve hot pressing.
Chinese patent 1769325A discloses and prepares polymer microballoon with styrene monomer and diglycol dimethyl propylene acid esters cross-linking monomer, then the polymer surfaces nickel plating of above-mentioned preparation and gold are obtained electric conductive polymer microballoon, this conducting polymer microballoon contacts with electrode surface under the condition of thermo-compression bonding, to provide the function of conduction.
Chinese patent 102176337A discloses a kind of method preparing composite conducting particles and anisotropic conductive film, and polystyrene microsphere is conducting particles matrix, and microspherulite diameter is 5 microns; Surfaces of Polystyrene Microparticles plates one deck nickel, then coated one deck silver layer again on nickel dam.Composite conducting particles prepared by the method is for anisotropic conductive film.
Chinese patent 1659188A discloses a kind of fluoropolymer resin particle, and with this resin particle for core, metal cladding forms conducting particles on resin particle surface.When adopting the jointing material containing this conducting particles to carry out distributing board connection, apply pressure and the conduction in distributing board between metal wiring just can be caused to connect.
Japan Patent 11-209714 proposes disperse conductive particles in dielectric adhesive, forms Anisotyopic conductive adhesive.This kind of conductive particle is made up of macromolecule resin, and each particle has core and the shell harder than core, then on shell, forms conductive metal layer.
Japan Patent 2002-033022 describes a kind of electroconductive resin particle and the anisotropic conductive adhesive with sandwich construction.The conductive particle that this binding agent contains can be used for the stability keeping conduction to connect, and prevents the destruction of transparency electrode.In order to meet above-mentioned requirement, conductive particle has at least one deck inner resin layer hard unlike the resin bed of outermost, then metal level is wrapped in the outside of resin particle.
Along with electronic product function constantly significantly improves, microelectronic circuit design constantly requires accurate and reliable, therefore not only microelectrode volume becomes less and less, its conductive contact area reduces thereupon, require that the sphere diameter of conductive micro-balloons also reduces accordingly, in manufacture craft process, hot pressing temperature also reduces to avoid damaging microcircuit gradually simultaneously.Along with hot pressing temperature reduces, conductive composite microsphere disclosed in above document or under stress not yielding, easily fragmentation, make metal outer and microelectrodes bad, cause resistance to increase and be not suitable for conduction use, or lack suitable bounce-back under stress after distortion to reply, the cold and hot change of applied environment causes electric conducting material to expand with heat and contract with cold, and causes microballoon to be out of shape and cannot keep compact siro spinning technology with microelectrode, thus cause Electrode connection to lose efficacy, the application requirement of high-end electric conducting material can not be met.
Summary of the invention
For solving the problem, the object of the present invention is to provide a kind of pliable and tough conductive micro-balloons with special machine performance, being suitable for the increasingly small conduction of electrode and connecting, and making electrode have superperformance.
Another object of the present invention is to provide a kind of anisotropic conductive material adopting above-mentioned pliable and tough conductive micro-balloons.
Another object of the present invention is to provide a kind of anisotropic conductive film, and this anisotropic conductive film contains the above-mentioned pliable and tough conductive micro-balloons with special machine performance, and the conduction connection that applicable electrode is increasingly small has superperformance again.
Another object of the present invention is to provide a kind of electric current syndeton, and this electric current syndeton contains the pliable and tough conductive micro-balloons that tool special machine performance combines, and the conduction connection that applicable electrode is increasingly small has superperformance again.
For achieving the above object, technical scheme of the present invention is: a kind of pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and at least one deck metal conducting layer, described pliable and tough conductive micro-balloons has following mechanical performance: described pliable and tough conductive micro-balloons is soft, be out of shape along with the geometry of contact environment but do not break during pressurized and be dispersed into fragment, there is suitable bounce-back recovery function simultaneously.Such mechanical performance combines and the conductive metal layer of complex microsphere of the present invention and the contact area of microelectrode is increased, and keep close contact with microelectrode, strong adhesion, not easily be separated, the phenomenon such as loose contact, allow microelectrode longer service life, more reliable, highly meticulous application requirement can be met.In actual application, both solved HTHP and easily decomposed in conjunction with microelectronic element, break, the problem such as to lose, and also solved microelectrode because of hot pressing inequality and cause the problem of loose contact.
Preferably, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50400megapascal is less than when sphere diameter pressurized reduces by half.
Preferably, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50300megapascal is less than to press speed 2.66 milli when ox/second, pressurized reduced by half at sphere diameter.
Preferably, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50200megapascal is less than to press speed 0.88 milli when ox/second, pressurized reduced by half at sphere diameter.
Preferably, described mechanical performance comprises the elastic recovery rate R of described pliable and tough conductive micro-balloons
ecoverybe greater than 20%.
Preferably, described mechanical performance comprises the elastic recovery rate R of described pliable and tough conductive micro-balloons
ecoverybe greater than 40%.
Preferably, described mechanical performance comprises described pliable and tough conductive micro-balloons and is depressed into after conductive micro-balloons distortion stops and is still monolithic entity, instead of breaks and be dispersed into fragment.
The fluoropolymer resin of above-mentioned conductive micro-balloons is prepared by polymerization reaction; Polymerization reaction comprises emulsion polymerisation, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersin polymerization, suspension polymerisation and seeding polymerization.
Outside polymerization, prepares polymer by polymerization reaction outside at microballoon; Polymerization reaction comprises emulsion polymerisation, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersin polymerization and suspension polymerisation.
Above-mentioned polymerization reaction suitable monomers, as described in this patent, comprises the monomer that one or more contain at least one unsaturated bond.Suitable monomer may include two, three, four or more unsaturated bond, as (methyl) esters of acrylic acid containing unsaturated bond.Include but not limited to (C2-C18) alkane chain diol two (methyl) acrylate, particularly preferably multi-functional (methyl) acrylate monomer, especially (C2-C10) alkane chain diol two (methyl) acrylate, further preferred (C2-C8) alkane chain diol two (methyl) acrylate.Suitable (C2-C18) alkane chain diol two (methyl) acrylate includes but not limited to 1,2-ethylene glycol bisthioglycolate (methyl) acrylate, 1,3-ethylene glycol bisthioglycolate (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,5-pentanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,8-ethohexadiol two (methyl) acrylate and 1,10-decanediol two (methyl) acrylate.
Preferably, polymerization reaction suitable monomers comprises one or more (methyl) acrylate monomers containing at least one unsaturated bond.
Polymerization reaction also can be selected to comprise one or more appropriate aromatic monomers containing at least one unsaturated bond, and described aromatic monomer can be polymerized with described (methyl) acrylate monomer containing at least one unsaturated bond.
Suitable aromatic monomer containing at least one unsaturated bond, and can be polymerized with (methyl) acrylate monomer containing at least one unsaturated bond.Suitable aromatic monomer includes but not limited to styrene, divinylbenzene, divinyl naphthalene, diallyl phthalate, N, N-divinyl aniline.As described in this specification, various polymerisable aromatic monomer all adopts in scope in the present invention.
Then functionalization is carried out to resulting polymers.Monomer with functionalization group optional can with the monomer of (methyl) acrylate and aromatic monomer copolymerization.Suitable band functional group monomer includes but not limited to dialkylene thioether, divinylsulfone, ethylene propylene acid amides, cyanacrylate, divinyl fourth diether, divinyl ether, diallyl maleate, pi-allyl acryloxy propionic ester, 2,2 '-two (4-(methyl) acrylic acid propoxyphenyl) propane, 2,2 '-two (4-(methyl) acrylic acid diethoxy phenyl) propane, 1,2,4-benzenetricarboxylic acid triallyl.
Other particular monomers being suitable for preparing functional polymer include but not limited to AMS, 4-1-chloro-4-methyl-benzene, 4-nitrostyrolene, methyl acrylate, methyl methacrylate, isobutyl methacrylate, acrylonitrile, vinyl pyrrolidone, GMA, methacrylate, lauryl methacrylate, vinyl acetate, vinyl chloride, butadiene, isoprene, diallyl phthalate, methacrylyl methyltrimethoxy silane, methacryloxypropyl trimethoxy silane, PAG methyl acrylate, 2-bromoethyl acrylate, 2-ethyl cyano group propernoic acid ester, methacrylic acid propinyl ester, 2-methyl-2-acrylic acid-2-sulphur ethyl ester, acrylic acid, methacrylic acid, 2-methyl-2-acrylic acid-2-(phosphonato) ethyl ester, 2-methyl-2-acrylic acid-2-(phosphonato) propyl ester, 2-methyl-2-acrylic acid-2-(phosphonato) butyl ester, phosphoric acid hydrogen two (methylacryoyloxyethyl) ester, acetoacetate methacrylic acid glycol ester, acrylate caprolactone, 2-aminoethyl methacrylate, 2-methyl-2-acrylic acid-2-(4-morpholinyl) ethyl ester, dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylamide, Methacrylamide, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc., and above mixture.
Functionalization refers to chemical reagent by chemical reaction introducing functionalization group, chemical reagent used comprises any reagent can introducing functionalization group with the polymer reaction in microballoon outside, functional group such as fluorine, chlorine, bromine, iodine, amino, hydroxyl, sulfydryl, carboxyl, carboxylate or the epoxy radicals introduced, or the combination of any above group.The chemical reagent be suitable for is such as, but be not limited to bischlormethyl ether, dihydroxymethyl amine, ethylenediamine, 1,6-hexamethylene diamine, diaminomethane, polyvinylamine, ammoniacal liquor, polyethylene glycol oxide and derivative thereof.Functionalization group comprises single, two and multiple group or repeats or depend on a part for long-chain or short chain, as the ethyoxyl in oligomer or poly(ethylene oxide), amino in oligomer or polyvinylamine, hydroxyl in oligomer or polyvinyl alcohol, the vinyl mercapto etc. of the sulfydryl in oligomer or polymerization.Polyvinyl based on but be not limited to, polystyrene, polyacrylate, and the derivative comprising functionalization group on polymer microballoon surface can be connected to by atomic migration initiated polymerization or redox reaction.Atomic migration initiated polymerization has a detailed description and relevant references at United States Patent (USP) 6071980.Redox Initiator refers to that the polymerization of monomer is by oxidising agent and the such process of transfer initiation of going back electronics between original reagent.At JournalofAppliedPolymerScience, Volume42, Issue11, pages2885-2891,1991 report the example of cerium ion as redox initiator.For atomic migration initiated polymerization, there is nanometer may contain halogen atom group before the polymer microballoon polymerization of micrometer structure.For redox initiate polymerization reaction, there is nanometer and may contain before the polymer microballoon polymerization of micrometer structure, but be not limited to, hydroxyl, mercapto, aldehyde radical, sulfhydryl, amino etc.Before polymerization, redox reaction may by aqueous phase, and the fluoropolymer resin microsphere surface of monomer phase or functionalization causes.
This section of open described conducting metal, not special restriction, the conducting metal be suitable for includes but not limited to gold, silver, Bo ， Palladium, copper, iron, nickel, titanium, zinc, tin, and aluminium is plumbous, cobalt, indium, cadmium, chromium, germanium, antimony, bismuth etc.; Also has alloy as nickel and phosphorus, silver and tin, copper and tin, plumbous and tin, the alloy that silver is made up of two or more metal with plumbous and tin etc.
Preferably, gold, silver, platinum, copper, nickel etc.
Above-mentioned conducting metal generally can be implemented by following gold-plated method.First, can the solution containing acid be used to carry out surface etching or be called alligatoring cleaned polymer microballoon, thus form fulcrum on polymer microballoon.Then the polymer microballoon after surface treatment or alligatoring can be immersed in the solution of stannous chloride and palladium bichloride, microsphere surface is activated.The fine nucleus of palladium catalyst so can be formed on microballoon.Subsequently, can use time phosphatization acid sodium, boron sodium chloride, dimethyl amine borane, hydrazine etc. carry out reduction reaction, thus on microballoon, form uniform palladium nucleus.Then, the blapharoplast obtained is disperseed in the plating solution, can use sodium hypophosphite that nickel salt is reduced, microballoon forms nickel coating, then, in certain embodiments, the microballoon being coated with nickel can be added in enough golden chemical plating solutions, carry out the reaction changing plating or chemical gilding, form Gold plated Layer from face in the most external of microballoon.
This section discloses described pliable and tough conductive micro-balloons particle diameter or diameter is 0.01 μm to 1000 μm, but is not limited to above-mentioned size, and according to actual needs, this size can be less than 0.01 μm or be greater than 1000 μm.
The present invention also provides a kind of application of pliable and tough conductive micro-balloons, and described pliable and tough conductive micro-balloons is for the preparation of anisotropic conductive material.
Technical scheme of the present invention also comprises: a kind of anisotropic conductive material, comprises insulating resin binding agent and is dispersed in the as claimed in claim 1 pliable and tough conductive micro-balloons in described insulating resin binding agent.Described pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and at least one deck metal conducting layer, this pliable and tough conductive micro-balloons has unique mechanical performance and combines, described mechanical performance combines and makes conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized, but it is not broken, this mechanical performance combines and the contact area of microballoon conductive metal layer of the present invention and microelectrode is increased, the pliable and tough conductive micro-balloons of the present invention simultaneously has suitable bounce-back recovery function, still can keep close contact with microelectrode expanding with heat and contract with cold in environment, strong adhesion, not easily be separated, the phenomenon such as to peel off, allow microelectrode longer service life, more reliable, highly meticulous application requirement can be met.
Resin in above-mentioned insulating resin binding agent, is not particularly limited, and can be one or both and two or more mixing in known resin, the vinylites such as such as vinylacetate system resin, vinyl chloride-based resin, acrylic resin, phenylethylene resin series; The thermoplastic resins such as polyolefin-based resins, ethene-vinyl acetate resin copolymer, polyamide series resin; The curable resin that epoxy system resin, polyurethane series resin, polyimides system resin, unsaturated polyester (UP) system resin and they and its curing agent are formed; SBS; SIS, their thermoplastic block copolymers such as hydride; Styrene-Butadiene rubber, chloroprene rubber, propylene be fine-elastic type etc. such as styrene block copolymer rubber.The curing mode of curable resin comprises hot curing, photocuring, normal temperature cure etc.One or more other additive is as organic solvent, and antioxidant, heat stabilizer, light stabilizer etc. also can be used together as required.
A kind of anisotropic conductive film, comprises above-mentioned anisotropic conductive material.Described anisotropic conductive material, comprises insulating resin binding agent and is dispersed in the as claimed in claim 1 pliable and tough conductive micro-balloons in described insulating resin binding agent.Described pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and at least one deck metal conducting layer, this pliable and tough conductive micro-balloons has unique mechanical performance and combines, described mechanical performance combines and makes conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized, but it is not broken, there is suitable bounce-back recovery function simultaneously, this mechanical performance combines and the contact area of microballoon conductive metal layer of the present invention and microelectrode is increased, and keep close contact with microelectrode, strong adhesion, not easily be separated, the phenomenon such as to peel off, allow microelectrode longer service life, more reliable, highly meticulous application requirement can be met.
A kind of electric current syndeton, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and described first microcircuitry elements and the second microcircuitry elements include anisotropic conductive film according to claim 9.Described anisotropic conductive film, comprises anisotropic conductive material according to claim 8.Described anisotropic conductive material, comprises insulating resin binding agent and is dispersed in the as claimed in claim 1 pliable and tough conductive micro-balloons in described insulating resin binding agent.Described pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and mechanical performance that at least one deck metal conducting layer tool is special combines, make conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized but not broken fly into pieces, there is suitable bounce-back simultaneously and reply.
First microcircuitry elements of this section of open described conduction connection and the second microcircuitry elements, suitable selection can be done according to application target, connect as being applied to thin-film package (TCP), flexible print circuit (FPC), Indium tin oxide electrode and driver IC loop (DriverICCircuit), and the micro-pattern electrode terminal in liquid crystal display (LCD) panel, connect semiconductor chip and liquid crystal display glass substrate (COG), connect semiconductor chip and flexible printed wiring (COF) and chip on board to encapsulate (COB), or for connecting semiconductor chip and semiconductor substrate (FCA), and similar microelectrode application.The structure that a kind of electric current connects, the structure that described electric current connects comprises the first microcircuitry elements and the second microcircuitry elements, and the structure tundish that described first microcircuitry elements is connected with the electric current of the second microcircuitry elements contains pliable and tough conductive micro-balloons according to claim 1.Described pliable and tough conductive micro-balloons comprises macromolecule copolymer resin and at least one deck metal conducting layer, the mechanical performance combination that tool is special, make conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized but not broken fly into pieces, there is suitable bounce-back simultaneously and reply.A kind of electrically conductive connection method, the anisotropic conductive film that decentralized configuration is had the right described in requirement 10 between the first microcircuitry elements needing conduction to connect and the second microcircuitry elements, then mobile in opposite directions the first microcircuitry elements and the second microcircuitry elements, makes the first microcircuitry elements be connected via pliable and tough conductive micro-balloons conduction according to claim 1 with the second microcircuitry elements.Described anisotropic conductive film, comprises a kind of anisotropic conductive material according to claim 9.Described anisotropic conductive material, comprises insulating resin binding agent and is dispersed in the as claimed in claim 1 pliable and tough conductive micro-balloons in described insulating resin binding agent.Described pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and mechanical performance that at least one deck metal conducting layer tool is special combines, make conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized but not broken fly into pieces, there is suitable bounce-back simultaneously and reply.
In of the present invention, (methyl) acrylate comprises methacrylate and acrylate and their derivative; Namely one micron μm equals micrometre, and a nanometer and nm equal part per billion meter; Power represents with milli ox or milli newton, and a milli ox and millinewton or mN equal one thousandth newton, and pressure represents i.e. megapascal with megapascal (MPa) or MPa, and a MPa equals a Megapascal.
Also it should be noted that, term used herein " comprises " clear and definite descriptive nature, number, step, operation, or composition, but does not get rid of one or more character, number, step, operation, the existence of composition and/or their combination or increase.
The beneficial effect of the technical program is: the invention provides a kind of pliable and tough conductive micro-balloons, this pliable and tough conductive micro-balloons has unique mechanical performance, described mechanical performance makes the very soft and flexible of conductive micro-balloons of the present invention, be out of shape along with the geometry of institute's contact environment during pressurized, but can not brokenly disintegrate, there is suitable bounce-back recovery function simultaneously, such mechanical performance makes the conductive metal layer of complex microsphere of the present invention and the contact area of microelectrode increase, and keep close contact with microelectrode, strong adhesion, not easily be separated, the phenomenons such as loose contact, allow microelectrode longer service life, more reliable, highly meticulous application requirement can be met.In actual application, both solved HTHP and easily decomposed in conjunction with microelectronic element, break, the problem such as to lose, also solved the loose contact problem that microelectrode causes because of hot pressing inequality.
Adopt anisotropic conductive material, anisotropic conductive film that pliable and tough conductive micro-balloons of the present invention is produced, there is all technical being better than existing product, in microelectrode application, adopt pliable and tough conductive micro-balloons of the present invention or containing other products of the pliable and tough conductive micro-balloons of the present invention, the problem that microelectronic circuits loose contact and pliable and tough conductive micro-balloons are easy to lose efficacy can be solved.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described, but the present invention is not limited to these embodiments.
In the process preparing fluoropolymer resin ball, the sphere diameter of fluoropolymer resin ball is controlled by the use amount of the sphere diameter of seed and seed and regulated; When using the seed of the monomer of fixed amount and fixed amount, when seed sphere diameter reduces, the sphere diameter of obtained fluoropolymer resin ball also reduces; When using the seed of the monomer of fixed amount and fixing sphere diameter, when the use amount of seed increases, the sphere diameter of the fluoropolymer resin ball obtained also reduces.
The instrument being applicable to test microballoon engineering properties of the present invention comprises
hM2000, FischerTechnology, Inc. and MCT-210MicroCompressionTester, ShimadzuCorporation, above-mentioned two instruments all possess pressure probe and the planar compression platform of plane, and each single microballoon is accept pressure test in the middle of two planes on instrument.
The all tests of the present invention use above-mentioned instrument to carry out at the environment of 25 DEG C or room temperature.
Generally be used in the industry now representing microballoon hardness be ball pressurized diameter distortion 10 that is 10% time K value, the definition of K value can see United States Patent (USP) 5486941A:
Wherein F represents heavy burden pressure, the distortion of sphere diameter 10% when S represents pressurized, R represent ball originally non-pressurized time radius.
Very large by the impact of sphere diameter by the visible K value of above formula, even the microballoon of identical material and structure, when sphere diameter requires with microelectrode and reduces, K value can significantly rise, the difficulty causing microballoon to design and select.Another one difficulty is, as described in the background art, microelectrode more and more requires conductive micro-balloons, and not only sphere diameter is little but also very soft and tough, but when the real reaction using apparatus measures microballoon to pressure, its sphere diameter of the microballoon of little sphere diameter distortion 10% is a very small change, soft microballoon only needs minimum power just can reach the sphere diameter distortion of 10% when just starting pressurized, and so little load pressure exists large error when measurement, causes larger difficulty to the design of microballoon and selection.
The engineering properties that pliable and tough conductive micro-balloons of the present invention is out of shape under pressure, represent by standardization stress-strain behavior (normalizedstress-strainbehavior) such as following form, carry out specification by reducing of sphere diameter after microballoon pressurized with the microsphere diameter of originally non-pressurized, the pressure of application carried out specification with the sectional area of microballoon originally non-pressurized simultaneously:
Wherein ε is compression strain (compressivestrain), Δ d is the distance of microballoon compression, and D is originally bulb diameter, so ε represents with percentage.
Wherein σ is standardization compression stress (normalizedcompressivestress), and P is the actual contact compressed by sphere diameter, and R is the originally radius of a ball, so σ represents by megapascal (MPa) or MPa (megapascal).σ
50the standardization stress in compression sigma of i.e. ε when being 50% that reduce by half after causing sphere diameter pressurized.
Stress-coping behavior changes along with the speed of test pressure, under the environment of 25 DEG C or room temperature, low or the height of microballoon molecular structure test pressure speed within instrument test time frame (timeframe) that hardness is high is all difficult to dispersive stress effectively, its σ
50change is little, but microballoon softer then σ σ
50larger with test pressure velocity variations, so the present invention is listed in two different test pressure speed, 0.88 and 2.65mN/sec (milli ox/second), two of obtaining standardization stress in compression sigma
50numerical value, represents the soft or hard degree of this tested conductive micro-balloons with this.
In addition, tester is in test microballoon distortion termination, and when namely microballoon sphere diameter does not increase with pressure and continues to reduce, test process terminates thereupon, the state of then this microballoon of observable distortion termination.
The elastic recovery rate of test microballoon is different with the mode that above-mentioned test microballoon distortion stops, the elastic recovery rate of test microballoon first compresses then microballoon is decompressed to milli ox (mN) low-pressure to a maximum pressure preset, reduce and sphere diameter reply at the corresponding sphere diameter of process Instrumental record of pressurization and decompression, microballoon pressurized is post-decompression elastic recovery rate R more simultaneously
ecoveryas following formulae discovery:
Recovery＝L
2/L
1
Wherein L
1the distortion of pressurized microballoon before decompression under maximum pressure, and L
2the reply of microballoon sphere diameter after the low-pressure being decompressed to a milli ox, so R
ecoveryrepresent with percentage.
The elastic recovery rate R that the present invention lists
ecoveryto record under pressure x velocity 0.88mN/sec.
Embodiment 1
Prepare the fluoropolymer resin of 10 μm of basis material microballoons and complex microsphere: the polystyrene seed aqueous suspension getting 13.1g26.0% particle diameter 2.8 μm, 450g deionized water, the 0.23g10% sodium dodecyl benzenylsulfonate aqueous solution joins in 2000mL tetra-mouthfuls of round-bottomed flasks, pass into nitrogen, after stirring, be heated to 60 DEG C.Get 153.5g divinylbenzene, the 10.7g10% sodium dodecyl benzenylsulfonate aqueous solution, 165g deionized water, stir with homogeneous mixer after mixing, add in four mouthfuls of round-bottomed flasks.Stir after 2 hours, cool to 40 DEG C, add 0.2g30% hydrogen peroxide.Get 1.1g TBHP, the 0.3g10% sodium dodecyl benzenylsulfonate aqueous solution, 65g deionized water, mixing homogeneous mixer stirs, and adds in four mouthfuls of round-bottomed flasks, then adds 56.3g20% aqueous povidone solution, 25g deionized water.After stirring 45 minutes at 40 DEG C, be heated to 60 DEG C.After stirring 30 minutes at 60 DEG C, be heated to 65 DEG C.After stirring 15 minutes at 65 DEG C, be heated to 70 DEG C.After exothermic reaction, be heated to 90 DEG C, continue stirring after 45 minutes, cooling flask, to 25 DEG C, filters to isolate basis material microballoon, i.e. the polymer core of complex microsphere, particle diameter 10 μm.
Embodiment 2
Synthetic polymer is outside at embodiment 1 microballoon, namely generates fluoropolymer resin outside: get 400.0g15.4% and remove short grained embodiment 1 microsphere suspension liquid, 150g deionized water, be added in 2000mL tetra-mouthfuls of round-bottomed flasks, pass into nitrogen, be stirred and heated to 70 DEG C.Get 0.08g rongalite, the 0.36g10% sodium dodecyl benzenylsulfonate aqueous solution, be mixed into 25.6g deionized water uniformly solution, add 13.0g homogeneous solution and enter round-bottomed flask.Get 0.11g TBHP, be mixed into 12.9g deionized water uniformly solution.Get 2.8g methyl methacrylate, 11.5g GMA, 0.03g1,6-hexanediyl ester, be mixed into even monomer solution.Within every 15 minutes, add each 1.0g of above-mentioned two aqueous solution, altogether 180 minutes joining days.Within every 15 minutes, add the above-mentioned monomer solution of 1.3g, altogether 150 minutes joining days.After the aqueous solution adds, continue stirring 60 minutes, cooling flask, to 25 DEG C, filters to isolate the microballoon of cladding material.
Embodiment 3
Functionalization embodiment 2 microballoon: get 100.0g embodiment 2 microsphere suspension liquid, 200mL absolute ethyl alcohol, is added in 500mL round-bottomed flask, and magnetic agitation is disperseed, then gets 50mL ethylenediamine, joins round-bottomed flask.Be heated to 80 DEG C to keep 12 hours.Cooling flask is to 25 DEG C, and isolated by filtration obtains the microballoon of functionalization, namely on kernel, forms funtion part, and described funtion part is made up of high molecular polymer and has functional group.
Embodiment 4
Activation embodiment 3 microballoon: 1.0g embodiment 3 microballoon is joined in the aqueous solution of 20mL, ultrasonic, while stir 30 minutes, microballoon is fully disperseed.Stannous chloride aqueous solution 20mL is joined in these slurries.The concentration of the aqueous solution of this stannous chloride is 20g/L, is heated to 40 DEG C, stirs 10 minutes.Make tin ion be adsorbed onto microsphere surface and complete sensitized treatment.And then filtering solution, clean with the aqueous hydrochloric acid solution of 0.01M.And then disperse with the aqueous hydrochloric acid solution of the 0.01M of 20mL, then add the palladium bichloride of the 1.5g/L of 20mL, be heated to 60 DEG C, stir 10 minutes, carry out the activation processing that microsphere surface catches palladium ion.And then filtering solution, use washed with de-ionized water microballoon, again microballoon is distributed in the aqueous solution of 20mL, ultrasonic, while stir this slurries, add the sodium hypophosphite of the 10g/L of 10mL simultaneously, keep 10 minutes, complete the reduction of residue palladium ion.
Embodiment 5
Form metal and overlay on embodiment 4 microballoon: the microballoon obtained after embodiment 4 being activated joins in the sodium citrate aqueous solution of the 100mL containing 0.1M, use the NaOH adjusted to ph of 0.1M to 9 after ultrasonic 30 minutes, be heated to 40 DEG C while stirring, mixing speed is 150rpm.Then nickel ion is contained liquid and reducing agent to contain liquid and join in slurry with the speed of 1mL/min respectively.After two kinds of liquid add, keep stirring and maintaining the temperature at 40 DEG C, until no longer produce bubble.The formula that nickel ion contains liquid is the natrium citricum of the nickelous sulfate of 0.57M, 0.1M.The formula that reducing agent contains liquid is the NaOH of the sodium hypophosphite of 1.4M, 2.0M.Thus, the plating powder with nickel metallization plated film obtained.Then need to implement gold-plated by displacement method on nickel dam surface by application, obtain gold-plated complex microsphere.
Embodiment 6-16,
Embodiment 6 to 10 uses the seed of different-grain diameter and different monomers and combination of monomers to be prepared as follows the conductive micro-balloons of the listed different sphere diameter of table and character by above step, wherein numbering 5 to 7 is comparative examples, the pliable and tough complex microsphere of the present invention is 8 ~ 10, commercially available prod comparative example is numbering 11 to 16 in addition, and the result of all engineering properties tests all arranges in the following table.
The result of integration test, the applicability that variant microballoon conducts electricity at microelectrode, as the row display the rightest in table, is applicable to being applied in the microballoon that microelectrode conduction connects and represents with symbol zero, is not suitable for being applied in microballoon that microelectrode conduction connects with symbol × represent.
The measuring mechanical property result of each conductive composite microsphere
The visible employing embodiment of the present invention 8,9,10 or the similar mechanical performance of tool in conjunction with the beneficial effect of conductive micro-balloons are: described mechanical performance combines and makes conductive micro-balloons of the present invention very soft, be out of shape along with the geometry of contact environment during pressurized, but not broken, microballoon conductive metal layer of the present invention and microelectrodes area are increased.The pliable and tough conductive micro-balloons of embodiment 8,9,10 is very soft, its stress in compression sigma of standardizing
50be less than 300megapascal to press speed 2.66 milli when ox/second, pressurized reduced by half at sphere diameter, be less than 200megapascal to press speed 0.88 milli when ox/second, pressurized reduced by half at sphere diameter, and the σ of other comparative examples and commercially available prod
50all at more than 400megapascal.Further, the pliable and tough conductive micro-balloons of the present invention has very strong toughness, the elastic recovery rate R of microballoon
ecoverybe greater than 40%, microballoon stops being depressed into spheroid distortion, when namely microballoon sphere diameter does not reduce with the increase of pressure, still keeps monolithic entity, and can not disintegrate and fragmentate.These mechanical performances combine, and make pliable and tough conductive micro-balloons of the present invention be very suitable for the use of microelectrode, can meet day by day meticulous application requirement.
Embodiment 17,
The anisotropic conductive material that applicable microelectrode conduction uses, comprises insulating resin binding agent and is dispersed in the pliable and tough conductive micro-balloons in described insulating resin binding agent.Described pliable and tough conductive micro-balloons is similar or identical with embodiment 8 to 10.Component and the preparation method of described resin adhesive belong to known technology, as described in patent documentation JP200580022240.0, do not repeat them here.
Embodiment 18,
The anisotropic conductive film that applicable microelectrode conduction uses, comprises anisotropic conductive material and anisotropic conducting film.Described anisotropic conductive material is identical with embodiment 17.Described film forming method is known technology, does not repeat them here.
Embodiment 19,
A meticulous electric current syndeton, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and the micro-structural tundish that described first microcircuitry elements is connected with the electric current of the second microcircuitry elements contains anisotropic conductive material.The preparation method of described anisotropic conductive material is identical with embodiment 17.Above-mentioned first microcircuitry elements and the second microcircuitry elements are the circuit element that electronic equipment is provided with microelectrode, belong to known technology, do not repeat them here.
Embodiment 20,
A meticulous electric current syndeton, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and the micro-structural tundish that described first microcircuitry elements is connected with the second microcircuitry elements electric current contains anisotropic conductive film.The preparation method of described anisotropic conductive film is identical with embodiment 18.Above-mentioned first microcircuitry elements and the second microcircuitry elements are the circuit element that electronic equipment is provided with microelectrode, belong to known technology, do not repeat them here.
Embodiment 21,
A meticulous electric current syndeton, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and the micro-structural tundish that described first microcircuitry elements is connected with the second microcircuitry elements electric current contains pliable and tough conductive micro-balloons.The preparation method of described pliable and tough conductive micro-balloons, with embodiment 8 to 10 or similar identical.Above-mentioned first microcircuitry elements and the second microcircuitry elements are the circuit element that electronic equipment is provided with microelectrode, belong to known technology, do not repeat them here.
In above-described embodiment, the pliable and tough conductive micro-balloons with the combination of unique mechanical performance is core of the present invention, described mechanical performance combines and makes conductive micro-balloons of the present invention very soft, easily be out of shape along with contact environment geometry during pressurized, but it is not easily broken, there is suitable bounce-back recovery function simultaneously, this mechanical performance combines and microballoon conductive metal layer of the present invention and microelectrodes area is increased, and keep close contact with microelectrode, strong adhesion, not easily be separated, the phenomenons such as loose contact, allow microelectrode longer service life, more reliable, highly meticulous application requirement can be met.In actual application, both solved HTHP and easily decomposed in conjunction with microelectronic element, break, the problem such as to lose, and also solved microelectrode because of hot pressing inequality and cause the problem of loose contact.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (13)
1. a pliable and tough conductive micro-balloons, comprise macromolecule copolymer resin and at least one deck metal conducting layer, it is characterized in that, described pliable and tough conductive micro-balloons has following mechanical performance: described pliable and tough conductive micro-balloons is soft, be out of shape along with the geometry of contact environment but do not break during pressurized and be dispersed into fragment, there is suitable bounce-back recovery function simultaneously.
2. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50400megapascal is less than when sphere diameter pressurized reduces by half.
3. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50300megapascal is less than to press speed 2.66 milli when ox/second, pressurized reduced by half at sphere diameter.
4. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises the standardization stress in compression sigma of described pliable and tough conductive micro-balloons
50200megapascal is less than to press speed 0.88 milli when ox/second, pressurized reduced by half at sphere diameter.
5. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises the elastic recovery rate R of described pliable and tough conductive micro-balloons
ecoverybe greater than 20%.
6. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises the elastic recovery rate R of described pliable and tough conductive micro-balloons
ecoverybe greater than 40%.
7. pliable and tough conductive micro-balloons as claimed in claim 1, is characterized in that, described mechanical performance comprises described pliable and tough conductive micro-balloons and is depressed into after microballoon distortion stops and is still monolithic entity, instead of breaks and be dispersed into fragment.
8. an application for pliable and tough conductive micro-balloons, is characterized in that, described pliable and tough conductive micro-balloons is for the preparation of anisotropic conductive material.
9. an anisotropic conductive material, is characterized in that, described anisotropic conductive material comprises insulating resin binding agent and is dispersed in the as claimed in claim 1 pliable and tough conductive micro-balloons in described insulating resin binding agent.
10. an anisotropic conductive film, is characterized in that, described anisotropic conductive film comprises anisotropic conductive material according to claim 9.
11. 1 kinds of electric current syndetons, is characterized in that, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and described first microcircuitry elements and the second microcircuitry elements include anisotropic conductive material according to claim 9.
12. 1 kinds of electric current syndetons, is characterized in that, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and described first microcircuitry elements and the second microcircuitry elements include anisotropic conductive film according to claim 10.
13. 1 kinds of electric current syndetons, is characterized in that, described electric current syndeton comprises the first microcircuitry elements and the second microcircuitry elements, and described first microcircuitry elements and the second microcircuitry elements include pliable and tough conductive micro-balloons according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393633A (en) * | 2017-06-26 | 2017-11-24 | 张家港康得新光电材料有限公司 | Conductive metal balls and 3D display device |
| CN109705770A (en) * | 2019-01-11 | 2019-05-03 | 成都其其小数科技有限公司 | A kind of elastic conduction microballoon and preparation method for anisotropic conductive film |
| CN115109277A (en) * | 2022-07-28 | 2022-09-27 | 苏州纳微科技股份有限公司 | Conductive microsphere with surface protrusion structure and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002052333A (en) * | 2000-08-09 | 2002-02-19 | Sekisui Chem Co Ltd | Coating method for fine particle, coated fine particle, anisotropic conductive adhesive, anisotropic conductive bonding film, and conductive connection structure |
| CN1340573A (en) * | 2000-07-13 | 2002-03-20 | 三井武田化学株式会社 | Multi-layer structure conductive resin granule and anisotropic conductive adhesive made up by its use |
| US20070295943A1 (en) * | 2005-02-22 | 2007-12-27 | Cheil Industries Inc. | Polymer Particles and Conductive Particles Having Enhanced Conducting Properties, and Anisotropic Conductive Packaging Materials Containing the Same |
| CN102136313A (en) * | 2010-12-06 | 2011-07-27 | 苏州纳微生物科技有限公司 | Compound microsphere, anisotropic conductive material, anisotropic conductive film and conductive structure |
| CN102668251A (en) * | 2010-12-24 | 2012-09-12 | 索尼化学&信息部件株式会社 | Anisotropic conductive adhesive film, connection structure and method for manufacturing same |
| CN104106182A (en) * | 2012-02-20 | 2014-10-15 | 迪睿合电子材料有限公司 | Anisotropic conductive connection material, connection structure, manufacturing method and connection method for connection structure |
-
2015
- 2015-06-30 CN CN201510381262.1A patent/CN105070351A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340573A (en) * | 2000-07-13 | 2002-03-20 | 三井武田化学株式会社 | Multi-layer structure conductive resin granule and anisotropic conductive adhesive made up by its use |
| JP2002052333A (en) * | 2000-08-09 | 2002-02-19 | Sekisui Chem Co Ltd | Coating method for fine particle, coated fine particle, anisotropic conductive adhesive, anisotropic conductive bonding film, and conductive connection structure |
| US20070295943A1 (en) * | 2005-02-22 | 2007-12-27 | Cheil Industries Inc. | Polymer Particles and Conductive Particles Having Enhanced Conducting Properties, and Anisotropic Conductive Packaging Materials Containing the Same |
| CN102136313A (en) * | 2010-12-06 | 2011-07-27 | 苏州纳微生物科技有限公司 | Compound microsphere, anisotropic conductive material, anisotropic conductive film and conductive structure |
| CN102668251A (en) * | 2010-12-24 | 2012-09-12 | 索尼化学&信息部件株式会社 | Anisotropic conductive adhesive film, connection structure and method for manufacturing same |
| CN104106182A (en) * | 2012-02-20 | 2014-10-15 | 迪睿合电子材料有限公司 | Anisotropic conductive connection material, connection structure, manufacturing method and connection method for connection structure |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107393633A (en) * | 2017-06-26 | 2017-11-24 | 张家港康得新光电材料有限公司 | Conductive metal balls and 3D display device |
| CN109705770A (en) * | 2019-01-11 | 2019-05-03 | 成都其其小数科技有限公司 | A kind of elastic conduction microballoon and preparation method for anisotropic conductive film |
| CN109705770B (en) * | 2019-01-11 | 2021-01-05 | 苏州纽劢特新材料科技有限公司 | Elastic conductive microsphere for anisotropic conductive adhesive film and preparation method |
| CN115109277A (en) * | 2022-07-28 | 2022-09-27 | 苏州纳微科技股份有限公司 | Conductive microsphere with surface protrusion structure and preparation method and application thereof |
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