CN100369939C - Coated particles - Google Patents
Coated particles Download PDFInfo
- Publication number
- CN100369939C CN100369939C CNB2005100998555A CN200510099855A CN100369939C CN 100369939 C CN100369939 C CN 100369939C CN B2005100998555 A CNB2005100998555 A CN B2005100998555A CN 200510099855 A CN200510099855 A CN 200510099855A CN 100369939 C CN100369939 C CN 100369939C
- Authority
- CN
- China
- Prior art keywords
- particle
- organic compound
- functional group
- compound
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Coated particles having excellent connection reliability. The coated particles each comprises a core particle having a surface layer made of a metal, wherein the core surface has been partly modified with an organic compound through a functional group (A) having bondability to the metal.
Description
The application is that application number is 018178073, and name is called the dividing an application of patent application of " coated particle ".
Technical field
The present invention relates to particle, be called for short coated particle through coating.
Background technology
The anisotropic conductive particle that is electrically connected usefulness is used to the electrode connection material of liquid crystal display, and is used to install the anisotropic conducting film in the LSI chip.Having made this anisotropic conducting film in using, for example is to be dispersed in the insulating material and with this dispersion liquid and to be molded as film shape being coated with metallic particle.When this anisotropic conducting film inserted between two electrodes and heats under pressure, the insulating material fusing was coated with metallic particle just as conductive particle, and electrode just is electrically connected mutually simultaneously.
Yet,, be necessary to be increased in the content that adds conductive particle in the anisotropic conducting film, in order that the high connection reliability of the degree that obtains along with the more and more littler recent trend of interelectrode distance.Yet this can cause the cross conduction of (for example) adjacent particle, and for example problem of short circuit and so between the adjacent electrode has taken place the result.For alleviating these problems, for example, Japan speciallys permit open communique, and clear-62-40183 has described a kind of method, and it comprises uses and the inconsistent resin-coated metallic particle that is covered with of thin film layer resin, grinds the gained material then and makes particle.The open communique of Japan special permission puts down-and 08-335407 then described a kind of method, comprises being coated with being covered with metallic particle with little method for coating.Yet, the aforesaid method defectiveness.For example, between resin that is used for being coated with and the metal bonded intensity a little less than covering on the metallic particle because resin only is physical adsorption.After coating is handled, the accumulative particle is ground to form one by one in the particulate step, the resin of coating can peel off, perhaps the thickness of coating resin can reduce, therefore being covered with the metallic particle surface can expose, this not only can produce conduction in electrode direction, and cross conduction can take place, and this has just increased the probability of horizontal short circuit.Another shortcoming of aforesaid method is, because resin is the form of layer in surface of metal particles, when coated particle and adhesive resin or tackiness agent were kneaded together, resin layer can peel off.In addition, even if when at elevated temperatures the anisotropic conducting film that contains coated particle being carried out hot pressing, resin also can peel off from the coated particle surface.
Summary of the invention
In view of the present situation of above-mentioned this technology, an object of the present invention is to provide the reliable coated particle of connectivity.
The present invention relates to coated particle, it contains the particle that the metallic surface is arranged as core, is to modify gained with organic compound by carrying out part surface to above-mentioned core particle in conjunction with the functional group (A) with metal.
The preferred coated particle of the present invention is the particle that organic compound is grafted to the particle surface gained of metallic surface, or contain the particle that the metallic surface is arranged as core, with the organic compound that contains the functional group (A) that can be incorporated into metal above-mentioned core particle is carried out the particle that part surface is modified gained.
If organic compound that coated particle of the present invention has included the particle of metallic surface and grafting in the above, coated particle then of the present invention preferably makes in order to the below method: the compound that will contain polymerization or chain transfer functional group or catalysed partial (C) is incorporated into the particulate surface that the metallic surface is arranged as core, with polymerization or chain transfer functional group or catalysed partial (C) carry out graft polymerization as priming site then, so that partly modify the particulate surface with organic compound.
Preferably carry out above-mentioned graft polymerization in the mode of syndiotaxy.Specifically, preferably use cyclic monomer to carry out the open loop syndiotaxy, this is because the cause that reaction product is taken out easily.
Above-mentioned organic compound preferably has positive charge or negative charge.This organic compound is preferably insulating compound.
Below describe the present invention in detail.
Here said " modifying with the organic compound part surface " is meant that this organic compound does not cover whole surface fully.
Coated particle of the present invention contains a kind of particle as core, and its surface is to be material (being called " particle that the metallic surface is arranged " here) with the metal.
Above-mentioned metal there is not any restriction, as long as it has electroconductibility.Therefore, comprising the metal of gold, platinum, silver, copper, iron, nickel, aluminium and chromium and so on, and the metallic compound of ITO and scolder and so on.Wherein, because gold has lower resistance, so gold is preferred.
There is the particle of metallic surface not have what restriction to above-mentioned, as long as its outermost layer is with metal.Therefore, it can be the particle that is made by above-mentioned metal fully, or forms the layer of above-mentioned metal or the particle that the surface obtains by gas deposition, plating, coating or any other suitable method on the core particle of organic or inorganic compound.
With organic compound via the functional group that can be incorporated into metal (A) partly finishing as this type of of core particle of metallic surface is arranged, can obtain coated particle of the present invention thus.
What restriction the functional group (A) that can be incorporated into metal is not had, and it can be any group that can form ionic linkage, covalent linkage or coordinate bond with metal.Therefore, it comprises salt, silanol, carboxyl, amino, ammonium, nitro, hydroxyl, carbonyl, mercaptan, sulfonic acid, sulfonium, boric acid, oxazoline, pyrrolidone, phosphoric acid and nitrile group.Because coordinate bond is suitable for the coupling with metal, it is wise therefore using the group that contains S, N or P atom.When metal is gold, for example, can use the thiol group that can form coordinate bond with gold.
What restriction organic compound is not had, comprising (no) stable hydrocarbon, aromatic hydrocarbons, (no) saturated fatty acid, aromatic carboxylic acid, (no) saturated ketone, aromatic ketone, (no) saturated alcohol, aromatic alcohol, (no) saturated amine, aromatic amine, (no) saturated mercaptan, aromatic thiol, silicoorganic compound and their derivative, derived from wherein one or more polycondensation product and derived from one or more polymkeric substance wherein.The term that uses above " (no) is saturated " is meant " saturated and unsaturated ".
Above-mentioned polycondensation product or polymkeric substance be meant, for example, and polyolefine such as polyethylene and polyhutadiene; Polyethers such as polyoxyethylene glycol and polypropylene glycol; Polystyrene, poly-(methyl) vinylformic acid, poly-(methyl) acrylate, poly-(vinyl alcohol), polyvinyl ester, resol, melamine resin, allylic resin, furane resin, polyester, Resins, epoxy, silicone resin, poly-imide resin, urethane, teflon, propenyl-styrene resin, styrene butadiene resin, ethenoid resin, versamid 900, polycarbonate, polyoxymethylene, polyethersulfone, polyphenylene oxide, carbohydrate, starch, Mierocrystalline cellulose and polypeptide.These organic compound can use separately, also can be used in combination wherein two or more.
If as the anisotropic conductive particle, then above-mentioned organic compound is preferably selected from insulating compound with coated particle of the present invention.
To carrying out the restriction especially of aforesaid method that part is modified with this type of organic compound, it can be any can the organifying compound via functional group (A) coupling in the method for metallic surface.For example, this method comprises organic compound is grafted on the metallic surface, comprises that specifically the organic granular that will contain the functional group (A) that can be incorporated into metal carries out coupling, and this method comprises uses the organic compound coating metal surfaces, for example produces micropore then on coating.
Wherein, especially can use organic compound is grafted on the metallic surface, and will contain the method that the organic granular of the functional group (A) that can be incorporated into metal carries out coupling.
Therefore, organic compound can be grafted on the particulate surface of metallic surface, obtain coated particle of the present invention thus.
To the not restriction especially of particulate surface method that organic compound is grafted to the metallic surface; comprising; 1) provides the organic compound that contains the functional group (A) that can be incorporated into metal; and the gained compound guided to method on the metallic surface; 2) make reactive functional groups (the B) (hydroxyl for example that contains the functional group (A) that can be incorporated into metal and can form covalent linkage by chemical reaction; carboxyl; amino; epoxy group(ing); silyl; silanol or isonitrile acyl group) compound and metallic surface reaction; substitute the method for this organic compound then with a kind of reactive functional groups (B) by a step or polystep reaction; 3) will contain the compound of polymerization or chain transfer functional group or catalysed partial (C); be incorporated into via the functional group that can be incorporated into metal (A) on the particulate surface of metallic surface, then the method for carrying out graft polymerization as priming site with polymerization or chain transfer functional group or catalysed partial (C).
Wherein, the preferred method (3) of utilizing graft polymerization of using,
Promptly be, the compound that will contain polymerization or chain transfer functional group or catalysed partial (C) is incorporated on the particulate surface of metallic surface via the functional group that can be incorporated into metal (A), carry out graft polymerization with polymerization or chain transfer functional group or catalysed partial (C) as priming site then, can obtain coated particle of the present invention thus.
Above-mentioned polymerization or chain transfer functional group or catalysed partial (C) they have been the functional groups or the catalyzer of the effect of graft polymerization priming site, comprising, cracked group such as azo and peresters group fully; The chain transfer group is as mercaptan, sulfide, dithiocarbamate, nitroxyl and halogen group; The group such as ethene, thiazolinyl and the acetylene group that contain unsaturated link(age); Cyclic group is as cyclic ester, ring methylal, lactone, lactan, epimino ether, cycloolefin, cyclosiloxane and phosphine nitrile (phosphazene) group, aldehyde, ketone, isocyanato, hydroxyl amino and carboxylic group; And halogen compounds, oxyhalogen compound and contain the organic ammonium salt of the central metal of one or more Li of being selected from, Na, Mg, Ti, V, Cr, Fr, Co, Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta, W, Re, Os and Ir; And organometallic compound.
If the mode with the open loop syndiotaxy is carried out above-mentioned graft polymerization, yet, used metathesis reaction catalyzer, as contained a kind of muriate, organometallic compound, alkylidene complex compound, vinylidene complex compound or similar carbene complex compound or the Herba ainsliaeae yunnanensis complex compound that is selected among Ti, V, Cr, Zr, Nb, Mo, Ru, Ta, W, Re, Os and the Ir as central metal as above-mentioned polymerization or chain transfer functional group or catalysed partial (C).As the object lesson of metathesis reaction catalyzer, metal chloride such as TiCl4, VOCl3, MoCl5, ReCl5, IrCl3, ZrCl4, NbCl5, WCl6, RuCl3, VCl4, TaCl5, WOCl4 and OsCl3 are arranged; Organometallic compound such as tridecyl ammonium molybdate; And organometallic complex, as dichloro two (three ring octyl group hexyl phosphines) benzal ruthenium (IV).Wherein, the preferred central metal that uses is a ruthenium.
For example, according to used polymerization or chain transfer functional group or catalysed partial (C), above-mentioned graft polymerization can be carried out in the mode of radical polymerization, ionic polymerization, polycoordination, metathesis polymerization, polycondensation or polyaddition reaction.Wherein, the technology of active radical polymerization, anionoid polymerization, cationoid polymerisation and the metathesis polymerization of the length that preferred use can the controlling polymers chain.Best especially is ring-opening metathesis polymerization, because its response procedures is simple.
In ring-opening metathesis polymerization, the chain length of controlling polymers more simply, and can remove catalyst metal easily, different with living polymerization simultaneously, a part end in office can not keep halogen or similar activity control group.
If in the mode of radical polymerization, ionic polymerization, ring-opening polymerization, isomerization polymerization, cyclopolymerization, elimination polymerization, addition polymerization, polycondensation or addition polymerization, then to the not restriction especially of monomer of above-mentioned graft polymerization, it can be any polymerisable monomer.For example, comprising ethene, divinyl, styrene derivatives; (methyl) vinylformic acid, their ester derivative or amide derivatives; The compound that contains vinyl group is as vinyl acetate derivative or Vinyl Ether derivative; The compound that contains cyclic olefin is as cyclooctadiene and norbornene derivative; Cyclic ethers is as ethylene oxide,1,2-epoxyethane derivative, tetrahydrofuran derivatives and triazole derivative; Ring-type carboxylic aldehyde, as 1,3-dioxepane derivative and 4H, 7H-1,3-dioxepin; Cyclic ester is as 6-caprolactone, glycollide and carbonic acid trimethylene; Cyclammonium is as aziridine and 1-methyl azetidine; Cyclical sulfide is as propylene sulfide; The azoles quinoline derivant; Lactan is as azetidine (azetidinone), pyrrolidone and ε-Ji Neixianan; Cyclosiloxane is as hexamethyl cyclotrisiloxane; Ring phosphine nitrile is as chlordene phosphine nitrile; Aldehydes is as formaldehyde and acetaldehyde; Amphyl; Anils; The compound that contains isocyano is as isocyanic acid hexamethylene ester; The compound that contains oh group is as ethylene glycol and tetramethylene glycol; Contain amino compound, as hexamethylenediamine; The compound that contains carboxylic group is as hexanodioic acid and terephthalic acid; Amino acid derivative; And urea derivative.These monomers can use separately or general's two or more being used in combination wherein.
If above-mentioned graft polymerization is a metathesis polymerization, yet the monomer of graft polymerization preferably can carry out metathesis polymerization.Cycloolefin or derivatives thereof preferably is such as cyclobutene, cyclopentenes, cyclooctene and cyclooctadiene; Poly-cycloolefin and derivative thereof are as norbornylene, norbornadiene, dicyclopentadiene and three cyclopentadiene; And contain heteroatomic cycloolefin, as 2,3-dihydrofuran, outer-3,6-epoxy-1,2,3,6-Tetra Hydro Phthalic Anhydride, 9-oxabicyclo [6.1.0] ninth of the ten Heavenly Stems-4-alkene, outer-N-methyl-7-oxabicyclo [2.2.1] heptan-1,4-alkene-2,3-dicarboxyl imide and 1,4-dihydro-1,4-epoxy naphthalene.These monomers can use separately or general's two or more being used in combination wherein.
When carrying out above-mentioned graft polymerization, the organic compound that is used for being modified with the particulate surface of metallic surface is preferably with positive charge or negative charge.When organic compound has the plus or minus electric charge in molecule, between organic compound molecule with intramolecularly repulsive interaction can take place, therefore, in the particulate step that they is grafted to the metallic surface, the control meeting of grafting density is than being easier to.In addition, the gathering of conductive particle can be avoided, their dispersivenesses in adhesive resin can be promoted.
For making above-mentioned organic compound contain the plus or minus electric charge in molecule, preferably side chain and/or its end at molecule contains functional group.Functional group comprises, for example, and ammonium, sulfonium, sulfonic acid, carboxyl, phosphoric acid, boric acid and nitryl group, and their salt.
To the not restriction especially of method of introducing this type of functional group, so long as in the step of carrying out polyreaction, can copolymerization contain the monomer methods of this type of functional group, or can after polyreaction, the method that this type of functional group introduces side chain be got final product by chemical reaction.
When carrying out above-mentioned graft polymerization reaction, can use chain-transfer agent, catalyzer, promotor etc. as required.If containing the compound of polymerization or chain transfer functional group or catalysed partial (C) is metal chloride or organometallic compound, then can be with for example organo-aluminium compound (as triethyl aluminum), lithium alkylide (as butyllithium), organo-tin compound (as tin methide), phenyldiazomethane and diazoacetic acid methyl esters as promotor.
The above-mentioned compound that contains polymerization or chain transfer functional group or catalysed partial (C) can be organic compound or mineral compound.
To the not restriction especially of aforesaid method of introducing the compound that contains polymerization or chain transfer functional group or catalysed partial (C) on the particulate surface of metallic surface is being arranged, comprise, 3-1) make the compound that contains polymerization or chain transfer functional group or catalysed partial (C) contain the functional group (A) that can be incorporated into metal, and the gained compound is incorporated into the last method of metallic surface, 3-2) make compound that contains the functional group (A) that can be incorporated into metal and reactive functional groups (B) and the particle reaction that the metallic surface is arranged, in a step or a plurality of step, substitute the method for polymerization or chain transfer functional group or catalysed partial (C) then with reactive functional groups (B), 3-3) make compound that contains the functional group (A) that can be incorporated into metal and the particle reaction that the metallic surface is arranged, pass through for example Cement Composite Treated by Plasma reactive functional groups (B) modification of surfaces then, and in a step or a plurality of step, substitute the method for polymerization or chain transfer functional group or catalysed partial (C) with reactive functional groups (B).
Aforesaid method 3-1) in, introduce the compound that contains polymerization or chain transfer functional group or catalysed partial (C) having on the particulate surface of metallic surface, employed compound does not have any restriction, it can be any functional group (A) that can be incorporated into metal and compound of polymerization or chain transfer functional group or catalysed partial (C) of containing in or same molecule, as 2,2 '-azobis isobutyronitrile, 2, the two amidino groups two propane dihydrochlorides of 2 '-azo, mercapto-phenol, the sulfydryl hexanol, with mercaptan end capped poly-(vinyl alcohol), 4-hydroxyphenyl dimethyl sulfonium methylsulfuric acid ester, thiohydracrylic acid, 2,2 '-two pyridines-4,4 '-dicarboxylic acid, Thioctic Acid, 4-acetic acid imidazoles, Histidine, halfcystine, methionine(Met), right-sulfydryl vinylbenzene, right-Sodium styrene sulfonate, right-dimethyl sulphide phenyl methyl vinylformic acid methylsulfuric acid ester, vinyl cyanide, two (tricyclohexyl phosphines)-right-sulfonation-benzal ruthenium (IV) dichloride sodium etc.
To the aforesaid method 3-2 that introduces the compound that contains polymerization or chain transfer functional group or catalysed partial (C) is being arranged on the particulate surface of metallic surface) there is not any restriction, for example, can use the method that may further comprise the steps: will contain reactive functional groups (B), as hydroxyl, carboxyl, amino, epoxy group(ing), silyl, the group of silanol or isocyano is guided on the metallic surface with a kind of compound that can be incorporated into the functional group (A) of metal, make reactive functional groups (B) then and contain and to react with the compound of the covalently bound functional group of reactive functional groups (B), in order to realize the introducing of polymerization or chain transfer functional group or catalysed partial (C).
Specifically comprise following method: oh group is guided on the particle of metallic surface with mercapto-phenol, used 2-(4-SULPHURYL CHLORIDE) ethyl trichloro silicane this group to be converted to the method for SULPHURYL CHLORIDE group (this is chain transfer functional group (C)) by the silane coupling then; Oh group is guided on the particle of metallic surface with 4-hydroxyphenyl dimethyl sulfonium methylsulfuric acid ester, by the esterification condensation reaction these groups are converted to the method for vinyl (this is polymer functional group (C)) then with methacrylic chloride; Introduce amino acid group with Histidine having on the particle of metallic surface, use 4-(chloromethyl) phenyl isocyanate to be converted into the method for cl radical (this is chain transfer functional group (C)) by addition reaction then; Oh group is guided on the particle of metallic surface with the sulfydryl undecyl alcohol, be converted into the norbornylene group with 2-norbornylene-6-dimethyl dichlorosilane (DMCS) by the silane coupling then, convert thereof into the method for ruthenium group (this is chain transfer catalyst (C) part) by dichloro two (the three ring octyl group hexyl phosphines) coordination of benzal ruthenium (IV) again.
To introducing the above-mentioned method 3-2 of compound that contains polymerization or chain transfer functional group or catalysed partial (C) having on the particulate surface of metallic surface) restriction especially, for example, can use the method that may further comprise the steps: introduce the compound that contains the functional group (A) that can be incorporated into metal, this compound-modifiedly becomes reactive functional groups (B) with a part by for example Cement Composite Treated by Plasma or oxide treatment then, and by aforesaid method 3-2) convert thereof into polymerization or chain transfer functional group or catalysed partial (C).
Particulate of the present invention can also be attached on the metallic surface by the organic granular that will contain the functional group (A) that can be incorporated into metal and obtain.
Above-mentioned organic granular is the particle that above-mentioned organic compound constitutes.
When carrying out part surface with above-mentioned organic granular when modifying, modify back conductive particle accumulative trend a little less than, therefore, in that to make particle be kept to the power that particle is subjected in the single depolymerization step less, so be coated with up not conference of organic compound flake-off.
Organic granular is preferably in its surface or inside has the plus or minus electric charge, and they will repel mutually and can not assemble mutually like this.
The method that makes plus or minus electric charge on the particle band is not had any restriction, be included in its manufacturing step, organic or inorganic ionic compound and above-mentioned organic granular blended method; By chemical bonding this compounds is guided to the lip-deep method of organic granular, this compounds is guided to the lip-deep method of organic granular by physical adsorption; Come the method on ion modification organic granular surface by chemical treatment; And the method by mode ion modification organic granular surfaces such as plasma bodys.
To the restriction especially of method of the functional group (A) that organic granular contained to be incorporated into metal, be included in its manufacturing step itself and organic granular blended method; By chemical bonding it is guided to the lip-deep method of organic granular; By physical adsorption it is guided to the lip-deep method of organic granular; Modify organic particle surface so that the method for the group that can be incorporated into metal is provided to the surface by chemical treatment; And modify organic particle surface by methods such as plasma bodys, so that the method for the group that can be incorporated into metal is provided to the surface.
To the not restriction especially of particle diameter of organic granular, still, when coated particle of the present invention was used as the anisotropic conductive particle, it was preferably at 1-2, in the scope of 000nm.In this scope, can guarantee the insulativity between the adjacent conductive particle, simultaneously, when coated particle of the present invention mutually combines under pressure, can realize electroconductibility.
What restriction is the method for making above-mentioned organic granular do not had, and can be the known any method in this field, for example, and the pulverizing of letex polymerization, still precipitation polymerization, dispersion polymerization, suspension polymerization and hardening resin.
To with the restriction especially of the thickness of organic layer on the coated particle of the present invention of above-mentioned organic compound modified formation, can be with modified area with other factor and different.Yet when coated particle of the present invention was used as the anisotropic conductive particle, this thickness was preferably 1-2,000nm.In this scope, can guarantee the insulativity between the adjacent conductive particle, and when coated particle of the present invention mutually combines under pressure, can realize electroconductibility.
To on the coated particle of the present invention with the restriction especially of percentage ratio of above-mentioned organic compound modified area, but can be different with modifying with the thickness of the molecular weight of organic compound and structure and organic layer.Yet, preferably account for the 10-90% that is covered with the metallic particle surface-area usually.In this scope, when coated particle of the present invention is used as the anisotropic conductive particle, can guarantees the insulativity between the adjacent conductive particle, and when coated particle of the present invention mutually combines under pressure, can realize electroconductibility.The scope that is more preferably is 20-90%.
Coated particle of the present invention, its as on the particulate surface that the metallic surface is arranged of core with organic compound by partly having carried out finishing thereon in conjunction with functional group (A) that can bond, combination between organic layer and the metal is very firm, so organic layer is difficult to flake-off.Therefore, when coated particle of the present invention is used as the anisotropic conductive particle, can guarantee the connection reliability of high level, keep the insulation between the adjacent particle simultaneously.
If,, can easily control the area and the thickness of modification, therefore can make this modification be suitable for using the requirement of coated particle with the organic compound modified particulate surface that the metallic surface is arranged by the grafted method.In addition, when by graft polymerization during with the organic compound modified particle surface that the metallic surface arranged, used monomer can be selected, consequently, just can control the structure of layer easily, and can provide such as these functions of tack, aggregation tendency, hydrophobicity and wetting ability; Can obtain excellent service performance thus.
Specific embodiments
Below some embodiment will more particularly understand the present invention.Yet these embodiment never provide constraints in scope of the present invention.
(embodiment 1)
In argon gas atmosphere, 1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, with being dissolved in the 500g distilled water that 5g is purchased with end capped poly-(vinyl alcohol) (molecular-weight average is 20,000) of sulfydryl.
In argon gas atmosphere, the 10g particle is dispersed in this solution at the gold grain that covers that diameter is about 5 μ m, this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted poly-(vinyl alcohol), clean particle with hot water, drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 2)
In argon gas atmosphere, 1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, be dissolved in 500g with what 5g was purchased in the tetrahydrofuran (THF) that distillation is purified with end capped poly-(methyl methacrylate) (molecular-weight average is 12,000) of sulfydryl.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted poly-(methyl methacrylate), clean particle with tetrahydrofuran (THF), drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 3)
In the built-up type flask of the 500mL that separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor are housed, with 99g methyl methacrylate, 1g methacrylic acid and 1.5g thioacetic acid, stir together at 85 ℃, add 0.1g 2 then, 2 '-azobis isobutyronitrile carries out 1.5 hours polyreactions again.After purification and the drying, obtained end capped poly-(the methyl methacrylate)-Sipacril 2739OF (molecular-weight average is 20,000) of sulfydryl.
In argon gas atmosphere, above-mentioned poly-(methyl methacrylate)-Sipacril 2739OF (5g) is dissolved in 500g in the tetrahydrofuran (THF) that distillation is purified.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, this mixture is stirred 12 hours at 40 ℃ again.Remove by filter unreacted poly-(methyl methacrylate)-Sipacril 2739OF, clean particle with tetrahydrofuran (THF), drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 4)
In the built-up type flask of the 500mL that separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor are housed, 5 mmole thiohydracrylic acids are dissolved in 500mL in the tetrahydrofuran (THF) that distillation is purified.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted thiohydracrylic acid, clean particle with tetrahydrofuran (THF), dry then, and again it is scattered in the 500mL tetrahydrofuran (THF).
In argon gas atmosphere, add in this dispersion liquid that 5g is purchased with end capped poly-(methyl methacrylate) (molecular weight 15,000) of epoxy group(ing), the gained mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted poly-(methyl methacrylate), clean particle with tetrahydrofuran (THF), drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 5)
1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, 5 mmole sulfydryl undecyl alcohols is being dissolved in 500mL in the tetrahydrofuran (THF) that distillation is purified.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted sulfydryl undecyl alcohol, clean particle with tetrahydrofuran (THF), dry then, and again it is scattered in 200mL distilled water.
In this dispersion liquid, add 5 moles of methylol methacrylic esters, after fully stirring, add cerous nitrate (cerric) ammonium solution for preparing 10g 0.1mol/L with the aqueous solution of 1N nitric acid, and mixture was stirred 10 hours.Mixture is filtered, use the washed with methanol particle, drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 6)
1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, 5 mmole mercapto-phenols is being dissolved in 200mL in the tetrahydrofuran (THF) that distillation is purified.
In the argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted mercapto-phenol, clean particle, the dry then toluene that also again it is scattered in the 500mL purification with tetrahydrofuran (THF).
In this dispersion liquid, add 5 mmole 2-(4-SULPHURYL CHLORIDE) ethyl trichlorosilane, this mixture was stirred 6 hours at 40 ℃.Remove by filter unreacted 2-(4-SULPHURYL CHLORIDE) ethyl trichlorosilane, clean particle with toluene, and in argon gas atmosphere with its redispersion in the toluene of purifying.
In argon gas atmosphere, in this dispersion liquid, add 10 mmole cupric bromides, 20 mmole 4,4 '-two-just-heptyl-2,2 '-two pyridines, 5 moles of methyl methacrylates and 2.5 mmole p-toluenesulfonyl chlorides, and mixture stirred 12 hours at 90 ℃.After being cooled to room temperature, add 100g just-hexane, leach particle then, with just-hexane further cleans, drying obtains the surface and is insulated the coated particle that organic compound is partly modified.
(embodiment 7)
1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, 5 mmole mercapto-phenols is being dissolved in 500mL in the tetrahydrofuran (THF) that distillation is purified.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted mercapto-phenol, clean particle with tetrahydrofuran (THF), dry then, again it is scattered in the tetrahydrofuran (THF) of 500mL purification.
In this dispersion liquid, add 5 mmoles (right-chloromethyl) phenyl-trichloro-silicane, and mixture was stirred 6 hours at 40 ℃.Remove by filter unreacted (right-chloromethyl) phenyl-trichloro-silicane, clean particle with toluene, then in argon gas atmosphere with its redispersion in the tetrahydrofuran (THF) of purifying.
In this dispersion liquid, add 100 mmole N, the N-diethyldithiocarbamate, and with mixture stirring at room 18 hours.Remove by filter unreacted N, the N-diethyldithiocarbamate is cleaned particle with toluene, then in argon gas atmosphere with its redispersion in the toluene of purifying.
In argon gas atmosphere, in this dispersion liquid, add 2 mmole methyl methacrylates, 0.02 mmole methacrylic acid, when 40 ℃ are stirred 3 hours, with the high voltage mercury lamp (product of SEN Light:, the mixture width of cloth is shone HLR 100T-1) as light source.Leach particle after being cooled to room temperature, with just-hexane further cleans and dryly obtains the surface and be insulated the coated particle that organic compound is partly modified.
(embodiment 8)
1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, and in the built-up type flask of 000mL, the sulfydryl undecyl alcohol that 5 mmoles is contained thiol group is dissolved in 500mL in the tetrahydrofuran (THF) that distillation is purified.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted sulfydryl undecyl alcohol, clean particle with tetrahydrofuran (THF), drying also is scattered in it in toluene of 500mL purification more then.
In this dispersion liquid, add 5 mmole 2-norbornylene-6-dimethyl dichlorosilane (DMCS)s, mixture is stirred at 40 ℃ reacted in 6 hours, convert hydroxyl to the norbornylene group.Remove by filter unreacted 2-norbornylene-6-dimethyl dichlorosilane (DMCS), clean particle with toluene, then in argon gas atmosphere with its redispersion in the toluene that 500mL purifies.
In this dispersion liquid, add the dichloride of 5 mmoles, this mixture was reacted in stirring at room in 30 minutes, the norbornylene group is changed into ruthenium carbene group as the dichloro of metathesis polymerization catalyzer two (three ring octyl group hexyl phosphines) benzal ruthenium (IV).Remove by filter the dichloride of unreacted dichloro two (three ring octyl group hexyl phosphines) benzal ruthenium (IV), clean particle with toluene, then in argon gas atmosphere with its redispersion toluene that 400mL purifies in.
In argon gas atmosphere, the norbornylene that adding 2 mmoles are dissolved in the 100mL purifying methylbenzene in this dispersion liquid carries out graft polymerization in 30 minutes as the monomer that carries out graft polymerization in room temperature.Leach particle, use washed with methanol, drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 9)
With vinylbenzene (500 mmole), 5 mmole methacryloyl oxyphenyl dimethyl sulfonium methylsulfuric acid esters, 5 mmoles 2; two (2-amidine propane) dihydrochlorides of 2 '-azo and 250mL distilled water are weighed; and they are all packed into have 1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor; in the built-up type flask of 000mL; stir the mixture with 200rpm; and in nitrogen atmosphere, carry out 7 hours polyreactions in 60 ℃, obtaining 18% average particulate diameter is the dispersion liquid that 220nm, surface have sulfonium group latex particle.
With distilled water above-mentioned latex particle dispersion liquid is diluted to 1%, in argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this diluent of 500mL, and this mixture was stirred 12 hours at 40 ℃.By 3 microns hole strainer filtering mixts, use the washed with methanol particle again, drying obtains the surface and is insulated the coated particle that organic compound is partly modified then.
(embodiment 10)
With vinylbenzene (500 mmole), 1.92 mmoles right-Sodium styrene sulfonate, 0.94 mmole Potassium Persulfate and 475mL distilled water weighs, and they are all packed in the built-up type flask of the 100mL that has separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor, stir the mixture with 200rpm, and in nitrogen atmosphere, carry out 12 hours polyreactions in 60 ℃, obtaining 18% average particulate diameter is the dispersion liquid that 105nm, surface have the latex particle of sulfonic acid group.
With distilled water above-mentioned latex particle dispersion liquid is diluted to 1%, in argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this diluent of 500mL, and this mixture was stirred 12 hours at 40 ℃.By 3 microns hole strainer filtering mixts, use the washed with methanol particle then, drying obtains the surface and is insulated the coated particle that organic compound is partly modified.
(embodiment 11)
With vinylbenzene (250 mmole), 250 mmole glycidyl methacrylate, 5 mmoles 2, two (2-amidine propane) dihydrochlorides of 2 '-azo and 549mL distilled water are weighed, and they are all packed in the built-up type flask of the 100mL that has separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor, stir the mixture with 200rpm, and in nitrogen atmosphere, carry out 2 hours polyreactions in 70 ℃.Add 40 mmole glycidyl methacrylate then, carrying out polymerization in 12 hours again, to obtain 10% average particulate diameter be the dispersion liquid that 120nm, surface have the latex particle of sulfonic acid group.
In this latex particle dispersion liquid, add 250 mmole 3-thiohydracrylic acids, back flow reaction 5 hours.The eccentric cleaning particle, obtaining 10% average particulate diameter with distilled water diluting then is the dispersion liquid that 120nm, surface have the latex particle of sulfonic acid group.
In argon gas atmosphere, the gold grain that covers that the 5g particle diameter is about 5 μ m is dispersed in the above-mentioned latex particle dispersion liquid of 100mL, and this mixture was stirred 12 hours at 40 ℃.By the strainer filtering mixt in 3 microns holes, use the washed with methanol particle again, drying obtains the surface and is insulated the coated particle that organic compound is partly modified.
(Comparative Examples 1)
In argon gas atmosphere, 1 of separable four neck lids, agitating vane, three-way tap, condenser and temperature sensor is being housed, in the built-up type flask of 000mL, poly-(vinyl alcohol) (molecular-weight average is 10,000) of 5g is dissolved in the 500g distilled water.
In argon gas atmosphere, the gold grain that covers that the 10g particle diameter is about 5 μ m is dispersed in this solution, and this mixture was stirred 12 hours at 40 ℃.Remove by filter unreacted poly-(vinyl alcohol), clean particle with hot water, drying is insulated the coated particle that organic compound is partly modified to obtain the surface then.
(Comparative Examples 2)
With the 10g particle diameter be about 5 μ m cover gold grain and 5g vinylidene fluoride resin is added in the mixing device, handled 3 hours at 90 ℃, obtain the surface and be insulated the coated particle that organic compound is partly modified.
(test)
The organic coating thickness and the fraction of coverage of the coated particle that measurement obtains in embodiment 1-11 and Comparative Examples 1 and 2, the ratio of latter's area that to be particulate surface that the metallic surface arranged applied by organic compound.
Then, with the micronizer mill (product of Nisshin Cngineering: Current Jet CJ-2.5) at 1N/cm
2Or 5N/cm
2Described coated particle is handled down in the effect of power, becomes single each particle and state independently, carries out fraction of coverage then and measures.With the naked eye judge after micronizer mill is handled and whether have aggregation.The result is presented in the table 1.
| Coating organic compound species | Before converting individual particle to | Whether micronizer mill exists aggregation and fraction of coverage after handling | |||||
| Organic coating thickness | Fraction of coverage | 1N/cm 2 | 5N/cm 2 | ||||
| Aggregation | Fraction of coverage | Aggregation | Fraction of coverage | ||||
| Embodiment 1 | Poly-(vinyl alcohol) | 15nm | 65％ | Find | 65％ | Do not find | 65％ |
| Embodiment 2 | Poly-(methyl methacrylate) | 10nm | 65％ | Find | 65％ | Do not find | 65％ |
| Embodiment 3 | Methyl methacrylate-acrylic acid copolymer | 15nm | 60％ | Find | 60％ | Do not find | 60％ |
| Embodiment 4 | Poly-(methyl methacrylate) | 12nm | 67％ | Find | 67％ | Do not find | 67％ |
| Embodiment 5 | Poly-(hydroxy methyl methacrylate) | 20nm | 72％ | Find | 72％ | Do not find | 72％ |
| Embodiment 6 | Poly-(methyl methacrylate) | 22nm | 80％ | Find | 80％ | Do not find | 79％ |
| Embodiment 7 | Poly-(methyl methacrylate) | 25nm | 82％ | Find | 82％ | Do not find | 81％ |
| Embodiment 8 | Poly-(norbornylene) | 30nm | 77％ | Find | 77％ | Do not find | 77％ |
| Embodiment 9 | Surface sulfonium-granules of polystyrene | - | 43％ | Do not find | 41％ | Do not find | 12％ |
| Embodiment 10 | Sulfonic acid surfactant-granules of polystyrene | - | 58％ | Do not find | 57％ | Do not find | 25％ |
| Embodiment 11 | Surface mercaptan-poly-(methyl methacrylate) particle | - | 69％ | Do not find | 69％ | Do not find | 32％ |
| Comparative Examples 1 | Poly-(vinyl alcohol) | 15nm | ～100％ | Find | 65％ | Do not find | 18％ |
| Comparative Examples 2 | Poly-(vinylidene fluoride) | 15nm | 65％ | Find | 58％ | Do not find | 20％ |
By table 1 as seen, the coated particle that obtains in the Comparative Examples 1 and 2 fraction of coverage in changing the step of individual particle into significantly lowers, and the reduction of the coated particle fraction of coverage that obtains in embodiment 1-11 is less; Particularly the fraction of coverage of the coated particle that obtains in embodiment 1-8 does not almost reduce.
Handle even if carry out micronizer mill, in the coated particle that embodiment 9-11 obtains, all do not observe aggregation with very little power.
With regard to industrial application, above-mentioned the present invention can provide connectivity reliable coated particle.
Claims (6)
1. anisotropic conductive particle, it comprises the conductive metal surface particles as core, the surface of described conductive metal surface particles is modified by the functional moieties that can be incorporated into conductive metal with organic compound, described organic compound is an insulating compound, the lip-deep organic compound of conductive metal surface particles obtains by the following method: introduce the compound with polymer functional group or chain transfer functional group or catalysed partial on the conductive gold metal surface, carry out graft polymerization with each polymer functional group or chain transfer functional group or catalysed partial as priming site then.
2. anisotropic conductive particle as claimed in claim 1 is characterized in that, the thickness of partly modifying the organic layer that forms behind the particle surface with organic compound is 1-2,000nm.
3. anisotropic conductive particle as claimed in claim 1, it is characterized in that, described conductive metal surface particles is to be covered with metallic particle, this is covered with metallic particle and is included in the surperficial core that forms conductive metal layer and obtain of core grain, and, account for the 10-90% that is covered with the metallic particle surface-area with organic compound modified surface.
4. anisotropic conductive particle as claimed in claim 1 is characterized in that, the functional group that can be incorporated into conducting metal is by coordinate bond and melts combine.
5. anisotropic conductive particle as claimed in claim 1 is characterized in that, described graft polymerization is to carry out in the mode of ring-opening metathesis polymerization.
6. each described anisotropic conductive particle in the claim as described above is characterized in that described organic compound has positive electricity or negative electricity.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000322974 | 2000-10-23 | ||
| JP2000322974 | 2000-10-23 | ||
| JP2000322975 | 2000-10-23 | ||
| JP200128324 | 2001-02-05 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018178073A Division CN1244112C (en) | 2000-10-23 | 2001-05-30 | Coated particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1747073A CN1747073A (en) | 2006-03-15 |
| CN100369939C true CN100369939C (en) | 2008-02-20 |
Family
ID=36166544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100998555A Expired - Fee Related CN100369939C (en) | 2000-10-23 | 2001-05-30 | Coated particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100369939C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103365023A (en) * | 2012-04-05 | 2013-10-23 | 精工爱普生株式会社 | Electrophoresis particle, method of manufacturing electrophoresis particle, electrophoresis dispersion liquid, electrophoresis sheet, electrophoresis device and electronic apparatus |
| CN103365024A (en) * | 2012-04-09 | 2013-10-23 | 精工爱普生株式会社 | Electrophoretic particle, manufacturing method of electrophoretic particle, electrophoretic dispersed liquid, electrophoretic sheet, electrophoretic apparatus, and electronic equipment |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5446222B2 (en) * | 2008-11-14 | 2014-03-19 | 住友電気工業株式会社 | Conductive paste, electromagnetic shielding film using the same, and electromagnetic shielding flexible printed wiring board |
| JP6772401B2 (en) | 2018-07-10 | 2020-10-21 | 日本化学工業株式会社 | Coating particles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101720A (en) * | 1987-04-03 | 1988-11-16 | 罗纳普朗克公司 | Closely knit polymer/metal composite particles, its aqueous dispersion and preparation method and in biologically application |
| JPH07105725A (en) * | 1993-10-05 | 1995-04-21 | Soken Kagaku Kk | Anisotropic conductive adhesive agent |
| JP2749122B2 (en) * | 1989-05-16 | 1998-05-13 | 株式会社日本触媒 | Magnetic substance-containing spherical fine particles, production method thereof and use thereof |
| CN1244112C (en) * | 2000-10-23 | 2006-03-01 | 积水化学工业株式会社 | Coated particle |
-
2001
- 2001-05-30 CN CNB2005100998555A patent/CN100369939C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101720A (en) * | 1987-04-03 | 1988-11-16 | 罗纳普朗克公司 | Closely knit polymer/metal composite particles, its aqueous dispersion and preparation method and in biologically application |
| JP2749122B2 (en) * | 1989-05-16 | 1998-05-13 | 株式会社日本触媒 | Magnetic substance-containing spherical fine particles, production method thereof and use thereof |
| JPH07105725A (en) * | 1993-10-05 | 1995-04-21 | Soken Kagaku Kk | Anisotropic conductive adhesive agent |
| CN1244112C (en) * | 2000-10-23 | 2006-03-01 | 积水化学工业株式会社 | Coated particle |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103365023A (en) * | 2012-04-05 | 2013-10-23 | 精工爱普生株式会社 | Electrophoresis particle, method of manufacturing electrophoresis particle, electrophoresis dispersion liquid, electrophoresis sheet, electrophoresis device and electronic apparatus |
| CN103365023B (en) * | 2012-04-05 | 2017-07-21 | 精工爱普生株式会社 | Electrophoresis particle, the manufacture method of electrophoresis particle, electrophoresis dispersion, electrophoretic sheet, electrophoretic apparatus and electronic equipment |
| CN103365024A (en) * | 2012-04-09 | 2013-10-23 | 精工爱普生株式会社 | Electrophoretic particle, manufacturing method of electrophoretic particle, electrophoretic dispersed liquid, electrophoretic sheet, electrophoretic apparatus, and electronic equipment |
| CN103365024B (en) * | 2012-04-09 | 2017-07-21 | 精工爱普生株式会社 | Electrophoresis particle, the manufacture method of electrophoresis particle, electrophoresis dispersion, electrophoretic sheet, electrophoretic apparatus and electronic equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1747073A (en) | 2006-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1244112C (en) | Coated particle | |
| CN104380392B (en) | The electroconductive particle of tape insulation particle, conductive material and connection structural bodies | |
| CN102585245B (en) | High-dispersivity super-amphiphobic microsphere and self-cleaning epoxy resin paint prepared from same | |
| CN103124999B (en) | Conductive particles, anisotropic conductive material and connection structure | |
| CN101120026A (en) | Polymer particles and encapsulated compositions using organoborane amine complexes | |
| CN1231506C (en) | Copolymers of ethylene with C3-C12 olefins | |
| US20030107026A1 (en) | Conductive composition | |
| CN103748636A (en) | Conductive particles, conductive material, and connection structure | |
| CN100369939C (en) | Coated particles | |
| CN104245132A (en) | High activity catalyst for hydrosilylation reactions and methods of making the same | |
| CN102585244B (en) | Fluorine-containing nanoparticles with high dispersibility and bonding property and superamphiphobic surface | |
| CN103069504A (en) | Conductive particle, conductive particle manufacturing method, anisotropic conductive material, and connective structure | |
| CN105210157A (en) | Conductive particles, conducting material, and connection structure | |
| CN107849427A (en) | Particle, connecting material and connection structural bodies | |
| CN102990062B (en) | Method for preparing composite microsphere | |
| US20010038925A1 (en) | Polymeric organic coatings and method of manufacture thereof | |
| CN1332400C (en) | Coated conductive particle, conductive material, anisotropic conductive adhesive and anisotropic conductive junction structure | |
| CN102585243A (en) | Functional fluorine-containing microsphere and self-cleaning surface built by same | |
| CN104471650A (en) | Conductive particle, conductive material and connecting structure | |
| CN108138024A (en) | Particle, connecting material and connection structural bodies | |
| CN104619754A (en) | Organic-inorganic hybrid particle, conductive particle, conductive material and connection structure | |
| CN101260110B (en) | Alpha-(8-quinolineoxy)mono-substituted zinc phthalocyanine and preparation method thereof | |
| CN103748635A (en) | Conductive particles, conductive material, and connection structure | |
| CN102844110A (en) | Substrate for ligand immobilization and method for producing same | |
| CN105593947B (en) | Solar cell module electroconductive particle, conductive material and the solar cell module of back-contact |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080220 Termination date: 20130530 |