WO2017130892A1 - 導電材料及び接続構造体 - Google Patents
導電材料及び接続構造体 Download PDFInfo
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- WO2017130892A1 WO2017130892A1 PCT/JP2017/002089 JP2017002089W WO2017130892A1 WO 2017130892 A1 WO2017130892 A1 WO 2017130892A1 JP 2017002089 W JP2017002089 W JP 2017002089W WO 2017130892 A1 WO2017130892 A1 WO 2017130892A1
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- solder
- conductive
- electrode
- particles
- conductive material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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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
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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
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
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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
- H05K3/36—Assembling printed circuits with other printed circuits
-
- 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
- H05K3/36—Assembling printed circuits with other printed circuits
- H05K3/361—Assembling flexible printed circuits with other printed circuits
- H05K3/363—Assembling flexible printed circuits with other printed circuits by soldering
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- 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
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
Definitions
- the present invention relates to a conductive material including conductive particles having solder.
- the present invention also relates to a connection structure using the conductive material.
- Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
- anisotropic conductive material conductive particles are dispersed in a binder.
- the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
- FOG Glass
- COF Chip on Film
- an anisotropic conductive material containing conductive particles is disposed on the glass epoxy substrate. To do.
- a flexible printed circuit board is laminated, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
- the following Patent Document 1 describes an anisotropic conductive material including conductive particles and a resin component that cannot be cured at the melting point of the conductive particles.
- the conductive particles include tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd ), Metals such as gallium (Ga) and thallium (Tl), and alloys of these metals.
- Patent Document 1 a resin heating step for heating the anisotropic conductive resin to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described.
- Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG. In Patent Document 1, the conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive resin is heated.
- Patent Document 2 discloses an adhesive tape that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Yes.
- This adhesive tape is in the form of a film, not a paste.
- Patent Document 3 discloses a thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component.
- the flux component (1) a salt of dicarboxylic acid or tricarboxylic acid and diethanolamines or triethanolamine, and (2) addition of carboxylic acid anhydride with diethanolamines or triethanolamines The reactants are listed.
- the conventional conductive powder and anisotropic conductive paste containing conductive particles having a solder layer on the surface may have low storage stability. Furthermore, in the conventional anisotropic conductive paste, when the conductive material is disposed on the connection target member at the time of connection between the electrodes and then left for a long time, the solder may hardly aggregate on the electrodes. As a result, conduction reliability tends to be low.
- An object of the present invention is a conductive material that has high storage stability and exhibits excellent solder cohesion even after being left standing for a long time after the conductive material is placed on the connection target member. Is to provide. Another object of the present invention is to provide a connection structure using the conductive material.
- the outer surface portion of the conductive portion includes a plurality of conductive particles having solder, a thermosetting component, and a flux, and the flux is a salt of an acid and a base.
- the flux is present as a solid at 25 ° C.
- the single flux is solid at 25 ° C. in a state where it is not mixed with the conductive particles and the thermosetting component.
- the flux is a salt of an organic compound having a carboxyl group and an organic compound having an amino group.
- the average particle diameter of the flux is 30 ⁇ m or less in a conductive material at 25 ° C.
- the ratio of the average particle diameter of the flux to the average particle diameter of the conductive particles is 3 or less.
- the melting point of the flux is not lower than ⁇ 50 ° C. of the solder in the conductive particles and not higher than + 50 ° C. of the solder in the conductive particles.
- the conductive particles are solder particles.
- thermosetting component includes a thermosetting compound having a triazine skeleton.
- the flux is attached on the surface of the conductive particles.
- the conductive particles have an average particle diameter of 1 ⁇ m or more and 40 ⁇ m or less.
- the content of the conductive particles is 10% by weight or more and 90% by weight or less in 100% by weight of the conductive material.
- the conductive material is a conductive paste.
- a first connection target member having at least one first electrode on the surface
- a second connection target member having at least one second electrode on the surface
- the first A connection portion connecting the second connection target member and the second connection target member, wherein the material of the connection portion is the conductive material described above, and the first electrode and the second electrode Is provided that is electrically connected by a solder part in the connection part.
- the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode.
- the solder portion in the connection portion is arranged in 50% or more of the area of 100% of the portion where the first electrode and the second electrode face each other.
- the conductive material according to the present invention includes a plurality of conductive particles having solder on the outer surface portion of the conductive portion, a thermosetting component, and a flux, and the flux is a salt of an acid and a base, In the conductive material at 25 ° C., the flux is present as a solid, so that the storage stability of the conductive material can be improved, and the conductive material is placed on the connection target member and then left for a long time. Since it exhibits excellent solder cohesiveness, high conduction reliability can be expressed.
- FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
- 2A to 2C are cross-sectional views for explaining each step of an example of a method for manufacturing a connection structure using a conductive material according to an embodiment of the present invention.
- FIG. 3 is a cross-sectional view showing a modification of the connection structure.
- FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used as a conductive material.
- FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used for the conductive material.
- FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for the conductive material.
- the conductive material according to the present invention includes a plurality of conductive particles and a binder.
- the conductive particles have a conductive part.
- the conductive particles have solder on the outer surface portion of the conductive portion.
- Solder is contained in the conductive part and is a part or all of the conductive part.
- the binder is a component excluding conductive particles contained in the conductive material.
- the conductive material according to the present invention includes a thermosetting component and a flux as the binder.
- the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
- the flux is a salt of an acid and a base. Furthermore, in the conductive material according to the present invention, the flux exists in a solid state in a conductive material at 25 ° C. More specifically, in the conductive material according to the present invention, the flux exists as a solid at 25 ° C. in the conductive material at 25 ° C.
- whether or not the flux is solid in the conductive material at 25 ° C. can be determined as follows.
- a flux that is not liquid at 25 ° C. a flux that keeps its shape when a conductive material containing the flux at 25 ° C. is allowed to stand for 5 minutes is defined as a solid flux at 25 ° C.
- the semi-solid flux at 25 ° C. is not included in the solid flux at 25 ° C.
- the present invention since the above configuration is provided, the storage stability of the conductive material can be improved. Furthermore, since the present invention is provided with the above-described configuration, it exhibits excellent solder cohesion even after being left to stand for a long time after the conductive material is disposed on the connection target member. It can be expressed.
- the single flux is solid at 25 ° C. without being mixed with the conductive particles and the thermosetting component.
- the flux alone before being mixed with the conductive particles and the thermosetting component is preferably solid at 25 ° C. In these cases, it is easy to cause the flux to exist as a solid in a conductive material at 25 ° C.
- unit is a solid at 25 degreeC.
- a flux that is not liquid at 25 ° C. a flux that keeps its shape when the flux alone is allowed to stand at 25 ° C. for 5 minutes is defined as a solid flux at 25 ° C., and the flux alone at 25 ° C.
- a flux that does not retain its shape when allowed to stand for 5 minutes is defined as a semi-solid flux at 25 ° C.
- the semi-solid flux at 25 ° C. is not included in the solid flux at 25 ° C.
- connection structure When obtaining the connection structure, after arranging the conductive material on the first connection target member, the laminated body of the first connection target member and the conductive material has the second connection target member on the conductive material. May be temporarily stored before deployment. In this invention, even if the said laminated body is stored, the connection structure excellent in conduction
- the solder in the conductive particles can be efficiently arranged on the electrode even if the electrode width is narrow.
- the electrode width is narrow, there is a tendency that the solder of the conductive particles is difficult to gather on the electrode, but in the present invention, the solder can be sufficiently gathered on the electrode even if the electrode width is narrow.
- the solder in the conductive particles is easily located between the upper and lower electrodes, and the solder in the conductive particles is used as the electrode. (Line) can be arranged efficiently.
- the solder in the conductive particles is arranged more efficiently on the electrode.
- the solder in the conductive particles it is difficult for a part of the solder in the conductive particles to be arranged in a region (space) where no electrode is formed, and the amount of solder arranged in a region where no electrode is formed can be considerably reduced.
- the solder that is not located between the opposing electrodes can be efficiently moved between the opposing electrodes. Therefore, the conduction reliability between the electrodes can be improved.
- cured material of an electroconductive material can be improved.
- a conductive material is used for the optical semiconductor device, heat is generated during light irradiation, and a cured product of the conductive material is exposed to a high temperature.
- the conductive material according to the present invention is excellent in the heat resistance of a cured product, it can be suitably used for an optical semiconductor device.
- the thermosetting compound contains a thermosetting compound having a triazine skeleton, the heat resistance of the cured product is increased.
- the present invention it is possible to prevent displacement between the electrodes.
- the electrode of the first connection target member and the electrode of the second connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the first connection target member and the second connection target member are overlaid, the shift is corrected and the first connection target member electrode and the second connection target are corrected.
- the electrode of the member can be connected (self-alignment effect).
- the conductive material is preferably liquid at 25 ° C., and preferably a conductive paste.
- the viscosity ( ⁇ 25) at 25 ° C. of the conductive material is preferably 10 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, and further preferably 100 Pa.
- the viscosity ( ⁇ 25) can be appropriately adjusted depending on the type and amount of the compounding component.
- the viscosity ( ⁇ 25) can be measured using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) and the like at 25 ° C. and 5 rpm.
- E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) and the like at 25 ° C. and 5 rpm.
- the conductive material can be used as a conductive paste and a conductive film.
- the conductive film is preferably an anisotropic conductive film. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the conductive material is preferably a conductive paste.
- the conductive material is preferably used for electrical connection of electrodes.
- the conductive material is preferably a circuit connection material.
- (meth) acrylate means one or both of “acrylate” and “methacrylate”
- (meth) acryl means one or both of “acryl” and “methacryl”.
- (Meth) acryloyl means one or both of “acryloyl” and “methacryloyl”.
- the conductive particles electrically connect the electrodes of the connection target member.
- the conductive particles have solder on the outer surface portion of the conductive portion.
- the conductive particles may be solder particles formed by solder.
- the solder particles have solder on the outer surface portion of the conductive portion.
- both the center part and the outer surface part of an electroconductive part are formed with the solder.
- the solder particles are particles in which both the central portion and the conductive outer surface are solder.
- the solder particles do not have base particles as core particles.
- the solder particles are different from conductive particles including base particles and conductive portions arranged on the surface of the base particles.
- the solder particles include, for example, solder preferably at 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more.
- the said electroconductive particle may have a base material particle and the electroconductive part arrange
- the conductive particles have solder on the outer surface portion of the conductive portion.
- the conductive particles are less likely to collect on the surface, and the solder joint property between the conductive particles is low, so the conductive particles that have moved onto the electrodes tend to move out of the electrodes, and the effect of suppressing displacement between the electrodes Tend to be lower. Therefore, the conductive particles are preferably solder particles formed by solder.
- a carboxyl group or an amino group is present on the outer surface of the conductive particles (the outer surface of the solder). It is preferable that a carboxyl group is present, and an amino group is preferably present.
- a group containing a carboxyl group or an amino group is shared on the outer surface of the conductive particle (the outer surface of the solder) via a Si—O bond, an ether bond, an ester bond or a group represented by the following formula (X). Bonding is preferred.
- the group containing a carboxyl group or an amino group may contain both a carboxyl group and an amino group. In the following formula (X), the right end and the left end represent a binding site.
- the bond form between the solder surface and the group containing a carboxyl group may not include a coordinate bond, and may not include a bond due to a chelate coordinate.
- the conductive particle is a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group or an amino group ( Hereinafter, it is preferably obtained by reacting a hydroxyl group on the surface of the solder with a functional group capable of reacting with the hydroxyl group using a compound X). In the above reaction, a covalent bond is formed.
- solder particles in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder can be easily obtained. It is also possible to obtain solder particles in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder via an ether bond or an ester bond.
- Examples of the functional group capable of reacting with the hydroxyl group include a hydroxyl group, a carboxyl group, an ester group, and a carbonyl group.
- a hydroxyl group or a carboxyl group is preferred.
- the functional group capable of reacting with the hydroxyl group may be a hydroxyl group or a carboxyl group.
- Examples of the compound having a functional group capable of reacting with a hydroxyl group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4- Aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, Hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic
- Glutaric acid or glycolic acid is preferred. Only 1 type may be used for the compound which has the functional group which can react with the said hydroxyl group, and 2 or more types may be used together.
- the compound having a functional group capable of reacting with the hydroxyl group is preferably a compound having at least one carboxyl group.
- the compound X preferably has a flux action, and the compound X preferably has a flux action in a state of being bonded to the solder surface.
- the compound having a flux action can remove the oxide film on the surface of the solder and the oxide film on the surface of the electrode.
- the carboxyl group has a flux action.
- Compounds having a flux action include levulinic acid, glutaric acid, glycolic acid, adipic acid, succinic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4-aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid , 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid and 4-phenylbutyric acid.
- Glutaric acid, adipic acid or glycolic acid is preferred.
- action only 1 type may be used and 2 or more types may be used together.
- the functional group capable of reacting with the hydroxyl group in the compound X is preferably a hydroxyl group or a carboxyl group.
- the functional group capable of reacting with the hydroxyl group in the compound X may be a hydroxyl group or a carboxyl group.
- the compound X preferably has at least two carboxyl groups.
- the method for producing conductive particles includes, for example, using conductive particles and mixing the conductive particles, a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group, a catalyst, and a solvent.
- conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be easily obtained by the mixing step.
- this electroconductive particle using electroconductive particle, this electroconductive particle, the compound which has the functional group and carboxyl group which can react with the said hydroxyl group, the said catalyst, and the said solvent are mixed, and it heats. It is preferable.
- conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be obtained more easily.
- the solvent examples include alcohol solvents such as methanol, ethanol, propanol and butanol, acetone, methyl ethyl ketone, ethyl acetate, toluene and xylene.
- the solvent is preferably an organic solvent, and more preferably toluene. As for the said solvent, only 1 type may be used and 2 or more types may be used together.
- the catalyst examples include p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, and the like.
- the catalyst is preferably p-toluenesulfonic acid.
- the said catalyst only 1 type may be used and 2 or more types may be used together.
- the heating temperature is preferably 90 ° C or higher, more preferably 100 ° C or higher, preferably 130 ° C or lower, more preferably 110 ° C or lower.
- the conductive particles react with the isocyanate compound to the hydroxyl group on the surface of the solder using the isocyanate compound. It is preferable that it is obtained through the process of making it. In the above reaction, a covalent bond is formed.
- the hydroxyl group on the surface of the solder with the isocyanate compound it is possible to easily obtain conductive particles in which the nitrogen atom of the group derived from the isocyanate group is covalently bonded to the surface of the solder.
- a group derived from an isocyanate group can be chemically bonded to the surface of the solder in the form of a covalent bond.
- a silane coupling agent can be easily reacted with a group derived from an isocyanate group. Since the conductive particles can be easily obtained, the group containing a carboxyl group is introduced by a reaction using a silane coupling agent having a carboxyl group, or the reaction using a silane coupling agent is performed. It is preferably introduced later by reacting a compound derived from a silane coupling agent with a compound having at least one carboxyl group.
- the conductive particles are preferably obtained by reacting the isocyanate compound with a hydroxyl group on the surface of the solder using the isocyanate compound and then reacting a compound having at least one carboxyl group.
- the compound having at least one carboxyl group preferably has a plurality of carboxyl groups.
- isocyanate compound examples include diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI). Isocyanate compounds other than these may be used. After reacting this compound on the surface of the solder, the surface of the solder is represented by the formula (X) by reacting the residual isocyanate group and a compound having reactivity with the residual isocyanate group and having a carboxyl group. A carboxyl group can be introduced through the group to be formed.
- MDI diphenylmethane-4,4'-diisocyanate
- HDI hexamethylene diisocyanate
- TDI toluene diisocyanate
- IPDI isophorone diisocyanate
- the isocyanate compound a compound having an unsaturated double bond and having an isocyanate group may be used. Examples include 2-acryloyloxyethyl isocyanate and 2-isocyanatoethyl methacrylate. After reacting the isocyanate group of this compound on the surface of the solder, reacting the compound having a functional group having reactivity with the remaining unsaturated double bond and having a carboxyl group, A carboxyl group can be introduced to the surface via a group represented by the formula (X).
- silane coupling agent examples include 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Silicone) and 3-isocyanatepropyltrimethoxysilane (“Y-5187” manufactured by MOMENTIVE). As for the said silane coupling agent, only 1 type may be used and 2 or more types may be used together.
- Examples of the compound having at least one carboxyl group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4-amino Butyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecane Examples include acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic acid, arachidic acid
- the carboxyl group of the compound having a plurality of carboxyl groups is reacted with the hydroxyl group on the surface of the solder.
- the group containing can be left.
- the conductive particles are used and the isocyanate compound is used to react the hydroxyl group on the surface of the solder with the isocyanate compound, and then the compound having at least one carboxyl group is reacted.
- the conductive particles in which a group containing a carboxyl group is bonded to the surface of the solder via the group represented by the above formula (X) are obtained.
- conductive particles in which a group containing a carboxyl group is introduced on the surface of the solder can be easily obtained by the above-described steps.
- the following method can be given as a specific method for producing the conductive particles.
- Conductive particles are dispersed in an organic solvent, and a silane coupling agent having an isocyanate group is added. Thereafter, a silane coupling agent is covalently bonded to the surface of the solder using a reaction catalyst between a hydroxyl group and an isocyanate group on the surface of the solder of the conductive particles.
- a hydroxyl group is produced
- Conductive particles are dispersed in an organic solvent, and a compound having an isocyanate group and an unsaturated double bond is added. Thereafter, a covalent bond is formed using a reaction catalyst of a hydroxyl group and an isocyanate group on the surface of the solder of the conductive particles. Thereafter, the unsaturated double bond introduced is reacted with a compound having an unsaturated double bond and a carboxyl group.
- the reaction catalyst for hydroxyl groups and isocyanate groups on the surface of the solder of the conductive particles includes tin catalysts (dibutyltin dilaurate, etc.), amine catalysts (triethylenediamine, etc.), carboxylate catalysts (lead naphthenate, potassium acetate, etc.) And a trialkylphosphine catalyst (such as triethylphosphine).
- the compound having at least one carboxyl group is a compound represented by the following formula (1): Is preferred.
- the compound represented by the following formula (1) has a flux action.
- the compound represented by following formula (1) has a flux effect
- X represents a functional group capable of reacting with a hydroxyl group
- R represents a divalent organic group having 1 to 5 carbon atoms.
- the organic group may contain a carbon atom, a hydrogen atom, and an oxygen atom.
- the organic group may be a divalent hydrocarbon group having 1 to 5 carbon atoms.
- the main chain of the organic group is preferably a divalent hydrocarbon group.
- a carboxyl group or a hydroxyl group may be bonded to a divalent hydrocarbon group.
- Examples of the compound represented by the above formula (1) include citric acid.
- the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A) or the following formula (1B).
- the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A), and more preferably a compound represented by the following formula (1B).
- R represents a divalent organic group having 1 to 5 carbon atoms.
- R in the above formula (1A) is the same as R in the above formula (1).
- R represents a divalent organic group having 1 to 5 carbon atoms.
- R in the above formula (1B) is the same as R in the above formula (1).
- a group represented by the following formula (2A) or the following formula (2B) is bonded to the surface of the solder.
- a group represented by the following formula (2A) is preferably bonded to the surface of the solder, and more preferably a group represented by the following formula (2B) is bonded.
- the left end portion represents a binding site.
- R represents a divalent organic group having 1 to 5 carbon atoms.
- R in the above formula (2A) is the same as R in the above formula (1).
- R represents a divalent organic group having 1 to 5 carbon atoms.
- R in the above formula (2B) is the same as R in the above formula (1).
- the molecular weight of the compound having at least one carboxyl group is preferably 10,000 or less, more preferably 1000 or less, and even more preferably 500 or less. From the viewpoint of suppressing migration more effectively and from the viewpoint of further effectively reducing the connection resistance in the connection structure, the molecular weight of the compound having at least one carboxyl group is preferably 80 or more, more preferably. Is 100 or more, more preferably 120 or more.
- the molecular weight means a molecular weight that can be calculated from the structural formula when the compound having at least one carboxyl group is not a polymer and when the structural formula of the compound having at least one carboxyl group can be specified. Further, when the compound having at least one carboxyl group is a polymer, it means a weight average molecular weight.
- the conductive particles may have a conductive particle main body and an anionic polymer disposed on the surface of the conductive particle main body.
- the conductive particles are preferably obtained by surface-treating the conductive particle body with an anionic polymer or a compound that becomes an anionic polymer.
- the conductive particles are preferably a surface treated product of an anionic polymer or a compound that becomes an anionic polymer.
- the anion polymer and the compound used as the said anion polymer only 1 type may respectively be used and 2 or more types may be used together.
- the anionic polymer is a polymer having an acidic group.
- an anionic polymer for example, a (meth) acrylic polymer copolymerized with (meth) acrylic acid, synthesized from a dicarboxylic acid and a diol, and having carboxyl groups at both ends are used.
- Polyester polymer having a carboxyl group at both ends obtained from an intermolecular dehydration condensation reaction of dicarboxylic acid, a polyester polymer synthesized from dicarboxylic acid and diamine and having a carboxyl group at both ends, and a modification having a carboxyl group
- a method of reacting the carboxyl group of the anionic polymer with the hydroxyl group on the surface of the conductive particle main body using Poval (“GOHSEX T” manufactured by Nippon Synthetic Chemical Co., Ltd.) or the like can be mentioned.
- anion portion of the anionic polymer examples include the carboxyl group, and other than that, a tosyl group (p—H 3 CC 6 H 4 S ( ⁇ O) 2 —), a sulfonate ion group (—SO 3 —) ), And phosphate ion groups (—PO 4 ⁇ ) and the like.
- a compound having a functional group that reacts with a hydroxyl group on the surface of the conductive particle main body and having a functional group that can be polymerized by addition or condensation reaction is used as another method of the surface treatment.
- the method of polymerizing on the surface of an electroconductive particle main body is mentioned.
- the functional group that reacts with the hydroxyl group on the surface of the conductive particle body include a carboxyl group and an isocyanate group, and the functional group that polymerizes by addition and condensation reactions includes a hydroxyl group, a carboxyl group, an amino group, and (meta ) An acryloyl group is mentioned.
- the weight average molecular weight of the anionic polymer is preferably 2000 or more, more preferably 3000 or more, preferably 10,000 or less, more preferably 8000 or less.
- the weight average molecular weight is not less than the above lower limit and not more than the above upper limit, a sufficient amount of charge and flux properties can be introduced on the surface of the conductive particles. Thereby, the cohesiveness of electroconductive particle can be effectively improved at the time of conductive connection, and the oxide film on the surface of an electrode can be effectively removed at the time of connection of the connection object member.
- the weight average molecular weight is not less than the above lower limit and not more than the above upper limit, it is easy to dispose an anionic polymer on the surface of the conductive particle main body, and effectively increase the cohesiveness of the conductive particles during conductive connection. And the conductive particles can be more efficiently arranged on the electrode.
- the weight average molecular weight indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
- the weight average molecular weight of the polymer obtained by surface-treating the conductive particle main body with a compound that becomes an anionic polymer is obtained by dissolving the solder in the conductive particles, and diluting the conductive particles with dilute hydrochloric acid that does not cause decomposition of the polymer. After removal, it can be determined by measuring the weight average molecular weight of the remaining polymer.
- the acid value per 1 g of the conductive particles is preferably 1 mgKOH or more, more preferably 2 mgKOH or more, preferably 10 mgKOH or less, more preferably 6 mgKOH or less.
- the acid value can be measured as follows. 1 g of conductive particles is added to 36 g of acetone and dispersed with an ultrasonic wave for 1 minute. Thereafter, phenolphthalein is used as an indicator and titrated with a 0.1 mol / L potassium hydroxide ethanol solution.
- FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used as a conductive material.
- the conductive particles 21 shown in FIG. 4 are solder particles.
- the conductive particles 21 are entirely formed of solder.
- the conductive particles 21 do not have base particles in the core and are not core-shell particles.
- both the center part and the outer surface part of an electroconductive part are formed with the solder.
- FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used as a conductive material.
- the electroconductive particle 31 shown in FIG. 5 is equipped with the base material particle 32 and the electroconductive part 33 arrange
- the conductive portion 33 covers the surface of the base particle 32.
- the conductive particles 31 are coated particles in which the surface of the base particle 32 is covered with the conductive portion 33.
- the conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion).
- the conductive particle 31 includes a second conductive portion 33A between the base particle 32 and the solder portion 33B. Therefore, the conductive particles 31 are composed of the base particle 32, the second conductive portion 33A disposed on the surface of the base particle 32, and the solder portion 33B disposed on the outer surface of the second conductive portion 33A.
- FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used as a conductive material.
- the conductive portion 33 in the conductive particle 31 has a two-layer structure.
- the conductive particle 41 shown in FIG. 6 has a solder part 42 as a single-layer conductive part.
- the conductive particles 41 include base particles 32 and solder portions 42 disposed on the surfaces of the base particles 32.
- the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
- the substrate particles are preferably substrate particles excluding metal, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
- the substrate particles may be copper particles.
- the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide , Polyacetal, polyimide, polyamideimide, polyether ether Tons, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer,
- polyolefin resins such as polyethylene, polypropylene,
- the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
- the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and And a crosslinkable monomer.
- non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
- Oxygen atom-containing (meth) acrylate compounds Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
- Nitrile-containing monomers such as (meth) acrylonitrile
- Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether
- Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stea
- crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-
- the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
- examples of inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
- the particles formed from the silica are not particularly limited.
- firing may be performed as necessary.
- grains obtained by performing are mentioned.
- examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
- the substrate particles are metal particles
- examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
- the metal particles are preferably copper particles.
- the substrate particles are preferably not metal particles.
- the method for forming the conductive part on the surface of the base particle and the method for forming the solder part on the surface of the base particle or the surface of the second conductive part are not particularly limited.
- Examples of the method for forming the conductive portion and the solder portion include a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, And a method of coating the surface of the substrate particles with a paste containing metal powder or metal powder and a binder. Electroless plating, electroplating or physical collision methods are preferred.
- Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like is used.
- the melting point of the substrate particles is preferably higher than the melting point of the solder part.
- the melting point of the substrate particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, and particularly preferably higher than 450 ° C.
- the melting point of the substrate particles may be less than 400 ° C.
- the melting point of the substrate particles may be 160 ° C. or less.
- the softening point of the substrate particles is preferably 260 ° C. or higher.
- the softening point of the substrate particles may be less than 260 ° C.
- the conductive particles may have a single layer solder portion.
- the conductive particles may have a plurality of layers of conductive parts (solder part, second conductive part). That is, in the conductive particles, two or more conductive portions may be stacked.
- the solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower.
- the solder part is preferably a metal layer (low melting point metal layer) having a melting point of 450 ° C. or lower.
- the low melting point metal layer is a layer containing a low melting point metal.
- the solder in the conductive particles is preferably metal particles having a melting point of 450 ° C. or lower (low melting point metal particles).
- the low melting point metal particles are particles containing a low melting point metal.
- the low melting point metal is a metal having a melting point of 450 ° C. or lower.
- the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
- the solder in the conductive particles preferably contains tin.
- the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably. It is 70% by weight or more, particularly preferably 90% by weight or more.
- the tin content is determined using a high-frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.
- ICP-AES high-frequency inductively coupled plasma emission spectrometer
- EDX-800HS fluorescent X-ray analyzer
- the solder is melted and joined to the electrodes, and the solder conducts between the electrodes. For example, since the solder and the electrode are not in point contact but in surface contact, the connection resistance is lowered.
- the use of conductive particles having solder on the outer surface of the conductive portion increases the bonding strength between the solder and the electrode, and as a result, the solder and the electrode are more unlikely to peel off, and the conduction reliability is effective. To be high.
- the low melting point metal constituting the solder part and the solder particles is not particularly limited.
- the low melting point metal is preferably tin or an alloy containing tin.
- the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy.
- the low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, or tin-indium alloy because of its excellent wettability to the electrode. More preferred are a tin-bismuth alloy and a tin-indium alloy.
- the material constituting the solder is preferably a filler material having a liquidus of 450 ° C. or lower based on JIS Z3001: Welding terms.
- the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like.
- the solder in the conductive particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, molybdenum and palladium. Moreover, from the viewpoint of further increasing the bonding strength between the solder and the electrode, the solder in the conductive particles preferably contains nickel, copper, antimony, aluminum, or zinc.
- the content of these metals for increasing the bonding strength is preferably 0% in 100% by weight of the solder in the conductive particles. 0.0001% by weight or more, preferably 1% by weight or less.
- the melting point of the second conductive part is preferably higher than the melting point of the solder part.
- the melting point of the second conductive part is preferably more than 160 ° C, more preferably more than 300 ° C, still more preferably more than 400 ° C, still more preferably more than 450 ° C, particularly preferably more than 500 ° C, most preferably Preferably it exceeds 600 degreeC. Since the solder part has a low melting point, it melts during conductive connection. It is preferable that the second conductive portion does not melt during conductive connection.
- the conductive particles are preferably used by melting solder, preferably used by melting the solder part, and used without melting the solder part and melting the second conductive part. It is preferred that Since the melting point of the second conductive part is higher than the melting point of the solder part, it is possible to melt only the solder part without melting the second conductive part during conductive connection.
- the absolute value of the difference between the melting point of the solder part and the melting point of the second conductive part exceeds 0 ° C, preferably 5 ° C or more, more preferably 10 ° C or more, still more preferably 30 ° C or more, particularly preferably Is 50 ° C. or higher, most preferably 100 ° C. or higher.
- the second conductive part preferably contains a metal.
- the metal which comprises the said 2nd electroconductive part is not specifically limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.
- the second conductive part is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and even more preferably a copper layer.
- the conductive particles preferably have a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably have a nickel layer or a gold layer, and still more preferably have a copper layer.
- the thickness of the solder part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
- the thickness of the solder part is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. .
- the thickness of the conductive part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.5 ⁇ m or less, Especially preferably, it is 0.3 micrometer or less.
- the thickness of the conductive portion is the thickness of the entire conductive layer when the conductive portion is a multilayer. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not hardened, and the conductive particles are sufficiently deformed when connecting the electrodes. .
- the thickness of the outermost conductive layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably Is 0.1 ⁇ m or less.
- the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is further increased. Lower. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.
- the thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a field emission scanning electron microscope (FE-SEM).
- FE-SEM field emission scanning electron microscope
- the obtained conductive particles are added to “Technobit 4000” manufactured by Kulzer so as to have a content of 30% by weight, and dispersed to prepare an embedded resin for inspecting conductive particles.
- a cross section of the conductive particles is cut out using an ion milling device ("IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass through the vicinity of the center of the conductive particles dispersed in the embedded resin for inspection.
- the image magnification is set to 50,000 times, 50 conductive particles are randomly selected, and the conductive portion of each conductive particle is observed. It is preferable to do. It is preferable to measure the thickness of the conductive part in the obtained conductive particles and arithmetically average it to obtain the thickness of the conductive part.
- FE-SEM field emission scanning electron microscope
- the average particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less, particularly preferably. Is 30 ⁇ m or less.
- the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrodes, and there are many solders in the conductive particles between the electrodes. It is easy to arrange and the conduction reliability is further enhanced.
- the “average particle size” of the conductive particles indicates a number average particle size.
- the average particle diameter of the conductive particles is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
- the average particle diameter of electroconductive particle with the electroconductive particle single body before mixing with a thermosetting component and a flux, and the electroconductive particle in the electroconductive material after mixing with a thermosetting component and a flux are generally the same
- the shape of the conductive particles is not particularly limited.
- the conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
- the content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 10% by weight or more, particularly preferably 20% by weight or more, most preferably. It is 30% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 60% by weight or less, and particularly preferably 50% by weight or less.
- the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrodes, and more solder in the conductive particles is arranged between the electrodes. It is easy to do and the conduction reliability is further increased. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
- thermosetting compound is a compound that can be cured by heating.
- examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
- an epoxy compound or an episulfide compound is preferable, and an epoxy compound is more preferable.
- the conductive material preferably contains an epoxy compound.
- the said thermosetting compound only 1 type may be used and 2 or more types may be used together.
- the thermosetting compound preferably includes a thermosetting compound having a nitrogen atom. It is more preferable to include a thermosetting compound having a skeleton.
- thermosetting compound having a triazine skeleton examples include triazine triglycidyl ether and the like. PAS, TEPIC-VL, TEPIC-UC) and the like.
- the above-mentioned epoxy compound includes an aromatic epoxy compound. Crystalline epoxy compounds such as resorcinol-type epoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, and benzophenone-type epoxy compounds are preferred.
- An epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder is preferable. The melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher.
- the content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
- thermosetting agent thermosets the thermosetting compound.
- examples of the thermosetting agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cation initiator, and a thermal radical generator.
- the said thermosetting agent only 1 type may be used and 2 or more types may be used together.
- the imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
- the thiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .
- the solubility parameter of the thiol curing agent is preferably 9.5 or more, and preferably 12 or less.
- the solubility parameter is calculated by the Fedors method.
- the solubility parameter of trimethylolpropane tris-3-mercaptopropionate is 9.6, and the solubility parameter of dipentaerythritol hexa-3-mercaptopropionate is 11.4.
- the amine curing agent is not particularly limited, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5].
- examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.
- thermal cation initiator examples include iodonium cation curing agents, oxonium cation curing agents, and sulfonium cation curing agents.
- examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
- examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate.
- sulfonium-based cationic curing agent examples include tri-p-tolylsulfonium hexafluorophosphate.
- the thermal radical generator is not particularly limited, and examples thereof include azo compounds and organic peroxides.
- examples of the azo compound include azobisisobutyronitrile (AIBN).
- examples of the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.
- the reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower.
- the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrode.
- the reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
- the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder in the conductive particles, and is preferably 5 ° C. or higher. Is more preferable, and higher by 10 ° C. or more is more preferable.
- the reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
- the content of the thermosetting agent is not particularly limited.
- the content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 75 parts by weight or less.
- the content of the thermosetting agent is not less than the above lower limit, it is easy to sufficiently cure the conductive material.
- the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.
- the conductive material includes a flux.
- the flux is a combination of the acid which has the effect which wash
- the above-mentioned flux which is a salt of this specific acid and base
- the storage stability of the conductive material increases, and after the conductive material is placed on the connection target member, it is left for a long time. Since it exhibits excellent solder cohesiveness, a conductive material that can exhibit high conduction reliability can be provided.
- the flux is preferably a salt of an acid and a base and is solid at 25 ° C.
- the flux is, for example, a salt of an organic compound having a carboxyl group and a compound having an amino group, and is preferably a salt of an organic compound having a carboxyl group and an organic compound having an amino group.
- the storage stability of the conductive material is effectively increased, and after the conductive material is disposed on the connection target member, it exhibits excellent solder cohesion even when left for a long time, and exhibits high conduction reliability. Therefore, the above-mentioned flux which is a salt of a specific acid and base is preferably solid at 25 ° C. As for the said flux, only 1 type may be used and 2 or more types may be used together.
- the flux can be obtained, for example, by neutralizing a carboxylic acid or carboxylic anhydride and an amino group-containing compound.
- the flux is preferably a neutralization reaction product of a carboxylic acid or carboxylic anhydride and an amino group-containing compound.
- carboxylic acid or carboxylic acid anhydride examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, malic acid, alicyclic carboxylic acid, cyclohexyl carboxylic acid, which is a cyclic aliphatic carboxylic acid, 1,4 -Cyclohexyldicarboxylic acid, aromatic carboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, ethylenediaminetetraacetic acid, and acid anhydrides thereof.
- the acid and the organic compound having a carboxyl group preferably have a plurality of carboxyl groups.
- the organic compound having a plurality of carboxyl groups include dicarboxylic acid and tricarboxylic acid.
- the organic compound having the acid and the carboxyl group preferably has an alkyl group, and the total number of carbon atoms of the alkyl group and the carboxyl group is preferably 4 or more, preferably Is 8 or less.
- an ester of carboxylic acid may be used.
- carboxylic acid esters include alkyl esters of the above carboxylic acids.
- alkyl group of the alkyl ester of the carboxylic acid include an alkyl group having 1 to 4 carbon atoms, and the carbon number of the alkyl group is preferably 3 or less, more preferably 2 or less.
- examples of the amino group-containing compound having no aromatic skeleton include diethanolamine, triethanolamine, methyldiethanolamine, ethyldiethanolamine, cyclohexylamine, and dicyclohexylamine.
- examples of the amino group-containing compound having an aromatic skeleton include benzylamine, benzhydrylamine, 2-methylbenzylamine, 3-methylbenzylamine, and 4-tert-butylbenzylamine.
- examples of secondary amines include N-methylbenzylamine, N-ethylbenzylamine, N-phenylbenzylamine, N-tert-butylbenzylamine, and N-isopropylbenzylamine.
- Tertiary amines include N, N-dimethylbenzylamine, imidazole compounds, and triazole compounds.
- the amino group-containing compound is an aromatic amine compound or an aliphatic alicyclic ring.
- a formula amine compound is preferred.
- the active temperature (melting point) of the flux is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. Storage stability becomes still higher that the active temperature of the said flux is more than the said minimum.
- the melting point of the flux is preferably the melting point of the solder in the conductive particles ⁇ 50 ° C. or more, more preferably the solder melting point in the conductive particles.
- the melting point is ⁇ 30 ° C. or more, preferably the melting point of the solder in the conductive particles + 50 ° C. or less, more preferably the melting point of the solder in the conductive particles + 30 ° C. or less, more preferably less than the melting point of the solder in the conductive particles. is there.
- the melting point of the flux is not less than the above lower limit and not more than the above upper limit, the flux effect is more effectively exhibited and the solder is more efficiently arranged on the electrode.
- the melting point of the flux is preferably lower than the reaction start temperature of the thermosetting agent, more preferably 5 ° C. or more, More preferably, it is 10 ° C. or lower.
- the flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
- the above flux exists as a solid.
- the viscosity of the conductive material may increase due to a partial reaction between the thermosetting component and the flux.
- the reaction between the flux and the thermosetting compound is promoted by moisture in the air, or the flux and the solder
- metal ions are generated by the reaction with the surface of the solder, which adversely affects the cohesiveness of the solder and the insulation between adjacent electrodes.
- the flux is solid in a conductive material at 25 ° C, only the surface of the flux needs to be affected by the above, so it has high storage stability, high conductivity even after standing for a long time, and insulation. Sex can be expressed.
- the flux exists in a solid state, and when the flux is dissolved at a temperature lower than the melting point of the solder, when the conductive material is a paste, at room temperature (23 ° C.) Thixotropic properties can be imparted to the conductive material. Thereby, sedimentation of conductive particles can be prevented, shape retention after application can be exhibited, and the outflow of the conductive material to unnecessary portions can be further prevented.
- the conductive material is a film, since the flux is solid, the liquid content in the conductive material can be reduced, so that the cutability of the film can be improved, and bleeding from the cut surface is suppressed. can do.
- the flux when the flux is melted at a temperature lower than the melting point of the solder, since the flux is melted at the melting point of the solder, the melt viscosity of the conductive material is sufficiently lowered, and the solder cohesion is further improved. be able to.
- the flux when the flux is melted at a temperature lower than the melting point of the solder, the flux is dissolved in the thermosetting compound or the thermosetting agent above the melting point of the solder, and further, the thermosetting compound or the thermosetting agent.
- the flux component is taken into the curing system by the reaction between the carboxyl group and amino group of the flux. Thereby, high insulation between adjacent electrodes can be expressed, and further corrosion of the electrodes can be prevented.
- the average particle diameter of the flux is preferably 30 ⁇ m or less.
- the flux can be present in the conductive material without reacting with the resin, and the storage stability of the conductive material can be further enhanced.
- the average particle size of the flux is preferably 0.1 ⁇ m or more.
- the “average particle size” of the flux indicates the number average particle size.
- the average particle diameter of the flux is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
- the average particle diameter of the flux there is a difference in the average particle diameter of the flux between the flux alone before being mixed with the conductive particles and the thermosetting component and the flux in the conductive material after being mixed with the conductive particles and the thermosetting component. If not, the average particle size can be evaluated with the flux alone before being mixed with the conductive particles and the thermosetting component.
- the ratio of the average particle diameter of the flux to the average particle diameter of the conductive particles is preferably 3 or less, more preferably Is 1 or less, more preferably 0.2 or less.
- the ratio is less than or equal to the upper limit, the flux can be effectively brought into contact with the conductive particles, and the flux performance during heating can be further enhanced.
- the above ratio is preferably 0.005 or more, more preferably 0.01 or more, and further preferably 0.02 or more.
- the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
- the conductive material is made of insulating particles. It is preferable to contain. In the conductive material, the insulating particles may not be attached to the surface of the conductive particles. In the conductive material, the insulating particles are preferably present away from the conductive particles.
- the average particle diameter of the insulating particles is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 25 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 50 ⁇ m or less.
- the average particle diameter of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material, and between the connection target members connected by the solder in the conductive particles The interval becomes even more moderate.
- the “average particle size” of the insulating particles indicates the number average particle size.
- the average particle diameter of the insulating particles is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating an average value.
- the average particle diameter of the insulating particles is generally the same.
- the material for the insulating particles includes an insulating resin and an insulating inorganic substance.
- said insulating resin the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned.
- As said insulating inorganic substance the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.
- the insulating resin that is the material of the insulating particles include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable resins and water-soluble resins.
- thermoplastic resin examples include vinyl polymers and vinyl copolymers.
- thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
- water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
- the content of the insulating particles is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. It is as follows.
- the conductive material may not contain insulating particles. When the content of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material, and the interval between the connection target members connected by the solder in the conductive particles becomes even more reasonable.
- the conductive material may be, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a lubricant as necessary.
- various additives such as an antistatic agent and a flame retardant may be included.
- connection structure includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided.
- the material of the connection portion is the conductive material described above, and the connection portion is formed of the conductive material described above.
- the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
- the method for manufacturing the connection structure includes the step of disposing the conductive material on the surface of the first connection target member having at least one first electrode on the surface, using the conductive material described above, A second connection target member having at least one second electrode on the surface opposite to the first connection target member side of the material, the first electrode and the second electrode A step of arranging the first connection target member and the second connection target member by connecting the first connection target member and the second connection target member by heating the conductive material to a temperature equal to or higher than the melting point of the solder in the conductive particles. Forming a portion with a cured product of the conductive material, and electrically connecting the first electrode and the second electrode with a solder portion in the connection portion.
- the conductive material is heated above the curing temperature of the thermosetting component and the thermosetting compound.
- connection structure since a specific conductive material is used, solder in a plurality of conductive particles easily collects between the first electrode and the second electrode.
- the solder can be efficiently arranged on the electrode (line).
- a part of the solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved.
- a conductive paste is used instead of a conductive film. It is preferable to use it.
- the thickness of the solder part between the electrodes is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less.
- Solder wet area on the surface of the electrode (area where the solder is in contact with 100% of the exposed area of the electrode, electrically connected to the first electrode and the first electrode before forming the connecting portion)
- the area of contact of the solder part after forming the connecting part with respect to the exposed area of 100% with the second electrode is preferably 50% or more, more preferably 70% or more, preferably Is 100% or less.
- the second connection target member in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the second connection is applied to the conductive material.
- the weight of the target member is added, or pressure is applied in at least one of the step of arranging the second connection target member and the step of forming the connection portion, and the second connection target member It is preferable that the pressure of pressurization is less than 1 MPa in both the step of disposing and the step of forming the connecting portion. By not applying a pressure of 1 MPa or more, the aggregation of the solder in the conductive particles is considerably promoted.
- the method for manufacturing a connection structure from the viewpoint of suppressing the warpage of the connection target member, in the method for manufacturing a connection structure according to the present invention, at least one of the step of arranging the second connection target member and the step of forming the connection portion is performed.
- the pressure of pressurization may be less than 1 MPa in both the step of performing pressure and arranging the second connection target member and the step of forming the connection portion.
- the pressurization may be performed only in the step of arranging the second connection target member, or the pressurization may be performed only in the step of forming the connection portion.
- Pressurization may be performed in both the step of arranging the connection target member and the step of forming the connection portion.
- the case where the pressure is less than 1 MPa includes the case where no pressure is applied.
- the pressure of pressurization is preferably 0.9 MPa or less, more preferably 0.8 MPa or less.
- the pressure of the pressurization is 0.8 MPa or less, the aggregation of the solder in the conductive particles is further promoted more remarkably than when the pressure of the pressurization exceeds 0.8 MPa.
- connection target member in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the second connection is applied to the conductive material.
- the weight of the target member is preferably added, and in the step of arranging the second connection target member and the step of forming the connection portion, the conductive material exceeds the weight force of the second connection target member. It is preferable that no pressure is applied. In these cases, the uniformity of the amount of solder can be further enhanced in the plurality of solder portions.
- the thickness of the solder portion can be increased more effectively, and a large amount of solder in a plurality of conductive particles tends to gather between the electrodes, and the solder in the plurality of conductive particles is more efficiently distributed on the electrode (line). Can be arranged. In addition, it is difficult for a part of the solder in the plurality of conductive particles to be disposed in the region (space) where the electrode is not formed, and the amount of solder in the conductive particle disposed in the region where the electrode is not formed is further increased. Can be reduced. Therefore, the conduction reliability between the electrodes can be further enhanced. In addition, the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
- connection portion if the weight of the second connection target member is added to the conductive material without applying pressure, the connection portion is Solder arranged in a region (space) where no electrode is formed before it is formed is more likely to gather between the first electrode and the second electrode, and solder in a plurality of conductive particles can be The present inventors have also found that it can be arranged more efficiently on the line).
- a configuration in which a conductive paste is used instead of a conductive film and a configuration in which the weight of the second connection target member is added to the conductive paste without applying pressure are used in combination. This has a great meaning in order to obtain the effects of the present invention at a higher level.
- WO2008 / 023452A1 describes that it is preferable to pressurize with a predetermined pressure at the time of bonding from the viewpoint of efficiently moving the solder powder to the electrode surface, and the pressurizing pressure further ensures the solder area.
- the pressure is set to 0 MPa or more, preferably 1 MPa or more.
- a predetermined pressure may be applied to the adhesive tape by its own weight.
- WO2008 / 023452A1 it is described that the pressure applied intentionally to the adhesive tape may be 0 MPa, but there is no difference between the effect when the pressure exceeding 0 MPa is applied and when the pressure is set to 0 MPa. Not listed.
- WO2008 / 023452A1 recognizes nothing about the importance of using a paste-like conductive paste instead of a film.
- a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied.
- the conductive film in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is.
- the melt viscosity of the conductive film compared with the conductive paste, the melt viscosity of the conductive film cannot be sufficiently lowered at the melting temperature of the solder, and the aggregation of the solder tends to be hindered.
- FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
- connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3.
- Part 4 is formed of the conductive material described above.
- the conductive material includes solder particles as conductive particles.
- the connecting portion 4 includes a solder portion 4A in which a plurality of solder particles are gathered and joined to each other, and a cured product portion 4B in which a thermosetting component is thermally cured.
- solder particles are used as the conductive particles in order to form the solder portion 4A.
- both the central portion and the outer surface of the conductive portion are formed of solder.
- the first connection object member 2 has a plurality of first electrodes 2a on the surface (upper surface).
- the second connection target member 3 has a plurality of second electrodes 3a on the surface (lower surface).
- the first electrode 2a and the second electrode 3a are electrically connected by the solder portion 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A.
- no solder exists in a region (cured product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
- connection structure 1 a plurality of solder particles gather between the first electrode 2 a and the second electrode 3 a, and after the plurality of solder particles melt, After the electrode surface wets and spreads, it solidifies to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. That is, by using solder particles, the solder portion 4A, the first electrode 2a, and the solder as compared with the case where the outer surface portion of the conductive portion is made of conductive particles such as nickel, gold or copper are used. The contact area between the portion 4A and the second electrode 3a increases. For this reason, the conduction
- connection structure 1 shown in FIG. 1 all of the solder portions 4A are located in the facing region between the first and second electrodes 2a and 3a.
- the connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection portion 4X.
- the connection part 4X has the solder part 4XA and the hardened
- most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a are opposed to each other, and a part of the solder portion 4XA is first and second. You may protrude to the side from the area
- the solder part 4XA protruding laterally from the region where the first and second electrodes 2a and 3a are opposed is a part of the solder part 4XA and is not a solder separated from the solder part 4XA.
- the amount of solder away from the solder portion can be reduced, but the solder away from the solder portion may exist in the cured product portion.
- connection structure 1 If the amount of solder particles used is reduced, the connection structure 1 can be easily obtained. If the amount of the solder particles used is increased, it becomes easy to obtain the connection structure 1X.
- the first electrode 2a and the second electrode 2a are arranged in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a.
- the solder portions 4A and 4XA in the connection portions 4 and 4X are preferably disposed at 70% or more, particularly preferably 80% or more, and most preferably 90% or more.
- the portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is seen.
- the solder portion in the connection portion is preferably disposed.
- the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode.
- 60% or more (more preferably 70% or more, still more preferably 80%) of the solder portion in the connection portion is formed on the facing portion of the first electrode and the second electrode. % Or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 99% or more).
- connection structure 1 using the conductive material Next, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
- the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared.
- a conductive material 11 including a thermosetting component 11B, a plurality of solder particles 11A, and a specific flux is disposed on the surface of the first connection target member 2.
- the used conductive material contains a thermosetting compound and a thermosetting agent as the thermosetting component 11B.
- the conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the conductive material 11 is disposed, the solder particles 11A are disposed both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
- the arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by an inkjet device.
- the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared.
- the 2nd connection object member 3 is arrange
- the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
- the conductive material 11 is heated to a temperature equal to or higher than the melting point of the solder particles 11A (third step).
- the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder).
- the solder particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect).
- the thermosetting component 11B is thermoset. As a result, as shown in FIG.
- connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11.
- the connection part 4 is formed of the conductive material 11
- the solder part 4A is formed by joining a plurality of solder particles 11A
- the cured part 4B is formed by thermosetting the thermosetting component 11B. If the solder particles 11A are sufficiently moved, the first electrode 2a and the second electrode are moved after the movement of the solder particles 11A not located between the first electrode 2a and the second electrode 3a starts. It is not necessary to keep the temperature constant until the movement of the solder particles 11A is completed.
- the electrode of the first connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the electrodes of the second connection target member is shifted, the shift is corrected and the first connection target member is corrected. Can be connected to the electrode of the second connection target member (self-alignment effect). This is because the molten solder self-aggregated between the electrode of the first connection target member and the electrode of the second connection target member is the electrode of the first connection target member and the electrode of the second connection target member.
- connection structure with alignment As the area where the solder and the other components of the conductive material are in contact with each other is minimized, the energy becomes more stable. Therefore, the force that makes the connection structure with alignment, which is the connection structure with the smallest area, works. Because. At this time, it is desirable that the conductive material is not cured, and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at that temperature and time.
- connection structure 1 shown in FIG. 1 is obtained.
- the second step and the third step may be performed continuously.
- the laminated body of the 1st connection object member 2, the electrically-conductive material 11, and the 2nd connection object member 3 which are obtained is moved to a heating part, and the said 3rd connection object is carried out.
- You may perform a process.
- the laminate In order to perform the heating, the laminate may be disposed on a heating member, or the laminate may be disposed in a heated space.
- the heating temperature in the third step is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 450 ° C. or lower, more preferably 250 ° C. or lower, and still more preferably 200 ° C. or lower.
- a heating method in the third step a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the solder and the curing temperature of the thermosetting compound, or a connection structure The method of heating only the connection part of these is mentioned.
- instruments used in the method of locally heating include a hot plate, a heat gun that applies hot air, a soldering iron, and an infrared heater.
- the metal directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin.
- the upper surface of the hot plate is preferably formed.
- the first and second connection target members are not particularly limited. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor
- the first and second connection target members are preferably electronic components.
- At least one of the first connection target member and the second connection target member is preferably a semiconductor chip, a resin film, a flexible printed circuit board, a rigid flexible circuit board, or a flexible flat cable.
- a substrate, a flexible flat cable, or a rigid flexible substrate is more preferable.
- the second connection target member is preferably a semiconductor chip, a resin film, a flexible printed board, a rigid flexible board, or a flexible flat cable, and more preferably a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
- Resin films, flexible printed boards, flexible flat cables, and rigid flexible boards have the property of being highly flexible and relatively lightweight.
- the solder in the conductive particles tends not to collect on the electrodes.
- a conductive paste even if a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board is used, the solder in the conductive particles can be efficiently collected on the electrodes, The conduction reliability can be sufficiently increased.
- the conduction reliability between the electrodes by not applying pressure is improved. The improvement effect can be obtained more effectively.
- connection target member Peripherals, area arrays, etc. exist in the form of the connection target member.
- the electrodes are present only on the outer peripheral portion of the substrate.
- the area array substrate there are electrodes in the plane.
- the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode.
- the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode.
- the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode.
- the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
- the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
- the trivalent metal element include Sn, Al, and Ga.
- Thermosetting compound 1 Resorcinol type epoxy compound, “Epolite TDC-LC” manufactured by Kyoeisha Chemical, epoxy equivalent 120 g / eq
- Thermosetting compound 2 highly reactive epoxy compound, “EP-3300S” manufactured by ADEKA Corporation, epoxy equivalent 165 g / eq
- Thermosetting agent 1 Trimethylolpropane tris (3-mercaptopropinate), “TMMP” manufactured by SC Organic Chemical Co., Ltd.
- Thermosetting agent 2 Todipentaerythritol hexakis (3-mercaptopropionate), “DPMP” manufactured by SC Organic Chemical Co., Ltd.
- Latent epoxy thermosetting agent 1 T & K TOKA's “Fujicure 7000”
- Preparation method of flux 1 A three-necked flask was charged with 160 g of acetone and 32 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved at room temperature until uniform. Thereafter, 26 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours after completion of the addition. Precipitated white crystals were collected by filtration, washed with acetone, and vacuum-dried to obtain flux 1. The average particle diameter was measured with 50 arbitrary particles using a scanning electron microscope (“S-4300SEN” manufactured by Hitachi, Ltd.), and the average value was calculated. The melting point was determined by measuring the endothermic peak with DSC (“DSC6200” manufactured by Seiko Instruments Inc.).
- Preparation method of flux 2 The white crystals obtained by the same method as in flux 1 were pulverized in a mortar until the average particle size became 10 ⁇ m, and flux 2 was obtained.
- Method for producing flux 4 The white crystals obtained by the same method as in flux 1 were pulverized in a mortar until the average particle size became 0.05 ⁇ m, and flux 4 was obtained.
- Method for producing flux 5 A three-necked flask was charged with 160 g of acetone and 31 g of cyclohexanecarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved at room temperature until uniform. Thereafter, 24 g of cyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours after completion of the addition. Precipitated white crystals were collected by filtration, washed with acetone, and vacuum dried. Then, it grind
- Method for producing flux 6 A three-necked flask was charged with 160 g of acetone and 35 g of adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved at room temperature until uniform. Thereafter, 26 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours after completion of the addition. Precipitated white crystals were collected by filtration, washed with acetone, and vacuum dried. Then, it grind
- Preparation method of flux 7 In a three-necked flask, 26.8 g of triethanolamine was added to 12.6 g of citric acid monohydrate, and citric acid was dissolved while stirring in an oil bath at 120 ° C. The obtained triethanolamine citrate salt was liquid at 25 ° C.
- the flux alone before being mixed with the conductive particles and the thermosetting component and the flux in the conductive material after being mixed with the conductive particles and the thermosetting component was the same.
- Solder particles 1 (SnBi solder particles, melting point 139 ° C., “DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter 12 ⁇ m))
- Solder particles 2 SAC solder particles, melting point 217 ° C., “DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter 12 ⁇ m))
- solder particles 3 A three-necked flask was charged with 160 g of acetone and 32 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved at room temperature until uniform. Then, after putting 100 g of solder particles 1 and stirring for 15 minutes, 26 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes. A flux was deposited on the surface. Thereafter, the solder particles were washed once with acetone and vacuum dried to obtain solder particles 3.
- Examples 1 to 17 and Comparative Examples 1 and 2 (1) Preparation of anisotropic conductive paste The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Tables 1 and 2 to obtain anisotropic conductive pastes. In the obtained anisotropic conductive paste, the flux was present in the states shown in Tables 1 and 2.
- connection structure As a first connection target member, a copper electrode having a diameter of 250 ⁇ m and a thickness of 10 ⁇ m at a pitch of 400 ⁇ m is provided on the surface of a semiconductor chip body (size 5 ⁇ 5 mm, thickness 0.4 mm). A semiconductor chip arranged in an area array was prepared. The number of copper electrodes is 10 ⁇ 10 in total per 100 semiconductor chips.
- the same pattern is formed on the surface of the glass epoxy substrate body (size 20 ⁇ 20 mm, thickness 1.2 mm, material FR-4) with respect to the electrodes of the first connection target member.
- a glass epoxy substrate was prepared in which a gold electrode was disposed and a solder resist film was formed in a region where the gold electrode was not disposed.
- the level difference between the surface of the copper electrode and the surface of the solder resist film is 15 ⁇ m, and the solder resist film protrudes from the copper electrode.
- the anisotropic conductive paste immediately after fabrication was applied to the upper surface of the glass epoxy substrate so as to have a thickness of 50 ⁇ m to form an anisotropic conductive paste layer.
- a semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other.
- the weight of the semiconductor chip is added to the anisotropic conductive paste layer. From this state, the temperature of the anisotropic conductive paste layer was changed to the solder melting point (139 ° C. in Examples 1 to 9, 12 to 17 and Comparative Examples 1 and 2, and in Examples 10 and 11 after 5 seconds from the start of temperature increase. 217 ° C.).
- the temperature of the anisotropic conductive paste layer was the melting point of the solder + 21 ° C. (160 ° C. in Examples 1 to 9, 12 to 17 and Comparative Examples 1 and 2, and in Examples 10 and 11.
- the anisotropic conductive paste layer was cured by heating to 238 ° C. and holding for 5 minutes to obtain a connection structure. No pressure was applied during heating.
- Viscosity The viscosity ( ⁇ 25) at 25 ° C. of the anisotropic conductive paste was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
- Viscosity after storage is within ⁇ 25% of viscosity before storage
- Viscosity after storage does not correspond to the standard of ⁇
- viscosity after storage is within ⁇ 50% of viscosity before storage
- ⁇ Standard of ⁇
- ⁇ The viscosity after storage is within ⁇ 75% of the viscosity before storage
- ⁇ Does not correspond to the criteria of ⁇ , ⁇ and ⁇
- solder placement accuracy 1 In the obtained connection structure, when the portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is viewed, The ratio X of the area where the solder part in the connection part is arranged in the area of 100% of the part facing the second electrode was evaluated.
- the solder placement accuracy 1 on the electrode was determined according to the following criteria.
- Ratio X is 70% or more ⁇ : Ratio X is 60% or more and less than 70% ⁇ : Ratio X is 50% or more and less than 60% X: Ratio X is less than 50%
- solder placement accuracy on electrode 2 In the obtained connection structure, when the portion where the first electrode and the second electrode face each other in the direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode is seen, The ratio Y of the solder part in the connection part arrange
- the solder placement accuracy 2 on the electrode was determined according to the following criteria.
- Ratio Y is 99% or more ⁇ : Ratio Y is 90% or more and less than 99% ⁇ : Ratio Y is 70% or more and less than 90% X: Ratio Y is less than 70%
- connection resistance The average value of connection resistance is 10 14 ⁇ or more ⁇ : The average value of connection resistance is 10 8 ⁇ or more and less than 10 14 ⁇ ⁇ : The average value of connection resistance is 10 6 ⁇ or more and less than 10 8 ⁇ : The average value of the connection resistance is 10 5 ⁇ or more and less than 10 6 ⁇ ⁇ : The average value of the connection resistance is less than 10 5 ⁇
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Abstract
Description
本発明に係る導電材料は、複数の導電性粒子と、バインダーとを含む。上記導電性粒子は、導電部を有する。上記導電性粒子は、導電部の外表面部分に、はんだを有する。はんだは、導電部に含まれ、導電部の一部又は全部である。上記バインダーは、上記導電材料に含まれる導電性粒子を除く成分である。
上記導電性粒子は、接続対象部材の電極間を電気的に接続する。上記導電性粒子は、導電部の外表面部分にはんだを有する。上記導電性粒子は、はんだにより形成されたはんだ粒子であってもよい。上記はんだ粒子は、はんだを導電部の外表面部分に有する。上記はんだ粒子は、中心部分及び導電部の外表面部分のいずれもがはんだにより形成されている。上記はんだ粒子は、中心部分及び導電性の外表面のいずれもがはんだである粒子である。上記はんだ粒子は、コア粒子として、基材粒子を有さない。上記はんだ粒子は、基材粒子と、上記基材粒子の表面上に配置された導電部とを備える導電性粒子とは異なる。上記はんだ粒子は、例えば、はんだを好ましくは80重量%以上、より好ましくは90重量%以上、更に好ましくは95重量%以上で含む。上記導電性粒子は、基材粒子と、該基材粒子の表面上に配置された導電部とを有していてもよい。この場合に、上記導電性粒子は、導電部の外表面部分に、はんだを有する。
上記熱硬化性化合物は、加熱により硬化可能な化合物である。上記熱硬化性化合物としては、オキセタン化合物、エポキシ化合物、エピスルフィド化合物、(メタ)アクリル化合物、フェノール化合物、アミノ化合物、不飽和ポリエステル化合物、ポリウレタン化合物、シリコーン化合物及びポリイミド化合物等が挙げられる。導電材料の硬化性及び粘度をより一層良好にし、導通信頼性及び接続信頼性をより一層高める観点から、エポキシ化合物又はエピスルフィド化合物が好ましく、エポキシ化合物がより好ましい。上記導電材料は、エポキシ化合物を含むことが好ましい。上記熱硬化性化合物は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記熱硬化剤は、上記熱硬化性化合物を熱硬化させる。上記熱硬化剤としては、イミダゾール硬化剤、フェノール硬化剤、チオール硬化剤、アミン硬化剤、酸無水物硬化剤、熱カチオン開始剤及び熱ラジカル発生剤等がある。上記熱硬化剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記導電材料は、フラックスを含む。フラックスの使用により、導電性粒子におけるはんだを電極上により一層効果的に配置することができる。また、本発明では、上記フラックスが、金属の表面を洗浄する効果を有する酸と、その酸を中和する作用を有する塩基との組み合わせであり、これら酸と塩基との塩である。
導電材料の硬化物により接続される接続対象部材間の間隔、並びに導電性粒子におけるはんだにより接続される接続対象部材間の間隔を高精度に制御する観点からは、上記導電材料は、絶縁性粒子を含むことが好ましい。上記導電材料において、上記絶縁性粒子は、導電性粒子の表面に付着していなくてもよい。上記導電材料中で、上記絶縁性粒子は導電性粒子と離れて存在することが好ましい。
上記導電材料は、必要に応じて、例えば、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。
本発明に係る接続構造体は、少なくとも1つの第1の電極を表面に有する第1の接続対象部材と、少なくとも1つの第2の電極を表面に有する第2の接続対象部材と、上記第1の接続対象部材と、上記第2の接続対象部材とを接続している接続部とを備える。本発明に係る接続構造体では、上記接続部の材料が、上述した導電材料であり、上記接続部が、上述した導電材料により形成されている。本発明に係る接続構造体では、上記第1の電極と上記第2の電極とが、上記接続部中のはんだ部により電気的に接続されている。
3つ口フラスコに、アセトン160gと、グルタル酸(和光純薬工業社製)32gとを入れ、室温で均一になるまで溶解させた。その後、ベンジルアミン(和光純薬工業社製)26gを30分かけて滴下し、滴下完了後2時間室温で撹拌した。析出した白色結晶をろ過により分取し、アセトンで洗浄し、真空乾燥し、フラックス1を得た。平均粒子径は走査型電子顕微鏡(日立製作所社製「S-4300SEN」)を用いて、任意の粒子50個で測定し、平均値を算出した。また融点はDSC(セイコーインスツル社製「DSC6200」)にて吸熱ピークを測定した。
フラックス1と同様の方法で得られた白色結晶について、平均粒子径が10μmになるまで乳鉢にて粉砕して、フラックス2を得た。
フラックス1と同様の方法で得られた白色結晶について、平均粒子径が1μmになるまで乳鉢にて粉砕して、フラックス3を得た。
フラックス1と同様の方法で得られた白色結晶について、平均粒子径が0.05μmになるまで乳鉢にて粉砕して、フラックス4を得た。
3つ口フラスコに、アセトン160gと、シクロヘキサンカルボン酸(和光純薬工業社製)31gとを入れ、室温で均一になるまで溶解させた。その後、シクロヘキシルアミン(東京化成工業製)24gを30分かけて滴下し、滴下完了後2時間室温で撹拌した。析出した白色結晶をろ過により分取し、アセトンで洗浄し、真空乾燥した。その後、乳鉢にて、平均粒子径が10μmになるまで粉砕し、フラックス5を得た。
3つ口フラスコに、アセトン160gと、アジピン酸(和光純薬工業社製)35gとを入れ、室温で均一になるまで溶解させた。その後、ベンジルアミン(和光純薬工業社製)26gを30分かけて滴下し、滴下完了後2時間室温で撹拌した。析出した白色結晶をろ過により分取し、アセトンで洗浄し、真空乾燥した。その後、乳鉢にて、平均粒子径が10μmになるまで粉砕し、フラックス6を得た。
3つ口フラスコに、クエン酸一水和物12.6gに、トリエタノールアミン26.8gを添加し、120℃のオイルバスで撹拌しながらクエン酸を溶解させた。得られたクエン酸トリエタノールアミン塩は、25℃で液体であった。
3つ口フラスコに、グルタル酸35.0gに、トリエタノールアミン37.25gを添加し、120℃のオイルバスで撹拌しながらグルタル酸を溶解させた。得られたグルタル酸トリエタノールアミン塩は、25℃で半固体であった。
3つ口フラスコに、アセトン160gと、グルタル酸(和光純薬工業社製)32gとを入れ、室温で均一になるまで溶解させた。その後、はんだ粒子1を100g入れて15分攪拌させた後、ベンジルアミン(和光純薬工業社製)26gを30分かけて滴下し、滴下完了後2時間室温で撹拌することで、はんだ粒子の表面にフラックスを析出させた。その後、はんだ粒子をアセトンで1回洗浄し、真空乾燥して、はんだ粒子3を得た。
(1)異方性導電ペーストの作製
下記の表1,2に示す成分を下記の表1,2に示す配合量で配合して、異方性導電ペーストを得た。得られた異方性導電ペーストにおいて、フラックスは、表1,2に示す状態で存在していた。
第1の接続対象部材として、半導体チップ本体(サイズ5×5mm、厚み0.4mm)の表面に、400μmピッチで直径250μm、厚み10μmの銅電極が、エリアアレイにて配置されている半導体チップを準備した。銅電極の数は、半導体チップ1個当たり、10個×10個の合計100個である。
(1)粘度
異方性導電ペーストの25℃での粘度(η25)を、E型粘度計(東機産業社製「TVE22L」)を用いて、25℃及び5rpmの条件で測定した。
異方性導電ペーストをシリンジに入れ、23℃で24時間保管した。保管後に、異方性導電ペーストの25℃での粘度(η25)を、E型粘度計(東機産業社製「TVE22L」)を用いて、25℃及び5rpmの条件で測定した。保存安定性を下記の基準で判定した。
○○:保管後の粘度が保管前の粘度の±25%以内
○:○○の基準に相当せず、保管後の粘度が保管前の粘度の±50%以内
△:○○及び○の基準に相当せず、保管後の粘度が保管前の粘度の±75%以内
×:○○、○及び△の基準に相当しない
得られた接続構造体を断面観察することにより、上下の電極間に位置しているはんだ部の厚みを評価した。
得られた接続構造体において、第1の電極と接続部と第2の電極との積層方向に第1の電極と第2の電極との対向し合う部分をみたときに、第1の電極と第2の電極との対向し合う部分の面積100%中の、接続部中のはんだ部が配置されている面積の割合Xを評価した。電極上のはんだの配置精度1を下記の基準で判定した。
○○:割合Xが70%以上
○:割合Xが60%以上、70%未満
△:割合Xが50%以上、60%未満
×:割合Xが50%未満
得られた接続構造体において、第1の電極と接続部と第2の電極との積層方向と直交する方向に第1の電極と第2の電極との対向し合う部分をみたときに、接続部中のはんだ部100%中、第1の電極と第2の電極との対向し合う部分に配置されている接続部中のはんだ部の割合Yを評価した。電極上のはんだの配置精度2を下記の基準で判定した。
○○:割合Yが99%以上
○:割合Yが90%以上、99%未満
△:割合Yが70%以上、90%未満
×:割合Yが70%未満
得られた接続構造体(n=15個)において、上下の電極間の1接続箇所当たりの接続抵抗をそれぞれ、4端子法により、測定した。接続抵抗の平均値を算出した。なお、電圧=電流×抵抗の関係から、一定の電流を流した時の電圧を測定することにより接続抵抗を求めることができる。導通信頼性を下記の基準で判定した。但し、n=15個中一つでも上下の電極間が導通していない場合には、「×」と判定した。
○○:接続抵抗の平均値が50mΩ以下
○:接続抵抗の平均値が50mΩを超え、70mΩ以下
△:接続抵抗の平均値が70mΩを超え、100mΩ以下
×:接続抵抗の平均値が100mΩを超える、又は接続不良が生じている
得られた接続構造体(n=15個)において、85℃、湿度85%の雰囲気中に100時間放置後、横方向に隣接する電極間に、15Vを印加し、抵抗値を25箇所で測定した。絶縁信頼性を下記の基準で判定した。但し、n=15個中一つでも横方向に隣接する電極間が導通している場合には、「×」と判定した。
○○○:接続抵抗の平均値が1014Ω以上
○○:接続抵抗の平均値が108Ω以上、1014Ω未満
○:接続抵抗の平均値が106Ω以上、108Ω未満
△:接続抵抗の平均値が105Ω以上、106Ω未満
×:接続抵抗の平均値が105Ω未満
2…第1の接続対象部材
2a…第1の電極
3…第2の接続対象部材
3a…第2の電極
4,4X…接続部
4A,4XA…はんだ部
4B,4XB…硬化物部
11…導電材料
11A…はんだ粒子(導電性粒子)
11B…熱硬化性成分
21…導電性粒子(はんだ粒子)
31…導電性粒子
32…基材粒子
33…導電部(はんだを有する導電部)
33A…第2の導電部
33B…はんだ部
41…導電性粒子
42…はんだ部
Claims (14)
- 導電部の外表面部分に、はんだを有する複数の導電性粒子と、
熱硬化性成分と、
フラックスとを含み、
前記フラックスが、酸と塩基との塩であり、
25℃の導電材料中で、前記フラックスが固体で存在する、導電材料。 - 前記導電性粒子及び前記熱硬化性成分と混合されていない状態で、前記フラックス単体が、25℃で固体である、請求項1に記載の導電材料。
- 前記フラックスが、カルボキシル基を有する有機化合物とアミノ基を有する有機化合物との塩である、請求項1又は2に記載の導電材料。
- 前記フラックスの平均粒子径が、30μm以下である、請求項1~3のいずれか1項に記載の導電材料。
- 前記フラックスの平均粒子径の、前記導電性粒子の平均粒子径に対する比が、3以下である、請求項1~4のいずれか1項に記載の導電材料。
- 前記フラックスの融点が、前記導電性粒子におけるはんだの融点-50℃以上、前記導電性粒子におけるはんだの融点+50℃以下である、請求項1~5のいずれか1項に記載の導電材料。
- 前記導電性粒子がはんだ粒子である、請求項1~6のいずれか1項に記載の導電材料。
- 前記熱硬化性成分が、トリアジン骨格を有する熱硬化性化合物を含む、請求項1~7のいずれか1項に記載の導電材料。
- 前記導電性粒子の表面上に、前記フラックスが付着している、請求項1~8のいずれか1項に記載の導電材料。
- 前記導電性粒子の平均粒子径が1μm以上、40μm以下である、請求項1~9のいずれか1項に記載の導電材料。
- 導電材料100重量%中、前記導電性粒子の含有量が10重量%以上、90重量%以下である、請求項1~10のいずれか1項に記載の導電材料。
- 導電ペーストである、請求項1~11のいずれか1項に記載の導電材料。
- 少なくとも1つの第1の電極を表面に有する第1の接続対象部材と、
少なくとも1つの第2の電極を表面に有する第2の接続対象部材と、
前記第1の接続対象部材と前記第2の接続対象部材とを接続している接続部とを備え、
前記接続部の材料が、請求項1~12のいずれか1項に記載の導電材料であり、
前記第1の電極と前記第2の電極とが前記接続部中のはんだ部により電気的に接続されている、接続構造体。 - 前記第1の電極と前記接続部と前記第2の電極との積層方向に前記第1の電極と前記第2の電極との対向し合う部分をみたときに、前記第1の電極と前記第2の電極との対向し合う部分の面積100%中の50%以上に、前記接続部中のはんだ部が配置されている、請求項13に記載の接続構造体。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020187000792A KR102618237B1 (ko) | 2016-01-25 | 2017-01-23 | 도전 재료 및 접속 구조체 |
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TWI778950B (zh) | 2022-10-01 |
CN108028090A (zh) | 2018-05-11 |
JP6966322B2 (ja) | 2021-11-17 |
TW201732841A (zh) | 2017-09-16 |
JPWO2017130892A1 (ja) | 2018-11-15 |
TW202331749A (zh) | 2023-08-01 |
KR102618237B1 (ko) | 2023-12-28 |
CN108028090B (zh) | 2020-11-13 |
KR20180105110A (ko) | 2018-09-27 |
JP2021185579A (ja) | 2021-12-09 |
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