CN1809899A - Coated conductive particle, anisotropic conductive material, and conductive connection structure - Google Patents
Coated conductive particle, anisotropic conductive material, and conductive connection structure Download PDFInfo
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- CN1809899A CN1809899A CN 200480017288 CN200480017288A CN1809899A CN 1809899 A CN1809899 A CN 1809899A CN 200480017288 CN200480017288 CN 200480017288 CN 200480017288 A CN200480017288 A CN 200480017288A CN 1809899 A CN1809899 A CN 1809899A
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Abstract
The invention provides a coating conductive particle which is adapted to the conductive connection of the electronic instrument or the electronic part with high connective reliability, the anisotropic conductive material which uses the coating conductive particle and the conductive connection structural body which process conductive connection through the coating conductive particle and the anisotropic conductive material. The coating conductive particle comprises a particle with conductive metal surface, an insulation particle which coats the particle with the conductive metal surface and a plurality of projections arranged on the surface of the particle with conductive metal surface.
Description
Technical field
The present invention relates to connect coating conducting particle, anisotropic conductive material and the conduction connecting structure body of reliability excellence.
Background technology
Particle with metal surface; except can be used as various resin filling materials, modifier use; can also be blended in the adhesive resin as electrically conductive microparticle; in electronic productses such as LCD, PC, portable type communication instrument; to be used for small-sized electromechanical components such as semiconductor element are electrically connected to substrate, or the so-called anisotropic conductive material that is electrically connected between the substrate will be used.
In recent years, owing to be accompanied by the miniaturization of electronic instrument and electronic unit, distributions such as substrate become fine, therefore, seek the raising of the micronize and the particle diameter precision of electrically conductive microparticle.Connect reliability in order to ensure height, be necessary to make the use level of the electrically conductive microparticle in the anisotropic conductive material to increase, but in such substrate etc. with fine distribution, exist to cause by the conducting of the horizontal direction between the electrically conductive microparticle of adjacency etc., thereby between adjacent electrode, produce problem such as said short circuit.In order to address this problem, proposed to use the anisotropic conductive material of the coating conducting particle that the surface of electrically conductive microparticle is coated with insulator.This coating conducting particulate be because the insulator of element can be sought electric insulation, and makes a concerted effort etc. partly to remove insulator by applying hot pressing, seeks conducting thereby can expose the conductive surface.
As such method with insulator coating conducting microparticle surfaces, known for example have, record carries out interfacial polymerization, suspension polymerisation, emulsion polymerisation etc. in the presence of electrically conductive microparticle in patent documentation 1, carry out the method for microencapsulation by resin, the infusion process of passing through to make it dry behind the dispersed electro-conductive particulate in resin solution of record is carried out the method for microencapsulation in patent documentation 2, the method of passing through spray drying, hydridization (Ha イ Block リ ダ イ ゼ one シ ョ Application) of record in patent documentation 3, in addition, also has method by vacuum evaporation etc.
, in such method, make the thickness of insulating barrier become constant and be difficult, in addition, coated a plurality of electrically conductive microparticles sometimes simultaneously.Use the coating conducting particle to conduct electricity when connecting, even control the particle diameter of electrically conductive microparticle to heavens, at the uneven thickness of insulating coating for the moment, when heat or pressure fixing are between electrode, pressure can not transmit equably, causes poor flow easily thereby become.For example, the formation method that insulation by above-mentioned hydridization coats, owing to be to make insulation particulate pass through the method for the power of physics, therefore, can not form coating layer with individual layer on the surface of electrically conductive microparticle attached to the surface of electrically conductive microparticle as coating layer, the control of the thickness of insulating coating is difficult, in addition, because because of the heat or the impact of heating or frictional heat causes, toner fusion, distortion, therefore, the coating of carrying out homogeneous is difficult.In addition, because the contact area of resin micropowder and metal surface becomes big, when being used for being difficult to apply the device of heat or pressure as liquid crystal cell etc., insulating coating is difficult to remove, and its result exists to cause the problem that poor flow is such.
In patent documentation 4 and patent documentation 5, put down in writing by electrostatic interaction or hydridization method and a little less than the surface of electrically conductive microparticle makes the insulation particulate, adhered to the coating conducting particle that forms.; the insulation particulate in the coating conducting particle that obtains with such method and the adhesion of electrically conductive microparticle are owing to only resulting from van der waals force and electrostatic force; very faint; when in adhesive resin, disperseing or in abutting connection with the contact of particle; the insulation particulate is stripped from, and existence can not be guaranteed the problem of sufficient insulating properties.On the other hand, when with strong adhesion such insulation particulate being combined on the surface of electrically conductive microparticle, even carry out heat pressure adhesive, the insulation particulate can not peeled off yet, thereby the possibility of not conducting is arranged sometimes.
In addition, though electrically conductive microparticle is distributed to mostly in the adhesive resin of insulating properties and uses as anisotropic conductive material, but use such anisotropic conductive material to conduct electricity when connecting, in the time conduction will being connected the operation high speed, then there is the such problem of poor flow that is easy to generate in order to enhance productivity.Can think, if this is owing to want then can not get rid of the adhesive resin between electrode and the electrically conductive microparticle fully, thereby adhesive resin to be residual between electrode and electrically conductive microparticle to connect at a high speed.
Patent documentation 1: the spy opens flat 4-362104 communique
Patent documentation 2: the spy opens clear 62-40183 communique
Patent documentation 3: the spy opens flat 7-105716 communique
Patent documentation 4: the spy opens flat 4-259766 communique
Patent documentation 5: the spy opens flat 3-112011 communique
Summary of the invention
In view of above-mentioned present situation, the object of the present invention is to provide a kind of coating conducting particle, anisotropic conductive material and conduction connecting structure body that connects the reliability excellence.
The present invention relates to a kind of coating conducting particle, this coating conducting particle is the coating conducting particle of surface coated insulation particulate that comprises the particle with the surface that is made of conductive metal and will have the particle on the surface that the metal by above-mentioned conductivity constitutes, and the particle with the surface that is made of above-mentioned conductive metal has a plurality of projections on the surface.
Below, explain the present invention.
The insulation particulate that coating conducting particle of the present invention comprises particle with the surface that is made of conductive metal (below, be called the metal surface particle) and above-mentioned metal surface particle is coated.By using the insulation particulate to coat on the surface of metal surface particle like this, can be when the conduction of using coating conducting particle of the present invention to carry out substrate etc. connects, even have the substrate of fine distribution etc., horizontal conducting that electrically conductive microparticle by adjacency causes etc. can not take place yet, in addition, vertically, carry out hot pressing by applying heat and pressure, expose the metal surface of metal surface particle, thus conducting positively.
Above-mentioned metal surface particle has a plurality of projections on the surface.By have a plurality of projections on the surface, when using, the removing property of electrode and the interparticle adhesive resin of coating conducting is uprised as anisotropic conductive material, even when connecting at a high speed, also conducting positively.In addition,,, also can break through this oxidation package overlay film and conducting, therefore, connect reliability and improve even on the aluminium electrode that connects, form the oxidation package overlay film owing to have such projection.
As above-mentioned metal surface particle, be the particle that comprises conductive metal on top layer, and as long as have projection on the surface, then there is no particular limitation, can enumerate, and for example, only comprises the particle of metal; Formed the particle of metal level by evaporation, plating, coating etc. on the surface of the core particle that includes organic compounds or inorganic compound; Imported the particle etc. of the minuteness particle of metal on the surface of the core particle of insulating properties.Wherein, when coating conducting particle of the present invention is used in anisotropic conductive material, the particle that has formed the conductive metal layer on the surface of the core particle that comprises resin during owing to pressing between electrode distortion bonding area is increased, therefore, from this point of connective stability, be preferred.
As above-mentioned core particle, there is no particular limitation, can enumerate, for example, comprise polyethylene, polypropylene, polystyrene, polypropylene, polyisobutene, polyolefin such as polybutadiene, polymethyl methacrylate, acrylic resins such as polymethyl acrylate, polyalkylene terephthalates, polysulfones, Merlon, polyamide, phenolic resins such as phenol formaldehyde resin, melmacs such as melamine resin, benzoguanamine resins such as benzoguanamin formaldehyde resin, urea-formaldehyde resin, epoxy resin, (no) saturated polyester resin, PETG, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, the material of polyether sulfone etc.Wherein, use polymerization more than a kind or 2 kinds or 2 kinds the various polymerizable monomers with ethene unsaturated group and the particle of the resin that forms owing to obtain suitable hardness easily, so preferably.
Above-mentioned polymerizable monomer with ethene unsaturated group can be non-cross-linkable monomer, also can be cross-linkable monomer.
As above-mentioned non-crosslinked monomer, can enumerate, for example, styrene, AMS, p-methylstyrene, to styrene monomers such as chlorostyrene, 1-chloro-4-methyl-benzenes; (methyl) acrylic acid, maleic acid, maleic anhydride etc. contain the monomer of carboxyl; (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl ester, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid glycol ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) alkyl-acrylates such as (methyl) acrylic acid five fluorine propyl ester; (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid glyceride, polyoxyethylene (methyl) acrylate, (methyl) glycidyl acrylate etc. contain (methyl) esters of acrylic acid of oxygen atom; (methyl) acrylonitrile etc. contains the monomer of itrile group; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; Vinyl acetate classes such as vinylacetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester, PVF, vinyl chloride, propionate; Unsaturated hydrocarbons such as ethene, propylene, butylene, methylpentene, isoprene, butadiene etc.
As above-mentioned cross-linkable monomer, can enumerate, for example, multifunctional (methyl) esters of acrylic acids such as tetramethylol methane four (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acrylic acid glyceride, two (methyl) acrylic acid glyceride, two (methyl) polyalkylene glycol acrylate ester, two (methyl) acrylic acid polypropylene glycol ester; (different) triallyl cyanurate, trimellitic acid triallyl, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether etc.; γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, trimethoxy silane base styrene, vinyltrimethoxy silane etc. contain the monomer of silane; Omega-dicarboxylic acids such as phthalic acid; Two amines; Dially phthalate, benzoguanamine, triallyl isocyanate etc.
The preferred of the average grain diameter of above-mentioned core particle is limited to 0.5 μ m down, is limited to 100 μ m on preferably.If aggegation when forming metal level, takes place in less than 0.5 μ m easily, the coating conducting particle that uses the core particle of generation aggegation and make causes the short circuit between adjacent electrode sometimes, if surpass 100 μ m, the metal level of the coating conducting particle that obtains is peeled off sometimes easily, and reliability reduces.The following 1 μ m that is limited to that is more preferably is more preferably and is limited to 20 μ m.In addition, the average grain diameter of above-mentioned core particle can be handled the particle diameter of using up instrumentations such as learning microscope, electron microscope, particle size distribution meter with adding up and tries to achieve.
The coefficient of alteration of the average grain diameter of above-mentioned core particle is preferably below 10% or 10%.If surpass 10%, use the coating conducting particle that obtains at random to control opposed electrode gap and become difficult.In addition, so-called above-mentioned coefficient of alteration is that the standard deviation that will obtain from particle size distribution removes with average grain diameter and the numerical value that obtains.
The preferred of the 10%K value of above-mentioned core particle is limited to 1000MPa down, is limited to 15000MPa on preferably.If not enough 1000MPa because the intensity of the coating conducting particle that obtains is insufficient, when compression, produces the destruction of particle, thereby can not realize the function as electric conducting material sometimes, if surpass 15000MPa, lesion electrode sometimes.The following 2000MPa of being limited to that is more preferably is more preferably and is limited to 10000MPa.In addition, above-mentioned 10%K value, (for example can use the slight compression exerciser, the PCT-200 that Shimadzu Seisakusho Ltd. makes etc.), mensuration level and smooth pressure head end face that the diamond rounding post by diameter 50 μ m the constitutes compression displacement (mm) when the condition lower compression particle of compression speed 2.6mN/ second, maximum testing load 10g is tried to achieve by following formula.
F: the loading value (N) when 10% compression of particle
S: the compression displacement (mm) when 10% compression of particle
R: the radius of particle (mm)
In addition, in order to obtain the core particle that the 10%K value satisfies above-mentioned condition, core particle comprises preferably that polymerization has the polymerizable monomer of above-mentioned ethene unsaturated group and the resin that forms, at this moment, as constituent, be more preferably and contain 20 weight % or the above cross-linkable monomer of 20 weight % at least.
The preferred recovery rate of above-mentioned core particle is more than 20% or 20%.If less than 20%, when the coating conducting particle that compression obtains, owing to can not recover original state after the distortion, so cause bad connection sometimes.Be more preferably more than 40% or 40%.In addition, above-mentioned recovery rate is meant the recovery rate after the loading of load 9.8mN on the particle.
As above-mentioned metal, get final product so long as have the metal of conductivity, there is no particular limitation, can enumerate, for example, metal or metallic compounds such as ITO, scolding tin such as gold, silver, copper, platinum, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium, silicon.
Above-mentioned metal level can be a single layer structure, also can be the laminated construction that comprises multilayer.When comprising laminated construction, preferred outermost layer contains golden.Since outermost layer is made the layer that contains gold, the corrosion resistance height, and contact resistance is little, and therefore, the coating conducting particle that obtains is excellent more particle.
As above-mentioned metal layer thickness, there is no particular limitation, preferred is limited to 0.005 μ m down, is limited to 1 μ m on preferably.If less than 0.005 μ m, sometimes can not obtain effect of sufficient as conductive layer, if surpass 1 μ m, the proportion of the coating conducting particle that obtains sometimes too uprises, or the hardness that comprises the core particle of resin can not become the hardness that can fully be out of shape.The following 0.01 μ m that is limited to that is more preferably is more preferably and is limited to 0.3 μ m.
In addition, when the outermost layer of above-mentioned metal level was made the gold layer, the preferred of the thickness of gold layer was limited to 0.001 μ m down, was limited to 0.5 μ m on preferably.If less than 0.001 μ m, the covered with metal layer difficulty that becomes can not be expected the raising effect of corrosion resistance or contact resistance value sometimes equably, if surpass 0.5 μ m, is high price for the ratio of its effect.The following 0.01 μ m that is limited to that is more preferably is more preferably and is limited to 0.2 μ m.
As the method that forms above-mentioned conductive metal layer, there is no particular limitation, can enumerate, and for example, the electroless plating of the metal evaporation method of physics, chemistry covers known methods such as method, but from the easy degree of operation, preferred electroless plating covers method.As covering the metal level that method forms with electroless plating, can enumerate, for example, gold, silver, copper, platina, palladium, nickel, rhodium, ruthenium, cobalt, tin and their alloy etc., but in coating conducting particle of the present invention, owing to can form the coating of homogeneous with high density, so part or all of preferred metal layers forms by electroless plating nickel.
Form golden layer method as the outermost layer at above-mentioned metal level, there is no particular limitation, can enumerate, and for example, electroless plating covers, replaces known method such as plating, plating, sputter etc.
As the projection of above-mentioned metal surface particle surface, as long as the surface of projection is a conductive metal at least, then there is no particular limitation, can be identical with above-mentioned metal level, and also can be different.
Be limited to 0.05 μ m under the height of above-mentioned projection preferred.If less than 0.05 μ m is difficult to obtain jut sometimes and exposes the effect that such what is called is given projection from insulating coating easily when connecting.The following 0.1 μ m that is limited to that is more preferably.
Be limited on the height of above-mentioned projection preferred above-mentioned metal surface particle diameter 40%.If surpass 40%, projection becomes and fractures easily, or is absorbed in dearly in the electrode and damaged danger, perhaps uses the covering property conducting particles that obtains at random to control the opposed electrode gap difficulty that becomes sometimes.Be limited to 20% on being more preferably.
As the quantity of above-mentioned projection, there is no particular limitation, but preferably the average bump count of each coating conducting particle is more than 8 or 8.If 8 of less thaies can not be brought into play sometimes as giving the stable high connective stability of the effect of projection.
Have the method for the metal surface particle of such projection as manufacturing, there is no particular limitation, can enumerate, for example, when 1) forming the conductive metal layer on the surface of core particle, Yi Bian seed that contains organic and/or inorganic materials or organic material is entered, Yi Bian the method that the conductive metal layer is grown up; When 2) forming the conductive metal layer on the surface of core particle, make with the high material heterogeneity of metal compatibility ground attached to the core particle surface, the projection that comprises conductive metal being grown up, form the method for conductive metal layer simultaneously with the many part of the high material of above-mentioned metal compatibility; 3) surface that has the core particle that comprises as seed of the organic material of projection or inorganic material (below, be also referred to as the projection particle) on the surface forms the method for conductive metal layer.
As above-mentioned 1) the concrete method of method, can enumerate, for example, when core particle water-soluble serous that comprises resin added to the electroless plating that contains nickel salt, reducing agent, coordination agent etc. and carries out electroless plating nickel in bathing, the decomposition of nickel dam and plating bath self takes place to form on core particle simultaneously, with this self analyte nuclear, carry out the method etc. of the growth of the growth of nickel overlay film and projection simultaneously as projection.
As above-mentioned 2) the concrete method of method, can enumerate, for example, after palladium bichloride is poured on the surface of core particle into, by in the thin solution of palladium bichloride, under the stirring that relaxes, extremely stably carry out the reduction of palladium bichloride, form palladium as the starting point of electroless plating nickel on heterogeneity ground, core particle surface, then, add the method for carrying out electroless plating nickel in the electroless plating bath that contains nickel salt, reducing agent, coordination agent etc. to.
In the method, in the many parts of palladium, compare with the part that palladium is few, because the speed of separating out of nickel becomes big, as a result of, plating carries out with the state of so-called projection.
As 3) the concrete method of method, can enumerate, for example, make by the whole bag of tricks such as hydridization behind the projection particle of surface attachment seed of core particle, form the method for metal levels by electroless plating nickel etc. on the surface of the projection particle that obtains; Mixing and polymerism drop that contains the polymerism unsaturated monomer that obtains or the surface that in medium, makes the polymerism drop of kind of particle swelling to major general's polymerism unsaturated monomer and medium with polymerizable monomer, make as sub-aggegation of the seed of projection or combination, and after being manufactured on the particle (projection particle) that the surface has projection by the polymerization drop, form the method etc. of metal levels by electroless plating nickel etc. on the surface of the projection particle that obtains.
Behind the surface that the is combined in above-mentioned core particle chemistry of particles that will become projection and/or physics, form the method for conductive metal layer on the surface of this core particle and particulate, preference is as having: mix and preparation contains the operation that the polymerism drop of polymerism unsaturated monomer is distributed to the dispersion liquid in the medium to major general's polymerism unsaturated monomer and medium, in above-mentioned dispersion liquid, add seed, and make the operation of seed attached to the surface of polymerism drop, make the polymerism polymerization of fluid drops that seed adheres to and obtain the operation of projection particle, the projection particle that obtains is carried out the method for the operation of metal deposition.
As other method, for example, can also be by having: the medium that will plant particle and contain the polymerism unsaturated monomer mixes prepare the operation that the kind particle is distributed to the dispersion liquid in the medium, above-mentioned kind of particle absorbing polymer unsaturated monomer made the operation of polymerism drop, in dispersion liquid, add seed, and make the operation of seed attached to the surface of polymerism drop, make the polymerism polymerization of fluid drops that seed adheres to and obtain the operation of projection particle, the projection particle that obtains is carried out the metal surface particle that the method manufacturing of the operation of metal deposition has projection.
As above-mentioned insulation particulate, so long as insulating properties, then there is no particular limitation, can enumerate, and for example, except the particulate of the resin that contains insulating properties, contains the particulate etc. of the inorganic matter of insulating properties such as silicon dioxide in addition.Wherein, the particulate that preferably contains insulative resin.As the resin of above-mentioned insulating properties, there is no particular limitation, can enumerate, and for example, is used for the resin of above-mentioned core particle etc.These resins can use separately, also can use simultaneously more than 2 kinds or 2 kinds.
The preferred of the particle diameter of above-mentioned insulation particulate is limited to 5nm down, is limited to 1000nm on preferably.If not enough 5nm, the interparticle distance of the coating conducting of adjacency is littler than the distance of beating of electronics, causes easily and sew that if surpass 1000nm, necessary pressure and heat too become big when hot pressing sometimes.The following 10nm of being limited to that is more preferably is more preferably and is limited to 500nm.
In addition, because little insulation particulate enters between the space that is coated by big insulation particulate, can improve coating density, so can use the different insulation particulate more than 2 kinds or 2 kinds of particle diameter simultaneously.At this moment, the particle diameter of preferred little insulation particulate is below 1/2 or 1/2 of particle diameter of big insulation particulate, and in addition, the quantity of preferred little insulation particulate is below 1/4 or 1/4 of quantity of big insulation particulate.
In addition, also there is no particular limitation for the ratio of the height of the projection of the particle diameter of above-mentioned insulation particulate and metal surface particle.Fig. 1～Fig. 4 is the each several part recess front cross-sectional view of the various example of height that the projection of insulation particle diameter of particulate and metal surface particle is shown.For example, as shown in Figure 1, form a plurality of projections 11 on the surface of the metal surface particle 1 that contains metal, the diameter of insulation particulate 2 can be than the height of this projection 11, promptly big to the size of the outermost side of projection 11 from the surface of metal surface particle 1.In addition, Fig. 1 and following Fig. 2～Fig. 4 after all, just illustrate the relation of the height of the footpath of the particulate that insulate and projection model utility.
In addition, as shown in Figure 2, the height of the projection 11 that the footpath of insulation particulate 2 also can form than the surface at metal surface particle 1 is little.In addition, as shown in Figure 3, the little insulation particulate 2 of height of the projection 11 that is provided with outside at a plurality of ratios of metal surface particle 1 configuration side-prominently, the outer surface of metal surface particle 1 also can coat by being insulated property material.
In addition, as shown in Figure 4, can also use the insulation particulate 2A in the footpath littler and the insulation particulate 2B in big footpath simultaneously than the height of the projection 11 that forms on the surface of metal surface particle 1.That is, can use the insulation particulate of multiple size.
In addition, in Fig. 1～Fig. 4, metal surface particle 1 is formed by metal, but metal surface particle 1 as shown in Figure 5 on the surface of the particle main body 1A that contains the insulating properties material, also can be the structure of metal level 1B, 1C lamination.At this moment, also comprise the part that has formed projection 11, and the outer surface of metal surface particle 1 is formed by metal.Point out also that in addition in Fig. 5, insulating fine particles has been omitted diagram.
In addition, as shown in Figure 6,, shown in the right side of Fig. 6, also can form metal surface particle 21 by the plated film 23 that formation contains metal at the outer surface of insulating particle 22.At this moment, form rapid plated film growth part, thereby constitute jut 23a in the part of plated film 23.Like this, when the formation of plated film, plated film is partly sharply grown up, thereby form a plurality of jut 23a.In addition, though insulating properties particle 22 can be made of suitable material, be contemplated to be the material that can form the plated film 23 that contains metal.In addition, replace insulating particle 22, can also form metal film at the particle surface that comprises the insulating properties material, and on this metal film, form plated film 23.
The CV value of above-mentioned insulation particulate preferable particle size is below 20% or 20%.If surpass 20%, the thickness of the coating layer of the coating conducting particle that the obtains heterogeneity that becomes during hot pressing, is difficult to exert pressure equably between electrode, and poor flow takes place sometimes.In addition, the CV value of above-mentioned particle diameter can calculate by following formula.
Standard deviation/average grain diameter * 100 of CV value (the %)=particle diameter of particle diameter
As the assay method of above-mentioned particle size distribution, before the clad metal surface particle, can measure with the particle size distribution meter, can wait with the graphical analysis that SEM takes a picture after coating and measure.
Above-mentioned insulation particulate preferably has positive charge.Owing to have a positive charge, can carry out and the combining of metal surface particle with heteroagglutination method described later, in addition, and because Coulomb repulsion between the above-mentioned insulation particulate, the aggegation between the particulate of can suppressing to insulate, thus form the coating layer of individual layer.That is, during insulation particulate positively charged, the insulation particulate with individual layer attached on the particle of metal surface.In addition, when such positive charge is based on ammonium or sulfonium base, work as the functional group (A) that metal described later is had bonding, the insulation particulate easily with the metal formation chemical bond on the surface of direct metal surface particle.Therefore, above-mentioned insulation particulate preferably comprises the resin with ammonium or sulfonium base.Wherein, be more preferably and comprise resin with sulfonium base.
As insulation particulate with above-mentioned positive charge, can enumerate, when the insulation particulate is made, make method that polymerizable monomer with positive charge sneaks into, by the radical initiator with positive charge carry out polymerization method, use method that dispersion stabilizer with positive charge or emulsifying agent make etc.These methods also can be used more than 2 kinds or 2 kinds simultaneously.In the middle of these, it is preferred using the method for the polymerizable monomer with positive charge, the method for use radical initiator.
As polymerizable monomer with above-mentioned positive charge, can enumerate, for example, N, N-dimethylaminoethyl methacrylate, N, N-dimethyl aminopropyl acrylamide, N, N, N-trimethyl-N-2-methylacryoyloxyethyl ammonium chloride etc. contain monomer, methacrylic acid phenyl diformazan sulfonium base methyl esters sulfate of ammonium etc. and have monomer of sulfonium base etc.As radical initiator, can enumerate, for example with above-mentioned positive charge, 2,2 '-azo two { 2-methyl-N-[2-(1-hydroxybutyl)]-propionamide }, 2,2 '-azo two [2-(2-imidazoline-2-yl) propane], 2,2 '-azo two (2-amidine propane) and their salt etc.
In coating conducting particle of the present invention, above-mentioned metal surface particle and insulation particulate preferably carry out chemical bonding by the functional group (A) that metal had bonding.Because by chemical bonding, with only by van der waals force or electrostatic force in conjunction with comparing, adhesion is strong, can prevent that insulating particle peels off when mixing adhesive resin etc., perhaps when using the coating conducting particle as anisotropic conductive material, because with the contacting of adjacency particle, the insulation particulate peels off and causes and sew.On the other hand, as mentioned above, because above-mentioned metal surface particle has projection, in any case insulating particle engages securely, by hot pressing, projection all can advance insulating particle, thereby can positively conduct electricity connection.In addition, owing to such chemical bonding only forms between metal surface particle and insulation particulate, and not combination between the insulating particle, so the coating layer that is formed by the insulation particulate is an individual layer.Thus, as metal surface particle and insulation particulate,, just can easily make the uniform particle diameter of coating conducting particle of the present invention if use the uniform particle of particle diameter.
As above-mentioned functional group (A), so long as can form the group of ionic bond, covalent bond, coordinate bond with metal, then there is no particular limitation, can enumerate, for example, silylation, silanol group, carboxyl, amino, ammonium, nitro, hydroxyl, carbonyl, mercapto, sulfonic group, sulfonium base, boronate, oxazolinyl, pyrrolidone-base, phosphate, itrile group etc.Wherein, preferably can complex bound functional group, can preferably use have S, the functional group of N, P atom.For example, when metal is gold, preferably have the functional group, particularly mercapto, the thioether group that gold are formed the S atom of coordinate bond.
As using such functional group (A) to make metal surface particle and insulation particulate carry out the method for chemical bonding, there is no particular limitation, can enumerate for example, 1) the insulation particulate that will have functional group (A) on the surface imports to the method on the surface of metal surface particle; 2) compound that will have functional group (A) and a reactive functional groups (B) imports to the metal surface, then, makes reactive functional groups (B) and the reaction of insulation particulate and the method for bonding etc. by single step reaction or multistep reaction.
Above-mentioned 1) method in, as being manufactured on the method that the surface has the insulation particulate of functional group (A), there is no particular limitation, can enumerate, and for example, sneaks into the have functional group monomer methods of (A) when making the insulation particulate; Import the method for functional group (A) by chemical bond on the surface of insulation particulate; The surface of chemical treatment insulation particulate is modified as the method for functional group (A); Surface modification with particulates that will insulate such as plasmas is method of functional group (A) etc.
As above-mentioned 2) method, can enumerate, for example, make in a part, have functional group (A) and hydroxyl, the compound and the metal surface particle reaction of carboxyl, amino, epoxy radicals, silicyl, silanol group, NCO isoreactivity functional group (B), then, make have on the surface can covalently bound functional group the organic compound particle and the method for reactive functional groups (B) reaction etc.As such compound that in a part, has functional group (A) and reactive functional groups (B), can enumerate, for example, 2-aminoothyl mercaptan, p-aminophenyl thiophenol etc.If use the 2-aminoothyl mercaptan, surface at the metal surface particle makes 2-aminoothyl mercaptan bonding by the SH group, for an other amino, can for example pass through, make insulating particle in surface reaction, with metal surface particle and the combination of insulation particulate with epoxide group or carboxyl etc.
When using coating conducting particle of the present invention to carry out interelectrode connection, carry out hot pressing, the metal surface of metal surface particle is exposed carry out conducting by applying heat and pressure.Expose said here metal surface, the state that at least a portion that is meant the metal surface of metal surface particle can not hinder insulation particulate ground to be connected with direct electrode.In addition,, according to the kind of the electronic unit of coating conducting Particle Density in the anisotropic conductive material or connection etc. and different, needn't limit as the condition of above-mentioned hot pressing, but usually under 120～220 ℃ temperature, 9.8 * 10
4～4.9 * 10
6Carry out under the pressure of Pa.
As the state that exposes of the metal surface of metal surface particle, can think has 3 kinds of following modes.
The 1st kind of mode is by hot pressing, the insulating particle fusion, thus expose the metal surface of metal surface particle.The 2nd kind of mode is by hot pressing, the insulating particle distortion, thus expose the metal surface of metal surface particle.The 3rd kind of mode is by hot pressing, and metal surface particle and insulating particle dissociate, thereby expose the metal surface of metal surface particle.
Wherein, preferably the metal surface of metal surface particle is exposed conduct electricity connection by the 2nd kind of mode.During according to the 1st kind of mode, the insulating particle of fusion sometimes ooze out and pollute adhesive resin or substrate or even make the interparticle coating layer fusion of coating conducting of insulation adjacency, thereby do not show sufficient insulating properties, during according to the 3rd kind of mode, metal surface particle during hot pressing and insulating particle and when being listed in the direction of pressing, insulating particle is embedded between metal surface particle and the substrate and can not dissociates, and connects reliability sometimes and reduces.In addition, because the metal surface particle has projection on the surface, become according to the metal surface of the metal surface particle of the 2nd kind of mode and the 3rd kind of mode and to expose easily.
According to any mode wherein, the metal surface of metal surface particle is exposed and is conducted electricity connection, though also depend on the condition of hot pressing, the relativeness of the hardness that usually can be by the metal surface particle and the hardness of insulating particle is controlled.Here the hardness of said particle is meant the relative hardness under the hot pressing condition, for example, compares with the metal surface particle, and the softening temperature of insulating particle is low, when having only insulating particle to soften under the hot pressing condition, can claim that insulating particle is soft.
In addition, in order to expose the metal surface that makes the metal surface particle, preferably with the clad ratio of insulating particle, that is, all ratios of surface area that the area of the part that is coated by insulating particle accounts for the metal surface particle are 5～50%.If less than 5%, insulation between the coating conducting particle of adjacency is insufficient, if surpass 50%, in the 1st kind of mode, sometimes in addition make the insulation adjacency the interparticle coating layer fusion of coating conducting, thereby do not show sufficient insulating properties, in the 2nd kind of mode, even the insulating particle distortion is crushing, the metal surface can not exposed sometimes fully yet, in the 3rd kind of mode,, be necessary other insulating particle is extruded because the insulating particle of hot pressing direction dissociates, metal surface particle and insulating particle that perhaps might be when hot pressing and when being listed in the direction of pressing, insulating particle are embedded between metal surface particle and the substrate and can not dissociate.
Adjustment to the relativeness between the hardness of the hardness of such metal surface particle and insulating particle further describes.For example, as above-mentioned metal surface particle, when being chosen in harder metals such as comprising copper, nickel, iron, gold; Aluminum oxynitride harder metal oxides such as (stopping up ア Le ミ); Inorganic particulates such as silicon dioxide; The use level of cross-linkable monomer is when the harder material of the material etc. of metal level is set on the core particle of the above resin of 50 weight % or 50 weight %, as above-mentioned insulation particulate, by selecting following material, by any mode, the exposing of metal surface that can adjust the metal surface particle conducted electricity connection.
As the method for making coating conducting particle of the present invention, so long as the method for chemical bonding is carried out on the surface that makes above-mentioned insulation particulate contact have the metal surface particle of above-mentioned projection, then there is no particular limitation, for example, preferably have at least: in organic solvent and/or water, to particle with the surface that comprises conductive metal by van der waals force or electrostatic interaction but the operation 1 of insulation microparticle agglutination and will have the particle on the surface that comprises conductive metal and the method that the insulation particulate carries out the operation 2 of chemical bonding.The agglutination of operation 1 is the method that is called as the heteroagglutination method, if use this method, because can be rapidly and metal surface particle and the chemical reaction of insulation between the particulate are taken place by the solvent effect, therefore, do not need necessity or necessary above pressure, in addition, owing to the temperature controlling that system is all is also easy, therefore, the insulation particulate is difficult to be out of shape by heat etc.Relative therewith, if import the insulation particulate by the dry method that uses original homogenizer or mixer etc., loads such as cost necessity easily or necessary above pressure or frictional heat, when the insulation particulate is harder than metal surface particle, sometimes damage the metal surface particle, or metal level is peeled off, in addition, when the insulation particulate is softer than metal surface particle, or the glass transition temperature of insulation particulate is when low, because collision or frictional heat with the metal surface particle, the distortion of insulation particulate, sometimes contact area becomes big, or the insulation thickness heterogeneity that becomes, or insulation particulate lamination adheres to, or insulation particulate fusion, bonding and can not single-particleization between the coating conducting particle.
As above-mentioned organic solvent, so long as do not dissolve the solvent of insulation particulate, then there is no particular limitation.
Coating conducting particle of the present invention is because the surface by insulation particulate clad metal surface particle, therefore, even when using as anisotropic conductive material, also do not sew between the particle of adjacency.In addition, owing to have projection, when connecting, the metal surface of metal surface particle is easily exposed, thereby obtain certain conducting by hot pressing on the surface of above-mentioned metal surface particle.In addition, at metal surface particle and insulation particulate when carrying out chemical bonding, when when mixing or with the adjacency particle, contact with adhesive resin etc., the adhesion of insulation particulate and metal surface excessively a little less than, the particulate that insulate can not peel off etc.In addition, the insulation particulate forms the coating layer of individual layer, and the particle size distribution of insulation particulate is little, and the contact area of insulation particulate and metal surface is certain, therefore, can make the particle diameter of the coating conducting particle homogeneous that becomes.
Coating conducting particle of the present invention can be used for purposes such as anisotropic conductive material, infrared reflection material, electromagnetic shielding material.Wherein, in the adhesive resin that is distributed to insulating properties, can be suitable as anisotropic conductive material and use.
The anisotropic conductive material that coating conducting particle of the present invention is distributed in the insulating properties adhesive resin also is one of the present invention.
In addition, in this manual, anisotropic conductive material also comprises anisotropic conductive film, anisotropic conductive paste, anisotropically conducting adhesive, anisotropic conductive printing ink etc.
As above-mentioned insulating properties adhesive resin, so long as the getting final product of insulating properties, there is no particular limitation, can enumerate, for example, thermoplastic resins such as acrylate, ethylene-vinyl acetate resin, styrene-butadiene block copolymer and hydrogenation thing thereof, styrene-isoprene block copolymer and hydrogenation thing thereof; Thermosetting resins such as epoxy resin, acrylate, melmac, urea resin, phenolic resins; The resin that the beta-unsaturated esters of the acrylate of polyalcohol, polyester acrylate, polybasic carboxylic acid etc. solidify by ultraviolet ray, electron ray etc. etc.Wherein, preferably pass through the bonding solid of heat and/or photocuring.
In anisotropic conductive material of the present invention, except adhesive resin and coating conducting particle of the present invention as necessary composition, in the scope of not damaging problem realization of the present invention, can also optionally add, for example, in the various additives such as filler, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, antistatic agent, fire retardant more than a kind or 2 kinds or 2 kinds.
In anisotropic conductive material of the present invention, preferably functional group of containing in the insulation particulate of the coating conducting particle of the present invention that contains and the functional group in the adhesive resin carry out chemical bonding.Above-mentioned insulation particulate and adhesive resin by chemical bond and, be distributed to the excellent in stability of the coating conducting particle of the present invention in the adhesive resin, the insulating particle of heat fusing can not ooze out and contaminated electrode or liquid crystal simultaneously, and, can obtain the anisotropic conductive material of long-term connective stability and reliability excellence.
As making coating conducting particle of the present invention be distributed to method in the above-mentioned adhesive resin, there is no particular limitation, can use originally known process for dispersing, can enumerate, for example, in adhesive resin, add after the coating conducting particle, with the method for mixing dispersions such as planetary-type mixer; After use homogenizer etc. is distributed to the coating conducting particle in water or the organic solvent equably, in adhesive resin, add, use the method for the mixing dispersion of planetary-type mixer again; After dilution such as adhesive resin water or organic solvent, add the coating conducting particle, give the method etc. of the shearing force of machinery with the method for mixing dispersions such as planetary-type mixer etc.These process for dispersing can use separately, also can use simultaneously more than 2 kinds or 2 kinds.
In addition, when giving with above-mentioned shearing force, preferred suitably selection does not apply the such method or the condition of mechanical shear stress of the structure destruction that is dispersed in the coating conducting particle of the present invention in the adhesive resin etc. is carried out.
As the method for making above-mentioned anisotropic conductive film, there is no particular limitation, can enumerate, for example, make coating conducting particle suspension of the present invention in the material that in adhesive resin, has added solvent, and this suspension curtain coating made tunicle to the film of the demoulding, the film that will evaporate solvent from tunicle batches method on roller etc.Conducting electricity by above-mentioned anisotropic conductive film when connecting, the film of tunicle with the demoulding rolled out, tunicle is placed on the electrode that connect, overlapping thereon counter electrode, and the method that connects by hot pressing etc.
Above-mentioned anisotropy is stuck with paste and can for example be passed through, anisotropically conducting adhesive is made pasty state manufacturing, and it is encased in the suitable dispenser, the thickness that coating is wished on the electrode that should connect, superimposed thereon again counter electrode connects resin solidification by hot pressing.
Above-mentioned anisotropic conductive printing ink, can for example pass through, solvent is joined in the anisotropic-electroconductive adhesive, and make it to have the viscosity that is suitable for printing and make, it is carried out screen painting on the electrode that should connect, make solvent evaporation then, counter electrode and connect by hot pressing is incompatible thereon superposes.
Coating film thickness as above-mentioned anisotropic conductive material, calculate by the average grain diameter of the coating conducting particle of the present invention that uses and the method for connection electrode, preferred coating conducting particle is clamped between the connection electrode, and fully be full of by adhesive linkage between the connection substrate.
Adopt coating conducting particle of the present invention or anisotropic conductive material of the present invention, electronic units such as IC chip or substrate conduction is connected and the conduction connecting structure body that forms also is one of the present invention.
According to the present invention, can provide the coating conducting particle, anisotropic conductive material and the conduction connecting structure body that connect the reliability excellence.
The simple declaration of accompanying drawing
[Fig. 1] Fig. 1 is the partial notch profile that illustrates by an example of the mode of insulation particulate clad metal surface particle.
[Fig. 2] Fig. 2 is another the routine partial notch profile that illustrates by the mode of insulation particulate clad metal surface particle.
[Fig. 3] Fig. 3 is another the routine partial notch profile that illustrates by the mode of insulation particulate clad metal surface particle.
[Fig. 4] Fig. 4 is another the routine partial notch profile that illustrates by the mode of insulation particulate clad metal surface particle.
[Fig. 5] Fig. 5 is the figure that metal surface particles Deformation example is shown.
[Fig. 6] Fig. 6 is the figure that the other variation of metal surface particle is shown.
Symbol description
1 ... the metal surface particle
2 ... the insulation particulate
11 ... the jut of metal surface particle
21 ... the metal surface particle
22 ... the insulation particulate
23 ... plated film
23a ... jut
The preferred plan that carries out an invention
Below, enumerate embodiment the present invention is described in further detail, but the present invention is not subjected to the qualification of these embodiment.
(embodiment 1)
1. the manufacturing that has the metal surface particle of projection
(1) manufacturing of seed
4 mouthfuls of separated type flask lids are being installed, agitator, three-way cock, cooling water pipe, in the separated type flask of the volume 1000ml of temperature sensor, take by weighing the 70mmol methyl methacrylate, the 10mmol glycidyl methacrylate, the 20mmol Ethylene glycol dimethacrylate, 3mmol methacrylic acid phenyl diformazan sulfonium base methyl esters sulfate, 2 of 3mmol, behind two [N-(2-carboxyethyl)-2-methyl-propionic acid amidine] 4 hydrates of 2 '-azo and the 470mL distilled water, stir with 200rpm, 70 ℃ are carried out polymerization in 5 hours under nitrogen atmosphere, obtain having on the surface particle of epoxide group.Then, add 1 of 30mmol, the 2-ethylenediamine by carry out reaction in 1 hour under 70 ℃, is transformed to amino with epoxide group.After reaction finishes; carry out removing of unreacted monomer, polymerization initiator etc. by the centrifugation operation; after adding 400mL distilled water and disperseing by ultrasonic irradiation; add the 30mmol glycidyl methacrylate; by under 70 ℃, carrying out reaction in 1 hour, amino is transformed to the polymerism methacryl.After reaction finishes, carry out removing, cleaning of 2 unreacted reactants by the centrifugation operation, again by disperse, obtain average grain diameter to be that 305nm, CV value are 8.8% with distilled water, the solid constituent rate is 10% the sub-dispersion liquid of seed that has polymerism functional group on the surface.
In addition, the particle diameter of seed and distribution are used dynamic light scattering particle size to distribute and are counted the manufacturing of (Da Peng electronics society, DLS8000) measure.
(2) manufacturing of kind particle
In the separated type flask of the volume 1000ml that 4 mouthfuls of separated type flask lids, agitator, three-way cock, cooling water pipe, temperature sensor are installed, take by weighing 500mmol styrene, 85mmol n-octyl mercaptan, 2mmol potassium peroxydisulfate, 2.5mmol sodium chloride and 585mL distilled water, stir with 200rpm, 70 ℃ are carried out polymerization in 24 hours under nitrogen atmosphere.After reaction finishes, carry out removing, cleaning of 2 unreacted reactants by the centrifugation operation, again by disperse, obtain average grain diameter to be that 900nm, CV value are 3.2% with distilled water, the solid constituent rate is 10% kind particle dispersion.
(3) manufacturing of projection particle
In the separated type flask of the volume 500ml that 4 mouthfuls of separated type flask lids, agitator, three-way cock, cooling water pipe, temperature sensor are installed, after taking by weighing the kind particle dispersion and 90mL distilled water that 10g obtains, drip the sub-dispersion liquid of seed that 1g obtains while stirring, will plant particle and seed carry out compoundization.Then, add 3% aqueous solution of 0.05g NaLS, 20g polyvinyl alcohol, obtain compoundization of kind/seed liquid.
In addition, with homogenizer mixing 120g divinylbenzene, 3g benzoyl peroxide, 0.7g NaLS and 800mL distilled water and carry out emulsification, obtain the polymerizable monomer emulsion.
The polymerizable monomer emulsion that obtains is added in compoundization of the kind/seed liquid, stir, under stream of nitrogen gas, carried out 24 hours, polymerizable monomer is absorbed on the sub-complex of kind/seed, obtain the polymerism drop in room temperature with 100rpm.Then, mixing speed is adjusted to 200rpm after, by being heated to 70 ℃, make the polymerism polymerization of fluid drops, obtain the projection particle.
When using scanning electron microscope to observe, the average grain diameter of the part that does not have projection of the projection particle that obtains is that 4.01 μ m, CV value are 3%, average per 1 24 of bump count average out to (as projected area, being 13.5%).
(4) has the manufacturing of the metal surface particle of projection
The projection particle that obtains is carried out degreasing, photosensitive processing, activation processing (ア Network チ ベ イ チ Application グ), generate palladium nuclear, the catalyst core of covering as electroless plating at resin surface.Then, be immersed in the bath of electroless plating nickel, form nickel coating.In addition, carry out non-electrolysis immersion gold plating, obtain having the metal surface particle of projection on the surface of nickel dam.
When using scanning electron microscope to carry out observable projection electroconductive particle, implemented metal deposition at the particle surface that contains projection, in addition, the quantity of projection is average 24, does not reduce because of the plating operation causes the quantity of projection.
2. the making of insulation particulate
4 mouthfuls of separated type flask lids are being installed, agitator, three-way cock, cooling water pipe, in the separated type flask of the volume 1000ml of temperature sensor, take by weighing glycidyl methacrylate by 50mmol, the 50mmol methyl methacrylate, the 3mmol Ethylene glycol dimethacrylate, 1mmol methacrylic acid phenyl diformazan sulfonium base methyl esters sulfate, 2 of 2mmol, 2 '-azo two 2-[N-(2-carboxyethyl) amidino groups] propane] monomer composition that constitutes and adding in the entry, making the solid constituent rate is after the 5 weight %, stir with 200rpm, 70 ℃ are carried out polymerization in 24 hours under nitrogen atmosphere.After reaction finishes, carry out freeze drying, the average grain diameter that obtains having on the surface sulfonium base and epoxide group is that the CV value of 180nm, particle diameter is 7% insulating particle.
3. the manufacturing of coating conducting particle
The metal surface particle with insulation particulate projection that obtains is distributed in the distilled water, the aqueous dispersions of 10 weight % of the particulate that obtains insulating under ultrasonic irradiation.
The metal surface particle with projection that 10g is obtained is distributed in the 500mL distilled water, adds the aqueous dispersions of 4g insulation particulate, at room temperature stirs 6 hours.After the reticular filter filtration with 3 μ m, use methanol cleaning again, drying obtains the coating conducting particle.
When observing, in the coating conducting particle that obtains, only form 1 layer of coating layer that coats by the insulation particulate on the surface of metal surface particle with scanning electron microscopy (SEM) with projection.With respect to from the coating area (that is, the projected area of the particle diameter of insulation particulate) of the insulation particulate of the area of the center 2.5 μ m of coating conducting particle the time, clad ratio is 30% by image analysis calculation.In addition, by observing with the section of TEM (TEM), the combination interface of insulation particulate and metal surface particle is 12% of the circumference of insulation particulate, therefore, is 12% of the surface area of insulation particulate with the interface bonded area of metal surface particle.
The coating conducting particle that obtains is distributed in the tert-butyl alcohol, weighing so that on the silicon chip of 10 * 10mm dried coated with conductive particulate weight be 0.00004g (about 240,000), after the drying, cover the silicon chip of 10 * 10mm, depress in adding of 100N, heated 30 seconds down at 200 ℃.Then, peel silicon chip, when observing the state of insulation particulate of coating conducting particle surface by SEM, extrude the insulation particulate of fusion, expose the projection of metal surface particle.
(embodiment 2)
1. the manufacturing of insulation particulate
4 mouthfuls of separated type flask lids are being installed, agitator, three-way cock, cooling water pipe, in the separated type flask of the volume 1000ml of temperature sensor, take by weighing glycidyl methacrylate by 50mmol, the 50mmol methyl methacrylate, the 3mmol Ethylene glycol dimethacrylate, 1mmol methacrylic acid phenyl diformazan sulfonium base methyl esters sulfate, 2 of 2mmol, 2 '-azo two 2-[N-(2-carboxyethyl) amidino groups] propane] monomer composition that constitutes and adding in the entry, making the solid constituent rate is 5 weight %, stir with 200rpm, 70 ℃ are carried out polymerization in 24 hours under nitrogen atmosphere.After reaction finishes, carry out freeze drying, the average grain diameter that obtains having on the surface sulfonium base and epoxide group is that the CV value of 180nm, particle diameter is 7% insulating particle.
2. the manufacturing of metal surface particle
(1) has the manufacturing of the metal surface particle of projection
In average grain diameter is in the core particle that contains tetramethylol methane tetraacrylate/divinylbenzene of 5 μ m, comprises alkali degreasing, acid neutralization, at SnCl
2Photosensitive processing in the solution, at PdCl
2The electroless plating of the activation processing in the solution (ア Network チ ベ イ チ Application グ) covers pretreatment procedure.In addition, so-called above-mentioned photosensitive processing is the surface adsorption Sn at megohmite insulant
2+The operation of ion, so-called activation processing (ア Network チ ベ イ チ Application グ) is to take place on the megohmite insulant surface
Reaction, and the operation of the catalyst core that Pd is covered as electroless plating.
Set up plating bath with having implemented the core particle method according to the rules that electroless plating covers pretreatment procedure, and be immersed in the electroless plating of heating and cover and carry out electroless plating in the bath and cover.Cover bath as electroless plating, use non-electrolytic nickel to bathe and carry out nickel plating.Here, form in the operation of Pd, when activation processing (ア Network チ ベ イ チ Application グ), in system, add the PdCl of some amounts on the core particle surface
2, Pd heterogeneity ground is adhered to from the teeth outwards, under ultrasonic wave 45Hz irradiation, carry out nickel plating, form nickel coating with projection.
Then, gold-plated by the displacement plating method again in surface enforcement, the metal surface particle that obtains having projection.
The nickel plating thickness of the metal surface particle that obtains is 90nm, and gold-plated thickness is 30nm.In addition, when observing by scanning electron microscopy (SEM), the height of projection be the metal surface particle diameter 10%.
(2) has the manufacturing of the metal surface particle of reactive functional groups
Then, in the separated type flask of the volume 2000ml that 4 mouthfuls of separated type flask lids, agitator, three-way cock are installed, the 2-aminoothyl mercaptan of 20mmol is dissolved in the 1000mL methyl alcohol, preparation feedback solution, the metal surface particle that 20g is obtained is distributed in the reaction solution under nitrogen atmosphere gas, at room temperature stirred 3 hours, by removing by filter unreacted 2-aminoothyl mercaptan, behind methanol cleaning, drying obtains having on the surface metal surface particle as the amino of reactive functional groups.
3. the manufacturing of coating conducting particle
Insulating particle is distributed in the acetone under ultrasonic irradiation, obtains the acetone soln of 10 weight % of insulating particle.
10g metal surface particle is distributed in the 500mL acetone, adds the acetone dispersion liquor of 4g insulating particle, at room temperature stirred 6 hours.After the reticular filter filtration with 3 μ m, use methanol cleaning again, drying obtains the coating conducting particle.
When observing, the coating conducting particle only forms 1 layer of coating layer that is coated by the insulation particulate on the surface of metal surface particle with scanning electron microscopy (SEM).With respect to from the coating area (that is, the projected area of the particle diameter of insulation particulate) of the insulation particulate of the area of the center 2.5 μ m of coating conducting particle the time, clad ratio is 40% by image analysis calculation.
The coating conducting particle that obtains is distributed in the tert-butyl alcohol, weighing so that on the silicon chip of 10 * 10mm the little sub-weight of dried coating conducting be 0.00004g (about 240,000), after the drying, cover the silicon chip of 10 * 10mm, depress in adding of 100N, after heating 30 seconds under 200 ℃, peel silicon chip, when observing the state of insulation particulate on coating particles surface by SEM, because the insulating particle distortion, expose the metal surface of metal surface particle, also is out of shape attached to the insulating particle of silicon chip one side.
These the results are shown in table 1.
4. the manufacturing of anisotropic conductive material
(1) manufacturing of anisotropic conductive film
Use planetary stirring machine to make the epoxy resin as adhesive resin (oiling シ エ Le エ Port キ シ society makes: " エ ピ コ one ト 828 ") of 100 weight portions and three (dimethylaminoethyl) phenol, toluene 100 weight portions dispersing and mixing fully, on the film of the demoulding, be coated with certain thickness, so that dried thickness is 10 μ m, evaporate toluene, do not contained the adhesiveness film of coating conducting particle.
In addition, in the epoxy resin as adhesive resin of 100 weight portions (oiling シ エ Le エ Port キ シ society makes: " エ ピ コ one ト 828 ") and three (dimethylaminoethyl) phenol, toluene 100 weight portions, add the coating conducting particle, use planetary stirring machine dispersing and mixing fully, after obtaining the adhesive resin dispersion, on the film of the demoulding, be coated with certain thickness, so that dried thickness is 7 μ m, evaporate toluene, obtain containing the adhesion film of coating conducting particle.In addition, to be set at the content that makes in the anisotropic conductive film be 200,000/cm to the addition of coating conducting particle
2
By on the adhesion film that contains the coating conducting particle that obtains at normal temperatures lamination do not contain the adhesion film of coating conducting particle, the anisotropic conductive film that to obtain having 2 layers of thickness of structure be 17 μ m.
In addition, the part that will contain the adhesive resin dispersion of coating conducting particle is cleaned with toluene, take out the coating conducting particle after, when observing, do not find that insulating particle peels off from the coating conducting particle by SEM.
(2) evaluation of connection status (insulating properties, resistance value)
The anisotropic conductive film that use obtains is clipped between the flexible print wiring board of the connection Wiring pattern with 200 * 200 μ m, with the state estimating insulating properties and the resistance value of hot pressing.
(3) evaluation of adaptation
The sample that uses in the evaluation with connection status is again after 55 ℃ * 6 hours～120 ℃ * 6 hours circulation is placed 300 hours down, observe section with SEM, observe between the particle-insulating particle of metal surface, the having or not of the interface peel between insulating particle-adhesive resin.
The results are shown in table 1.
(comparative example 1)
Have the making of the metal surface particle of projection similarly to Example 2, but do not carry out the importing of reactive functional groups, the coating by insulating particle.In addition, except in the making of anisotropic conductive material, use metal surface particle to replace carrying out similarly to Example 2 beyond the coating conducting particle with the projection that is not insulated the particle coating.
These the results are shown in table 1.
(comparative example 2)
The making of insulating particle is carried out similarly to Example 2.
When the manufacturing of metal surface particle, except the surface at core particle forms in the operation of Pd, with ultrasonic irradiation and stirring Pd is adhered to, adhere to Pd on uniform surface ground, and under ultrasonic wave 28Hz irradiation, carry out nickel plating, form beyond the nickel coating of smooth surface, obtain the metal surface particle similarly to Example 2.The thickness of the nickel coating of the metal surface particle that obtains is 90nm, and the thickness of gold plate is 30nm.
In addition, by scanning electron microscopy (SEM) when observing, for there not being the metal surface particle of projection.
Have the manufacturing of the metal surface particle of reactive functional groups, the manufacturing of coating conducting particle, the manufacturing of anisotropic conductive material, except using the metal surface particle do not have projection to replace having the metal surface particle of projection respectively, carry out similarly to Example 2.
These the results are shown in table 1.
[table 1]
| | Embodiment 2 | Comparative example 1 | Comparative example 2 | ||
| Height (%) with respect to the diameter of metal surface particle | 7.5 | 10 | 10 | - | |
| Clad ratio (%) by insulating particle | 30 | 40 | - | 40 | |
| Coated state by insulating particle | Individual layer | Individual layer | - | Individual layer | |
| The state of the insulating particle during hot pressing | Distortion | Distortion | - | Distortion | |
| Peeling off of insulating particle when adhesive resin disperses | Do not have | Do not have | - | Do not have | |
| The evaluation of connection status | Interparticle insulating properties | Well | Well | Between electrode, leak | Well |
| Resistance value (m Ω) | 100 | 100 | - | 210 | |
| The evaluation of adaptation | Between the particle-insulating particle of metal surface | Peel off at no interface | Peel off at no interface | - | Peel off at no interface |
| Between insulating particle-binder particles | Peel off at no interface | Peel off at no interface | - | Peel off at no interface | |
Industrial applicibility
According to the present invention, can provide the coating conducting particle that connects the reliability excellence, each is different to conductive material and conduction connecting structure body.
Claims (6)
1. coating conducting particle, it is the coating conducting particle of surface coated insulation particulate that comprises the particle with the surface that is made of conductive metal and will have the particle on the surface that the metal by above-mentioned conductivity constitutes, it is characterized in that the particle with the surface that is made of above-mentioned conductive metal has a plurality of projections on the surface.
2. according to the coating conducting particle of claim 1 record, it is characterized in that, the functional group (A) of insulation particulate by conductive metal being had bonding forms the coating layer of individual layer by chemical bonding on the particle with the surface that is made of conductive metal.
3. according to the coating conducting particles of claim 1 or 2 records, it is characterized in that the particle with the surface that is made of conductive metal comprises: core particle that constitutes by resin and the conductive metal layer that forms on the surface of above-mentioned core particle.
According to claim 1,2 or 3 the record the coating conducting particles, it is characterized in that, the following 0.05 μ m that is limited to of the height of projection, be limited on the height of projection the particle with the surface that constitutes by conductive metal diameter 40%.
5. an anisotropic conductive material is characterized in that, this material is that the coating conducting particles with claim 1,2,3 or 4 records are dispersed in the insulating properties adhesive resin and form.
6. a conduction connecting structure body is characterized in that, it is to connect electronic unit by the anisotropic conductive material conduction that the coating conducting particle of claim 1,2,3 or 4 records or claim 5 are put down in writing to form.
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| JP2003271540 | 2003-07-07 | ||
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| JP413653/2003 | 2003-12-11 |
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| CN100437838C CN100437838C (en) | 2008-11-26 |
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