CN102015906B - Conductive resin composition - Google Patents
Conductive resin composition Download PDFInfo
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- CN102015906B CN102015906B CN200980115570.2A CN200980115570A CN102015906B CN 102015906 B CN102015906 B CN 102015906B CN 200980115570 A CN200980115570 A CN 200980115570A CN 102015906 B CN102015906 B CN 102015906B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/08—Magnetic details
- H05K2201/083—Magnetic materials
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- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Provided is a conductive resin composition which has stable conductivity and is inexpensive even if the amount of conductive powder added to a curing resin composition is reduced. The conductive resin composition includes the following components (A) to (C): component (A): curing resin composition; component (B): ferromagnetic powder; and component (C): silver powder having a tap density from 0.1 to less than 1.5 g/cm3, and/or nickel powder having an apparent density from 0.1 to less than 1.0 g/cm3.
Description
Technical field
The present invention relates to a kind of conductive resin composition with ferromagnetic powder and silver powder and/or nickel powder that comprises.
Background technology
In conductive resin composition, be called conductive adhesive composition formation normally resinous principle be 5～25 % by weight, the metal-powders such as silver powder, nickel powder, palladium powder and bronze (below be called electric conduction powder) are 65～95 % by weight.Between metallics and metallics, there is the resinous principle layer, carries out insulation breakdown by resinous principle and make electric current logical.If the addition of metal-powder is lower than 65 % by weight, then conductivity may be unstable, perhaps do not present electroconductibility.This is because if a large amount of filler metal powder, then the resinous principle layer between between metallics is thickening, thereby is difficult to realize insulation breakdown.And, mostly be the high precious metal of price as the metal of electric conduction powder, the tendency that therefore exists the many conductive adhesive prices of addition of electric conduction powder to increase.And the material that can be used as electric conduction powder is limited, and the metal-powders such as aluminium, copper, iron and tin beyond the electric conduction powder even therefore sneak in the resinous principle, can not present electroconductibility owing to can form the oxide film thereon of oxygen and metal yet.Certainly, even fill in a large number the powder of the metal oxides such as silicon oxide (silica), aluminum oxide (alumina), ferric oxide (ferrite), can not present electroconductibility yet.
In recent years, the demand of the vehicle mounted electronic component of high reliability is being increased, and, the Reliability Enhancement of PC or mobile telephone also required gradually.Conductive adhesive is multiplex on the associated electrical part, requires equally high reliability.As the concrete test method of confirming reliability, can by be placed on hot and humid lower humidity test (such as 85 ℃ * 85%RH etc.) or repeatedly low temperature place and the variation of the thermal cycling test of high temperature placement, electroconductibility (resistance value or volume specific resistance) that thermal shock test (such as-40 ℃～80 ℃ repeatedly wait) is confirmed conductive adhesive and bonding force etc.There is thermograde in thermal cycling test when temperature is switched, but the temperature switching is not rapid, and in thermal shock test, switches owing to carry out sharp temperature, so thermal shock test is equivalent to the condition test harsher than thermal cycling test.And the electric conduction powder that is used for conductive adhesive uses precious metal more, when requiring high reliability, mostly require again on the other hand to reduce cost, thereby its low price becomes a problem.
In order to reduce cost, knownly put down in writing just like patent documentation 1, use electric conduction powder and silver-plated glass powder, yet, in fact because the tooling cost of silvered glass powder self increases, therefore be difficult to realize the low price of powder self, thereby can't significantly reduce cost.And, such as patent documentation 2 record, also adopt following technique: the Copper Powder Surface after plating 20 % by weight part silver, coat spherical silver powder with physics mode.Yet, when using copper, if do not improve the containing ratio of silver-colored composition on the whole, can't make the resistance value stabilization.Therefore, this kind technique finally can cause the containing ratio of precious metal to increase, thereby hinders cost.
As mixing silver powder and the composition with ferromagnetic magnet, known have the composition of putting down in writing in the patent documentation 3, yet the composition of patent documentation 3 has only used the powder with ferromagnetic magnet in order to weaken noise.And, in patent documentation 4, put down in writing ferritic use, yet, owing to be to use as ferric oxide, be the material different from having ferromagnetism ferrite based magnet therefore.In addition, in patent documentation 5, put down in writing and mixed ferromagnetism body particle and electroconductive particle in the resinous principle, but that is not added ferromagnetism body particle on the press plate for resin combination being blocked in when the silk screen printing.As its using method, adopt at the downside of substrate and place the technique that magnet attracts ferromagnetism body particle.In addition, if this resin combination is not calcined, will can not present conductivity.Therefore, it is still unresolved that combination has the problem of conductive adhesive that ferromagnetic powder and electric conduction powder obtain high reliability and low price.
The look-ahead technique document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-296158 communique
Patent documentation 2: Japanese Patent Laid-Open 2005-32471 communique
Patent documentation 3: Japanese Patent Laid-Open 2001-35249 communique
Patent documentation 4: Japanese patent laid-open 8-153414 communique
Patent documentation 5: Japanese Patent Laid-Open 2002-109958 communique
Summary of the invention
[problem that invention institute wish solves]
With respect to curable resin composition, if the addition of silver powder and/or nickel powder is less, will can not present the conductivity as conductive resin composition, therefore merely can't reduce cost by reducing electric conduction powder.And, even replace silver powder to realize cost degradation with silvering powder or alloy powder etc., because its reliability as conductive resin composition is lower, and the manufacturing step of its powder is complicated, process cost increase, and therefore are difficult to significantly reduce cost as conductive resin composition.
[solving the technique means of problem]
The present inventors have carried out making great efforts research in order to improve above-mentioned problem in view of described situation, and the result has finished the invention about following conductive resin composition, even reducing electric conduction powder, it also can present stable electroconductibility, and, both can realize high reliability, also can reduce cost.
The following describes main idea of the present invention.The first example of the present invention is a kind of conductive resin composition that comprises following (A)～(C) composition:
(A) composition: curable resin composition;
(B) composition: have ferromagnetic powder; And
(C) composition: tap density is 0.1～less than 1.5g/cm
3Silver powder and/or apparent density be 0.1～less than 1.0g/cm
3Nickel powder.
In the second example of the present invention, comprise (B) composition 10～100 weight parts with respect to (A) composition 100 weight parts.
In the 3rd example of the present invention, with respect to the gross weight of conductive resin composition of the present invention and comprise (C) composition 25～70 % by weight.
In the 4th example of the present invention, (B) median size of composition is 0.1 μ m～5 μ m.
In the 5th example of the present invention, (B) composition has the relict flux density of 1.0～14.0kG.
In the 6th example of the present invention, described (B) composition comprises anisotropy or isotropic magnet powder.
In the 7th example of the present invention, described magnet powder is ferrite based magnet powder.
In the 8th example of the present invention, described (A) composition is at least a curable resin composition that is selected among the group who is made of: hot curing resin composition, moisture-curable resin combination, Photocurable resin composition and solvent evaporates curable resin composition.
In the 9th example of the present invention, described (A) composition is at least a curable resin composition that is selected among the group who is made of: composition epoxy resin, episulfide resin composition, polyurethane resin composition, moisture-curable silicon resin composition, heat-curing type silicon resin composition, acrylic acid resin composition, methacrylic resin composition and vinyl ether resin composition.
[effect of invention]
By the present invention, a kind of conductive resin composition can be provided, even it reduces the addition that is added into the electric conduction powder in the curable resin composition, also can make stable conductivity, and can reduce cost.
Embodiment
The below describes the present invention in detail.Can be used for (A) composition of the present invention so long as by the resin combination that is heating and curing, moisture-curable, photocuring and solvent evaporates etc. are solidified, then indefinite.The concrete example of hot curing resin composition can be enumerated: composition epoxy resin, the polyurethane resin composition that comprises blocked isocyanate, heat-curing type silicon resin composition, the acrylic acid resin composition that comprises organo-peroxide and methacrylic resin composition etc.The concrete example of moisture-curable resin combination can be enumerated: polyurethane resin composition and moisture-curable silicon resin composition etc.The concrete example of Photocurable resin composition can be enumerated: comprise the acrylic acid resin composition of light trigger and methacrylic resin composition etc.The concrete example of solvent evaporates curable resin composition can be enumerated: coating composition and lacquer etc.Herein, the solvent evaporates curable resin composition refers to volatilization by solvent or drying and the resin combination of the solids components such as residual plastic or rubber.
Composition epoxy resin comprises: the compound that has the epoxy group(ing) of more than one Chemical formula 1 in the molecule; With at least a solidifying agent that is selected from polyamino compound, polyphenolic substance, multi-thioalcohol compound and the acid anhydrides.And, in order to improve the reactivity of these compositions, can be with tertiary amine compound as curing catalyst.Perhaps, also this tertiary amine compound can be used alone as solidifying agent.Solidifying agent and curing catalyst can be liquid and also can be solid (comprising powder), and indefinite.And, also can use single-liquid type that the compound that will have epoxy group(ing) and solidifying agent and/or curing catalyst all mix or respectively preparation and the binary liquid shape that mixes in use.Below the compound that has more than one epoxy group(ing) in the molecule is called epoxy compounds.
[changing 1]
The concrete example of described epoxy compounds can be enumerated: the epoxy compounds that the condensation by the polyatomic phenols such as Epicholorohydrin and bisphenols or polyvalent alcohol obtains, Racemic glycidol ether type epoxies such as bisphenol A-type, brominated bisphenol A type, Hydrogenated Bisphenol A type, Bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenolic varnish (novolac) type, phenol phenolic varnish type, ortho-cresol phenolic varnish type, three (hydroxyphenyl) methane type, four phenolic group ethane types.In addition, also can enumerate: the glycidyl ester type epoxy resin that the condensation by carboxylic acids such as Epicholorohydrin and phthalic acid derivatives or lipid acid obtains; The glycidyl amine type epoxy resin that reaction by Epicholorohydrin and amine, melamine acids, hydantoins obtains; And the Resins, epoxy that utilizes gained after the whole bag of tricks modification, but be not limited thereto.
The concrete example of monobasic epoxy compounds (compound that has an epoxy group(ing) in the molecule) can be enumerated: phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butyl-phenyl glycidyl ether, butylglycidyl ether, C12～C14 alcohol glycidyl ether, butane diglycidylether, hexane diglycidylether, hexanaphthene dimethyl diglycidylether or the glycidyl ether take polyoxyethylene glycol or polypropylene glycol as the basis etc., but be not limited thereto.
Episulfide resin composition comprises: the compound that has the epithio base of more than one Chemical formula 2 in the molecule; With at least a solidifying agent that is selected from polyamino compound, polyphenolic substance, multi-thioalcohol compound and the acid anhydrides.And, in order to improve the reactivity of these compositions, can be with tertiary amine compound as curing catalyst.Perhaps, also this tertiary amine compound can be used alone as solidifying agent.Solidifying agent and curing catalyst can be liquid and also can be solid (comprising powder), and indefinite.And, also can use single-liquid type that the compound that will have the epithio base and solidifying agent and/or curing catalyst all mix or respectively preparation and the binary liquid shape that mixes in use.Below the compound that has more than one epithio base in the molecule is called episulfide compounds.
[changing 2]
The concrete example of described episulfide compounds for example can be enumerated: 2,2-is two, and (4-(2,3-epithio propoxy-) phenyl) propane, it is two that (4-(2,3-epithio propoxy-) phenyl) methane, 1,6-two (2,3-epithio propoxy-) naphthalene, 1,1,1-three-(4-(2,3-epithio propoxy-) phenyl) ethane, 2, two (4-(2, the 3-epithio propoxy-) cyclohexyl) propane of 2-, two (4-(2,3-epithio propoxy-) cyclohexyl) methane, 1,1,1-three-(4-(2,3-epithio propoxy-) cyclohexyl) ethane, 2 of 1,5-PD, 3-epithio cyclohexyl) ether, 1, two (3,4-epithio octyl group) ether of 6-hexylene glycol etc., but be not limited thereto.
Below describe described solidifying agent or the curing catalyst that can be used for epoxy compounds or episulfide compounds in detail.The concrete example of described polyamino compound can be enumerated: Diethylenetriaminee (DETA), triethylenetetramine, m-xylene diamine, different fluorine that ketone diamines, 1, the two amino methyl hexanaphthenes of 3-, diaminodiphenyl-methane, m-phenylenediamine, diaminodiphenylsulfone(DDS), Dyhard RU 100, organic acid dihydrazide and piperidines etc., but be not limited thereto.
The concrete example of described polyphenolic substance can be enumerated: phenolic varnish type phenol resins and their modified phenol novolac resin by the aldehydes reactions such as the phenols such as phenol, alkylphenol and formaldehyde, Paraformaldehyde 96 are obtained are the polyphenol resins such as ZiLOG type phenol resins, dicyclopentadiene type phenol resins and multifunctional type phenol resins etc., but are not limited thereto.Especially preferably at room temperature be liquid polyphenolic substance.
The concrete example of described multi-thioalcohol compound can be enumerated: 3-thiohydracrylic acid-3-methoxyl group butyl ester, 3-thiohydracrylic acid-2-ethylhexyl, 3-thiohydracrylic acid tridecyl ester, the trimethylolpropane tris thiopropionate, tetramethylolmethane tetrathio propionic ester, Methyl Thioglycolate, thioglycollic acid-2-ethyl hexyl ester, the ethylene glycol bis mercaptoacetate, 1, the two mercaptoacetates of 4-butyleneglycol, the trimethylolpropane tris mercaptoacetate, tetramethylolmethane four mercaptoacetates, two (2-mercaptoethyl) ether, the 1-butyl sulfhydryl, the 1-hexylmercaptan, cyclohexylmercaptan, 1, the 4-succinimide mercaptans, 3-sulfydryl-2-butanols, γ mercaptopropyitrimethoxy silane, thiophenol, benzyl sulfhydrate, 1,3,5-tri-thiol methylbenzene, 1,3,5-tri-thiol methyl-2,4, the 6-Three methyl Benzene, the polyethers that contains terminal thiol group, the polythioether that contains terminal thiol group, the mercaptan compound that reaction by epoxy compounds and hydrogen sulfide obtains, have mercaptan compound of the terminal thiol group that the reaction by multi-thioalcohol compound and epoxy compounds obtains etc., but be not limited thereto.
The concrete example of described acid anhydrides can be enumerated: the cyclic acid anhydrides such as dodecenylsuccinic anhydride, PAPA, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methyl carbic anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic anhydride, tetrabromophthalic anhydride, aconitic anhydride etc., but be not limited thereto.
The concrete example of described tertiary amine compound can be enumerated: the Resins, epoxy take bisphenol A type epoxy resin etc. as representative and amine compound reaction be to midway crushed material, imdazole derivatives and the Diazabicyclic derivatives etc. of the epoxy adduct compound of stage gained, but be not limited thereto.
With respect to epoxy compounds or episulfide compounds 100 weight parts, solidifying agent is 30～120 weight parts, and preferred 50～100 weight parts, curing catalyst are 0.1～10 weight part, preferred 0.3～0.7 weight part.
Polyurethane resin composition is the composition that comprises following compositions: the compound with isocyanate group; Solidifying agent with the polyol compound with a plurality of hydroxyls and/or polyamino compound.Catalyzer can use organotin complex compound, organic zinc complex compound and tertiary amine compound.And, also can use the binary liquid shape that mixes all single-liquid types that form gained, reaches respectively preparation and mix in use.Below, the compound that will have isocyanate group is called isocyanate compound.
As described isocyanate compound, so long as in a molecule, have plural isocyanate group, then be not particularly limited, for example have: aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate.Concrete example as this compound, aromatic diisocyanate can be enumerated: 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 2,2 '-diphenylmethanediisocyanate, polyphenylene polymethylene polymeric polyisocyanate, 1,5-naphthylene vulcabond, 1,4-naphthylene vulcabond, p-phenylene vulcabond, meta-phenylene vulcabond, ortho-, meta-or p-xylylene vulcabond and meta-xylylene vulcabond etc., aliphatic diisocyanate can be enumerated: tetramethylene diisocyanate, hexamethylene diisocyanate and 2-methyl isophthalic acid, 5-pentane vulcabond etc.And alicyclic diisocyanate can be enumerated: 1-methylcyclohexane-2, and 4-vulcabond, isophorone diisocyanate and dicyclohexyl methyl hydride-4,4 '-vulcabond etc., be not particularly limited.And, also can use the compound with blocked isocyanate, blocked isocyanate seals isocyanate group with protecting group, produces isocyanate group by adding the heat abstraction protecting group.
The concrete example of described polyol compound can be enumerated: ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 4,4 '-dihydroxyl ditan, glycerol, 1,2,6-hexanetriol, 1,1,1-TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol and sucrose etc. have the compound of at least two hydroxyls in molecule, be not particularly limited.
The concrete example of described polyamino compound can be enumerated: Diethylenetriaminee (DETA), triethylenetetramine, m-xylene diamine, different fluorine that ketone diamines, 1, the two amino methyl hexanaphthenes of 3-, diaminodiphenyl-methane, m-phenylenediamine, diaminodiphenylsulfone(DDS), Dyhard RU 100, organic acid dihydrazide and piperidines etc., but be not limited thereto.
If consider the diversity of price or kind, what described catalyzer was fit to is the organotin complex compound.Specifically can enumerate: two sad dibutyl tins, acetic acid dibutyl tin, dibutyl tin laurate, 2 ethyl hexanoic acid butyl tin, stannous octoate, naphthenic acid tin, oleic acid tin and butyl acid tin etc., but be not limited thereto.And the concrete example of organic zinc complex compound can be enumerated: zinc acrylate resin, zinc acetate, zinc citrate, zinc salicylate, zinc oxalate, hexanodioic acid zinc, carbaminate, Phthalocyanine Zinc, mercaptan zinc (zinc thiolate) and Zinic stearas, zinc naphthenate, capric acid zinc, zinc butyrate, zinc neodecanoate, isopropylformic acid zinc, M-nitro benzoic acid zinc, zinc octoate and 2-ethyl hexyl alkanoic acid zinc etc.The concrete example of tertiary amine compound can be enumerated: the Resins, epoxy take bisphenol A type epoxy resin etc. as representative and amine compound reaction be to midway crushed material, imdazole derivatives and the Diazabicyclic derivatives etc. of the epoxy adduct compound of stage gained, but be not limited thereto.
With respect to isocyanate compound 100 weight parts, solidifying agent is 10～100 weight parts, and preferred 30～70 weight parts, catalyzer are 0.001～1 weight part, preferred 0.01～0.1 weight part.
The moisture-curable silicon resin composition comprises: have the organopolysiloxane with the hydroxyl of silicon atom bonding; With the silane compound with multifunctional hydrolization group as linking agent.And, carry out condensation reaction in order to make described compound, will comprise that the titanium of organic tin complex, amine compound, tetrels or the organic complex of zirconium are used as catalyzer.There is dealcoholizing-type in kind difference according to hydrolyzable group, takes off the oxime type, takes off acetic acid type and takes off ketone type etc.And, also can use and mix the binary liquid shape that all form the single-liquid type of gained and prepare and mix in use respectively.Below, the organopolysiloxane that will have with the hydroxyl of silicon atom bonding is called silanol.
Described silanol has plural hydroxyl in a molecule, usually preferred its molecular chain two ends are by hydroxy-end capped.In this silanol, there is no particular restriction with the kind of the organic group of silicon atom bonding, such as enumerating: alkyl such as methyl, ethyl, propyl group and butyl; The cycloalkyl such as cyclopentyl and cyclohexyl; The alkenyl such as vinyl and allyl group; The aryl such as phenyl, tolyl and naphthyl; The aralkyl such as 2-styroyl; Perhaps part or all of the hydrogen atom of these groups is not particularly limited by the halogen atom such as chlorine atom or the amino group that waits replacement etc.
Described linking agent is so long as have the compound of 2～3 hydrolization groups in a molecule, indefinite then, the silane series coupling agent of preferred Siliciumatom and hydrolyzable group bonding.The kind of this hydrolization group can be enumerated: the alkanoyloxies such as acetoxyl group, hot acyloxy and benzoyloxy group; The ketoxime bases such as dimethyl ketone oximido, methyl ethyl ketone oximido and metacetone oximido; The alkoxyl groups such as methoxyl group, oxyethyl group and propoxy-; The alkenyloxies such as pseudoallyl oxygen base and 1-Ethyl-2-Methyl vinyl oxygen base; The amino such as dimethylamino, diethylin, fourth amino and hexamethylene amino; The aminooxy such as dimethyl aminooxy and diethyl aminooxy; The amide group such as N-methylacetamide base, N-ethyl acetamide base and N-methylbenzene amide group etc., but be not limited thereto.From the consideration to human body or environment, preferred methoxyl group, oxyethyl group and propoxy-.
As the concrete example of described catalyzer, the organotin complex compound can be enumerated: two sad dibutyl tins, acetic acid dibutyl tin, dibutyl tin laurate, 2 ethyl hexanoic acid butyl tin, stannous octoate, naphthenic acid tin, oleic acid tin and butyl acid tin etc.And Titanium series catalyst can be enumerated: tetra isopropyl metatitanic acid (テ ト ラ イ ソ プ ロ ピ Le チ タ ネ one ト), tetra-n-butyl metatitanic acid, butyl metatitanic acid dipolymer, four octyl group metatitanic acids, titanium acetylacetone, octene glycolic acid titanium (チ タ Application オ Network チ レ Application グ リ コ レ one ト), four titanium acetylacetones, ethyl 3-oxobutanoate titanium, multi-hydroxy stearic acid titanium, lactic acid titanium and trolamine titanium etc.Zirconium-based catalyst can be enumerated: four n-propoxyzirconium, four n-butoxy zirconiums, tetrem acyl acetonyl zirconium, two (ethyl 3-oxobutanoate) zirconiums of only son's oxygen ethylacetoacetone base, two (ethyl 3-oxobutanoate) zirconiums of dibutoxy, tetrem acyl acetonyl zirconium and three butoxy zirconium stearates etc.Yet, be not limited thereto.And the compound that has amine in the structure of linking agent is useful as catalysts also.The concrete example of this amine compound can be enumerated: N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and 3-aminopropyl triethoxysilane etc.
With respect to silanol 100 weight parts, linking agent is 0.1～25 weight part, and preferred 1～20 weight part, catalyzer are 0.001～1 weight part, preferred 0.01～0.1 weight part.
The heat-curing type silicon resin composition comprises: have the organopolysiloxane with the vinyl of silicon atom bonding; With the organopolysiloxane that has with the hydrogen atom of silicon atom bonding.In order to make described compound carry out addition reaction, the complex compound of the platinum metals such as platinum, rhodium and palladium is used for catalyzer.If will have the compounds such as alkynyl, ethylidine and tertiary amine of π key or non-covalent electron pair as inhibitor, can temporarily suppress the reaction that causes because of catalyzer.As its form, form the single-liquid type of gained and the binary liquid shape that forms respectively by mixing all.Below, the organopolysiloxane that will have with the vinyl of silicon atom bonding is called vinylsiloxane, and the organopolysiloxane that will have with the hydrogen atom of silicon atom bonding is called hydrogen siloxane.
Described vinylsiloxane preferably has plural vinyl in a molecule shown in chemical formula 3.The compound that preferably has vinyl at two ends.
[changing 3]
(R
1The alkyl such as expression methyl, ethyl, propyl group, amyl group, octyl group, undecyl, octadecyl; Or the cycloalkyl such as cyclohexyl; Or the aryl such as phenyl, tolyl, xylyl, benzyl, 2-styroyl.R
2The expression vinyl.X, y represent 0～3 integer, and n, m represent the integer (in addition, x+y+m＞=2) more than 0, and n and m represent respectively to exist only in the molecule-Si (CH
3)
2The O-unit and-Si (H) (CH
3) total number of O-unit, existence both can be concentrated in each unit, but also Individual existence.）
Described hydrogen siloxane is as long as comprise plural in a molecule and hydrogen atom (Si-H) silicon atom bonding.Specifically can enumerate: the part have the hydrogen atom of any silicon atom bondings beyond terminal with two chemical formula 4, have all silicon atom bondings beyond terminal with two hydrogen atom chemical formula 5 and have chemical formula 6 with the hydrogen atom of the silicon atom bonding of two ends.
[changing 4]
(m represents the integer more than 2, and n represents the integer more than 1.And n and m represent respectively to exist only in the molecule-Si (CH
3)
2The O-unit and-Si (H) (CH
3) total number of O-unit, existence both can be concentrated in each unit, but also Individual existence.）
[changing 5]
(m represents the integer more than 2)
[changing 6]
(m represents the integer more than 0)
Described catalyzer is if the complex compound of platinum metals, useful as catalysts then, but from the diversity of price or kind, use platinum and rhodium more.Concrete example as platinum group catalyst, the platinum complex of 0 valency can be enumerated divinyl tetramethyl disiloxane platinum complex and tetrem thiazolinyl tetramethyl-Fourth Ring siloxanes platinum complex, the platinum complex of divalent can be enumerated dichloro bi triphenyl phosphine and close palladium complex, the platinum complex of 4 valencys can be enumerated Platinic chloride etc., but is not limited thereto.Concrete example as the rhodium series catalysts, the rhodium complex of 1 valency can be enumerated three (triphenyl phosphite) rhodium chloride complex compound (Network ロ ロ ト リ ス ト リ Off ェ ニ Le Off ォ ス Off ァ イ ト ロ ジ ウ ム Wrong body), the rhodium complex of divalent can be enumerated four acetic acid, two rhodium complexs, and the rhodium complex of 3 valencys can be enumerated praseodynium rhodium complex etc.; But be not limited thereto.
As the concrete example of described inhibitor, acetylene system alcohol can be enumerated: 1-ethynyl-1-hexalin, 2-methyl-3-butyne-2-alcohol, 3,5-dimethyl-1-hexin-3-alcohol and 3-methyl isophthalic acid-dodecyne-3-alcohol etc.Poly-methyl ethylene cyclosiloxane can be enumerated: 1,3,5,7-tetrem thiazolinyl tetramethyl-Fourth Ring siloxanes, divinyl tetramethyl disiloxane, tetrem thiazolinyl dimethyl sily oxide and trialkyl cyanurate etc.Other can be enumerated: diallyl maleate, dimethyl maleate, ethyl maleate, diallyl fumarate and DEF etc., but be not limited thereto.
With respect to vinylsiloxane 100 weight parts, hydrogen siloxane is 0.1～30 weight part, preferred 1～20 weight part, the significant quantity of described catalyzer is for example 0.001～1 weight part, preferred 0.01～0.1 weight part, inhibitor are 0.001～1 weight part, preferred 0.01～0.1 weight part.
Acrylic acid resin composition, methacrylic resin composition, vinyl ether resin composition are so long as have respectively the compound of more than one acrylic, methacrylic acid group, vinyl ether group, then indefinite in a molecule.Specifically can enumerate simple function, 2 officials energy, 3 officials energy, polyfunctional monomer or oligomer.Can enumerate: produce free radical activity kind or cationic species and carry out being heating and curing of high molecular by organo-peroxide or positively charged ion series initiators by heating, and produce free radical activity kind or cationic species and carry out the photocuring of high molecular by free base system light trigger or positively charged ion series initiators by ultraviolet ray or visible light homenergic ray.Below, the compound that will have acrylic, methacrylic acid group, vinyl ether group is called acrylic compound, methacrylic compound, vinyl ether compound, will all be generically and collectively referred to as vinyl compound.And, acrylic compound and methacrylic compound are generically and collectively referred to as (methyl) acrylic compound.And, organo-peroxide, free base system light trigger, positively charged ion series initiators are generically and collectively referred to as initiator.
Below describe (methyl) acrylic compound in detail.The concrete example of simple function (methyl) Acrylic Acid Monomer can be enumerated: (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid phenoxy ethyl, phenoxy group glycol ether (methyl) acrylate, phenoxy group TEG (methyl) acrylate, (methyl) vinylformic acid Nonylphenoxy ethyl ester, Nonylphenoxy TEG (methyl) acrylate, methoxyl group glycol ether (methyl) acrylate, ethoxydiglycol (methyl) acrylate, (methyl) vinylformic acid butoxyethyl, butoxytriglycol (methyl) acrylate, 2-ethylhexyl polyoxyethylene glycol (methyl) acrylate, nonyl phenyl polypropylene glycol (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, Racemic glycidol (methyl) acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, glycerol (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, epoxy chloropropane (being designated hereinafter simply as ECH) modification (methyl) butyl acrylate, ECH modification (methyl) vinylformic acid benzene oxygen ester, oxyethane (being designated hereinafter simply as EO) modification phthalandione (methyl) acrylate, EO modification succsinic acid (methyl) acrylate, caprolactone modification (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid-N, N-diethyl amino ethyl ester, morpholino (methyl) acrylate and EO modified phosphate (methyl) acrylate etc., but be not limited thereto.
The concrete example of 2 functionalities (methyl) Acrylic Acid Monomer can be enumerated: 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, EO modification neopentyl glycol two (methyl) acrylate, propylene oxide (being designated hereinafter simply as PO) modification neopentyl glycol two (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, EO modified bisphenol A two (methyl) acrylate, ECH modified bisphenol A two (methyl) acrylate, EO modified bisphenol S two (methyl) acrylate, hydroxypivalic acid ester neopentylglycol diacrylate, caprolactone modification hydroxypivalic acid ester neopentylglycol diacrylate, neopentyl glycol modification TriMethylolPropane(TMP) two (methyl) acrylate, stearic acid modified tetramethylolmethane two (methyl) acrylate, the diacrylate dicyclopentenyloxyethyl methacrylate, EO modification two (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate and tricarbimide two (methyl) acrylic ester etc., but be not limited thereto.
The concrete example of 3 functionalities (methyl) Acrylic Acid Monomer can be enumerated: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, PO modification trimethylolpropane tris (methyl) acrylate, ECH modification trimethylolpropane tris (methyl) acrylate, ECH modification glycerol three (methyl) acrylate and tricarbimide three (acryloxy ethyl) ester etc., but be not limited thereto.
The concrete example of multifunctional (methyl) Acrylic Acid Monomer can be enumerated: two-TriMethylolPropane(TMP) four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, alkyl-modified Dipentaerythritol five acrylate, Dipentaerythritol six (methyl) acrylate and caprolactone modification Dipentaerythritol six (methyl) acrylate etc., but be not limited thereto.
The concrete example of (methyl) vinylformic acid oligomer can be enumerated: epoxy (methyl) acrylate of bisphenol A-type, phenolic varnish type, polyvalent alcohol type, polynary acid type, polyhutadiene type; Reach urethane (methyl) acrylate of polyester type, polyether-type etc., but be not limited thereto.
The concrete example of vinyl ether compound can be enumerated: the ethylene glycol bisthioglycolate vinyl ether, 1, the ammediol divinyl ether, the propylene glycol divinyl ether, 1,4-butyleneglycol divinyl ether, 1,3-butyleneglycol divinyl ether, 1,2-butyleneglycol divinyl ether, 2,3-butyleneglycol divinyl ether, the 1-methyl isophthalic acid, the ammediol divinyl ether, the 2-methyl isophthalic acid, the ammediol divinyl ether, the 2-methyl isophthalic acid, 2-propylene glycol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexylene glycol divinyl ether, hexanaphthene-1,4-glycol divinyl ether, hexanaphthene-1,4-dimethanol divinyl ether, p-dimethylbenzene ethylene glycol bisthioglycolate vinyl ether (p-キ シ レ Application グ リ コ one Le ジ PVC ニ Le エ one テ Le), diethylene glycol divinyl ether, the triethylene glycol divinyl ether, the TEG divinyl ether, the polyoxyethylene glycol divinyl ether, the dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, four propylene glycol divinyl ethers, polypropylene glycol divinyl ether and ethylene glycol propylene glycol copolymers divinyl ether etc., but be not limited thereto.
The concrete example of described organo-peroxide can be enumerated: methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxidation-3,3, the peroxidation ketones such as 5-trimethylcyclohexanone, peroxidation methylcyclohexanone, acetyl peroxide ritalin and diacetone peroxide; 1, two (tert-butyl hydroperoxide)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (tert-butyl hydroperoxide) hexanaphthenes, 2 of 1-, two (tert-butyl hydroperoxide) octanes of 2-, normal-butyl-4, the ketal peroxide classes such as two (tert-butyl hydroperoxide) valerates of 4-and two (tert-butyl hydroperoxide) butane of 2,2-; Tertbutyl peroxide, cumene hydroperoxide hydrogen, diisopropylbenzenehydroperoxide, p-p-menthane hydroperoxide, 2,5-dimethylhexane-2, the hydroperoxide kinds such as 5-diperoxy hydrogen and 1，1，3，3-tetramethylbutylhydro-peroxide; Ditertiary butyl peroxide, tert-butyl peroxide isopropyl benzene, dicumyl peroxide, α, α '-two (tert-butyl hydroperoxide-meta-sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane and 2,5-dimethyl-2, class such as dialkyl peroxide such as 5-two (tert-butyl hydroperoxide) hexin-3 grade; Acetyl peroxide, peroxidation isobutyryl, peroxidation decoyl, decanoyl peroxide, lauroyl peroxide, peroxidation-3,5,5-trimethyl acetyl, peroxysuccinic acid, benzoyl peroxide, peroxidation-2,4 dichloro benzene acyl and peroxidation-diacyl peroxide classes such as meta-toluoyl; The peroxy dicarbonates such as di-isopropyl peroxydicarbonate, peroxy dicarbonate two 2-ethylhexyls, peroxy dicarbonate di-n-propyl ester, two-(4-tert-butylcyclohexyl) peroxy dicarbonate, peroxy dicarbonate tetradecane ester, peroxy dicarbonate two 2-ethoxy ethyl esters, peroxy dicarbonate dimethoxy isopropyl ester, two (3-methyl-3-methoxyl group butyl) peroxy dicarbonate and peroxy dicarbonate diallyl; The peroxidation tert-butyl acetate, the peroxidation tert-butyl isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester, new peroxide tert-butyl caprate, peroxidation neodecanoic acid isopropyl phenyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, the peroxidation lauric acid tert-butyl ester, peroxidized t-butyl perbenzoate, peroxidation m-phthalic acid di tert butyl carbonate, 2,5-dimethyl-2,5-two (benzoyl peroxidation) hexane, the peroxidation toxilic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate, peroxidation acid isopropyl phenyl ester, the own ester of peroxidation neodecanoic acid uncle, talkyl peropivalate, the new hecanoic acid t-butyl ester of peroxidation, the peroxyesters such as the peroxidation own ester of new caproic acid uncle and the new caproic acid isopropyl of peroxidation phenyl ester; And acetyl cyclohexyl sulfonyl-peroxide, peroxidation allylic carbon tert-butyl acrylate, but be not limited thereto.
The light trigger that can be used for photocuring can be enumerated: the free base system light trigger that produces the free radical activity kind by visible rays, ultraviolet ray, X ray and electron rays homenergic ray; Positively charged ion series initiators with the cationic species that produces Bronsted acid or Lewis acid etc.When being used for (methyl) acrylic compound, preferred free radical series initiators, but when being used for vinyl ether compound, can use free radical series initiators and/or positively charged ion series initiators.
The concrete example of described free base system light trigger can be enumerated: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the benzil dimethyl ketal, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, the 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethyl phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone and 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetophenones such as acetone oligomer; The st-yrax classes such as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, ortho-, meta-or p-benzoyl M-nitro benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyl-diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone, 4-benzoyl-N, N-dimethyl-N-[2-(1-oxygen-2-propenyl oxygen) ethyl] benzophenones such as phenyl trimethylammonium bromide and (4-benzoyl benzyl) trimethyl ammonium chloride; ITX, ITX, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxy-thioxanthone and 2-(3-dimethylamino-2-hydroxyl)-3, position muriate (2-(3-ジ メ チ Le ア ミ ノ-2-ヒ De ロ キ シ)-3 between 4-dimethyl-9H-thioxanthone-9-, 4-ジ メ チ Le-9H-チ オ キ サ Application ト Application-9-オ Application メ ソ Network ロ リ De) the thioxanthene ketone etc. such as, but be not limited thereto.
Described positively charged ion series initiators can be enumerated: diazonium salt, sulfonium salt and salt compounded of iodine etc.Concrete example can be enumerated: benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro borate, 4,4 '-the two hexafluorophosphates of two [two (2-hydroxyl-oxethyl phenyl) sulfonium] diphenyl sulfide, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluorophosphate and phenylbenzene-4-sulphur Phenoxyphenyl sulfonium hexafluorophosphate etc., but be not limited thereto.
With respect to vinyl compound 100 weight parts, add initiator 0.01～10 weight part, preferred 0.1～1 weight part.
Coating composition can be enumerated the composition that plastics (general-purpose plastics or engineering plastics etc.), rubber (diene series rubber or non-diene series rubber etc.) and thermoplastic elastomer is dissolved in gained in the solvent.The below describes coating composition in detail.In plastics, general-purpose plastics can be enumerated: polyethylene, polypropylene, vinyl chloride resin, polystyrene, ABS resin, PET resin, methacrylic resin (acrylic resin), polyvinyl alcohol; Engineering plastics can be enumerated: polycarbonate, polymeric amide, polyacetal, polybutylene terephthalate, fluorine resin etc.
About rubber, diene series rubber can be enumerated: natural rubber, synthetic polyisoprene, divinyl rubber, styrene-butadiene rubber(SBR), neoprene and paracril etc.On the other hand, non-diene series rubber can be enumerated: isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), urethanes, silicon rubber, chlorosulphonation rubber, chlorinatedpolyethylene, acrylic rubber, epichloro hydrin rubber and viton etc.And their multipolymer also is contained in the rubber.
Thermoplastic elastomer with intermediate characteristic of plastics and rubber can be enumerated: SIS(styrene isoprene styrene block copolymer), SEPS(styrene ethylene acrylonitrile/styrene alkene block copolymer) etc. polystyrene; Or TPO(TPO), TPV(thermoplastic vulcanizates elastomerics) ethylene series such as; The EVA(ethylene vinyl acetate copolymer), EEA(ethylene ethyl acrylate) the ethylene-vinyl acetate system such as; Perhaps other can be enumerated: vinyl chloride, polyurethane series, ester system, acid amides system, fluorine system, ionic polymerization system, iso-butylene system and silicon-type etc., but be not limited thereto.
And the solvent of dissolving plastics, rubber and thermoplastic elastomer is so long as make the solvent of each composition dissolves, then indefinite.The example of this solvent can be enumerated: the solvent of aliphatics hydrocarbon system, fragrant family and ester system.Particularly, the aliphatics hydrocarbon system can be enumerated normal hexane and petroleum solvent etc.; The fragrance family can be enumerated toluene and dimethylbenzene etc.; And ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether acetate etc. can be enumerated by ester system, but are not limited thereto.
In the scope that does not undermine characteristic of the present invention, can cooperate in right amount: the tinting materials such as pigment, dyestuff; The inorganic fillers such as metal powder, calcium carbonate, talcum, silica, aluminum oxide, aluminium hydroxide; The additives such as fire retardant, organic filler, softening agent, antioxidant, defoamer, silane series coupling agent, flow agent, rheology control agent, solvent.By adding above-mentioned thing, can obtain excellent composition and the cured article thereof such as mechanical strength of resin, bonding strength, operability, keeping quality.
Described (B) composition is to have a ferromagnetic powder, if with permanent magnet quite.Permanent magnet refers to accept from the outside supply of magnetic field or electric current and continues relatively chronically the object that holding magnet should have character.The concrete example of permanent magnet can be enumerated: the Al-Ni-Co series magnet take aluminium, nickel, cobalt as the main composition composition; Ferrite based magnet take iron and strontium or barium as the main composition composition; And the uncommon great soil group based magnet take neodymium, samarium, cobalt as the main composition composition.Relative therewith, soft iron of only just having magnet character when being magnetized by the external magnetic field etc. is called temporary magnet.In the present invention with relict flux density as the magnetic standard.The ferromagnetism of putting down in writing in this specification sheets refers to that relict flux density is more than 1.0.The relict flux density of (B) composition that is suitable in the present invention using is 1.0～14.0kG, preferred 1.0～7.0kG, more preferably 1.5～3.0kG.It is the Al-Ni-Co series magnet of 9.0～14.0kG, uncommon great soil group based magnet that Al-Ni-Co series magnet, uncommon great soil group based magnet can use relict flux density (Br), preferred 7.0～10.0kG, it is the ferrite based magnet of 1.0～5.0kG that the ferrite based magnet can use relict flux density (Br), preferred 1.5～3.0kG.
Can make the only stronger magnet of magnetic on specific direction.Be referred to as anisotropic magnet.Anisotropic magnet has the stronger feature of magnetic on specific direction, and has in the other direction the tendency without magnetic.In any direction magnetic all identical magnet be called isotropy, it has following characteristics, that is, although magnetic a little less than, use all to be with in any direction to be magnetic.
These isotropy or anisotropic magnet powder are can be added in the resin of plastics, rubber etc. to mix, and by compressing, spray, extrude etc. and shaping is cured as the magnet of specified shape.The manufacturing process of anisotropic magnet powder has mechanical orientation and these two kinds of working methods of magnetic field orientating.Mechanical orientation refers to distribute to be orientated by the mechanicalness between roller, and therefore using particle shape is tabular magnetic iron powder, to be convenient to orientation.On the other hand, magnetic field orientating is to come extrusion molding by the spray up n. device in magnetic field, and it uses the slightly circular magnet powder of particle shape, in order to be not subjected to resistance in flowing.Isotropic magnet powder is particle direct forming under the state of random direction.
Spendable (B) composition is so long as have ferromagnetic magnet powder in the present invention, indefinite then, but from considering in price preferred anisotropy or isotropic ferrite based magnet powder.And median size is below the 5 μ m, preferred 0.1 μ m～5 μ m, and more preferably the magnet powder of 0.9 μ m～3.5 μ m is fit to mixing to resin.And can use shaping density is 2.0～4.0g/cm
3, Coercive Force be 140kA/m following (for example 1～140kA/m), intrinsic Coercive Force be 300kA/m following (for example 1～300kA/m) and maximum energy-density be 10kJ/m
3Below (1～10kJ/m for example
3) the magnet powder.The concrete example of ferrite based magnet powder can be enumerated DOWA electronics limited-liability company (DOWA HOLDINGS Co., Ltd) manufacturing: mechanical orientation anisotropic ferrite powder OP-56 and NF-56; Magnetic field orientating anisotropic ferrite powder NF-350, OP-71, NP-110 and SF-120; And isotropic ferrite powder NEY, NRK, BOP-B and BOP-K.The concrete example of ferrite based magnet powder can also be enumerated field, family Industries, Inc (TODA KOGYO CORP.) manufacturing: magnetic field orientating anisotropic ferrite powder MA-951, FL-900, FM-201, FA-700 and FAN-800; Mechanical orientation anisotropic ferrite powder FS-317, FH-800, FH-801 and FX-7; And isotropic ferrite powder GP-500 and FB-105.OP-56, NF-350 and BOP-K that the preferred DOWA electronics of (B) of the present invention composition limited-liability company makes.
With respect to curable resin composition 100 weight parts, (B) addition of composition is 10～100 weight parts, preferred 10～70 weight parts.
(C) composition that uses in the present invention is from considering in price preferred silver powder and/or nickel powder with the diversity of particle shape.Basically preferred apparent density or the less powder of tap density.These powders preferably structurally have the space of appropriateness and have the powder of agglutinate structure.The tap density of silver powder is less than 1.5g/cm
3, preferred 0.1g/cm
3～1.5g/cm
3, more preferably 0.5g/cm
3～1.2g/cm
3, the apparent density of nickel powder is less than 1.0g/cm
3, preferred 0.1g/cm
3～1.0g/cm
3, more preferably 0.4g/cm
3～1.0g/cm
3Silver powder is different from nickel powder density, so silver powder adopts tap density, nickel powder employing apparent density.This is because nickel is less with silver-colored phase specific density, if to nickel powder instrumentation tap density, with the tendency that exists numerical value to make mistakes.The test method of tap density is abideed by JISZ2512, and the test method of apparent density is abideed by JISZ2504.
With respect to the gross weight (solids component (removing volatile component)) of resin combination of the present invention, (C) addition of composition is that 25 % by weight present electroconductibility when above.Preferred 25～70 % by weight, more preferably 25～60 % by weight.The concrete example of silver powder can be enumerated: (the MITSUI MINING ﹠amp of mining industry limited-liability company of Mitsui Metal Co., Ltd.; SMELTING CO., LTD.) the 3010(tap density made: 1.0g/cm
3), the G-14(tap density made of DOWA high-tech share company limited (DOWAHIGHTECH CO., LTD.): 0.8g/cm
3) and the Sylvest E-20(tap density made of DS power chemistry institute limited-liability company (Tokuriki Chemical Research Co., Ltd): 0.8g/cm
3) etc.And the concrete example of nickel powder can be enumerated: the NickelType210(apparent density that INCO Limited makes: 0.5g/cm
3), NickelType255(apparent density: 0.6g/cm
3) and NickelType287(apparent density: 0.85g/cm
3) etc.
In general, if be filled in a large number silver powder or nickel powder is 65～95 % by weight in solids component, then will stablize as the conductivity of conductive resin composition.It is 2.0g/cm that the powder of easily filling in a large number mostly is tap density
3Above silver powder or apparent density are 1.5g/cm
3Above nickel powder, most of spherical powder (also comprising non-setting) and flakey powder (laminar powder) all meet described condition.These powder secondary aggegations are less, are bordering on the progenitor state, therefore can fill in a large number, but on the other hand, the grid structure between the particle are scattered, is not the state that is suitable for conducting, if therefore do not fill in a large number, then conductivity is with unstable.And, finally have to fill in a large number, thereby cause cost to increase.On the other hand, because (C) composition has the secondary aggegation that structure is difficult for collapse, if therefore use separately, will be difficult to fill in a large number, thereby addition is restricted.Even if be filled to till the limit, conductivity is also unstable.Especially in the time can not using the composition of solvent or softening agent, be difficult to fill in a large number.
Resin combination of the present invention can reach (C) by raising (B) composition, and the dispersiveness of composition obtains better electroconductibility.Preferably making in the preparation the maximum particle diameter of each composition is below the 50 μ m, to improve dispersiveness.Dispersing method has Hu Foshi polishing (Hoover Muller) and paint regulator vibratory drilling method etc.And, in order to improve dispersiveness, when making resin combination, can use the small-sized electric stirrer of homogenizer, single-shaft variant, agitator kettle, ball mill and the triple-roller mill etc. of biaxial type.When carrying out dispersed validation test, can use grindometer or particle size analyzer.
Do not illustrate fully although become to assign to manifest conductive mechanism by combination (B) composition with (C), consider to have following viewpoint.Has by magnetic force the mutually power of tractive between the progenitor as the magnet powder of (B) composition.(B) composition and (C) in the composition that composition is fully disperseed is in the state that has silver powder between magnet powder and the magnet powder, and by the magnetic force of (B) composition, the particle of silver powder is squeezed each other, thus the Distance Shortened between the powder of silver powder.This means that the curable resin composition between the powder that is present in silver powder becomes film, thereby be easy to carry out insulation breakdown, to present conductivity.And infer that therefore (C) composition generation secondary aggegation and possess the grid structure that is suitable for conducting can be suitable for the present invention.
Embodiment
The below enumerates embodiment and illustrates in greater detail the present invention, but the present invention is not limited to these embodiment.
In embodiment 1～7 and comparative example 1～4, preparation (A) composition is the conductive resin composition that comprises the hot curing resin composition of epoxy compounds and acid anhydrides, and makes test piece, 120 ℃ of lower curing one hour.
[embodiment 1～7]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: the hybrid epoxidized compound of bisphenol A-type and F type (limited-liability company of the large Japanese ink of EPICLON EXA-835LV chemical plant (DIC Corporation) manufacturing)
■ solidifying agent: the mixture of the mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride (HN-5500 Hitachi changes into Industries, Inc (Hitachi Chemical))
The ■ curing catalyst: the Resins, epoxy amine adduct is curing catalyst (Amicure MY-24 aginomoto fine chemistry limited-liability company (Ajinomoto Fine-Techno Co., Inc.) manufacturing)
■ solvent: industrial dimethylbenzene (dimethylbenzene Japan alcohol is sold limited-liability company (JAPAN ALCOHOLTRADING COMPANY LIMITED))
(B) composition: have ferromagnetic powder
■ ferrite based magnet powder (the anisotropy field orientation is made with NF-350DOWA electronic material limited-liability company)
■ ferrite based magnet powder (the anisotropy mechanical orientation is made with OP-56DOWA electronic material limited-liability company)
■ ferrite based magnet powder (manufacturing of isotropy BOP-K DOWA electronic material limited-liability company)
(C) composition: tap density is less than 1.5g/cm
3Silver powder or apparent density be less than 1.0g/cm
3Nickel powder
The ■ tap density is 0.8g/cm
3Silver powder (manufacturing of G-14DOWA electronic material limited-liability company)
The ■ apparent density is 0.5g/cm
3Nickel powder (manufacturing of NickelType210INCO Limited)
Described host, described solidifying agent and described solvent are added in the stirrer, stirred 10 minutes.Then, add described (B) composition, stirred 10 minutes.Add described (C) composition, restir 30 minutes.At last, add described curing catalyst, stirred 10 minutes.Detailed preparation amount is abideed by table 1, and numerical value all represents with weight part.
[comparative example 1 and comparative example 2]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: the hybrid epoxidized compound of bisphenol A-type and F type (manufacturing of limited-liability company of the large Japanese ink of EPICLON EXA-835LV chemical plant)
■ solidifying agent: the mixture of the mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride (HN-5500 Hitachi changes into Industries, Inc)
The ■ curing catalyst: the Resins, epoxy amine adduct is curing catalyst (manufacturing of Amicure MY-24 aginomoto fine chemistry limited-liability company)
■ solvent: industrial dimethylbenzene (dimethylbenzene Japan alcohol is sold limited-liability company)
(C) composition: tap density is less than 1.5g/cm
3Silver powder
The ■ tap density is 0.8g/cm
3Silver powder (manufacturing of G-14DOWA electronic material limited-liability company)
(C ') composition: silver powder
The ■ tap density is 3.1g/cm
3Flakey silver powder (manufacturing of TCG-1 DS power chemistry institute limited-liability company)
Described host, described solidifying agent and described solvent are added in the stirrer, stirred 10 minutes.Then, add described (C) composition or (C ') composition, restir 30 minutes.Add at last described curing catalyst, stirred 10 minutes.Detailed preparation amount is abideed by table 1.
[comparative example 3 and comparative example 4]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: the hybrid epoxidized compound of bisphenol A-type and F type (manufacturing of limited-liability company of the large Japanese ink of EPICLON EXA-835LV chemical plant)
■ solidifying agent: the mixture of the mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride (HN-5500 Hitachi changes into Industries, Inc)
The ■ curing catalyst: the Resins, epoxy amine adduct is curing catalyst (manufacturing of Amicure MY-24 aginomoto fine chemistry limited-liability company)
■ solvent: industrial dimethylbenzene (dimethylbenzene Japan alcohol is sold limited-liability company)
(B) composition: have ferromagnetic powder
■ ferrite based magnet powder (the anisotropy field orientation is made with NF-350DOWA electronic material limited-liability company)
(C ') composition: silver powder
The ■ tap density is 3.1g/cm
3Flakey silver powder (manufacturing of TCG-1 DS power chemistry institute limited-liability company)
(C ") composition: nickel powder
The ■ apparent density is 1.1g/cm
3Flakey nickel powder (manufacturing of HCA-1NOVAMET company)
Described host, described solidifying agent and described solvent are added in the stirrer, stirred 10 minutes.Then, add described (B) composition, stir after 10 minutes, add described (C ') composition or described (C ") composition, restir 30 minutes.Add at last described curing catalyst, stirred 10 minutes.Detailed preparation amount is abideed by table 1.
[table 1]
In embodiment 8～14 and comparative example 5～8, preparation (A) composition is the conductive resin composition that comprises the moisture-curable resin combination of silanol and linking agent, and makes test piece, places 24 hours so that its curing under 25 ℃ * 50%RH.
[embodiment 8～14]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: two ends have the dimethyl silicone oil (the BY16-873 beautiful DOW CORNING limited-liability company in east (Dow Corning Toray Co., Ltd.) makes) of silicon hydroxyl
■ linking agent: 3-(2-aminoethyl) aminopropyl trimethoxysilane (the beautiful DOW CORNING in Z-6020 east limited-liability company makes)
■ additive: hydrophobicity fumed silica (AEROSIL R972 Japan AEROSIL limited-liability company (Nippon Aerosil Co., Ltd.) makes)
■ catalyzer: the two silicic acid three ethoxy esters of dibutyl tin (Neostann U-303 day east changes into limited-liability company (Nitto Kasei Co., Ltd.) and makes)
(B) composition: have ferromagnetic powder
■ ferrite based magnet powder (the anisotropy field orientation is made with NF-350DOWA electronic material limited-liability company)
■ ferrite based magnet powder (the anisotropy mechanical orientation is made with OP-56DOWA electronic material limited-liability company)
■ ferrite based magnet powder (manufacturing of isotropy BOP-K DOWA electronic material limited-liability company)
(C) composition: tap density is less than 1.5g/cm
3Silver powder or apparent density be less than 1.0g/cm
3Nickel powder
The ■ tap density is 0.8g/cm
3Silver powder (manufacturing of G-14DOWA electronic material limited-liability company)
The ■ apparent density is 0.5g/cm
3Nickel powder (manufacturing of NickelType210INCO Limited)
Described host and described linking agent are added in the stirrer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Then, add described additive and described (B) composition, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Add described (C) composition, Yi Bian carry out vacuum defoamation, Yi Bian stirred 120 minutes.Add at last described catalyzer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 5 minutes.Detailed preparation amount is abideed by table 2, and numerical value all represents with weight part.
[comparative example 5 and comparative example 6]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: two ends have the dimethyl silicone oil (the beautiful DOW CORNING in BY16-873 east limited-liability company makes) of silicon hydroxyl
■ linking agent: 3-(2-aminoethyl) aminopropyl trimethoxysilane (the beautiful DOW CORNING in Z-6020 east limited-liability company makes)
■ additive: hydrophobicity fumed silica (AEROSIL R972 Japan AEROSIL limited-liability company makes)
■ catalyzer: the two silicic acid three ethoxy esters of dibutyl tin (Neostann U-303 day east changes into limited-liability company and makes)
(C) composition: tap density is less than 1.5g/cm
3Silver powder
The ■ tap density is 0.8g/cm
3Silver powder (manufacturing of G-14DOWA electronic material limited-liability company)
(C ') composition: silver powder
The ■ tap density is 3.1g/cm
3Flakey silver powder (manufacturing of TCG-1 DS power chemistry institute limited-liability company)
Described host and described linking agent are added in the stirrer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Then, add described additive, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Add described (C) composition or described (C ') composition, Yi Bian carry out vacuum defoamation, Yi Bian stirred 120 minutes.At last, add described catalyzer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 5 minutes.Detailed preparation amount is abideed by table 2.
[comparative example 7 and comparative example 8]
Prepared following compositions in order to prepare conductive resin composition.
(A) composition: curable resin composition
■ host: two ends have the dimethyl silicone oil (the beautiful DOW CORNING in BY16-873 east limited-liability company makes) of silicon hydroxyl
■ linking agent: 3-(2-aminoethyl) aminopropyl trimethoxysilane (the beautiful DOW CORNING in Z-6020 east limited-liability company makes)
■ additive: hydrophobicity fumed silica (AEROSIL R972 Japan AEROSIL limited-liability company makes)
■ catalyzer: the two silicic acid three ethoxy esters of dibutyl tin (Neostann U-303 day east changes into limited-liability company and makes)
(B) composition: have ferromagnetic powder
■ ferrite based magnet powder (the anisotropy field orientation is made with NF-350DOWA electronic material limited-liability company)
(C ') composition: silver powder
The ■ tap density is 3.1g/cm
3Flakey silver powder (manufacturing of TCG-1 DS power chemistry institute limited-liability company)
(C ") composition: nickel powder
The ■ apparent density is 1.1g/cm
3Flakey nickel powder (manufacturing of HCA-1NOVAMET company)
Described host and described linking agent are added in the stirrer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Then, add described additive and described (B) composition, Yi Bian carry out vacuum defoamation, Yi Bian stirred 10 minutes.Add described (C ') composition or described (C ") composition, Yi Bian carry out vacuum defoamation, Yi Bian stirred 120 minutes.Add at last described catalyzer, Yi Bian carry out vacuum defoamation, Yi Bian stirred 5 minutes.Detailed preparation amount is abideed by table 2.
[table 2]
[test piece]
Cover wide 10mm * length 90～100mm at the sheet glass that is of a size of 2.0mm * 100mm * 100mm, and the brushing resin combination.At this moment, film coated surface is smooth, and the broadside that covers is parallel with test board, notes bubble is sneaked in the resin combination.Peel off at last and cover, under each condition of cure, make its curing.
[volume specific resistance]
After making described test piece, the resistance (R: Ω) when utilizing the tester with plate electrode to measure between electrode as 50mm.Then, measure the thickness (t:mm) of cured article with thin-film thickness meter.Based on these two mensuration, utilize formula 1 volume calculated resistivity.When the resistance that tester is measured surpasses higher limit, owing to can't calculate, therefore be recorded as " OL ".
[several 1]
ρ: volume specific resistance (Ω m)
R: interelectrode resistance value (R: Ω m)
A: with respect to the section area (wide 10mm * thick t:mm) of the sense of current
L: interelectrode length (50mm)
[reliability test]
After the test piece of having made embodiment 1～14, comparative example 1～8, it is solidified, and instrumentation initial volume specific resistance.For the test piece of having measured initial volume specific resistance, by humidity test (85 ℃ * 85%RH * 500h) or thermal shock test (once the circulation: after-40 * 30 minutes, with 85 ℃ * 30 minutes for once the circulation, circulate 100 times) test subject implement accelerated test, and then instrumentation volume specific resistance.Comprise heat-curing resin conductive resin composition the results are shown in table 3, comprise the moisture-curable resin conductive resin composition the results are shown in table 4.Too high and when surpassing the higher limit of tester, owing to can't calculate initial volume specific resistance, therefore " do not implement " reliability test in initial resistance value.
[table 3]
[table 4]
According to the result of table 3 and 4, as seen have ferromagnetic magnet powder and tap density for less than 1.5g/cm mixing
3Silver powder and/or apparent density be less than 1.0g/cm
3Nickel powder and in the curable resin composition that forms, can present stable conductivity.Especially according to embodiment 1 and comparative example 1 relatively or embodiment 8 and comparative example 5 more as can be known, the ferromagnetism powder helps the stable of volume specific resistance.In embodiment 4, embodiment 13, think that nickel powder is subject to humidity effect and the conductivity that causes is deteriorated although in humidity test, present, although the addition of nickel powder is less, still present in the early stage stable volume specific resistance.And, embodiment 1 and comparative example 3 relatively or relatively the waiting of embodiment 8 and comparative example 7, shown silver powder is limited tap density, nickel powder limited the availability of apparent density.
[utilizability on the industry]
Unleaded trend has been risen in the whole world, so scolding tin is replaced by Pb-free solder or solder paster, conductive adhesive etc. just gradually.Use the conductive adhesive of silver powder or nickel powder not have scolding tin or solder paster costliness from price.From now on, formally carrying out scolding tin when replacing, the conductive resin composition of the present invention that has reliability and can reduce cost can play a role.
Claims (7)
1. conductive resin composition is characterized in that: comprise following (A) to (C) composition:
(A) composition: curable resin composition;
(B) composition: relict flux density is the powder more than 1.0; And
(C) composition: the tap density of abideing by JISZ2512 is 0.1 to 0.8g/cm
3Silver powder and/or the apparent density of abideing by JISZ2504 be 0.1 to 1.0g/cm
3Nickel powder,
With respect to the gross weight of described conductive resin composition and comprise (C) composition 25 to 70 % by weight, (B) median size of composition is 0.1 μ m to 5 μ m, and (C) maximum particle diameter of composition is below the 50 μ m.
2. conductive resin composition according to claim 1 is characterized in that: comprise (B) composition 10 to 100 weight parts with respect to (A) composition 100 weight parts.
3. conductive resin composition according to claim 1 and 2, it is characterized in that: (B) composition has 1.0 to 14.0kG relict flux density.
4. conductive resin composition according to claim 1 and 2, it is characterized in that: described (B) composition comprises anisotropy or isotropic magnet powder.
5. conductive resin composition according to claim 4, it is characterized in that: described magnet powder is ferrite based magnet powder.
6. conductive resin composition according to claim 1 and 2 is characterized in that: described (A) composition is at least a kind of curable resin composition that is selected among the group who is made of hot curing resin composition, moisture-curable resin combination, Photocurable resin composition and solvent evaporates curable resin composition.
7. conductive resin composition according to claim 1 and 2 is characterized in that: described (A) composition is at least a kind of curable resin composition that is selected among the group who is made of composition epoxy resin, episulfide resin composition, polyurethane resin composition, moisture-curable silicon resin composition, heat-curing type silicon resin composition, acrylic acid resin composition, methacrylic resin composition and vinyl ether resin composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-143987 | 2008-05-31 | ||
| JP2008143987A JP5534127B2 (en) | 2008-05-31 | 2008-05-31 | Conductive resin composition |
| PCT/JP2009/002326 WO2009144925A1 (en) | 2008-05-31 | 2009-05-27 | Conductive resin composition |
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| CN102015906A CN102015906A (en) | 2011-04-13 |
| CN102015906B true CN102015906B (en) | 2013-04-17 |
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| CN200980115570.2A Active CN102015906B (en) | 2008-05-31 | 2009-05-27 | Conductive resin composition |
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| JP (1) | JP5534127B2 (en) |
| CN (1) | CN102015906B (en) |
| WO (1) | WO2009144925A1 (en) |
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| CN102841503B (en) * | 2012-09-18 | 2013-12-04 | 江苏科技大学 | Photolithographic electronic silver paste composition for touch screen and preparation thereof |
| KR102175447B1 (en) * | 2013-07-11 | 2020-11-06 | 세메다인 가부시키 가이샤 | Production method for electrically conductive cured article and curing method for pulsed light curing composition |
| TWI653312B (en) * | 2014-03-11 | 2019-03-11 | 日商味之素股份有限公司 | Film |
| CN104356801A (en) * | 2014-10-17 | 2015-02-18 | 苏州莱特复合材料有限公司 | Electromagnetic shielding metal powder composite coating and preparation method thereof |
| CN109643662B (en) * | 2016-08-19 | 2021-07-13 | 住友电木株式会社 | Chip bonding paste and semiconductor device |
| KR102213777B1 (en) * | 2018-02-02 | 2021-02-08 | 주식회사 엘지화학 | Adhesive film for semiconductor device |
| CN109251709A (en) * | 2018-08-28 | 2019-01-22 | 善仁（浙江）新材料科技有限公司 | It is a kind of can room temperature storage middle low-temperature cured conductive glue and preparation method thereof |
| JP7515273B2 (en) * | 2020-03-06 | 2024-07-12 | 株式会社ノリタケカンパニーリミテド | Conductive silicone rubber composition and composite using same |
| CN118176260A (en) * | 2021-11-02 | 2024-06-11 | 昭荣化学工业株式会社 | Heat-curable conductive resin composition and method for producing electronic component |
| JPWO2023080028A1 (en) * | 2021-11-02 | 2023-05-11 |
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| CN1065280A (en) * | 1990-02-23 | 1992-10-14 | 旭化成工业株式会社 | Compositions of cupric alloy |
| CN1737072A (en) * | 2004-08-18 | 2006-02-22 | 播磨化成株式会社 | Conductive adhesive agent and process for manufacturing article using the conductive adhesive agent |
| CN1892945A (en) * | 2005-07-01 | 2007-01-10 | 松下电器产业株式会社 | Movable contact assembly, method of manufacturing the same, and switch using the same |
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| JPS492324B1 (en) * | 1970-12-29 | 1974-01-19 | ||
| US5851644A (en) * | 1995-08-01 | 1998-12-22 | Loctite (Ireland) Limited | Films and coatings having anisotropic conductive pathways therein |
| JP2001319523A (en) * | 2000-05-10 | 2001-11-16 | Jsr Corp | Conductive paste composition |
| JP2002203428A (en) * | 2000-12-27 | 2002-07-19 | Jsr Corp | Conductive paste composition |
| CN1564744A (en) * | 2001-07-03 | 2005-01-12 | 阿什兰公司 | Induction heating using dual susceptors |
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2008
- 2008-05-31 JP JP2008143987A patent/JP5534127B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065280A (en) * | 1990-02-23 | 1992-10-14 | 旭化成工业株式会社 | Compositions of cupric alloy |
| CN1737072A (en) * | 2004-08-18 | 2006-02-22 | 播磨化成株式会社 | Conductive adhesive agent and process for manufacturing article using the conductive adhesive agent |
| CN1892945A (en) * | 2005-07-01 | 2007-01-10 | 松下电器产业株式会社 | Movable contact assembly, method of manufacturing the same, and switch using the same |
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| JP2009286977A (en) | 2009-12-10 |
| JP5534127B2 (en) | 2014-06-25 |
| CN102015906A (en) | 2011-04-13 |
| WO2009144925A1 (en) | 2009-12-03 |
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