CN102136314B - Preparation method of composite microspheres, anisotropy conducting material and anisotropy conducting film - Google Patents
Preparation method of composite microspheres, anisotropy conducting material and anisotropy conducting film Download PDFInfo
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- CN102136314B CN102136314B CN2010105750379A CN201010575037A CN102136314B CN 102136314 B CN102136314 B CN 102136314B CN 2010105750379 A CN2010105750379 A CN 2010105750379A CN 201010575037 A CN201010575037 A CN 201010575037A CN 102136314 B CN102136314 B CN 102136314B
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- complex microsphere
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- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical compound CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZARXZEARBRXKMO-UHFFFAOYSA-N n,n-bis(ethenyl)aniline Chemical compound C=CN(C=C)C1=CC=CC=C1 ZARXZEARBRXKMO-UHFFFAOYSA-N 0.000 description 1
- KLDBIKVBMQMTGH-UHFFFAOYSA-N n,n-bis(ethenyl)prop-2-enamide Chemical compound C=CN(C=C)C(=O)C=C KLDBIKVBMQMTGH-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a preparation method of composite microspheres, an anisotropy conducting material and an anisotropy conducting film, comprising the following steps: a macromolecular polymer core and at least one layer of metal conducting layer are prepared; at least one function part is arranged between the core and the metal conducting layer, wherein the function part is composed of a macromolecular polymer and is provided with a functional group; according to the function part, the metal conducting layer formed on microspheres and the microspheres tightly contact, have the advantages of stronger adhesive force and longer service life, are more reliable and can satisfy the higher application requirements, and the phenomena of breaking, wrinkling, stripping and the like can be almost avoided. Meanwhile, in the field of the electric connection of microelectrodes, the composite microspheres disclosed by the invention can solve the problem that the metal conducting layer of the composite microspheres has big possibility of breaking, wrinkling, stripping and the like, and also can better solve the problem of bad contact because of uneven hot pressing of microelectrodes.
Description
Technical field
The present invention relates to the preparation method of electronic product, be specifically related to a kind of complex microsphere and adopt the anisotropic conductive material of this complex microsphere and the preparation method of anisotropic conductive film.
Background technology
The electrical connection field extensive use of anisotropic conductive material between the microelectrode of electronic equipment, it mainly is made up of insulating resin binding agent and the complex microsphere that is dispersed in the described insulating resin binding agent, and the performance of complex microsphere is most important; Complex microsphere generally is made up of the kernel and the conducting metal shell of insulation, and is initial, though kernel hardness is high; But contact badly with metal shell, the metal shell pressurized has been prone to fold, produces and breaks and come off; Particularly in the hot pressing processing technology of carrying out the microelectrode electrical connection, cause the loose contact of part microelectrode, promptly a part of microelectrode to be electrically connected easily through conductive micro-balloons because hot pressing is uneven; Part microelectrode does not touch conductive micro-balloons because hot pressing is uneven, makes to connect and loses efficacy, in order to solve the uneven problem of hot pressing; Propose soft nuclear or between stone and metal shell, set up soft formation; When hot pressing is uneven, the place that pressure is big, conductive micro-balloons deforms compression and makes the little zone of pressure also can make microelectrode pass through the conductive micro-balloons electrical connection.
Japan 08-193186 discloses a kind of conductive particle that is used for the anisotropic conductive adhesive.Anisotropy conductiving glue includes the insulated particle that wraps up conductive metal layer.Each particle is all by the hard nuclear and the soft formation of parcel.Soft formation is a material softer than nuclear, and fully distortion connects transparent indium-tin-oxide (ITO) electrode under hot pressing.In order to remedy the imbalance under any a plurality of electrode hot pressing, soft layer is thick.
Japan 11-209714 has introduced conductive particle and has been dispersed in the dielectric adhesive, forms the anisotropy conductiving glue stick.This type particle is made up of acrylic resin.Each particle has a flexible nuclear and ratio to examine hard shell and is plated in top metal level.Yet nuclear is soft flexible, and the proportion of shell/nuclear is limited in 1/20 to 2/1.
Japan 2000-315425 discloses a kind of conductive particle that contains graft polymer layer.The polymeric layer that at first is grafted on the resin particle is to come off from resin for the metal level that stops parcel produces to break or produce wrinkle.Metal level is wrapped on the polymer layer of grafting then.
Japan 2002-033022 has introduced electroconductive resin particle and the anisotropic conductive adhesive with sandwich construction.This binding agent contains soft conductive particle and can be used for the destruction that low-pressure keeps connection stability to prevent transparency electrode.In order to satisfy above-mentioned requirement, the internal layer of conductive particle is softer than the metal level of outside.
The nuclear that Japan 2002-302506 discloses a kind of conductive particle has the preparation method of reducing agent.Reducing agent and oxidant react produce free radical stimulate polymerization reaction on nuclear, form polymeric layer.Polymeric layer account for whole particle weight 5 to 70%.But whole particle be soft because of its vitrification point at 0 ℃ or be lower than under the rubbery state temperature commonly used of particle.
But the distortion of thicker soft formation also cause easily metal shell distortion, fold, break and peel off, the useful life and the reliability of product all descend; In addition; The tightness of plating shell and adhesion property are relatively poor on kernel or soft formation, also cause product quality can not satisfy higher application requirements, have subsequently invention propose by resin kernel, conductive metal layer and be located at conductive metal layer and the resin kernel between polymeric layer; This scheme has obtained certain beneficial effect to the solution of foregoing problems; Make the quality of product obtain certain raising, but the diameter of resin kernel is not easy to do evenly, in addition; Though the tightness of plating shell and adhesion property obtain certain raising on the polymeric layer, still can not satisfy higher application requirements.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind ofly can overcome the hot pressing inequality, can obtain the preparation method of the conduction complex microsphere of good each item performance index again.
Another object of the present invention provides a kind of preparation method who adopts the anisotropic conductive material of this conduction complex microsphere.
Another purpose of the present invention provides a kind of preparation method of anisotropic conductive film, and this anisotropic conductive film contains can overcome the hot pressing inequality, can obtain the conduction complex microsphere of good each item performance index again.
For achieving the above object; Technical scheme of the present invention is: a kind of preparation method of complex microsphere; It is outside with at least one functionalized polymer that said complex microsphere contains a polymer kernel; And have that one deck metal conducting layer is at the outermost layer of said complex microsphere at least, its preparation method may further comprise the steps:
(1), prepares the polymer microballoon that is predetermined composition and sphere diameter, promptly said polymer kernel;
(2), carry out the reaction of outer polymerization single polymerization monomer, it is outside to form at least one polymer with said polymer microballoon;
(3), have outside polymer microballoon of at least one polymer and active agent reaction, the systematic function group and in said polymer microballoon outside with said;
(4), the polymer microballoon that contains functional group is contacted with chemical reagent, in its environment, form layer of metal conductive layer at least at said polymer microballoon outermost layer.
Preferably, said polymer microballoon is carried out in the outer polymerization single polymerization monomer reaction, make said polymer comprise that one or more contain (methyl) acrylate monomer of at least one unsaturated linkage outside the composition in step (2).
Preferably; Said polymer microballoon is carried out in the outer polymerization single polymerization monomer reaction in step (2); Make said polymer comprise that also one or more contain the aromatic monomer of at least one unsaturated linkage outside the composition, and said aromatic monomer can with said (methyl) acrylate monomer polymerization that contains at least one unsaturated linkage.
Preferably, the said functional group that generates in the step (3) comprises a kind of in hydroxyl, carboxyl, amino, sulfydryl and the triphenylphosphinyl or several.
Preferably, the said functional group that generates in the step (3) is oxygen carbonyl alkane carboxyl and adjacent hydroxyl.
Preferably, the said functional group that generates in the step (3) is mercapto alkane sulfydryl and adjacent hydroxyl.
Preferably, the said functional group that generates in the step (3) is aminoalkylamino and adjacent hydroxyl.
A kind of preparation method of anisotropic conductive material is dispersed in the described complex microsphere of claim 1 in the insulating resin binding agent and processes.
A kind of preparation method of anisotropic conductive film processes film with the described a kind of anisotropic conductive material of claim 8.
Said complex microsphere comprises high molecular polymer kernel and one deck metal conducting layer at least, also is provided with at least one funtion part between said kernel and the metal conducting layer, and said funtion part is made up of high molecular polymer and is had a functional group.
Above-mentioned polymer microballoon is to prepare through 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 reaction is to prepare polymer at the microballoon skin through polymerization reaction; Polymerization reaction comprises emulsion polymerisation, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersin polymerization and suspension polymerisation.
The polymerization reaction suitable monomers is said as the entire chapter explanation, and one or more contain the monomer of at least one unsaturated linkage.Suitable monomers possibly include two, three, four or more unsaturated linkages.As contain (methyl) esters of acrylic acid of unsaturated linkage, be not limited only to (C2-C18) alkane chain diol two (methyl) acrylic acid ester.Especially preferably multi-functional (methyl) acrylate monomer is (C2-C10) alkane chain diol two (methyl) acrylic acid ester, further preferred (C2-C8) alkane chain diol two (methyl) acrylic acid ester.Suitable (C2-C18) alkane chain diol two (methyl) acrylic acid ester includes but not limited to 1,2-ethylene glycol bisthioglycolate (methyl) acrylic acid ester, 1,3-butanediol two (methyl) acrylic acid ester; 1,4-butanediol two (methyl) acrylic acid ester, 1; 5-pentanediol two (methyl) acrylic acid ester, 1,6-hexylene glycol two (methyl) acrylic acid ester; 1,8-ethohexadiol two (methyl) acrylic acid ester and 1,10-decanediol two (methyl) acrylic acid ester.
Suitable aromatic monomer contains at least one unsaturated linkage, and can with (methyl) acrylate monomer polymerization that contains at least one unsaturated linkage.Suitable aromatic monomer is not limited only to styrene, p-chloromethyl styrene, divinylbenzene, divinyl naphthalene, diallyl phthalate, N, N-divinyl aniline.Said as the disclosed patent of entire chapter, various polymerisable aromatic monomers within the scope of the present invention.
Other the band functional group monomer optional can with the monomer of (methyl) acrylic acid ester and aromatic monomer copolymerization.Suitable band functional group monomer includes but not limited to the dialkylene thioether, divinyl inkstone, divinyl acrylamide, triallyl (different) cyanurate; Divinyl fourth diether, divinyl ether, diallyl maleate, pi-allyl acryloxy propionic ester; 2,2 '-two (4-(methyl) acrylic acid propoxyl group phenyl) propane, 2,2 '-two (4-(methyl) acrylic acid diethoxy phenyl) propane; 1,2,4-benzenetricarboxylic acid triallyl.
Other particular monomers that are 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; The methacrylic acid hydroxyethyl ester, metering system dodecyl gallate, vinyl acetate, vinyl chloride; Butadiene, isoprene, diallyl phthalate, methacrylyl MTMS; Methacryloxypropyl trimethoxy silane, PAG methyl acrylate, 2-bromoethyl acrylic acid ester, 2-ethyl cyanic acid 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; The acetoacetate methacrylic acid glycol ester, acrylic acid ester 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) acrylic acid ester; Trimethylolpropane tris (methyl) acrylic acid ester, pentaerythrite four (methyl) acrylic acid ester, dipentaerythritol five (methyl) acrylic acid ester etc., and above mixture.
Functionalization is said as the entire chapter explanation; Be meant with using chemical reagent to introduce the functionalization group through chemical reaction; Used chemical reagent comprise any can with at the outside polymer reaction of microballoon; Introduce the reagent of functionalization group, the functional group of introducing is such as fluorine, chlorine, bromine, iodine, amino, hydroxyl, sulfydryl, carboxyl, carboxylate or epoxy radicals, or the combination of any above group.The chemical reagent that is suitable for for example but is not limited to bischlormethyl ether, dihydroxymethyl amine, ethylenediamine, hexamethylene diamine-[1,6], tetramino methane, polyvinylamine, ammoniacal liquor, polyethylene glycol oxide and derivative thereof.The functionalization group comprises single; Two; And a plurality of groups or repeat to occur or depend on the part of long-chain or short chain, like ethyoxyl in the oligomer or PEO, amino in the oligomer or polyvinylamine; Hydroxyl in the oligomer or polyvinyl alcohol, the vinyl mercapto of sulfydryl in the oligomer or polymerization etc.Polyvinyl based on, but be not limited to polystyrene, polyacrylate, and the derivative that comprises the functionalization group that can be connected to the polymer microballoon surface through atomic migration initiated polymerization or redox reaction.The atomic migration initiated polymerization has at United States Patent (USP) 6071980 to be described in detail and relevant references.Redox causes the polymerization be meant monomer to be by oxidising agent and to go back that the transfer of electronics causes such process between the original reagent.At Journal of Applied Polymer Science, Volume42, Issue 11, pages 2885-2891,1991. have reported the example of cerium ion as redox initiator.For the atomic migration initiated polymerization, have nanometer and before the polymer microballoon polymerization of micrometer structure, possibly contain the halogen atom group.For the redox initiate polymerization reaction, have nanometer and before the polymer microballoon polymerization of micrometer structure, possibly contain, but be not limited to hydroxyl, mercapto, aldehyde radical, sulfhydryl, amino etc.Before the polymerization, redox reaction maybe be by water, and cause on the polymer microballoon surface of monomer phase or functionalization.
Nuclear diameter is 0.01 μ m-1000 μ m in the prepared polymer, and the diameter that adds after the above funtion part is 0.01 μ m-1000 μ m.But be not limited to above-mentioned size, according to actual needs, this size can be less than 0.01um or greater than 1000um.
This piece of writing discloses described conducting metal, does not have special restriction, and suitable conducting metal includes but not limited to gold, silver, platinum, palladium, copper, iron, nickel, titanium, zinc, tin, aluminium, lead, cobalt, indium, cadmium, chromium, germanium, antimony, bismuth etc.; Also has alloy such as nickel and phosphorus, silver and tin, copper and tin, lead and tin, the alloy that silver and plumbous and tin etc. are made up of two kinds or multiple metal.
Preferably, gold, silver, platinum, copper, nickel etc.
Above-mentioned conducting metal generally can be implemented through following gold-plated method.At first, can use the solution that contains acid to carry out surface etching or be called alligatoring the polymer microballoon that cleaned, thereby on polymer microballoon, form fulcrum.Can the polymer microballoon after surface treatment or alligatoring be immersed in the solution of stannous chloride and palladium bichloride then, make the microsphere surface activation.So can on microballoon, form the fine nucleus of palladium catalyst.Subsequently, can use time phosphatization acid sodium, boron sodium chloride, dimethyl amine borate, hydrazine etc. carry out reduction reaction, thereby on microballoon, form uniform palladium nucleus.Then, the blapharoplast that obtains is dispersed in the plating bath, can uses sodium hypophosphite to make the nickel salt reduction; On microballoon, form nickel coating; Then, in certain embodiments, can the microballoon that be coated with nickel be added in enough gold plating solutions; Change the reaction of plating or chemical gilding, thereby form Gold plated Layer at the outermost layer of microballoon.
The mentioned a kind of anisotropic conductive material of the present invention comprises the insulating resin binding agent and is dispersed in the complex microsphere as claimed in claim 1 in the described insulating resin binding agent.Said complex microsphere comprises high molecular polymer kernel and one deck metal conducting layer at least, also is provided with at least one funtion part between said kernel and the metal conducting layer, and said funtion part is made up of high molecular polymer and is had a functional group.
Resin in the present technique scheme insulating resin binding agent; Not special the qualification; Can be one or both and the two or more mixing in the known resin, for example vinylacetate be vinylites such as resin, vinyl chloride-based resin, acrylic resin, phenylethylene resin series; Thermoplastic resins such as polyolefin-based resins, ethene one vinyl acetate resin copolymer, polyamide-based resin; Epoxy is that resin, polyurethane series resin, polyimides are that resin, unsaturated polyester (UP) are the curable resin that resin and they and its curing agent constitute; Styrene-butadiene one styrene block copolymer; Styrene one isoprene one styrene block copolymer, their thermoplastic block copolymers such as hydride; Elastic type such as styrene-butadiene copolymer rubber, chloroprene rubber, the fine styrene block copolymer rubber of propylene etc.The curing mode of curable resin comprises hot curing, photocuring, normal temperature cure etc.One or more other additive such as organic solvent, oxidation inhibitor, the Re Wending agent, the light temperature is decided agent etc. and also can and be used as required.
Content of the present invention said (methyl) acrylic acid ester comprises methacrylate and acrylic acid ester and their derivative; One micron is that μ m equals micrometre, and a nanometer is that nm equals part per billion meter.
Need to prove that also the term that uses among this paper " comprises " clear and definite descriptive nature, number, step, operation, or composition, but do not get rid of one or more character, number, step, operation, the existence or the increase of composition and/or their combination.
Adopt the beneficial effect of present technique scheme to be: to the invention provides a kind of concrete novel structure and application thereof of complex microsphere; Also be provided with at least one funtion part between the kernel of this complex microsphere and the metal conducting layer, said funtion part is made up of high molecular polymer and is had functional group, and this functional group makes and on the funtion part that high molecular polymer constitutes, plates conductive metal layer; Can make conductive metal layer tightr; Adhesive force is stronger, difficultly breaks, fold, phenomenon such as peels off, longer service life; More reliable, can satisfy higher application requirements.
Simultaneously be electrically connected the field at microelectrode, adopt complex microsphere of the present invention, the metal conducting layer that has both solved complex microsphere is prone to break, fold, problem such as peel off, the also reasonable problem that has solved the loose contact that microelectrode causes because of the hot pressing inequality.The anisotropic conductive material, the anisotropic conductive film that adopt complex microsphere of the present invention to produce; Has each item technical indicator that is superior to existing product; In the microelectrode application; Adopt complex microsphere of the present invention or contain other products of complex microsphere of the present invention, can solve the problem that loose contact that the hot pressing inequality brings and complex microsphere are easy to lose efficacy.
Embodiment
Illustrate in greater detail the present invention through embodiment below.But scope of the present invention is not limited to these embodiment.
Embodiment 1,
Preparing 6.7 μ m basis material microballoons is the polymer kernel of complex microsphere: the polystyrene seed aqueous suspension of getting 13.1g26.0% particle diameter 2.1 μ m; The 450g deionized water; 0.23g the 10% sodium dodecyl benzenylsulfonate aqueous solution joins in the 2000mL four-hole round-bottomed flask; Feed nitrogen, be heated to 60 ℃ after the stirring.Get the 18.8g divinylbenzene, 123.8g 1,6-hexanediyl ester 7.5g allyl methacrylate, and the 10.7g 10% sodium dodecyl benzenylsulfonate aqueous solution, the 165g deionized water mixes the back and stirs with the homogeneous mixer, adds in the four-hole round-bottomed flask.Stir after 2 hours, cool to 40 ℃, add 0.2g 30% hydrogen peroxide solution.Get the 1.1g TBHP, the 0.3g 10% sodium dodecyl benzenylsulfonate aqueous solution, the 65g deionized water mixes with the homogeneous mixer and stirs, and adds in the four-hole round-bottomed flask, adds the 56.3g 20% polyvinylpyrrolidone aqueous solution again, the 25g deionized water.After 45 minutes, be heated to 60 ℃ 40 ℃ of stirrings.After 30 minutes, be heated to 65 ℃ 60 ℃ of stirrings.After 15 minutes, be heated to 70 ℃ 65 ℃ of stirrings.After exothermic reaction, be heated to 90 ℃, continue to stir after 45 minutes, cooling flask to 25 ℃ filters to isolate the basis material microballoon, i.e. the polymer kernel of complex microsphere, particle diameter 6.7 μ m.
Embodiment 2,
Synthetic polymer is outside at embodiment 1 microballoon, and promptly generate the polymer outside: get 400.0g15.4% and remove short grained embodiment 1 microsphere suspension liquid, the 150g deionized water is added in the 2000mL four-hole round-bottomed flask, feeds nitrogen, is stirred and heated to 70 ℃.Get the 0.08g rongalite, the 0.36g 10% sodium dodecyl benzenylsulfonate aqueous solution is sneaked into the 25.6g deionized water and is become homogeneous solution, adds the 13.0g homogeneous solution and goes into round-bottomed flask.Get the 0.11g TBHP, sneak into the 12.9g deionized water and become homogeneous solution.Get the 2.8g methyl methacrylate, the 11.5g GMA, 0.03g 1, and the 6-hexanediyl ester is mixed into even monomer solution.Added each 1.0g of above-mentioned two aqueous solution in per 15 minutes, the per 15 minutes simultaneously above-mentioned monomer solutions of adding 1.3g.After the aqueous solution adds, continue to stir 60 minutes, cooling flask to 25 ℃ filters to isolate the microballoon of cladding material.
Embodiment 3,
Functionalization embodiment 2 microballoons: get 100.0g embodiment 2 microsphere suspension liquids, the 200mL absolute ethyl alcohol is added in the 500mL round-bottomed flask, and magnetic agitation is disperseed, and gets the 50mL ethylenediamine again, joins round-bottomed flask.Being heated to 80 ℃ kept 12 hours.Cooling flask to 25 ℃, isolated by filtration obtains the microballoon of functionalization, promptly on kernel, forms funtion part, and said funtion part is made up of high molecular polymer and is had a functional group.
Embodiment 4,
Activation embodiment 3 microballoons: the microballoon that obtains after 1g embodiment 3 functionalization is joined in the aqueous solution of 20mL, Yi Bian ultrasonic, Yi Bian stirred 30 minutes, microballoon is fully disperseed.20mL joins in these slurries with the stannous chloride aqueous solution.The concentration of the aqueous solution of this stannous chloride is 20g/L, is heated to 40 ℃, stirs 10 minutes.Make tin ion be adsorbed onto microsphere surface and accomplish the sensitization processing.And then filtering solution, with the aqueous hydrochloric acid solution cleaning of 0.01M.And then disperse with the aqueous hydrochloric acid solution of the 0.01M of 20mL, add the palladium bichloride of the 1.5g/L of 20mL then, be heated to 60 ℃, stirred 10 minutes, carry out the activation processing of microsphere surface seizure palladium ion.And then filtering solution, use the washed with de-ionized water microballoon, again microballoon is distributed in the aqueous solution of 20mL, on one side ultrasonic, stir this slurries on one side, add the sodium hypophosphite of the 10g/L of 10mL simultaneously, keep 10min, accomplish the reduction of residue palladium ion.
Embodiment 5,
Form metal and overlay on embodiment 4 microballoons: the microballoon that obtains after embodiment 4 activation is joined in the sodium citrate aqueous solution of the 100mL that contains 0.1M; NaOH with 0.1M after ultrasonic 30 minutes is adjusted pH value to 9; Be heated to 40 ℃ while stirring, mixing speed is 150rpm.Then nickel ion being contained liquid and reducing agent contains this liquid of liquid and joins in the slurry with the speed of 1mL/min respectively.After the adding of two kinds of liquid, keep a stirring and maintain the temperature at 40 ℃, till no longer producing bubble.The prescription that nickel ion contains liquid is the nickelous sulfate of 0.57M, the natrium citricum of 0.1M.The prescription that reducing agent contains liquid is sodium hypophosphite 1.40M, 2M NaOH.Thus, the microballoon that obtains with nickel-phosphor alloy coating.Implement gold-platedly then with displacement method on the surface, obtain gold-plated complex microsphere.
Embodiment 6,
Preparing 4.3 μ m basis material microballoons is the kernel of complex microsphere: adopt the same method of embodiment 1, increase the polystyrene seed consumption, obtain the basis material ball of particle diameter 4.3 μ m.
Embodiment 7,
Synthetic polymer is outside at embodiment 6 microballoons: get the microsphere suspension liquid of removing short grained embodiment 6 preparations, adopt embodiment 2 same methods to obtain the microballoon of cladding material.
Embodiment 8,
Functionalization embodiment 7 microballoons: have the microballoon of cladding material to adopt the method for embodiment 3 to carry out functionalization 100g embodiment 7 preparations; Obtain the microballoon of functionalization; Promptly on the kernel microballoon, form funtion part, said funtion part is made up of high molecular polymer and is had a functional group.
Embodiment 9,
Activation embodiment 8 microballoons: the microballoon that the method for reusing embodiment 4 obtains after to embodiment 8 functionalization use stannous chloride, palladium bichloride, sodium hypophosphite processing carrying out activation then.
Embodiment 10,
Form metal and overlay on embodiment 9 microballoons: the microballoon that the method for last repeated using embodiment 5 obtains after to embodiment 9 activation carries out plating, obtains having the microballoon of nickel-phosphor alloy coating.Implement gold-platedly then with displacement method on the surface, obtain gold-plated complex microsphere.
Embodiment 11,
Prepare 6.0 μ m polydivinylbenezene microballoons: adopt the same method of embodiment 1, monomer is changed to the divinyl benzo reduces the polystyrene seed consumption, obtain the polydivinylbenezene microballoon of particle diameter 6.0 μ m.
Embodiment 12,
Alligatoring embodiment 11 microballoons use chromium trioxide and sulfuric acid: the etching liquid 100ML that the chromium trioxide of preparation 0.5M and the sulfuric acid of 7.2M constitute; The polydivinylbenezene microballoon that adds 10g embodiment 11 particle diameters 6.0 μ m; Ultrasonic dispersion is 30 minutes under the normal temperature, is warmed up to 60 ℃ again and keeps 30 minutes.Repeat then to filter, wash, obtain microballoon through etching processing.
Embodiment 13,
Activation embodiment 12 microballoons: the microballoon that the method for then reusing embodiment 4 obtains after to embodiment 12 alligatoring is operated equally, obtains the polydivinylbenezene microballoon of activation.
Embodiment 14,
Form metal and overlay on embodiment 13 microballoons: the microballoon that the method for plating metal of repeated using embodiment 5 obtains after to embodiment 13 activation is operated equally, obtains gold-plated microballoon.
Embodiment 15,
Alligatoring embodiment 11 polydivinylbenezene microballoons use the concentrated sulfuric acid: get 98% the concentrated sulfuric acid of 100mL, add the microballoon of 10g embodiment 11 particle diameters 6.0 μ m, be warmed up to 80 ℃ after, kept 30 minutes.Then, the concentrated sulfuric acid that will contain microballoon joins in the frozen water of 3 times of volumes, filters, washs, and obtains the polymer microballoon of sulfonic acid surfactantization.
Embodiment 16,
Activation embodiment 15 microballoons: the microballoon that the method for then reusing embodiment 4 obtains after to embodiment 15 alligatoring is operated equally, obtains the polydivinylbenezene microballoon of activation.
Embodiment 17,
Form metal and overlay on embodiment 16 microballoons: the microballoon that the method for plating metal of repeated using embodiment 5 obtains after to embodiment 16 activation is operated equally, obtains gold-plated microballoon.
Embodiment 18,
Alligatoring embodiment 11 polydivinylbenezene microballoons use hydrogen peroxide solution and sulfuric acid: the etching liquid 100mL that the hydrogen peroxide solution of preparation 3.2M and the sulfuric acid of 6M constitute; The microballoon that adds 10g embodiment 11 particle diameters 6.0 μ m; Ultrasonic dispersion is 5 minutes under the normal temperature, is warmed up to 60 ℃ again and keeps 180 minutes.Repeat then to filter, wash, obtain microballoon through etching processing.
Embodiment 19,
Activation embodiment 18 microballoons: the microballoon that the method for then reusing embodiment 4 obtains after to embodiment 18 alligatoring is operated equally, obtains the polydivinylbenezene microballoon of activation.
Embodiment 20,
Form metal and overlay on embodiment 19 microballoons: the microballoon that the method for plating metal of repeated using embodiment 5 obtains after to embodiment 19 activation is operated equally, obtains gold-plated microballoon.
The THICKNESS CALCULATION of the coat of metal:
Utilize microballoon plating front weight change to calculate the thickness of the microsphere surface coat of metal.Go out thickness by computes.
d＝R-r
M×ρ
1×r
3/m＝(R
3-r
3)ρ
2
D is the thickness of nickel dam in the following formula, and R is the radius of nickel plating ball, and r is the radius of polymer microballoon, and M is the weightening finish of microballoon, and m is the weight of microballoon, ρ
1Be the density 1.07g/mL of polymer microballoon, ρ
2Density 7.9-8.5g/mL for nickel.
The coat of metal and the test of polymer drops binding ability:
Get 0.1g plating microballoon and be dispersed in the aqueous solution of 20mL, get a dispersion liquid again on slide, cover dispersion liquid with the cover glass of 0.3g, the iron block with 0.5kg is placed on the cover glass again, and cover glass 10 times moves around.Use microscopic examination plating microballoon then, the coat of metal situation of peeling off is estimated according to following standard.
In the following table, symbol zero expression is not observed the coat of metal and is peeled off, and symbol * expression is observed the coat of metal and peeled off.
There is the nickel particle of free state to exist in the embodiment 20 microballoon samples.
In the foregoing description, said in nuclear diameter be 0.01 μ m-1000 μ m, the diameter that adds after the above funtion part is 0.01 μ m-1000 μ m.But be not limited to above-mentioned size, according to actual needs, this size can be less than 0.01um or greater than 1000um.
Adopt the beneficial effect of present technique scheme to be: also be provided with at least one funtion part between kernel and the metal conducting layer, said funtion part is made up of high molecular polymer and is had functional group, and this functional group makes and on the funtion part that high molecular polymer constitutes, plates conductive metal layer; Can make conductive metal layer tightr; Adhesive force is stronger, difficultly breaks, fold, phenomenon such as peels off, longer service life; More reliable, can satisfy higher application requirements.
Embodiment 21,
A kind of anisotropic conductive material comprises the insulating resin binding agent and is dispersed in the complex microsphere in the described insulating resin binding agent.The preparation method of said complex microsphere is identical with embodiment 5 or 10.The component and the preparation method of said resin adhesive belong to known technology, and JP200580022240.0 is said like patent documentation, repeats no more at this.
Embodiment 22,
A kind of anisotropic conductive film comprises anisotropic conductive material and anisotropic conducting film.The preparation method of said anisotropic conductive material is identical with embodiment 21.Said film formation method is a known technology, repeats no more at this.
In the foregoing description, because core parts are complex microsphere of the present invention, it has unique funtion part; Said funtion part is made up of high molecular polymer and is had functional group, and this functional group makes and on the funtion part that high molecular polymer constitutes, plates conductive metal layer, can make conductive metal layer tightr; Adhesive force is stronger, difficultly breaks, fold, phenomenon such as peels off, longer service life; More reliable, can satisfy higher application requirements.Make in actual application that the metal conducting layer that has both solved complex microsphere is prone to break, fold, problem such as peel off, the also reasonable problem that has solved the loose contact that microelectrode causes because of the hot pressing inequality.
Above-described only is preferred implementation of the present invention, should be pointed out that for the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (9)
1. the preparation method of a complex microsphere, it is outside with at least one functionalized polymer that said complex microsphere contains a polymer kernel, and have that one deck metal conducting layer is at the outermost layer of said complex microsphere at least, and its preparation method may further comprise the steps:
(1), prepares the polymer microballoon that is predetermined composition and sphere diameter, promptly said polymer kernel;
(2), carry out the reaction of outer polymerization single polymerization monomer, it is outside to form at least one polymer with said polymer microballoon;
(3), have outside polymer microballoon of at least one polymer and active agent reaction, the systematic function group and in said polymer microballoon outside with said;
(4), the polymer microballoon that contains functional group is contacted with chemical reagent, in its environment, form layer of metal conductive layer at least at said polymer microballoon outermost layer.
2. the preparation method of complex microsphere as claimed in claim 1 carries out said polymer microballoon said polymer kernel being formed being comprised that one or more contain (methyl) acrylate monomer of at least one unsaturated linkage in the polymerization single polymerization monomer reaction in step (2).
3. the preparation method of complex microsphere as claimed in claim 1; Said polymer microballoon is carried out in the polymerization single polymerization monomer reaction in step (2); Said polymer kernel is formed is comprised that one or more contain the aromatic monomer of at least one unsaturated linkage, and said aromatic monomer can with said (methyl) acrylate monomer polymerization that contains at least one unsaturated linkage.
4. the said functional group that generates among the preparation method of complex microsphere as claimed in claim 1, step (3) comprises a kind of in hydroxyl, carboxyl, amino, sulfydryl and the triphenylphosphinyl or several.
5. like the preparation method of the arbitrary described complex microsphere of claim 1 to 4, the said functional group that generates in the step (3) is oxygen carbonyl alkane carboxyl and adjacent hydroxyl.
6. like the preparation method of the arbitrary described complex microsphere of claim 1 to 4, the said functional group that generates in the step (3) is mercapto alkane sulfydryl and adjacent hydroxyl.
7. like the preparation method of the arbitrary described complex microsphere of claim 1 to 4, the said functional group that generates in the step (3) is aminoalkylamino and adjacent hydroxyl
8. the preparation method of an anisotropic conductive material is characterized in that, the described complex microsphere of claim 1 is dispersed in the insulating resin binding agent processes.
9. the preparation method of an anisotropic conductive film is characterized in that, the described a kind of anisotropic conductive material of claim 8 is processed film.
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| CN102990062B (en) * | 2012-12-17 | 2014-07-23 | 苏州纳微科技有限公司 | Method for preparing composite microsphere |
| CN103182515B (en) * | 2013-03-22 | 2015-04-08 | 中国科学院上海应用物理研究所 | Precious metal composite material and precious metal micro-nano material, and preparation methods thereof |
| CN103706315B (en) * | 2013-12-24 | 2015-09-23 | 苏州纳微科技有限公司 | A kind of conductive micro-balloons preparation method being applicable to conductive material |
| CN106935314B (en) * | 2015-01-18 | 2018-10-30 | 昇印光电（昆山）股份有限公司 | A kind of transparent conductive film polymer layer structure |
| CN108461172B (en) * | 2018-02-22 | 2020-06-30 | 南方科技大学 | Conductive particle and preparation method and application thereof |
| CN108341600A (en) * | 2018-03-14 | 2018-07-31 | 江苏大学 | One kind preparing single layer SiO in glass surface2The method of microballoon film |
| CN111718449A (en) * | 2020-07-02 | 2020-09-29 | 长春工业大学 | Preparation method of polymer metal composite microspheres |
| CN114307883B (en) * | 2021-12-29 | 2023-01-31 | 苏州纳微科技股份有限公司 | Preparation method of nickel-plated microspheres suitable for anisotropic conduction |
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| 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 |
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