CN102272863A - Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure - Google Patents

Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure Download PDF

Info

Publication number
CN102272863A
CN102272863A CN2011800007058A CN201180000705A CN102272863A CN 102272863 A CN102272863 A CN 102272863A CN 2011800007058 A CN2011800007058 A CN 2011800007058A CN 201180000705 A CN201180000705 A CN 201180000705A CN 102272863 A CN102272863 A CN 102272863A
Authority
CN
China
Prior art keywords
electrode
electroconductive particle
particle
mentioned
electroconductive
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.)
Granted
Application number
CN2011800007058A
Other languages
Chinese (zh)
Other versions
CN102272863B (en
Inventor
石田浩也
结城彰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of CN102272863A publication Critical patent/CN102272863A/en
Application granted granted Critical
Publication of CN102272863B publication Critical patent/CN102272863B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/50—Fixed connections
    • H01R12/51—Fixed connections for rigid printed circuits or like structures
    • H01R12/52—Fixed connections for rigid printed circuits or like structures connecting to other rigid printed circuits or like structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29399—Coating material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01013—Aluminum [Al]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01024—Chromium [Cr]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0103—Zinc [Zn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01032—Germanium [Ge]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01042—Molybdenum [Mo]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01049—Indium [In]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01051—Antimony [Sb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01074—Tungsten [W]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01082—Lead [Pb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/0665—Epoxy resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

Disclosed are conductive particles which can inhibit electrode corrosion and increase conductivity reliability between electrodes, and a connection structure which uses the conductive particles. The conductive particles (1) have a conductive layer (3) on at least the outer surface (1a) thereof. When a liquid, wherein 1g of the conductive particles (1) has been added to 10mL of an ion-exchanged water, is heated at 121 DEG C for 24 hours whilst being hermetically sealed, the concentration of organic acid in the water phase of the post-heating liquid is not greater than 300 [mu]g/g in terms of conductive particles. The connection structure (21) is provided with a first member to be connected (22) having an electrode (22a), and a second member to be connected (23) having an electrode (23a), and a connection unit (24) which connects the first member to be connected (22) and the second member to be connected (23). The connection unit (24) is either formed from the conductive particles (1) or an anisotropic conductive material containing the conductive particles (1) and a binder resin. The electrodes (22a, 23a) are electrically connected by the conductive particles (1).

Description

The manufacture method of electroconductive particle, electroconductive particle, anisotropic conductive material and syndeton body
Technical field
The present invention relates to can be used in the manufacture method of electroconductive particle and this electroconductive particle of interelectrode electrical connection.In addition, the present invention relates to use the anisotropic conductive material and the syndeton body of this electroconductive particle.
Background technology
As anisotropic conductive material, anisotropic conductive paste, anisotropic conductive printing ink, anisotropically conducting adhesive (bonding drug), anisotropic conductive film and anisotropic conductive sheet etc. are by well-known.In these anisotropic conductive materials, electroconductive particle is scattered in thickener, printing ink or the resin.
In electronic equipments such as liquid crystal display (LCD) element or organic electroluminescent (EL) element, above-mentioned anisotropic conductive material is used for the transparency electrode as drive electrode is electrically connected.
As an example of above-mentioned anisotropic conductive material, the bonding film of anisotropic conductive that contains electroconductive particle and insulating properties bonding agent (then drug) is disclosed in the following patent documentation 1.Dissociated ion concentration in the bonding film of this anisotropic conductive is below the 60ppm.In the embodiment of patent documentation 1, measured chlorine ion concentration as dissociated ion.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 9-199207 communique
Summary of the invention
Invent problem to be solved
Put down in writing following content in the patent documentation 1:, when therefore stating the bonding film of anisotropic conductive in the use and carrying out interelectrode electrical connection, can suppress the corrosion of electrode because above-mentioned dissociated ion concentration, particularly chlorine ion concentration be below the 60ppm.
But,, may also can't fully suppress the corrosion of electrode even use the bonding film of anisotropic conductive of patent documentation 1.
In addition, with regard to transparency electrodes such as LCD element or organic EL, require to improve the processability of electrode, the low temperatureization that realizes electrode formation technology and the formation efficient that improves electrode.To satisfy these requirements is purpose, has used IZO electrode, AZO electrode, GZO electrode and ZnO electrode to replace the ITO electrode.
But, compare with the situation of using the ITO electrode, under the situation of using IZO electrode, AZO electrode, GZO electrode or ZnO electrode, there is the such problem of easy generating electrodes corrosion.Under the situation that the bonding film of anisotropic conductive by patent documentation 1 record connects IZO electrode, AZO electrode, GZO electrode or ZnO electrode, be easy to generate the corrosion of electrode sometimes.
The object of the present invention is to provide under a kind of situation about being electrically connected between to electrode, can suppress the burn into of electrode and can improve electroconductive particle, and the manufacture method of this electroconductive particle and the anisotropic conductive material and the syndeton body that uses this electroconductive particle of interelectrode conduction reliability.
Even the purpose that the present invention limits is to provide a kind of under the situation that IZO electrode, AZO electrode, GZO electrode or ZnO electrode are electrically connected, particularly, even under the situation that the IZO electrode is connected, also can suppress the electroconductive particle of electrode corrosion, the manufacture method that reaches this electroconductive particle and anisotropic conductive material and the syndeton body that uses this electroconductive particle.
The method of dealing with problems
Hold the present invention from big aspect, the invention provides a kind of electroconductive particle, it has conductive layer at outer surface at least, wherein, this electroconductive particle of 1g added in the 10mL ion exchange water obtain liquid, and under the sealing in 121 ℃ this liquid carried out heating in 24 hours after, in the liquid after heating, aqueous phase is below the 300 μ g/g with the organic acid concentration that electroconductive particle converts.
In a certain particular aspects of the electroconductive particle that the present invention relates to, this electroconductive particle has: basis material particle, and the above-mentioned conductive layer that coats the surface of this basis material particle.
In addition, hold the present invention from big aspect, the invention provides the manufacture method of above-mentioned electroconductive particle, this method uses that to contain the following organic acid of 6000 μ g/g and pH be 5.2～8.5 electroless plating liquid, applies by electroless plating and forms above-mentioned conductive layer.
The present invention relates to anisotropic conductive material, the electroconductive particle that it comprises adhesive resin and has formation of the present invention.
The present invention relates to the syndeton body, it possesses the 1st connecting object parts with electrode, the 2nd connecting object parts with electrode and the connecting portion that connects the 1st, the 2nd connecting object parts, wherein, above-mentioned connecting portion forms or is formed by the anisotropic conductive material that comprises this electroconductive particle and adhesive resin by having the electroconductive particle that constitutes of the present invention, and the electrode of the electrode of above-mentioned the 1st connecting object parts and above-mentioned the 2nd connecting object parts is electrically connected by above-mentioned electroconductive particle.
In aspect the syndeton body that the present invention relates to a certain specific, the electrode of above-mentioned the 1st, the 2nd connecting object parts is respectively IZO electrode, AZO electrode, GZO electrode or ZnO electrode.
The effect of invention
Electroconductive particle of the present invention and the electroconductive particle that utilizes the manufacture method of electroconductive particle of the present invention to obtain, because it has conductive layer and is below the 300 μ g/g from the organic acid concentration that converts with electroconductive particle of this electroconductive particle stripping at outer surface at least, therefore under the situation of using this electroconductive particle to carry out being electrically connected between electrode, can suppress the corrosion of electrode.Thus, can improve interelectrode conducting reliability.
Electroconductive particle of the application of the invention and the electroconductive particle that utilizes the manufacture method of electroconductive particle of the present invention to obtain, even under the situation that IZO electrode, AZO electrode, GZO electrode or ZnO electrode are electrically connected, particularly, even under the situation that the IZO electrode is connected, also can fully suppress the corrosion of this electrode.
Description of drawings
Fig. 1 is the profile that the electroconductive particle that one embodiment of the present invention relates to is shown.
Fig. 2 be model utility the front cross-sectional view of an example of the syndeton body that uses the electroconductive particle that one embodiment of the present invention relates to is shown.
Symbol description
1... electroconductive particle
1a... outer surface
2... basis material particle
2a... surface
3... conductive layer
21... syndeton body
22... the 1st connecting object parts
22a... electrode
22b... upper surface
23... the 2nd connecting object parts
23a... electrode
23b... lower surface
24... connecting portion
Embodiment
Below, by the specific embodiment of the present invention and embodiment are described in detail the present invention is described in detail.
(electroconductive particle)
Fig. 1 is the profile that the electroconductive particle that one embodiment of the present invention relates to is shown.
As shown in Figure 1, electroconductive particle 1 has the conductive layer 3 of the surperficial 2a of basis material particle 2 and this basis material particle 2 of coating.Electroconductive particle 1 is the coating particles that is obtained by the surperficial 2a of conductive layer 3 coating basis material particles 2.Therefore, electroconductive particle 1 has conductive layer 3 at outer surface 1a.
Present embodiment is characterised in that: 1g electroconductive particle 1 is added in the 10mL ion exchange water to obtaining liquid, and under the sealing in 121 ℃ this liquid carried out heating in 24 hours after, in the liquid after heating, aqueous phase is below the 300 μ g/g with the organic acid concentration that electroconductive particle converts.That is, with respect to every 1g electroconductive particle, in the liquid after the heating, the organic acid concentration of aqueous phase is below the 300 μ g.
Discoveries such as the inventor: there is considerable influence in the organic acid that contains in the electroconductive particle 1 to the corrosion of electrode.Further also find: in order fully to suppress the corrosion of electrode, making the organic acid concentration of stripping by said method is that the following this point of 300 μ g/g is extremely important.By making above-mentioned organic acid concentration is below the 300 μ g/g, under the situation of utilizing electroconductive particle 1 to carry out being electrically connected between electrode, or utilize under the situation that the anisotropic conductive material comprise electroconductive particle 1 and adhesive resin carries out being electrically connected between electrode, can suppress the corrosion of the electrode that causes by electroconductive particle 1 significantly.
In addition, in recent years, with regard to regard to the transparency electrode of the drive electrode of liquid crystal display (LCD) element or organic electroluminescent (EL) element etc., require to improve its electrode processability, realize that electrode forms the low temperatureization of technology and the formation efficient that improves electrode.To satisfy these requirements is purpose, has used IZO electrode, AZO electrode, GZO electrode and ZnO electrode to replace the ITO electrode.
For example, compare with the situation that forms the ITO electrode, when forming the IZO electrode, production of foreign matters is few, can form uniform electrode.In addition, the IZO electrode also has the following advantages: the etching speed when utilizing etching to form the electrode with pattern is slow, and etched precision is also comparatively excellent.In addition, compare with the situation of ITO electrode, the IZO electrode also has this advantage of damage of the aluminium auxiliary wiring that can suppress thin-film transistor (TFT) substrate etc.
But, compare with the situation of using the ITO electrode, when using IZO electrode, AZO electrode, GZO electrode or ZnO electrode, exist easy generating electrodes to corrode this problem.Yet,,, particularly,, also can suppress the corrosion of electrode significantly even when being the IZO electrode even electrode is IZO electrode, AZO electrode, GZO electrode or ZnO electrode by using the electroconductive particle 1 of present embodiment.
Be limited to 300 μ g/g on the above-mentioned organic acid concentration, preferred upper limit is 200 μ g/g.
Particularly, can measure above-mentioned organic acid concentration by following method.
Preparation has the quartz ampoule of opening, and it is cleaned up.In this quartz ampoule, add 1g electroconductive particle 1 and 10mL ion exchange water (resistivity 18M Ω).Next, utilize of opening fusion and the sealing of heater such as gas arc lamp, thereby obtain testing body quartz ampoule.This test body placed in 121 ℃ the baking oven, under sealing, carry out heating in 24 hours in 121 ℃.Then, Kaifeng quartz ampoule.Molecular filter by 0.1 μ m filters the liquid after heating in the quartz ampoule, thus the water in the liquid after obtaining to heat.Utilize the organic acid concentration of the aqueous phase that ion chromatograph obtains filtration to measure.It is DIONEX company " ICS-3000 " that make etc. that above-mentioned ion chromatograph can use commercially available product.
As above-mentioned organic acid, use formic acid, acetate, propionic acid and citric acid etc. usually.With regard to the electroconductive particle 1 of present embodiment, the total concentration of the formic acid, acetate, propionic acid and the citric acid that convert with electroconductive particle by the said method stripping is below the 300 μ g/g.Therefore, the total concentration of the formic acid, acetate, propionic acid and the citric acid of measuring by the said determination method that convert with electroconductive particle is below the 300 μ g/g.Above-mentioned organic acid concentration is preferably the summation of the concentration of formic acid, acetate, propionic acid and citric acid.Total concentration by making the formic acid, acetate, propionic acid and the citric acid that convert with electroconductive particle can suppress the corrosion of electrode significantly below 300 μ g/g.
Need to prove, heating and pressing (pressure) when connecting owing to electrode, and then, owing to used the long-time use of the syndeton body of electroconductive particle 1, may cause organic acid contained in the electroconductive particle 1 stripping from electroconductive particle 1.
As the method that makes above-mentioned organic acid concentration below 300 μ g/g, can enumerate material, the electroconductive particle 1 of the material that for example reduces basis material particle 2, conductive layer 3 or the method for the organic acid concentration of the material that in the formation operation of conductive layer 3, uses etc.Particularly, the method that is reduced in the organic acid concentration of the material that uses in the formation operation of conductive layer 3 is effective.
As basis material particle 2, can enumerate resin particle, inorganic particulate, organic-inorganic blend particle and metallic etc.
Basis material particle 2 is preferably the resin particle that is formed by resin.When using electroconductive particle 1 to carry out connecting between electrode, electroconductive particle 1 is arranged between electrode, make electroconductive particle 1 compression by pressing then.If basis material particle 2 is a resin particle, electroconductive particle 1 easy deformation when above-mentioned pressing then, thus can increase contact area between electroconductive particle 1 and the electrode.So, can improve interelectrode conducting reliability.
As the resin that is used to form above-mentioned resin particle, for example can enumerate: vistanex, acrylic resin, phenolic resins, melmac, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfones, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone and polyether sulfone etc.Since can be easily with the Hardness Control of basis material particle 2 in suitable scope, therefore the resin that is used to form above-mentioned resin particle is preferably the polymerizable monomer polymerization that makes more than a kind or 2 kinds and the polymer that obtains, and described polymerizable monomer is the monomer that has a plurality of ethene unsaturated groups in the molecule.
As the inorganic matter that is used to form above-mentioned inorganic particulate, can enumerate silicon dioxide and carbon black etc.As above-mentioned organic-inorganic blend particle, for example can enumerate: by the organic-inorganic blend particle that forms through crosslinked alkoxysilyl polymer and acrylic resin etc.
When basis material particle 2 is metallic, as the metal that is used to form this metallic, can enumerate: silver, copper, nickel, silicon, gold and titanium etc.
There is not particular restriction for the metal that is used to form conductive layer 3.As this metal, for example can enumerate: gold, silver, copper, platinum, palladium, zinc, iron, tin, lead, aluminium, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium, silicon and their alloy etc.In addition, as above-mentioned metal, can also enumerate tin-doped indium oxide (ITO) and scolding tin (は ん だ) etc.Wherein, owing to can further reduce interelectrode connection resistance, so the metal of conductive layer 3 is preferably: the alloy, nickel, palladium, copper or the gold that comprise tin and silver.
Conductive layer 3 is formed by one deck.Conductive layer also can be formed by multilayer.That is, conductive layer can have single layer structure, also can have two-layer above laminated construction.When conductive layer was formed by multilayer, outermost layer was preferably gold layer, nickel dam, palladium layer, copper layer or comprises tin and the alloy-layer of silver, more preferably gold layer or palladium layer, more preferably gold layer.When outermost layer is these preferred conductive layers, can further reduce interelectrode connection resistance.In addition, when outermost layer is the gold layer, can further improve corrosion resistance.
The preferred lower limit of the average grain diameter of electroconductive particle 1 is 0.5 μ m, is limited to 1 μ m under preferred, and preferred upper limit is 100 μ m, is limited to 20 μ m on preferred.If the average grain diameter of electroconductive particle 1 satisfies the above-mentioned preferred lower limit and the upper limit, then can increase the contact area between electroconductive particle 1 and the electrode fully, and when forming conductive layer 3, be difficult for forming the electroconductive particle 1 of cohesion.In addition, the interelectrode interval that connects via electroconductive particle 1 can not become excessive, and conductive layer 3 is difficult for peeling off from the surperficial 2a of basis material particle 2.
" average grain diameter " of electroconductive particle 1 represents number average bead diameter.Can observe and calculate mean value to any 50 electroconductive particles by utilizing electron microscope or light microscope, ask the average grain diameter of calculating electroconductive particle 1.
The preferred lower limit of the thickness of conductive layer 3 is 0.005 μ m, is limited to 0.01 μ m under preferred, and preferred upper limit is 1 μ m, is limited to 0.3 μ m on preferred.If the thickness of conductive layer 3 satisfies the above-mentioned preferred lower limit and the upper limit, then can obtain sufficient conductivity, and electroconductive particle 1 can not become really up to the mark, when connecting between electrode electroconductive particle 1 is out of shape fully.
Under the situation that conductive layer is formed by multilayer, the preferred lower limit of the thickness of outermost conductive layer is 0.001 μ m, is limited to 0.01 μ m under preferred, and preferred upper limit is 0.5 μ m, is limited to 0.1 μ m on preferred.If the thickness of above-mentioned outermost conductive layer satisfies the above-mentioned preferred lower limit and the upper limit, then can make the coating of outermost conductive layer even, corrosion resistance can be improved fully, and interelectrode connection resistance can be fully reduced.In addition, above-mentioned outermost layer is under the situation of gold layer, and the thickness of gold layer is thin more, and cost is low more.
Can observe the section of electroconductive particle 1 by for example using transmission electron microscope (TEM), measure the thickness of conductive layer 3.
Electroconductive particle can be metallic.When electroconductive particle was metallic, this electroconductive particle had conductive layer on the surface.As mentioned above,, the metallic cover particle can be, also metallic can be as long as electroconductive particle has conductive layer at outer surface at least.When electroconductive particle is metallic, also can measure organic acid concentration by said method.
When electroconductive particle is metallic, there is not particular restriction for the metal that is used for forming this metallic.As this metal, can enumerate the cited above-mentioned metal of metal as the conductive layer 3 that is used for forming electroconductive particle 1.Need to prove that the preferable range of the average grain diameter of metallic is identical with the average grain diameter of electroconductive particle 1.
(manufacture method of electroconductive particle)
The method that forms conductive layer 3 at the surperficial 2a of basis material particle 2 when obtaining electroconductive particle 1 does not have particular restriction.As the method that forms conductive layer 3, for example can enumerate: utilize method that electroless plating applies, utilize electric plating method, utilize the method for physical vapor deposition and at the surperficial 2a plating powder of basis material 2 or comprise metal dust and the method for the thickener of adhesive etc.As the above-mentioned method of utilizing physical vapor deposition, can enumerate: methods such as vacuum evaporation, ion plating and ion sputtering.Wherein, because the method for utilizing electroless plating to apply can form conductive layer 3 easily and can form uniform conductive layer 3, therefore preferably utilize the deposited method of electroless plating.
Utilizing electroless plating to apply in the method that forms conductive layer 3, carrying out catalyst chemical industry preface and electroless plating usually and apply operation.Below, describe utilizing electroless plating to apply an example that on the surperficial 2a of basis material particle 2, forms the method for conductive layer.
In above-mentioned catalyst chemical industry preface, on the surperficial 2a of basis material particle 2, form catalyst, this catalyst can become the starting point that is used for by the deposited formation of electroless plating coating.
As the method that on the surperficial 2a of basis material particle 2, forms above-mentioned catalyst, can enumerate for example following method: in the solution that comprises palladium bichloride and stannic chloride, add basis material particle 2, make the surperficial 2a activation of basis material particle 2 then by acid solution or aqueous slkali, thus the method that palladium is separated out at the surperficial 2a of basis material particle 2; In comprising the solution of palladium sulfate, add basis material particle 2, make the surperficial 2a activation of basis material particle 2 then by the solution that contains reducing agent, thereby make method that palladium separates out at the surperficial 2a of basis material particle 2 etc.As above-mentioned reducing agent, can use sodium hypophosphite or dimethylamine borane etc.
In above-mentioned electroless plating applies operation,, can use the suitable metal salt that for example contains nickel or copper etc. and the plating of reducing agent to bathe as electroless plating liquid.By basis material particle 2 being impregnated in the plating bath, can utilize electroless plating to apply, on the surperficial 2a of the basis material particle 2 that is formed with catalyst on the surperficial 2a, separate out conductive layer 3.As above-mentioned reducing agent, can use sodium hypophosphite, dimethylamine borane or hydrazine (ヒ ト ラ ヅ Application) etc.
Preferred above-mentioned electroless plating liquid contains the following organic acid of 9000 μ g/g, more preferably contains the following organic acid of 6000 μ g/g.At this moment, electroconductive particle is reached below the 300 μ g/g by the organic acid concentration of said method stripping, the organic acid concentration of above-mentioned electroless plating liquid is 6000 μ g/g when following, the organic acid concentration of electroconductive particle by the said method stripping can be controlled at below the 300 μ g/g more effectively.
The pH of preferred above-mentioned electroless plating liquid is 5.2～8.5.At this moment, making electroconductive particle easily is below the 300 μ g/g by the organic acid concentration of said method stripping.The pH of above-mentioned electroless plating liquid more preferably is limited to 6.0 down, is limited to 7.9 on more preferably.
Method as form the gold layer at outermost layer does not have particular restriction, preferably replaces the plating method.
(anisotropic conductive material)
The anisotropic conductive material that the present invention relates to comprises electroconductive particle of the present invention and adhesive resin.
There is not particular restriction for above-mentioned adhesive resin.As above-mentioned adhesive resin, can use the resin of known insulating properties.As above-mentioned adhesive resin, for example can enumerate: vinylite, thermoplastic resin, curable resin, thermoplastic block copolymers and elastomer etc.Above-mentioned adhesive resin can only use a kind, also can be used in combination more than 2 kinds.
As above-mentioned vinylite, for example can enumerate: vinyl acetate resin, acrylic resin and styrene resin etc.As above-mentioned thermoplastic resin, for example can enumerate: vistanex, vinyl-vinyl acetate copolymer and polyamide etc.As above-mentioned curable resin, for example can enumerate: epoxy resin, carbamate resins, polyimide resin and unsaturated polyester resin etc.Need to prove that above-mentioned curable resin is optional to be normal temperature cured type resin, thermosetting resin, light-cured type resin or moisture-curable resin.Above-mentioned curable resin also can be used in combination with curing agent.As above-mentioned thermoplastic block copolymers, for example can enumerate: the hydrogenation products of SBS, SIS, SBS, and the hydrogenation products of SIS etc.As above-mentioned elastomer, can list for example styrene-butadiene copolymer rubber or acrylonitrile-styrene block copolymerization rubber etc.
In the above-mentioned anisotropic conductive material, except above-mentioned electroconductive particle and adhesive resin, can also comprise for example various additives such as filler, extender, softening agent, plasticizer, polymerization catalyst, curing catalysts, colouring agent, antioxidant, heat stabilizer, light stabilizer, ultra-violet absorber, slipping agent, antistatic agent or fire retardant.
For the method for dispersed electro-conductive particle in above-mentioned adhesive resin, can adopt the process for dispersing of conventional known, there is not particular restriction.As the method for dispersed electro-conductive particle in above-mentioned adhesive resin, for example can enumerate: add electroconductive particle in adhesive resin after, use epicyclic mixer etc. is carried out mixing, the method for disperseing; After using homogenizer etc. to be dispersed in electroconductive particle in water or the organic solvent, add in the adhesive resin, and carry out with epicyclic mixer etc. mixing, the method for disperseing; And, after dilution such as adhesive resin water or organic solvent, add electroconductive particle, and carry out with epicyclic mixer etc. mixing, the method for disperseing etc.
Anisotropic conductive material of the present invention can be used as anisotropic conductive paste, anisotropic conductive printing ink, anisotropically conducting adhesive, anisotropic conductive film or anisotropic conductive sheet etc.To comprise under the situation of anisotropic conductive material as film-like adhesives such as anisotropic conductive film, anisotropic conductive sheets of electroconductive particle of the present invention, also can not contain the membranaceous bonding agent of electroconductive particle at the membranaceous bonding agent superimposed layer that comprises this electroconductive particle.
Content for the above-mentioned electroconductive particle in the above-mentioned anisotropic conductive material does not have particular restriction.Viewpoint from further raising conducting reliability, in above-mentioned anisotropic conductive material, the preferred lower limit of the content of above-mentioned electroconductive particle is 0.01 weight %, more preferably is limited to 0.1 weight % down, and preferred upper limit is 20 weight %, is limited to 10 weight % on more preferably.
(syndeton body)
Fig. 2 be model utility the front cross-sectional view of an example of the syndeton body that uses the electroconductive particle that one embodiment of the present invention relates to is shown.
The connecting portion 24 that syndeton body 21 shown in Figure 2 possesses the 1st connecting object parts the 22, the 2nd connecting object parts 23 and connects the 1st, the 2nd connecting object parts 22,23.Connecting portion 24 is formed by the anisotropic conductive material that comprises electroconductive particle 1 and adhesive resin.Connecting portion 24 also can be formed by electroconductive particle 1.At this moment, 1 of electroconductive particle is as connecting portion.Need to prove that in Fig. 2, skeleton map shows electroconductive particle 1.
The upper surface 22b of the 1st connecting object parts 22 has a plurality of electrode 22a.The lower surface 23b of the 2nd connecting object parts 23 has a plurality of electrode 23a.Electrode 22a and electrode 23a realize being electrically connected by electroconductive particle 1.Above-mentioned the 1st, the 2nd connecting object parts preferably have electrode respectively at least on a side surface.Connect between the electrode surface of preferred above-mentioned connecting portion with above-mentioned the 1st, the 2nd connecting object parts.
As the 1st, the 2nd connecting object parts 22,23, specifically can enumerate: electronic units such as semiconductor chip, capacitor and diode, and circuit substrates such as printed base plate, flexible printing substrate and glass substrate etc.
Manufacture method for syndeton body 21 does not have particular restriction.Concrete example as the manufacture method of syndeton body 21, can enumerate following method: between the 1st connecting object parts 22 and the 2nd connecting object parts 23, above-mentioned anisotropic conductive material is set, to obtain laminated body, then this laminated body is heated, pressurizes.
Temperature when above-mentioned laminated body is heated is about 120～220 ℃.Pressure when above-mentioned laminated body is pressurizeed is 9.8 * 10 4～4.9 * 10 6About Pa.
As electrode 22a, 23a, can enumerate: metal electrodes such as gold electrode, nickel electrode, tin electrode, aluminium electrode, copper electrode, molybdenum electrode or tungsten electrode.Need to prove, when above-mentioned electrode is the aluminium electrode, can be the electrode that is only formed by aluminium, also can be at the surperficial lamination aluminium lamination of metal oxide layer and the electrode that obtains.In addition, as above-mentioned electrode, can enumerate: ITO electrode, IZO electrode, AZO electrode, GZO electrode and ZnO electrode.
Electrode 22a, 23a are preferably ITO electrode, IZO electrode, AZO electrode, GZO electrode or ZnO electrode respectively, and more preferably IZO electrode, AZO electrode, GZO electrode or ZnO electrode are preferably the IZO electrode especially.
Even electrode 22a, 23a are than the IZO electrode, AZO electrode, GZO electrode or the ZnO electrode that are easier to the generating electrodes corrosion, particularly, even when being the IZO electrode,, also can significantly suppress the corrosion of electrode 22a, 23a by using the electroconductive particle 1 of present embodiment.
Below, enumerate embodiment and comparative example is specifically described the present invention.The present invention not only is defined in following embodiment.
(embodiment 1)
The making of electroconductive particle:
Preparing average grain diameter is that 5.0 μ m, the coefficient of variation are 4.9% divinylbenzene resin particle (" MicroPearl SP-205 " that ponding chemical industrial company makes).Use this particle, carried out following electroless plating nickel operation.
The solution that utilization contains 10 weight % ion adsorbents carries out handling in 5 minutes to above-mentioned resin particle, then, it is added in the palladium sulfate 0.01 weight % aqueous solution.Then, add dimethylamine borane and reduce processing, and filter, clean, thereby obtained being attached with the resin particle of palladium.
Next, sodium succinate is dissolved in the sodium succinate solution of preparing 1 weight % in the 500mL ion exchange water.In this solution, add being attached with the resin particle 10g of palladium, and mix, thereby be mixed with slurry.In slurry, add sulfuric acid, the pH of slurry is adjusted into 5.
Prepared the nickel plating solution of sulfur acid nickel 50g/L, sodium hypophosphite 20g/L, NaOH 4g/L, sodium succinate 15g/L and natrium citricum 5g/L.The organic acid concentration of this nickel-plating liquid is 5672 μ g/g, and pH is 7.5.PH is adjusted into 5 above-mentioned slurry and heats after 80 ℃, in slurry, drip nickel plating solution continuously, and stablize the carrying out that promotes the plating reaction by stirring to reach up to pH.Confirm no longer to produce hydrogen, stop the plating reaction.
At the electroless plating nickel particles that obtains, implement gold-plated by displacement plating method on the surface of nickel dam, thus, form double-deck conductive layer on the surface of resin particle, thereby made electroconductive particle, wherein, this double-deck conductive layer has nickel dam and the gold layer that is stacked in this nickel dam surface.
(embodiment 2～4)
Except the organic acid concentration of nickel-plating liquid or pH according to changing shown in the following table 1, obtained electroconductive particle according to similarly to Example 1 method.
(embodiment 5)
Except not forming the gold layer, made electroconductive particle according to method similarly to Example 1 on the surface of nickel dam.
(comparative example 1)
Except the organic acid concentration of nickel-plating liquid according to changing shown in the following table 1, obtained electroconductive particle according to similarly to Example 1 method.
(comparative example 2)
Except the organic acid concentration of nickel-plating liquid according to changing shown in the following table 1, obtained electroconductive particle according to similarly to Example 5 method.
(comparative example 3)
Except the organic acid concentration of nickel-plating liquid according to changing shown in the following table 1, obtained electroconductive particle according to similarly to Example 1 method.
(evaluation)
(1) mensuration of organic acid concentration
Preparation has the quartz ampoule of opening, and it is cleaned up.In this quartz ampoule, add electroconductive particle and the 10mL ion exchange water (resistivity 18M Ω) that 1g obtains.Next, utilize opening fusion and the sealing of gas arc lamp, thereby obtain testing body quartz ampoule.This test body placed in 121 ℃ the baking oven, carried out heating in 24 hours in 121 ℃.Then, Kaifeng quartz ampoule.Molecular filter by 0.1 μ m filters the liquid after heating in the quartz ampoule, thus the water in the liquid after obtaining to heat.Utilize chromatography of ions instrument apparatus (" ICS-3000 " that DIONEX company makes) that the organic acid concentration of the aqueous phase after filtering is measured.
(2) the connection resistance value at initial stage
(making of anisotropic conductive film)
Bisphenol A type epoxy resin (" Epikote 1009 " that Mitsubishi Chemical (former Japan Epoxy Resins) company makes) with 10 weight portions, 40 parts by weight of acrylic rubber (weight average molecular weight is about 800,000), the methylethylketone of 200 weight portions, the microcapsule-type curing agent of 50 weight portions (" HX3941HP " that chemical company of Asahi Chemical Industry makes), and the silane coupler of 2 weight portions (" SH-6040 " that Toray Dow Corning Silicone company makes) mixes, it is 3 weight % that the interpolation electroconductive particle makes its content, and make its dispersion, thereby obtained resin combination.
The resin combination that obtains is coated in one side has passed through on the demoulding treated side of PET (PETG) film that thickness that the demoulding handles is 50 μ m, utilize 70 ℃ of heated-air dryings 5 minutes, made anisotropic conductive film.The thickness of the anisotropic conductive film that obtains is 12 μ m.
(making of syndeton body 1)
The anisotropic conductive film that obtains is cut into the size of 5mm * 5mm.Stick on the substantial middle position of electrode one side that upper surface has the glass substrate (wide 200 μ m, long 1mm) of electrode with cutting the anisotropic conductive film that obtains, wherein, the electrode that upper surface had of described glass substrate is that a side has the electrode (high 0.2 μ m, live width and line-spacing (Line and Space) L/S=20 μ m/20 μ m) of resistance measurement with kind shown in the following table 1 of wiring.Next, two-layer flexible printed base plate (wide 200 μ m, long 1mm) that lower surface has identical electrodes is set and its position is adjusted, the electrode on its electrode and the above-mentioned glass substrate is coincided, fit then.Under the pressing condition of 10N and 180 ℃, the laminated body of this glass substrate and two-layer flexible printed base plate is carried out hot pressing, thereby obtain syndeton body 1.
(making of syndeton body 2)
The anisotropic conductive film that obtains is cut into the size of 2mm * 25mm.Stick on glass substrate (electrode one side of 10mm * 25mm * 0.8mm) that upper surface has electrode with cutting the anisotropic conductive film that obtains, wherein, the electrode that upper surface had of described glass substrate is that a side has the electrode (high 0.2 μ m, live width and line-spacing L/S=20 μ m/20 μ m) of resistance measurement with kind shown in the following table 1 of wiring.Next, two-layer flexible printed base plate (30mm * 20mm, live width and line-spacing L/S=20 μ m/20 μ m) that lower surface has gold electrode is set and its position is adjusted, the electrode on its gold electrode and the above-mentioned glass substrate is coincided, fit then.Under the pressing condition of 3MPa and 180 ℃, the laminated body of this glass substrate and two-layer flexible printed base plate is carried out pressing, thereby obtain syndeton body 2.
(mensuration that connects resistance value)
Measured the connection resistance value between the electrode of opposite of gained syndeton body 1,2 by four-terminal method.Obtain the mean value of the connection resistance value of the mean value of connection resistance value of 10 syndeton bodies 1 and 10 syndeton bodies 2 respectively, the connection resistance value at initial stage is judged according to following standard.
[connecting the criterion of resistance value]
00: connecting resistance value is below 2.0 Ω
Zero: the connection resistance value surpasses 2.0 Ω and is below 3.0 Ω
△: the connection resistance value surpasses 3.0 Ω and is below 5.0 Ω
*: connect resistance value and surpass 5.0 Ω
(3) through the time after the connection resistance value
The syndeton body 1,2 that will obtain in the evaluation of the connection resistance value at above-mentioned (2) initial stage was placed 1000 hours under 85 ℃, 85% hot and humid condition.Then, by four-terminal method measure through the time after the comparative electrode of syndeton body 1,2 between the connection resistance value.Obtain the mean value of the connection resistance value of the mean value of connection resistance value of 10 syndeton bodies 1 and 10 syndeton bodies 2 respectively, and according to the criterion identical with the connection resistance value at above-mentioned (2) initial stage to through the time after the connection resistance value judge.
The result is shown in following table 1.Need to prove, the concentration of formic acid, acetate, propionic acid and citric acid has been shown in the following table 1.Except that these 4 kinds, do not detect other organic acid.
Figure BDA0000073732450000151

Claims (6)

1. electroconductive particle, it has conductive layer at least on the outer surface,
Wherein, this electroconductive particle of 1g added in the 10mL ion exchange water obtain liquid, and under the sealing in 121 ℃ this liquid carried out heating in 24 hours after, in the liquid after heating, aqueous phase is below the 300 μ g/g with the organic acid concentration that electroconductive particle converts.
2. the described electroconductive particle of claim 1, it has:
The basis material particle, and
Coat the described conductive layer on the surface of this basis material particle.
3. the manufacture method of claim 1 or 2 described electroconductive particles, this method use that to contain the following organic acid of 6000 μ g/g and pH be 5.2～8.5 electroless plating liquid, apply by electroless plating and form described conductive layer.
4. anisotropic conductive material, it comprises adhesive resin and claim 1 or 2 described electroconductive particles.
5. syndeton body, it possesses the 1st connecting object parts with electrode, the 2nd connecting object parts with electrode and the connecting portion that connects the 1st, the 2nd connecting object parts, wherein,
Described connecting portion is formed or is formed by the anisotropic conductive material that comprises this electroconductive particle and adhesive resin by claim 1 or 2 described electroconductive particles,
The electrode of the electrode of described the 1st connecting object parts and described the 2nd connecting object parts is electrically connected by electroconductive particle.
6. the syndeton body shown in the claim 5, wherein, the electrode of described the 1st, the 2nd connecting object parts is respectively IZO electrode, AZO electrode, GZO electrode or ZnO electrode.
CN2011800007058A 2010-03-17 2011-03-15 Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure Active CN102272863B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010-060269 2010-03-17
JP2010060269 2010-03-17
PCT/JP2011/056042 WO2011115105A1 (en) 2010-03-17 2011-03-15 Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure

Publications (2)

Publication Number Publication Date
CN102272863A true CN102272863A (en) 2011-12-07
CN102272863B CN102272863B (en) 2013-09-04

Family

ID=44649190

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800007058A Active CN102272863B (en) 2010-03-17 2011-03-15 Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure

Country Status (4)

Country Link
JP (1) JP4804596B1 (en)
KR (1) KR101162890B1 (en)
CN (1) CN102272863B (en)
WO (1) WO2011115105A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108806824A (en) * 2011-12-21 2018-11-13 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN110000372A (en) * 2012-10-02 2019-07-12 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN110729071A (en) * 2019-12-19 2020-01-24 北京梦之墨科技有限公司 Liquid metal conductive paste and electronic device
CN112313032A (en) * 2018-06-26 2021-02-02 昭和电工材料株式会社 Anisotropic conductive film, method for producing same, and method for producing connection structure
CN113851910A (en) * 2018-10-05 2021-12-28 株式会社Isc Method for producing conductive particles

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014141636A (en) * 2012-12-25 2014-08-07 Cemedine Co Ltd Conductive composition, structure and junction device
JP6364220B2 (en) * 2013-04-15 2018-07-25 積水化学工業株式会社 Conductive particle, method for producing conductive particle, conductive material, and connection structure
CN105493207B (en) * 2014-02-24 2018-05-25 积水化学工业株式会社 The manufacturing method of connection structural bodies
JP6429228B2 (en) * 2014-04-24 2018-11-28 タツタ電線株式会社 Metal-coated resin particles and conductive adhesive using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09199207A (en) * 1996-01-19 1997-07-31 Sony Chem Corp Anisotropic conductive bonding film
CN1735660A (en) * 2003-01-07 2006-02-15 积水化学工业株式会社 Curing resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body
CN101042365A (en) * 2007-04-11 2007-09-26 浙江大学 Dissolved oxygen electrochemical sensor
JP2007299640A (en) * 2006-04-28 2007-11-15 Sekisui Chem Co Ltd Conductive fine particle and anisotropic conductive material
CN101346449A (en) * 2005-12-26 2009-01-14 日立化成工业株式会社 Adhesive composition, circuit connecting material and connecting structure of circuit member

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4165065B2 (en) * 2001-12-27 2008-10-15 日立化成工業株式会社 Adhesive, method for producing adhesive, and method for producing circuit connection structure using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09199207A (en) * 1996-01-19 1997-07-31 Sony Chem Corp Anisotropic conductive bonding film
CN1735660A (en) * 2003-01-07 2006-02-15 积水化学工业株式会社 Curing resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body
CN101346449A (en) * 2005-12-26 2009-01-14 日立化成工业株式会社 Adhesive composition, circuit connecting material and connecting structure of circuit member
JP2007299640A (en) * 2006-04-28 2007-11-15 Sekisui Chem Co Ltd Conductive fine particle and anisotropic conductive material
CN101042365A (en) * 2007-04-11 2007-09-26 浙江大学 Dissolved oxygen electrochemical sensor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108806824A (en) * 2011-12-21 2018-11-13 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN110000372A (en) * 2012-10-02 2019-07-12 积水化学工业株式会社 Electroconductive particle, conductive material and connection structural bodies
CN112313032A (en) * 2018-06-26 2021-02-02 昭和电工材料株式会社 Anisotropic conductive film, method for producing same, and method for producing connection structure
CN113851910A (en) * 2018-10-05 2021-12-28 株式会社Isc Method for producing conductive particles
CN110729071A (en) * 2019-12-19 2020-01-24 北京梦之墨科技有限公司 Liquid metal conductive paste and electronic device
CN110729071B (en) * 2019-12-19 2020-06-09 北京梦之墨科技有限公司 Liquid metal conductive paste and electronic device
US11776708B2 (en) 2019-12-19 2023-10-03 Beijing Dream Ink Technologies Co., Ltd. Liquid metal conductive paste and electronic device

Also Published As

Publication number Publication date
CN102272863B (en) 2013-09-04
JP4804596B1 (en) 2011-11-02
KR101162890B1 (en) 2012-07-05
WO2011115105A1 (en) 2011-09-22
JPWO2011115105A1 (en) 2013-06-27
KR20110126099A (en) 2011-11-22

Similar Documents

Publication Publication Date Title
CN102272863B (en) Conductive particle, method for manufacturing conductive particle, anisotropic conductive material, and connection structure
CN102884590B (en) Insulating-particle-adhered electrically conductive particle, process for producing insulating-particle-adhered electrically conductive particle, anisotropic conductive material, and connected structure
CN103650063B (en) Electroconductive particle, electric conducting material and connection structural bodies
CN103069504B (en) The manufacture method of electroconductive particle, electroconductive particle, anisotropic conductive material and connection structural bodies
JP5548053B2 (en) Conductive particles with insulating particles, method for producing conductive particles with insulating particles, anisotropic conductive material, and connection structure
JP4991666B2 (en) Conductive particles, anisotropic conductive materials, and connection structures
WO2011030715A1 (en) Conductive particles with attached insulating particles, method for producing conductive particles with attached insulating particles, anisotropic conductive material, and connection structure
CN103748636A (en) Conductive particles, conductive material, and connection structure
CN104380393A (en) Conductive particle, resin particle, conductive material, and connection structure
CN101689410A (en) Circuit connection material, the syndeton of circuit member of using it and the method for attachment of circuit member
TW201131583A (en) Anisotropic conductive adhesive composite and film, and circuit connecting structure including the same
KR20150048667A (en) Anisotropic conductive film and production method therefor
CN104471650A (en) Conductive particle, conductive material and connecting structure
CN106796826A (en) Conductive material
CN104106182B (en) Anisotropic conductive connecting material, connection structural bodies, the manufacturing method of connection structural bodies and connection method
CN103493297A (en) Anisotropic conductive film, connection method, and connected structure
JP6114671B2 (en) Conductive particles for touch panel, conductive material for touch panel, and connection structure for touch panel
CN105210157A (en) Conductive particles, conducting material, and connection structure
JP5476168B2 (en) Conductive particles, anisotropic conductive materials, and connection structures
CN107219949A (en) A kind of binding technique of touch-screen
CN103748635A (en) Conductive particles, conductive material, and connection structure
CN104603218B (en) Anisotropic conductive film, method of attachment and conjugant
JP2012142223A (en) Conductive particle, anisotropic conductive material and connection structure
JP2012064350A (en) Connection structure
JP5837738B2 (en) Conductive particle, anisotropic conductive material, connection structure, and method for producing conductive particle

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