WO2017179532A1 - 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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- WO2017179532A1 WO2017179532A1 PCT/JP2017/014656 JP2017014656W WO2017179532A1 WO 2017179532 A1 WO2017179532 A1 WO 2017179532A1 JP 2017014656 W JP2017014656 W JP 2017014656W WO 2017179532 A1 WO2017179532 A1 WO 2017179532A1
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- Prior art keywords
- conductive
- solder
- particles
- electrode
- conductive particles
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/14—Structural association of two or more 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
- H05K3/30—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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/11—Manufacturing methods
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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 content of solder particles in the anisotropic conductive material is, for example, 80% by weight or less.
- 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 material 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.
- conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive material is heated.
- Patent Document 2 discloses a solder paste in which solder powder and flux are mixed.
- the flux contains 1% by mass or more and 2% by mass or less of polyalkyl methacrylate.
- the flux contains 5% by mass or more and less than 15% by mass of stearamide.
- the solder paste has a viscosity of 50 Pa ⁇ s or more and 150 Pa ⁇ s or less.
- a plurality of first conductive particles having solder on the outer surface portion of the conductive portion, and silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface portion of the conductive portion.
- a conductive material including second conductive particles having, a thermosetting compound, and a thermosetting agent.
- the second conductive particles have gold, palladium, or platinum on the outer surface portion of the conductive portion.
- the viscosity of the conductive material at the melting point of the solder in the first conductive particles is 2 Pa ⁇ s or more and 10 Pa ⁇ s or less.
- the average particle size of the second conductive particles is smaller than the average particle size of the first conductive particles.
- the content of the second conductive particles is 10% by weight or less.
- the ratio of the content of the first conductive particles to the content of the second conductive particles is 3 or more and 80 or less on a weight basis.
- the thermosetting compound includes a thermosetting compound that is liquid at 25 ° C.
- thermosetting compound includes a thermosetting compound having a polyether skeleton.
- a flux having a melting point of 50 ° C. or higher and 190 ° C. or lower is included.
- a carboxyl group or an amino group is present on the outer surface of the first conductive particle.
- the first conductive particles are solder particles having solder at a central portion and an outer surface portion.
- the conductive material includes insulating particles that are not attached to either the surface of the first conductive particle or the surface of the second conductive particle.
- 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 second conductive particles, the second conductive particles are disposed in the solder portion, and the first electrode and the second electrode are in the connection portion.
- a connection structure is provided that is electrically connected by a solder portion.
- 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 connection part includes a cured part, a solder part, and an outer surface part of the conductive part, silver, ruthenium, Second conductive particles containing iridium, gold, palladium, or platinum, the second conductive particles are disposed in the solder portion, and the first electrode and the second electrode Is provided that is electrically connected by a solder part in the connection part.
- the second conductive particles have gold, palladium, or platinum on the outer surface portion of the conductive portion.
- 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 has a plurality of first conductive particles having solder on the outer surface portion of the conductive portion, and silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface portion of the conductive portion. Since the second conductive particles, the thermosetting compound, and the thermosetting agent are included, the solder can be efficiently arranged between the electrodes to be connected, and the conduction reliability and the insulation reliability are improved. be able to.
- a 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 A connection part connecting the second connection target member and the second connection target member, wherein the connection part includes a cured product part, a solder part, and an outer surface part of the conductive part, silver, ruthenium, Second conductive particles containing iridium, gold, palladium, or platinum, the second conductive particles are disposed in the solder portion, and the first electrode and the second electrode, Is electrically connected by the solder portion in the connection portion, and therefore, the conduction reliability and the insulation reliability can be improved.
- 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 first conductive particles that can be used for a conductive material.
- FIG. 5 is a cross-sectional view showing a second example of first conductive particles that can be used for the conductive material.
- FIG. 6 is a cross-sectional view showing a third example of the first conductive particles that can be used for the conductive material.
- the conductive material according to the present invention includes first conductive particles, second conductive particles, a thermosetting compound, and a thermosetting agent.
- the first conductive particles have a conductive part.
- the first 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 second conductive particle has a conductive part.
- the second conductive particles have silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface portion of the conductive portion.
- Silver, ruthenium, iridium, gold, palladium, or platinum is included in the conductive portion, and is a part or all of the conductive portion.
- the moving speed of the solder onto the electrodes is increased, so that the solder can be efficiently disposed between the electrodes to be connected, and conduction reliability and insulation can be achieved. Reliability can be increased.
- the electrode width or the inter-electrode width is narrow, it tends to be difficult to collect the solder on the electrodes.
- the solder can be sufficiently collected on the electrodes. it can.
- the solder since the above configuration is provided, when the electrodes are electrically connected, the solder is likely to gather between the upper and lower electrodes, and the solder is efficiently arranged on the electrodes (lines). can do. Also, in the present invention, when an electrode has a wide electrode width, the solder is more efficiently arranged on the electrode.
- the above-described effect is manifested by the presence of the second conductive particles between the plurality of first conductive particles at the time of the conductive connection, so that the first conductive particles become the second conductive particles. It is because it is attracted
- 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.
- 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.
- 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 ⁇ s or more. Yes, preferably 800 Pa ⁇ s or less, more preferably 600 Pa ⁇ s or less, and even more preferably 500 Pa ⁇ s or less.
- 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 viscosity ( ⁇ mp) of the conductive material at the melting point of the solder in the first conductive particles is preferably 2 Pa ⁇ s or more, more preferably 3 Pa ⁇ s or more, More preferably, it is 4 Pa ⁇ s or more, preferably 10 Pa ⁇ s or less, more preferably 9 Pa ⁇ s or less, and further preferably 8 Pa ⁇ s or less.
- the said viscosity ((eta) mp) can be suitably adjusted with the kind and compounding quantity of a compounding component.
- the melting point of the solder is a temperature that easily affects the movement of the first conductive particles onto the electrode.
- the viscosity ( ⁇ mp) can be measured using, for example, STRESSTECH (manufactured by EOLOGICA) under the conditions of strain control 1 rad, frequency 1 Hz, heating rate 20 ° C./min, measurement temperature range 40 ° C. to solder melting point ° C. It is. In this measurement, the viscosity at the melting point of the solder is read.
- 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 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) acryl means one or both of “acryl” and “methacryl”
- “(meth) acrylate” means one or both of “acrylate” and “methacrylate”.
- (meth) acryloyl means one or both of “acryloyl” and “methacryloyl”.
- the first conductive particles electrically connect the electrodes of the connection target member.
- the first conductive particles have solder on the outer surface portion of the conductive portion.
- the first 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 outer surface of the conductive portion 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 1st electroconductive particle may have a base material particle and the electroconductive part arrange
- the first conductive particles have solder on the outer surface portion of the conductive portion.
- the first conductive particles including base particles not formed by solder and solder portions arranged on the surface of the base particles are used.
- the first conductive particles are less likely to collect on the electrode, and the first conductive particles that have moved on the electrode are likely to move out of the electrode because the solder bonding property between the first conductive particles is low.
- the first conductive particles are solder particles formed of solder.
- a carboxyl group or an amino group is present on the outer surface of the first conductive particle (the outer surface of the solder). It is preferably present, a carboxyl group is preferably present, and an amino group is preferably present.
- the outer surface (outer surface of the solder) of the first conductive particle contains a carboxyl group or an amino group via a Si—O bond, an ether bond, an ester bond or a group represented by the following formula (X). It is preferred that the group is covalently bonded.
- 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 coordination bond, and may not include a bond due to a chelate coordination.
- the first conductive particles include a functional group capable of reacting with a hydroxyl group and a carboxyl group or an amino group. 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 having the above (hereinafter sometimes referred to as compound X). In the above reaction, a covalent bond is formed.
- First conductive particles in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder by reacting a hydroxyl group on the surface of the solder with a functional group capable of reacting with the hydroxyl group in the compound X It can be easily obtained, and the first conductive 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 can also be obtained.
- the compound X can be chemically bonded to the surface of the solder in the form of a covalent 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.
- Examples of the compound having a flux action include levulinic acid, glutaric acid, glycolic acid, succinic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4-aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3- Examples include methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid and 4-phenylbutyric acid. Glutaric acid or glycolic acid is preferred. As for the compound which has the said flux effect
- 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.
- first conductive particles in which a group containing the carboxyl group is covalently bonded to the surface of the solder are obtained. It is done.
- the method for producing the first conductive particles includes, for example, using the first conductive particles, the first conductive particles, a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group, a catalyst, and a solvent.
- the process of mixing In the first conductive particle manufacturing method, the first 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.
- the first conductive particles are used to form the first conductive particles, a compound having a functional group capable of reacting with the hydroxyl group and a carboxyl group, and the catalyst. It is preferable to mix and heat the solvent. By the mixing and heating process, the first 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 first conductive particles are formed by using an isocyanate compound to the hydroxyl group on the surface of the solder. It is preferably obtained through a step of reacting a compound. In the above reaction, a covalent bond is formed.
- the hydroxyl group on the surface of the solder with the isocyanate compound, the first conductive particles in which the nitrogen atom of the group derived from the isocyanate group is covalently bonded to the surface of the solder can be easily obtained. .
- a group derived from the 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 first 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 a silane coupling agent is used. After the reaction, it is preferably introduced by reacting a group derived from the silane coupling agent with a compound having at least one carboxyl group. The first conductive particles are preferably obtained by reacting a compound having at least one carboxyl group after reacting the isocyanate compound with a hydroxyl group on the surface of the solder using the isocyanate compound. .
- 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.
- MDI diphenylmethane-4,4'-diisocyanate
- HDI hexamethylene diisocyanate
- TDI toluene diisocyanate
- IPDI isophorone diisocyanate
- Isocyanate compounds other than these may be used.
- the above-mentioned formula (X) is applied to the surface of the solder 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 a group represented by:
- 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 above 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 first 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.
- the compound which has one is made to react, and the 1st electroconductive particle which the group containing a carboxyl group has couple
- the first 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 may be mentioned as a specific method for producing the first conductive particles.
- First 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 of a hydroxyl group and an isocyanate group on the surface of the solder of the first conductive particles.
- a hydroxyl group is produced
- First 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 first conductive particles. Thereafter, the unsaturated double bond introduced is reacted with a compound having an unsaturated double bond and a carboxyl group.
- a reaction catalyst for the hydroxyl group and isocyanate group on the surface of the solder of the first conductive particles As a reaction catalyst for the hydroxyl group and isocyanate group on the surface of the solder of the first conductive particles, a tin catalyst (dibutyltin dilaurate, etc.), an amine catalyst (triethylenediamine, etc.), a carboxylate catalyst (lead naphthenate, acetic acid) Potassium and the like), and trialkylphosphine catalysts (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 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).
- the left end represents a binding site.
- 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.
- 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 first conductive particles are disposed on the first conductive particle main body and the surface of the first conductive particle main body. It is preferable to have an anionic polymer.
- the first conductive particles are preferably obtained by surface-treating the first conductive particle main body with an anionic polymer or a compound that becomes an anionic polymer.
- the first conductive particles are preferably an anionic polymer or a surface treated product of a compound that becomes an anionic polymer.
- the said 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 at both ends is used.
- Polyester polymer having carboxyl group polymer obtained by intermolecular dehydration condensation reaction of dicarboxylic acid and having carboxyl group at both ends, polyester polymer synthesized from dicarboxylic acid and diamine and having carboxyl group at both ends, and carboxyl group
- 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.
- the first conductive particle body has a functional group that reacts with the hydroxyl group on the surface of the first conductive particle body, and is further polymerized by addition or condensation reaction.
- the method of polymerizing this compound on the surface of the 1st electroconductive particle main body using the compound which has a functional group which can be mentioned is mentioned.
- the functional group that reacts with the hydroxyl group on the surface of the first conductive particle main body include a carboxyl group and an isocyanate group, and the functional group that is polymerized by an addition or condensation reaction includes a hydroxyl group, a carboxyl group, an amino group, And a (meth) acryloyl group.
- 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.
- a sufficient amount of charge and flux properties can be introduced to the surface of the first conductive particles. Thereby, the cohesiveness of the first conductive particles can be effectively increased during the conductive connection, and the oxide film on the surface of the electrode can be effectively removed when the connection target member is connected.
- 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 first conductive particle main body, and the cohesiveness of the first conductive particles during conductive connection Can be effectively increased, and the first 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 first conductive particle body with a compound that becomes an anionic polymer is diluted hydrochloric acid that dissolves the solder in the first conductive particles and does not cause decomposition of the polymer. By removing the first conductive particles, the weight average molecular weight of the remaining polymer can be measured.
- FIG. 4 is a cross-sectional view showing a first example of first conductive particles that can be used for a conductive material.
- the first conductive particles 21 shown in FIG. 4 are solder particles.
- the first conductive particles 21 are entirely formed of solder.
- the 1st electroconductive particle 21 does not have a base particle in a core, and is not a core-shell particle.
- 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 the first conductive particles that can be used for the conductive material.
- the 1st electroconductive particle 31 shown in FIG. 5 is provided with the base particle 32 and the electroconductive part 33 arrange
- the conductive portion 33 covers the surface of the base particle 32.
- the first conductive particles 31 are coated particles in which the surface of the base particle 32 is coated with the conductive portion 33.
- the conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion).
- the first conductive particle 31 includes a second conductive portion 33A between the base particle 32 and the solder portion 33B. Accordingly, the first conductive particles 31 are disposed on the base particles 32, the second conductive portion 33A disposed on the surface of the base particles 32, and the outer surface of the second conductive portion 33A. And a solder portion 33B.
- FIG. 6 is a cross-sectional view showing a third example of first conductive particles that can be used for the conductive material.
- the conductive portion 33 in the first conductive particle 31 has a two-layer structure.
- the first conductive particles 41 shown in FIG. 6 have a solder portion 42 as a single-layer conductive portion.
- the first conductive particle 41 includes a base particle 32 and a solder portion 42 disposed on the surface of the base particle 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 base particle may be a core-shell particle including a core and a shell disposed on the surface of the core.
- the core may be an organic core, and the shell may be an inorganic shell.
- 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.
- the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles
- examples of inorganic materials for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
- the inorganic substance is preferably not a metal.
- the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
- examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
- the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
- the core is preferably an organic core.
- the shell is preferably an inorganic shell.
- the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core. .
- the material for the organic core includes the material for the resin particles described above.
- the inorganic materials mentioned as the material for the base material particles described above can be used.
- the material of the inorganic shell is preferably silica.
- the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material.
- the metal alkoxide is preferably a silane alkoxide.
- the inorganic shell is preferably formed of a silane alkoxide.
- 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 particle diameter of the substrate 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 60 ⁇ m or less, and even more preferably 50 ⁇ m or less.
- the particle diameter of the substrate particles is equal to or greater than the lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased and the conductive particles are connected via the conductive particles. Further, the connection resistance between the electrodes can be further effectively reduced. Further, when forming the conductive portion on the surface of the base particle, it becomes difficult to aggregate and it becomes difficult to form the aggregated conductive particles.
- the particle diameter of the substrate particles is not more than the above upper limit, the conductive particles are easily compressed, and the connection resistance between the electrodes connected through the conductive particles can be further effectively reduced. it can.
- the particle diameter of the substrate particles is particularly preferably 5 ⁇ m or more and 40 ⁇ m or less.
- the distance between the electrodes can be further reduced, and even if the thickness of the conductive portion is increased, small conductive particles are obtained. be able to.
- the particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
- the particle diameter of the base material particles indicates a number average particle diameter.
- the particle diameter of the substrate particles is determined using a particle size distribution measuring device or the like.
- the particle diameter of the substrate particles is preferably determined by observing 50 arbitrary substrate particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the substrate particles in the conductive particles, for example, it can be measured as follows.
- An embedded resin for inspecting conductive particles is prepared by adding to and dispersing in “Technobit 4000” manufactured by Kulzer so that the content of the conductive particles is 30% by weight.
- 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 embedding resin for inspection.
- IM4000 manufactured by Hitachi High-Technologies Corporation
- FE-SEM field emission scanning electron microscope
- the image magnification is set to 25000 times, 50 conductive particles are randomly selected, and the base particles of each conductive particle are observed. To do.
- the particle diameter of the base particle in each conductive particle is measured, and arithmetically averaged to obtain the particle diameter of the base particle.
- 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.
- the method for forming the conductive portion and the solder portion is preferably a method using electroless plating, electroplating, or physical collision.
- 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 base material particles is preferably higher than the melting points of the conductive part and 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 first conductive particles may have a single layer solder portion.
- the first conductive particles may have a plurality of layers of conductive portions (solder portions, second conductive portions). That is, in the first conductive particles, two or more conductive portions may be stacked.
- the first conductive particles preferably have solder on the outer surface portion of the conductive part.
- 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 first conductive particles is preferably metal particles (low melting metal particles) having a melting point of 450 ° C. or lower.
- 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 first conductive particles preferably contains tin.
- the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, More preferably, it is 70 weight% or more, Most preferably, it is 90 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 the first conductive particles having solder on the outer surface portion of the conductive portion increases the bonding strength between the solder and the electrode. Effectively increases.
- 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 first conductive particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, Metals such as bismuth, manganese, chromium, molybdenum, and palladium may be included.
- the solder in the first conductive particles preferably contains nickel, copper, antimony, aluminum, or zinc.
- the content of these metals for increasing the bonding strength is 100 weights of the solder in the first conductive particles. %, Preferably 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 first conductive particles are preferably used by melting solder, preferably by melting the solder part, and melting the solder part and melting the second conductive part. It is preferable to be used without using. 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 first 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 first conductive particles do not become too hard, and the first conductivity is obtained when connecting the electrodes. Deform the particles sufficiently.
- the average particle diameter of the first conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 3 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 40 ⁇ m or less. Particularly preferably, it is 30 ⁇ m or less.
- the average particle diameter of the first conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the first conductive particles can be more efficiently arranged on the electrodes, It is easy to dispose much solder in one conductive particle, and the conduction reliability is further enhanced.
- the “average particle diameter” of the first conductive particles indicates a number average particle diameter.
- the average particle diameter of the first conductive particles is obtained, for example, by observing 50 arbitrary first conductive particles with an electron microscope or an optical microscope and calculating an average value.
- the CV value of the particle diameter of the first conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less.
- the CV value of the particle diameter is not less than the above lower limit and not more than the above upper limit, the solder can be more efficiently arranged on the electrode.
- the CV value of the particle diameter of the conductive particles may be less than 5%.
- the CV value (coefficient of variation) of the particle diameter of the first conductive particles can be measured as follows.
- CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of first conductive particles Dn: Average value of particle diameter of first conductive particles
- the shape of the first conductive particles is not particularly limited.
- the shape of the first conductive particles may be spherical, or may be a shape other than a spherical shape such as a flat shape.
- the acid value of the first conductive particles is preferably 0.1 mg / KOH or more, more preferably 1 mg / KOH or more, preferably 10 mg / KOH or less, more preferably 7 mg / KOH or less.
- the acid value is not less than the above lower limit and not more than the above upper limit, the heat resistance of the cured product is further enhanced, and discoloration of the cured product is further suppressed.
- the acid value can be measured as follows. 1 g of the first conductive particles is added to 50 ml of a solution obtained by adding phenolphthalein to ethanol and neutralizing with 0.1 N-KOH, and then dispersing by ultrasonic treatment, followed by 0.1 N-KOH. Titrate.
- the content of the first conductive particles 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 first conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the first conductive particles can be more efficiently arranged on the electrodes, and the first between the electrodes. It is easy to dispose a large amount of solder in the conductive particles, and the conduction reliability is further enhanced. From the viewpoint of further improving the conduction reliability, it is preferable that the content of the first conductive particles is large.
- the second conductive particles have silver, ruthenium, iridium, gold, palladium, or platinum (a conductive portion containing silver, ruthenium, iridium, gold, palladium, or platinum) on the outer surface portion of the conductive portion.
- the second conductive particles may be metal particles formed of silver, ruthenium, iridium, gold, palladium, or platinum.
- the metal particles have silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface portion of the conductive portion.
- the metal particles are particles in which the central portion and the outer surface of the conductive portion are both silver, ruthenium, iridium, gold, palladium, or platinum.
- the metal particles do not have base particles as core particles.
- the metal particles are different from conductive particles including base particles and conductive portions arranged on the surface of the base particles.
- the outer surface part of the conductive part and the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum are preferably 80% by weight or more, more preferably silver, ruthenium, iridium, gold, palladium and platinum. 90% by weight or more, more preferably 95% by weight or more.
- the second conductive particles may have base particles and conductive portions arranged on the surface of the base particles. In this case, the second conductive particles include silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface portion of the conductive portion.
- the outer surface portion of the conductive portion of the second conductive particle is higher than the melting point of the outer surface portion of the conductive portion of the first conductive particle.
- the outer surface portion of the conductive portion of the second conductive particle and the conductive portion containing silver, ruthenium, iridium, gold, palladium, or platinum are obtained from the melting point of the outer surface portion of the conductive portion of the first conductive particle. Is preferably 50 ° C. or higher, and preferably 100 ° C. or higher.
- the melting point of the outer surface part of the conductive part of the second conductive particles and the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum is preferably 300 ° C. or higher, more preferably 400 ° C. or higher, still more preferably. Is 500 ° C. or higher.
- Examples of the base particles in the second conductive particles include base particles similar to the base particles in the first conductive particles.
- the second conductive particles may be conductive particles obtained by replacing the solder in the conductive particles 21 shown in FIG. 4 with silver, ruthenium, iridium, gold, palladium, or platinum.
- the second conductive particles may be conductive particles obtained by replacing the solder of the second conductive portion 33B in the conductive particles 31 shown in FIG. 5 with silver, ruthenium, iridium, gold, palladium, or platinum.
- the second conductive particles may be conductive particles obtained by replacing the solder of the solder portion 42 in the conductive particles 41 shown in FIG. 6 with silver, ruthenium, iridium, gold, palladium, or platinum.
- the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum may contain at least one metal selected from the group consisting of silver, ruthenium, iridium, gold, palladium and platinum.
- the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum may contain two or more metals selected from the group consisting of silver, ruthenium, iridium, gold, palladium and platinum.
- silver, ruthenium, iridium, gold, palladium and platinum may be alloyed.
- the second conductive particles may have silver, gold, palladium, or platinum on the outer surface portion of the conductive portion.
- the thickness of the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum 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, still more preferably. Is 0.3 ⁇ m or less.
- the thickness of the conductive part containing silver, ruthenium, iridium, gold, palladium or platinum is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained.
- the average particle diameter of the second conductive particles is preferably 3 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
- the second conductive particles can more efficiently arrange the solder in the first conductive particles on the electrode.
- the ratio of the average particle diameter of the first conductive particles to the average particle diameter of the second conductive particles is: Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 3 or more, Preferably it is 4 or less.
- the ratio (average particle diameter of the first conductive particles / average particle diameter of the second conductive particles) is not less than the lower limit and not more than the upper limit, the second conductive particles cause the first on the electrode.
- the solder in the conductive particles can be arranged more efficiently.
- the average particle diameter of the second conductive particles is smaller than the average particle diameter of the first conductive particles.
- the “average particle diameter” of the second conductive particles indicates a number average particle diameter.
- the average particle diameter of the second conductive particles is obtained, for example, by observing 50 arbitrary second conductive particles with an electron microscope or an optical microscope and calculating an average value.
- the shape of the second conductive particles is not particularly limited.
- the shape of the second conductive particles may be spherical or may be a shape other than a spherical shape such as a flat shape.
- the content of the second conductive particles is preferably 1% by weight or more, more preferably 3% by weight or more.
- the solder in the first conductive particles can be more efficiently arranged on the electrode by the second conductive particles.
- the content of the second conductive particles is preferably 10% by weight or less, more preferably 5% by weight or less.
- the second conductive particles can more efficiently arrange the solder in the first conductive particles on the electrode, and The joint strength by the connecting portion can be further increased.
- the ratio of the content of the first conductive particles to the content of the second conductive particles is based on weight. And preferably 3 or more, more preferably 10 or more, preferably 80 or less, more preferably 70 or less.
- 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.
- the said thermosetting compound only 1 type may be used and 2 or more types may be used together.
- thermosetting compound preferably includes a thermosetting compound having a polyether skeleton.
- thermosetting compound having a polyether skeleton examples include a compound having a glycidyl ether group at both ends of an alkyl chain having 3 to 12 carbon atoms and a polyether skeleton having 2 to 4 carbon atoms.
- a polyether type epoxy compound having a structural unit in which ⁇ 10 are bonded in series is exemplified.
- thermosetting compound preferably includes a thermosetting compound having a triazine 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.
- thermosetting compound preferably contains a thermosetting compound that is liquid at 25 ° C.
- 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.
- the content of the thermosetting compound is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the displacement between the electrodes can be further suppressed, The conduction reliability can be further improved. 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 lower limit and not more than the upper limit, the first conductive particles are 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 first conductive particles, and is preferably 5 ° C. or higher. More preferably, it is more preferably 10 ° C. or higher.
- 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 is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, based on 100 parts by weight of the whole thermosetting compound.
- the amount is 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 preferably contains a flux. By using flux, the solder can be more effectively placed on the electrode.
- the flux is not particularly limited. As the flux, a flux generally used for soldering or the like can be used.
- Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and pine resin. Etc. As for the said flux, only 1 type may be used and 2 or more types may be used together.
- Examples of the molten salt include ammonium chloride.
- Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid.
- Examples of the pine resin include activated pine resin and non-activated pine resin.
- the flux is preferably an organic acid having two or more carboxyl groups, pine resin.
- the flux may be an organic acid having two or more carboxyl groups, or pine resin.
- the above rosins are rosins whose main component is abietic acid.
- the flux is preferably rosins, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
- the active temperature (melting point) of the flux is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. or lower, even more preferably 160. ° C or lower, more preferably 150 ° C or lower, still more preferably 140 ° C or lower.
- the active temperature (melting point) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower.
- the activation temperature (melting point) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
- the flux having an active temperature (melting point) of 80 ° C. or higher and 190 ° C. or lower includes succinic acid (melting point 186 ° C.), glutaric acid (melting point 96 ° C.), adipic acid (melting point 152 ° C.), pimelic acid (melting point) 104 ° C.), dicarboxylic acids such as suberic acid (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), malic acid (melting point 130 ° C.) and the like.
- the boiling point of the flux is preferably 200 ° C. or lower.
- the melting point of the flux is preferably higher than the melting point of the solder in the first conductive particles, more preferably 5 ° C. or more, more preferably 10 It is more preferable that the temperature is higher than ° C.
- the melting point of the flux is preferably higher than the reaction start temperature of the thermosetting agent, more preferably 5 ° C or higher, more preferably 10 ° C or higher. More preferably.
- the flux may be dispersed in the conductive material or may be attached on the surface of the first conductive particles.
- the first conductive particles can be efficiently aggregated on the electrode portion. This is because, when heated at the time of joining, when the electrode formed on the connection target member is compared with the part of the connection target member around the electrode, the thermal conductivity of the electrode part is the heat conduction of the connection target member part around the electrode. When the rate is higher than the rate, the temperature rise of the electrode portion is caused quickly. At the stage where the melting point of the first conductive particles is exceeded, the inside of the first conductive particles dissolves, but the oxide film formed on the surface does not reach the melting point (activation temperature) of the flux, and therefore is removed. Not.
- the temperature of the electrode portion first reaches the melting point (activation temperature) of the flux, the oxide film on the surface of the first conductive particles preferentially coming on the electrode is removed, and the first conductive The conductive particles can spread on the surface of the electrode. Thereby, the first conductive particles can be efficiently aggregated on the electrode.
- the flux is preferably a flux that releases cations by heating.
- a flux that releases cations by heating the first conductive particles can be arranged more efficiently on the electrode.
- thermal cation initiator is an example of the flux that releases cations by heating.
- 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 may not contain flux.
- the flux content is not less than the above lower limit and not more than the above upper limit, it becomes more difficult to form an oxide film on the surface of the solder and the electrode, and the oxide film formed on the surface of the solder and the electrode is more effective. Can be removed.
- the conductive material preferably contains insulating particles.
- the insulating particles may not be attached to either the surface of the first conductive particles or the surface of the second conductive particles.
- the insulating particles are preferably present away from the first conductive particles, and the insulating particles are preferably present away from the second 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 distance between the connection target members connected by the cured material of the conductive material and the connection connected by the solder in the first conductive particles The interval between the target members becomes even more appropriate.
- the material for the insulating particles includes an insulating resin and an insulating inorganic substance.
- the insulating resin that is the material of the insulating particles include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked thermoplastic resins, heat Examples thereof include curable resins and water-soluble resins.
- Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer.
- Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate.
- Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof.
- Examples of the thermoplastic resin 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.
- a water-soluble resin is preferable, and polyvinyl alcohol is more preferable.
- the insulating inorganic material that is the material of the insulating particles include silica and organic-inorganic hybrid particles.
- the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
- the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
- 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 are more appropriate. become.
- 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.
- the connecting portion is a cured product of the conductive material described above.
- the connecting 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.
- connection part includes a cured product part, a solder part, and second conductive particles having silver, ruthenium, iridium, gold, palladium, or platinum on the outer surface part of the conductive part.
- the second conductive particles are disposed in the solder portion.
- the second conductive particles preferably have gold, palladium, or platinum on the outer surface portion of the conductive 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
- the first connection target member and the second connection target member are connected by heating the conductive material to a temperature equal to or higher than the melting point of the solder in the first conductive particles.
- the conductive material is heated above the curing temperature of the thermosetting component and the thermosetting compound.
- the second conductive particles are arranged in the solder portion.
- connection structure since the specific conductive material is used, the solder in the plurality of first conductive particles is caused to be the first electrode by the second conductive particles. It is easy to gather between the first electrode and the second electrode, and the solder can be efficiently arranged on the electrode (line). In addition, 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. In addition, it is possible to prevent electrical connection between laterally adjacent electrodes that should not be connected, and to improve insulation reliability.
- 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 average particle diameter of the second conductive particles may be equal to or less than the thickness of the solder portion between the electrodes, may be less than the thickness of the solder portion between the electrodes, and the solder between the electrodes. It may be 1/2 or less of the thickness of the part, and may be 1/3 or less of the thickness of the solder part between the electrodes.
- 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 the first 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, a cured portion 4B in which a thermosetting component is thermally cured, and second conductive particles 11C.
- 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.
- the second conductive particles 11 ⁇ / b> C are disposed in the solder portion 4 ⁇ / b> A.
- connection part 4 in the area
- connection part 4 the 2nd electroconductive particle 11C does not exist in the area
- cured material part 4B part) outside the solder part 4A gathered between the 1st electrode 2a and the 2nd electrode 3a.
- the second conductive particles 11C separated from the solder part 4A do not exist. If the amount is small, the second conductive particles 11C exist in a region outside the solder portion 4A (cured product portion 4B portion) gathered between the first electrode 2a and the second electrode 3a. May be.
- 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. 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.
- the second conductive particles 11C are disposed in the solder portion 4XA.
- 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 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.
- 50% or more (preferably 60% or more, more preferably 70% or more) of the area where the first electrode and the second electrode face each other is 100% or more. It is preferable that the solder part is 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 (preferably 70% or more, more preferably 90% or more) of the solder portion in the connection portion is formed on the facing portion of the first electrode and the second electrode. And more preferably 99% or more).
- the ratio of the number of the second conductive particles arranged in the solder portion out of the total number of the second conductive particles in the connection portion of 100%. Is preferably 50% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% 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.
- the thermosetting component 11B, the several solder particle 11A, and the several 2nd electroconductive particle 11C are included.
- Conductive material 11 is disposed (first step).
- 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 second conductive particles 11C existing between the plurality of solder particles 11A attract the solder particles 11A and promote the movement of the solder particles 11A.
- the solder particles 11A are effectively collected between the first electrode 2a and the second electrode 3a.
- the solder particles 11A are melted and joined together. Further, the thermosetting component 11B is thermoset.
- the 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.
- the second conductive particles 11C are arranged and taken in the solder portion 4A. 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 weight of the second connection target member 3 is added to the conductive material 11. For this reason, when the connection part 4 is formed, the solder particles 11A are effectively collected between the first electrode 2a and the second electrode 3a. In addition, if pressure is applied in at least one of the second step and the third step, the solder particles 11A tend to collect between the first electrode 2a and the second electrode 3a. The tendency to be inhibited becomes high.
- 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.
- 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 a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
- the second connection target member is 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. When a conductive film is used for connection of such a connection object member, there exists a tendency for a solder not to gather on an electrode.
- the conductive reliability between the electrodes can be efficiently collected by collecting the solder on the electrodes. Can be sufficiently increased.
- the conduction reliability between the electrodes by not applying pressure is improved. The improvement effect can be obtained more effectively.
- 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.
- Polymer A (1) Synthesis of first reaction product of bisphenol F with 1,6-hexanediol diglycidyl ether and bisphenol F type epoxy resin: 72 parts by weight of bisphenol F (containing 4,4′-methylene bisphenol, 2,4′-methylene bisphenol and 2,2′-methylene bisphenol in a weight ratio of 2: 3: 1), 1,6-hexanediol 270 parts by weight of diglycidyl ether and 30 parts by weight of bisphenol F type epoxy resin (“EPICLON EXA-830CRP” manufactured by DIC) were placed in a three-necked flask and dissolved at 100 ° C. under a nitrogen flow.
- bisphenol F type epoxy resin (“EPICLON EXA-830CRP” manufactured by DIC)
- the first reaction product contains a hydroxyl group derived from bisphenol F, 1,6-hexanediol diglycidyl ether, and an epoxy group of bisphenol F type epoxy resin. It was confirmed that the unit had a bonded structural unit in the main chain and an epoxy group at both ends.
- Thermosetting compound 1 Resorcinol type epoxy compound, “Epolite TDC-LC” manufactured by Kyoeisha Chemical Co., epoxy equivalent 120 g / eq
- Thermosetting compound 2 Epoxy compound, “EP-3300” manufactured by ADEKA, epoxy equivalent 160 g / eq
- Photopolymerization initiator Acylphosphine oxide compound, “DAROCUR TPO” manufactured by Ciba Japan
- Chain transfer agent pentaerythritol tetrakis (3-mercaptobutyrate), “Karenz MT PE1” manufactured by Showa Denko KK
- Latent epoxy thermosetting agent T & K TOKA "Fujicure 7000"
- Flux 1 25 parts by weight of glutaric acid and 25 parts by weight of monomethyl glutarate were placed in a three-necked flask and dissolved at 80 ° C. under a nitrogen flow. Thereafter, 57 parts by weight of benzylamine was added and reacted at 80 ° C. under reduced pressure (4 Torr or less) for 2 hours to obtain flux 1 that was solid at 25 ° C.
- Insulating particles average particle size 30 ⁇ m, CV value 5%, softening point 330 ° C., Sekisui Chemical Co., Ltd., divinylbenzene crosslinked particles
- Solder particles 1 Sn-3Ag-0.5Cu solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 30 ⁇ m) and citric acid (“citric acid” manufactured by Wako Pure Chemical Industries, Ltd.) are used as a catalyst.
- ST-5 manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 30 ⁇ m
- citric acid citric acid manufactured by Wako Pure Chemical Industries, Ltd.
- Solder particles 2 200 g of Sn-3Ag-0.5Cu solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 30 ⁇ m) and a silane coupling agent having an isocyanate group (“KBE-9007 manufactured by Shin-Etsu Silicone Co., Ltd.) ) 10 g and 70 g of acetone were weighed into a three-necked flask. While stirring at room temperature, 0.25 g of dibutyltin dilaurate, which is a reaction catalyst of the hydroxyl group and isocyanate group on the surface of the solder particles, was added, and the mixture was heated at 100 ° C. for 2 hours under stirring in a nitrogen atmosphere. Thereafter, 50 g of methanol was added, and the mixture was heated at 60 ° C. for 1 hour under stirring in a nitrogen atmosphere.
- Sn-3Ag-0.5Cu solder particles (“ST-5” manufactured by Mitsui Kinzoku Co.
- the mixture was cooled to room temperature, the solder particles were filtered with filter paper, and the solvent was removed by vacuum drying at room temperature for 1 hour.
- solder particles are put into a three-necked flask, 70 g of acetone, 30 g of trimethyl citrate, and 0.5 g of monobutyltin oxide that is a transesterification reaction catalyst are added, and the mixture is stirred at 60 ° C. under a nitrogen atmosphere. Reacted for hours.
- ester group of trimethyl citrate was reacted with the silanol group derived from the silane coupling agent by a transesterification reaction to form a covalent bond.
- solder particles 2 After pulverizing the obtained solder particles with a ball mill, a sieve was selected so that a predetermined CV value was obtained. Thereby, solder particles 2 (CV value 20%) were obtained.
- CV value of particle diameter of solder particles and conductive particles The CV value was measured with a laser diffraction particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.).
- Second conductive particles 1 conductive particles (average particle diameter 15 ⁇ m) in which a gold layer (thickness 0.02 ⁇ m) is arranged on the surface of divinylbenzene resin particles
- Second conductive particle 2 conductive particle (average particle diameter 15 ⁇ m) in which a palladium layer (thickness 0.02 ⁇ m) is arranged on the surface of divinylbenzene resin particles
- Second conductive particle 3 conductive particle (average particle diameter 15 ⁇ m) in which a platinum layer (thickness 0.02 ⁇ m) is disposed on the surface of divinylbenzene resin particles
- Second conductive particles 6 Conductive particles (average particle size 15 ⁇ m) in which a ruthenium layer (thickness 0.02 ⁇ m) is arranged on the surface of divinylbenzene resin particles
- Second conductive particles 7 Conductive particles (average particle size 15 ⁇ m) in which an iridium layer (thickness 0.02 ⁇ m) is arranged on the surface of divinylbenzene resin particles
- Second conductive particle 4 conductive particle (average particle diameter 10 ⁇ m) in which a gold layer (thickness 0.02 ⁇ m) is arranged on the surface of divinylbenzene resin particles
- Second conductive particles 5 conductive particles (average particle diameter 30 ⁇ m) in which a gold layer (thickness 0.02 ⁇ m) is disposed on the surface of divinylbenzene resin particles
- Examples 1 to 13 and Comparative Examples 1 and 2 (1) Production of conductive material The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Tables 1 and 2 to obtain conductive materials (conductive paste).
- connection structure L / S was 45 ⁇ m / 45 ⁇ m, the electrode length was 3 mm, and a copper electrode pattern (copper electrode thickness 12 ⁇ m) was provided on the upper surface, and a plurality of copper foil lands were formed in the periphery.
- a long carrier tape was prepared.
- a semiconductor element having an L / S of 45 ⁇ m / 45 ⁇ m on the lower surface was prepared.
- the conductive paste was applied to a thickness of 100 ⁇ m on the copper electrode pattern to form a conductive paste layer.
- the semiconductor element was mounted with a mounter.
- solder paste (“M705-GRN360-K2V” manufactured by Senju Metal Industry Co., Ltd.) is applied to the plurality of copper foil lands, and then a 1005 size chip resistor component is mounted on the copper foil land coating film with a mounter. . Then, the reflow process was performed in the reflow furnace, and the connection structure which connected the semiconductor element and the chip resistance component to the electrode was obtained.
- Viscosity ( ⁇ 25) The viscosity ( ⁇ 25) at 25 ° C. of the conductive paste was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
- Viscosity The viscosity ( ⁇ mp) of the conductive paste at the melting point of the solder in the first conductive particles, using STRESSTECH (manufactured by EOLOGICA), strain control 1 rad, frequency 1 Hz, heating rate 20 ° C./min, The measurement temperature range was 40 ° C. to the melting point of the solder. In this measurement, the viscosity at the melting point of the solder was read.
- 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 solder portion, and the second electrode is viewed, The ratio X of the area where the solder portion is arranged in the area of 100% of the area 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%
- the ratio Y of the number of the second conductive particles arranged in the solder part was evaluated out of the total number of the second conductive particles in the connection part of 100%.
- the placement accuracy 2 of the second conductive particles in the solder portion was determined according to the following criteria.
- 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、第1の導電性粒子と、第2の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含む。
上記第1の導電性粒子は、接続対象部材の電極間を電気的に接続する。上記第1の導電性粒子は、導電部の外表面部分にはんだを有する。上記第1の導電性粒子は、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と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、中心部分及び導電部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。上記第1の導電性粒子は、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、上記第1の導電性粒子は、導電部の外表面部分に、はんだを有する。
ρ:第1の導電性粒子の粒子径の標準偏差
Dn:第1の導電性粒子の粒子径の平均値
上記第2の導電性粒子は、導電部の外表面部分に銀、ルテニウム、イリジウム、金、パラジウム又は白金(銀、ルテニウム、イリジウム、金、パラジウム又は白金を含む導電部)を有する。上記第2の導電性粒子は、銀、ルテニウム、イリジウム、金、パラジウム又は白金により形成された金属粒子であってもよい。上記金属粒子は、銀、ルテニウム、イリジウム、金、パラジウム又は白金を導電部の外表面部分に有する。上記金属粒子は、中心部分及び導電部の外表面のいずれもが銀、ルテニウム、イリジウム、金、パラジウム又は白金である粒子である。上記金属粒子は、コア粒子として、基材粒子を有さない。上記金属粒子は、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。上記導電部の外表面部分及び上記銀、ルテニウム、イリジウム、金、パラジウム又は白金を含む導電部は、例えば、銀、ルテニウム、イリジウム、金、パラジウム及び白金を好ましくは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。上記第2の導電性粒子は、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、上記第2の導電性粒子は、導電部の外表面部分に、銀、ルテニウム、イリジウム、金、パラジウム又は白金を有する。
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、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、フラックスを含むことが好ましい。フラックスの使用により、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。該フラックスは特に限定されない。フラックスとして、はんだ接合等に一般的に用いられているフラックスを使用できる。
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、上記第1の導電性粒子の表面及び上記第2の導電性粒子の表面のいずれの表面に付着していなくてもよい。上記導電材料中で、上記絶縁性粒子は上記第1の導電性粒子と離れて存在することが好ましく、上記絶縁性粒子は上記第2の導電性粒子と離れて存在することが好ましい。上記絶縁性粒子を含むことで、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、並びに第1の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ことができる。
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る。上記接続部が、上述した導電材料の硬化物である。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。
(1)ビスフェノールFと1,6-ヘキサンジオールジグリシジルエーテル、及びビスフェノールF型エポキシ樹脂との第1の反応物の合成:
ビスフェノールF(4,4’-メチレンビスフェノールと2,4’-メチレンビスフェノールと2,2’-メチレンビスフェノールとを重量比で2:3:1で含む)72重量部と、1,6-ヘキサンジオールジグリシジルエーテル270重量部と、ビスフェノールF型エポキシ樹脂(DIC社製「EPICLON EXA-830CRP」)30重量部とを、3つ口フラスコに入れ、窒素フロー下にて、100℃で溶解させた。その後、水酸基とエポキシ基との付加反応触媒であるテトラーn-ブチルスルホニウムブロミド0.1重量部を添加し、窒素フロー下にて、130℃で6時間、付加重合反応させることにより第1の反応物を得た。
上記第1の反応物100重量部を、3つ口フラスコに入れ、窒素フロー下にて、120℃で溶解させた。その後、信越シリコーン社製「KBE-9007」(3-イソシアネートプロピルトリエトキシシラン)2重量部を添加し、第1の反応物の側鎖水酸基と3-イソシアネートプロピルトリエトキシシランのイソシアネート基との反応触媒であるジラウリン酸ジブチルすず0.002重量部を添加し、窒素フロー下にて、120℃で4時間反応させた。その後、110℃にて5時間真空乾燥し、未反応のKBE-9007を除去した。
グルタル酸25重量部、及びグルタル酸モノメチル25重量部を3つ口フラスコに入れ、窒素フロー下にて、80℃で溶解させた。その後、ベンジルアミン57重量部を添加し、80℃で減圧下(4Torr以下)2時間反応させることにより、25℃で固体である、フラックス1を得た。
Sn-3Ag-0.5Cuはんだ粒子(三井金属社製「ST-5」、平均粒子径(メディアン径)30μm)と、クエン酸(和光純薬工業社製「クエン酸」)とを、触媒であるp-トルエンスルホン酸を用いて、トルエン溶媒中90℃で脱水しながら8時間攪拌することにより、はんだの表面にカルボキシル基を含む基が共有結合しているはんだ粒子1(CV値20%)を得た。
Sn-3Ag-0.5Cuはんだ粒子(三井金属社製「ST-5」、平均粒子径(メディアン径)30μm)200gと、イソシアネート基を有するシランカップリング剤(信越シリコーン社製「KBE-9007」)10gと、アセトン70gとを3つ口フラスコに秤量した。室温で撹拌しながら、はんだ粒子表面の水酸基とイソシアネート基との反応触媒であるジブチル錫ジラウレート0.25gを添加し、撹拌下、窒素雰囲気下にて100℃で2時間加熱した。その後、メタノールを50g添加し、撹拌下、窒素雰囲気下にて、60℃で1時間加熱した。
CV値を、レーザー回折式粒度分布測定装置(堀場製作所社製「LA-920」)にて、測定した。
(1)導電材料の作製
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、導電材料(導電ペースト)を得た。
L/Sが45μm/45μm、電極長さ3mmの銅電極パターン(銅電極の厚み12μm)を上面に有し、更にその周辺に複数の銅箔ランドが形成された長尺のキャリアテープを用意した。また、電極のL/Sが45μm/45μmを下面に有する半導体素子を用意した。上記長尺のキャリアテープの上面に、上記導電ペーストを銅電極パターン上で厚さ100μmとなるように、塗工し、導電ペースト層を形成した。次に、上記半導体素子をマウンターにて実装した。更に、はんだペースト(千住金属工業社製「M705-GRN360-K2V」)を上記複数の銅箔ランドに塗布後、1005サイズのチップ抵抗部品を上記銅箔ランドの塗布膜上にマウンターにて実装した。その後、リフロー炉にてリフロー処理して、半導体素子およびチップ抵抗部品を電極に接続した接続構造体を得た。
(1)粘度(η25)
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。
第1の導電性粒子におけるはんだの融点での導電ペーストの粘度(ηmp)を、STRESSTECH(EOLOGICA社製)を用いて、歪制御1rad、周波数1Hz、昇温速度20℃/分、測定温度範囲40℃~はんだの融点の条件で測定した。この測定において、はんだの融点での粘度を読み取った。
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の電極とはんだ部と第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、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、上記接続部内の第2の導電性粒子の全個数100%中、上記はんだ部内に配置されている第2の導電性粒子の個数の割合Yを評価した。はんだ部内での第2の導電性粒子の配置精度2を下記の基準で判定した。
○○○:個数の割合Yが95%以上
○○:個数の割合Yが90%以上、95%未満
○:個数の割合Yが80%以上、90%未満
△:個数の割合Yが50%以上、80%未満
×:個数の割合Yが50%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(第1の導電性粒子)
11B…熱硬化性成分
11C…第2の導電性粒子
21…第1の導電性粒子(はんだ粒子)
31…第1の導電性粒子
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…第1の導電性粒子
42…はんだ部
Claims (16)
- 導電部の外表面部分に、はんだを有する複数の第1の導電性粒子と、
導電部の外表面部分に、銀、ルテニウム、イリジウム、金、パラジウム又は白金を有する第2の導電性粒子と、
熱硬化性化合物と、
熱硬化剤とを含む、導電材料。 - 前記第2の導電性粒子が、導電部の外表面部分に、金、パラジウム又は白金を有する、請求項1に記載の導電材料。
- 前記第1の導電性粒子におけるはんだの融点での導電材料の粘度が2Pa・s以上、10Pa・s以下である、請求項1又は2に記載の導電材料。
- 前記第2の導電性粒子の平均粒子径が、前記第1の導電性粒子の平均粒子径よりも小さい、請求項1~3のいずれか1項に記載の導電材料。
- 前記第2の導電性粒子の含有量が10重量%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。
- 前記第1の導電性粒子の含有量の前記第2の導電性粒子の含有量に対する比が、重量基準で、3以上、80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。
- 前記熱硬化性化合物が、25℃で液状である熱硬化性化合物を含む、請求項1~6のいずれか1項に記載の導電材料。
- 前記熱硬化性化合物が、ポリエーテル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。
- 融点が50℃以上、190℃以下であるフラックスを含む、請求項1~8のいずれか1項に記載の導電材料。
- 前記第1の導電性粒子の外表面に、カルボキシル基又はアミノ基が存在する、請求項1~9のいずれか1項に記載の導電材料。
- 前記第1の導電性粒子が、中心部分及び外表面部分にはんだを有するはんだ粒子である、請求項1~10のいずれか1項に記載の導電材料。
- 前記第1の導電性粒子の表面及び前記第2の導電性粒子の表面のいずれにも付着していない絶縁性粒子を含む、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、
前記接続部が、硬化物部と、はんだ部と、前記第2の導電性粒子とを有し、
前記はんだ部内に、前記第2の導電性粒子が配置されており、
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。 - 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、
前記接続部が、硬化物部と、はんだ部と、導電部の外表面部分に、銀、ルテニウム、イリジウム、金、パラジウム又は白金を有する第2の導電性粒子とを有し、
前記はんだ部内に、前記第2の導電性粒子が配置されており、
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2の導電性粒子が、導電部の外表面部分に、金、パラジウム又は白金を有する、請求項14に記載の接続構造体。
- 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13~15のいずれか1項に記載の接続構造体。
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