WO2016190244A1 - 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 PDF

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Publication number
WO2016190244A1
WO2016190244A1 PCT/JP2016/065014 JP2016065014W WO2016190244A1 WO 2016190244 A1 WO2016190244 A1 WO 2016190244A1 JP 2016065014 W JP2016065014 W JP 2016065014W WO 2016190244 A1 WO2016190244 A1 WO 2016190244A1
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WIPO (PCT)
Prior art keywords
solder
conductive
electrode
particles
connection
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PCT/JP2016/065014
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English (en)
French (fr)
Japanese (ja)
Inventor
敬士 久保田
高橋　英之
敬三 西岡
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2016535202A priority Critical patent/JP6067191B1/ja
Priority to KR1020177010572A priority patent/KR102569944B1/ko
Priority to CN201680007414.4A priority patent/CN107210084A/zh
Publication of WO2016190244A1 publication Critical patent/WO2016190244A1/ja

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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
    • 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
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • 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
    • H01L2224/115—Manufacturing methods by chemical or physical modification of a pre-existing or pre-deposited material
    • H01L2224/1152—Self-assembly, e.g. self-agglomeration of the bump material in a fluid
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/83886—Involving a self-assembly process, e.g. self-agglomeration of a material dispersed in a fluid

Definitions

  • the present invention relates to a conductive material including conductive particles having solder.
  • the present invention also relates to a connection structure using the conductive material.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder.
  • the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • FOG Glass
  • COF Chip on Film
  • an anisotropic conductive material containing conductive particles is disposed on the glass epoxy substrate. To do.
  • a flexible printed circuit board is laminated, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
  • 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 material for the conductive particles include tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), and cadmium.
  • metals such as (Cd), gallium (Ga), silver (Ag), and thallium (Tl), and alloys of these metals.
  • Patent Document 1 a resin heating step for heating the anisotropic conductive resin to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described.
  • Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG. In Patent Document 1, the conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive resin is heated.
  • Patent Document 2 discloses an adhesive tape that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Yes.
  • This adhesive tape is in the form of a film, not a paste.
  • a semiconductor chip having a plurality of connection terminals is disposed so as to face a wiring board having a plurality of electrode terminals, and the electrode terminals of the wiring board and the above-mentioned semiconductor chip
  • a flip chip mounting method for electrically connecting a connection terminal is disclosed.
  • a resin composition containing solder powder and a convection additive is used.
  • solder powder or conductive particles may not be efficiently disposed on the electrodes (lines).
  • the moving speed of the solder powder or conductive particles onto the electrode may be slow.
  • the adhesive tape described in Patent Document 2 is a film, not a paste.
  • a part of the solder powder is easily placed in a region (space) where no electrode is formed.
  • Solder powder disposed in a region where no electrode is formed does not contribute to conduction between the electrodes.
  • the convection additive is added in the electrically conductive paste containing solder powder.
  • the convection additive may remain as a foreign substance in the cured product of the conductive paste.
  • the properties of the conductive paste may change due to the addition of a convective additive.
  • voids are likely to occur in the cured conductive paste. As a result, conduction reliability between electrodes may be lowered.
  • the conductive paste that can be used is limited.
  • a conductive material including a plurality of conductive particles having solder, a thermosetting compound, a thiol curing agent, and an amine curing agent on the outer surface portion of the conductive portion.
  • the conductive particles are solder particles.
  • a carboxyl group is present on the outer surface of the conductive particles.
  • thermosetting compound includes a thermosetting compound having a triazine skeleton.
  • the weight ratio of the thiol curing agent to the amine curing agent is 2: 1 to 50: 1.
  • the conductive material includes insulating particles that are not attached to the surface of the conductive particles.
  • the conductive particles have an average particle diameter of 1 ⁇ m or more and 40 ⁇ m or less.
  • the content of the conductive particles is 10% by weight to 80% by weight in 100% by weight of the conductive material.
  • the conductive material is liquid at 25 ° C. and is a conductive paste.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member and the A connection part connecting the second connection target member
  • the material of the connection part is the conductive material described above
  • the first electrode and the second electrode are in the conductive particles
  • a connection structure is provided that is electrically connected by solder.
  • the conductive material according to the present invention includes a plurality of conductive particles having solder, a thermosetting compound, a thiol curing agent, and an amine curing agent on the outer surface portion of the conductive portion, the electrode width is narrow. Also, the solder in the conductive particles can be efficiently arranged on the electrode, and the conduction 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 conductive particles that can be used as a conductive material.
  • FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used for the conductive material.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for the conductive material.
  • the conductive material according to the present invention includes a plurality of conductive particles and a binder.
  • the conductive particles have a conductive part.
  • the conductive particles have solder on the outer surface portion of the conductive portion. Solder is contained in the conductive part and is a part or all of the conductive part.
  • the conductive material according to the present invention contains a thermosetting compound and a thermosetting agent as the binder.
  • the thermosetting agent includes a thiol curing agent and an amine curing agent.
  • thermosetting compound In the present invention, specific conductive particles are used, and two specific thermosetting agents are used in combination in order to cure the thermosetting compound.
  • the solder in the conductive particles can be efficiently disposed on the electrode even if the electrode width is narrow.
  • the electrode width is narrow, there is a tendency that the solder of the conductive particles is difficult to gather on the electrode, but in the present invention, the solder can be sufficiently gathered on the electrode even if the electrode width is narrow.
  • the solder in the conductive particles easily collects between the upper and lower electrodes, and the solder in the conductive particles is removed from the electrode ( Line).
  • the solder in the conductive particles is arranged more efficiently on the electrode.
  • the solder in the conductive particles it is difficult for a part of the solder in the conductive particles to be arranged in a region (space) where no electrode is formed, and the amount of solder arranged in a region where no electrode is formed can be considerably reduced.
  • the solder that is not located between the opposing electrodes can be efficiently moved between the opposing electrodes. Therefore, the conduction reliability between the electrodes can be improved.
  • cured material of an electroconductive material can be improved.
  • a conductive material is used for the optical semiconductor device, heat is generated during light irradiation, and a cured product of the conductive material is exposed to a high temperature.
  • the conductive material according to the present invention is excellent in the heat resistance of a cured product, it can be suitably used for an optical semiconductor device.
  • the thermosetting compound contains a thermosetting compound having a triazine skeleton, the heat resistance of the cured product is increased.
  • the cured material of the conductive material can cope with high-speed transmission.
  • the dielectric constant of the cured material of the conductive material can be lowered. For this reason, it can respond to high-speed transmission.
  • the conductive material according to the present invention can be suitably used for high-speed transmission because the dielectric constant of the cured product can be lowered.
  • 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 electrode of the first connection target member 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 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) acrylate means one or both of “acrylate” and “methacrylate”
  • (meth) acryloxy means one or both of “acryloxy” and “methacryloxy”.
  • (meth) acryl means one or both of “acryl” and “methacryl”.
  • the conductive particles electrically connect the electrodes of the connection target member.
  • the conductive particles have solder on the outer surface portion of the conductive portion.
  • the conductive particles may be solder particles formed by solder.
  • the solder particles have solder on the outer surface portion of the conductive portion.
  • both the center part and the outer surface part of an electroconductive part are solder, and are formed of solder.
  • the solder particles do not have base particles as core particles.
  • the solder particles are different from conductive particles including base particles and conductive portions arranged on the surface of the base particles.
  • the solder particles include, for example, solder preferably at 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight or more.
  • the said electroconductive particle may have a base material particle and the electroconductive part arrange
  • the conductive particles are less likely to collect on the surface, and the solder joint property between the conductive particles is low, so the conductive particles that have moved onto the electrodes tend to move out of the electrodes, and the effect of suppressing displacement between the electrodes Tend to be lower. Therefore, the conductive particles are preferably solder particles formed by solder.
  • a carboxyl group or an amino group is present on the outer surface of the conductive particles (the outer surface of the solder). It is preferable that a carboxyl group is present, and an amino group is preferably present.
  • a group containing a carboxyl group or an amino group is shared on the outer surface of the conductive particle (the outer surface of the solder) via a Si—O bond, an ether bond, an ester bond or a group represented by the following formula (X).
  • a group containing a carboxyl group or an amino group is covalently bonded through an ether bond, an ester bond or a group represented by the following formula (X).
  • the group containing a carboxyl group or an amino group may contain both a carboxyl group and an amino group.
  • the right end and the left end represent a binding site.
  • the bond form between the solder surface and the group containing a carboxyl group may not include a coordinate bond, and may not include a bond due to a chelate coordinate.
  • the conductive particle is a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group or an amino group ( Hereinafter, it is preferably obtained by reacting a hydroxyl group on the surface of the solder with a functional group capable of reacting with the hydroxyl group using a compound X). In the above reaction, a covalent bond is formed.
  • solder particles in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder can be easily obtained. It is also possible to obtain solder particles in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder via an ether bond or an ester bond.
  • Examples of the functional group capable of reacting with the hydroxyl group include a hydroxyl group, a carboxyl group, an ester group, and a carbonyl group.
  • a hydroxyl group or a carboxyl group is preferred.
  • the functional group capable of reacting with the hydroxyl group may be a hydroxyl group or a carboxyl group.
  • Examples of the compound having a functional group capable of reacting with a hydroxyl group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4- Aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, Hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic
  • Glutaric acid or glycolic acid is preferred. Only 1 type may be used for the compound which has the functional group which can react with the said hydroxyl group, and 2 or more types may be used together.
  • the compound having a functional group capable of reacting with the hydroxyl group is preferably a compound having at least one carboxyl group.
  • the compound X preferably has a flux action, and the compound X preferably has a flux action in a state of being bonded to the solder surface.
  • the compound having a flux action can remove the oxide film on the surface of the solder and the oxide film on the surface of the electrode.
  • the carboxyl group has a flux action.
  • 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.
  • the method for producing conductive particles includes, for example, using conductive particles and mixing the conductive particles, a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group, a catalyst, and a solvent.
  • conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be easily obtained by the mixing step.
  • this electroconductive particle using electroconductive particle, this electroconductive particle, the compound which has the functional group and carboxyl group which can react with the said hydroxyl group, the said catalyst, and the said solvent are mixed, and it heats. It is preferable.
  • conductive particles in which a group containing a carboxyl group is covalently bonded to the surface of the solder can be obtained more easily.
  • the solvent examples include alcohol solvents such as methanol, ethanol, propanol and butanol, acetone, methyl ethyl ketone, ethyl acetate, toluene and xylene.
  • the solvent is preferably an organic solvent, and more preferably toluene. As for the said solvent, only 1 type may be used and 2 or more types may be used together.
  • the catalyst examples include p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, and the like.
  • the catalyst is preferably p-toluenesulfonic acid.
  • the said catalyst only 1 type may be used and 2 or more types may be used together.
  • the heating temperature is preferably 90 ° C or higher, more preferably 100 ° C or higher, preferably 130 ° C or lower, more preferably 110 ° C or lower.
  • the conductive particles react with the isocyanate compound to the hydroxyl group on the surface of the solder using the isocyanate compound. It is preferable that it is obtained through the process of making it. In the above reaction, a covalent bond is formed.
  • the hydroxyl group on the surface of the solder with the isocyanate compound it is possible to easily obtain conductive particles in which the nitrogen atom of the group derived from the isocyanate group is covalently bonded to the surface of the solder.
  • a group derived from an isocyanate group can be chemically bonded to the surface of the solder in the form of a covalent bond.
  • a silane coupling agent can be easily reacted with a group derived from an isocyanate group. Since the conductive particles can be easily obtained, the group containing a carboxyl group is introduced by a reaction using a silane coupling agent having a carboxyl group, or the reaction using a silane coupling agent is performed. It is preferably introduced later by reacting a compound derived from a silane coupling agent with a compound having at least one carboxyl group.
  • the conductive particles are preferably obtained by reacting the isocyanate compound with a hydroxyl group on the surface of the solder using the isocyanate compound and then reacting a compound having at least one carboxyl group.
  • the compound having at least one carboxyl group preferably has a plurality of carboxyl groups.
  • isocyanate compound examples include diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI). Isocyanate compounds other than these may be used. After reacting this compound on the surface of the solder, the surface of the solder is represented by the formula (X) by reacting the residual isocyanate group and a compound having reactivity with the residual isocyanate group and having a carboxyl group. A carboxyl group can be introduced through the group to be formed.
  • MDI diphenylmethane-4,4'-diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • the isocyanate compound a compound having an unsaturated double bond and having an isocyanate group may be used. Examples include 2-acryloyloxyethyl isocyanate and 2-isocyanatoethyl methacrylate. After reacting the isocyanate group of this compound on the surface of the solder, reacting the compound having a functional group having reactivity with the remaining unsaturated double bond and having a carboxyl group, A carboxyl group can be introduced to the surface via a group represented by the formula (X).
  • silane coupling agent examples include 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Silicone) and 3-isocyanatepropyltrimethoxysilane (“Y-5187” manufactured by MOMENTIVE). As for the said silane coupling agent, only 1 type may be used and 2 or more types may be used together.
  • Examples of the compound having at least one carboxyl group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4-amino Butyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecane Examples include acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic acid, arachidic acid
  • the carboxyl group of the compound having a plurality of carboxyl groups is reacted with the hydroxyl group on the surface of the solder.
  • the group containing can be left.
  • the conductive particles are used and the isocyanate compound is used to react the hydroxyl group on the surface of the solder with the isocyanate compound, and then the compound having at least one carboxyl group is reacted.
  • the conductive particles in which a group containing a carboxyl group is bonded to the surface of the solder via the group represented by the above formula (X) are obtained.
  • conductive particles in which a group containing a carboxyl group is introduced on the surface of the solder can be easily obtained by the above-described steps.
  • the following method can be given as a specific method for producing the conductive particles.
  • Conductive particles are dispersed in an organic solvent, and a silane coupling agent having an isocyanate group is added. Thereafter, a silane coupling agent is covalently bonded to the surface of the solder using a reaction catalyst between a hydroxyl group and an isocyanate group on the surface of the solder of the conductive particles.
  • a hydroxyl group is produced
  • Conductive particles are dispersed in an organic solvent, and a compound having an isocyanate group and an unsaturated double bond is added. Thereafter, a covalent bond is formed using a reaction catalyst of a hydroxyl group and an isocyanate group on the surface of the solder of the conductive particles. Thereafter, the unsaturated double bond introduced is reacted with a compound having an unsaturated double bond and a carboxyl group.
  • a reaction catalyst for the hydroxyl group and isocyanate group on the solder surface of the conductive particles As a reaction catalyst for the hydroxyl group and isocyanate group on the solder surface of the conductive particles, a tin catalyst (dibutyltin dilaurate, etc.), an amine catalyst (triethylenediamine, etc.), a carboxylate catalyst (lead naphthenate, potassium acetate, etc.), And a trialkylphosphine catalyst (such as triethylphosphine).
  • the compound having at least one carboxyl group is a compound represented by the following formula (1): Is preferred.
  • the compound represented by the following formula (1) has a flux action.
  • the compound represented by following formula (1) has a flux effect
  • X represents a functional group capable of reacting with a hydroxyl group
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • the organic group may contain a carbon atom, a hydrogen atom, and an oxygen atom.
  • the organic group may be a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • the main chain of the organic group is preferably a divalent hydrocarbon group.
  • a carboxyl group or a hydroxyl group may be bonded to a divalent hydrocarbon group.
  • Examples of the compound represented by the above formula (1) include citric acid.
  • the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A) or the following formula (1B).
  • the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A), and more preferably a compound represented by the following formula (1B).
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (1A) is the same as R in the above formula (1).
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (1B) is the same as R in the above formula (1).
  • a group represented by the following formula (2A) or the following formula (2B) is bonded to the surface of the solder.
  • a group represented by the following formula (2A) is preferably bonded to the surface of the solder, and more preferably a group represented by the following formula (2B) is bonded.
  • the left end portion represents a binding site.
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (2A) is the same as R in the above formula (1).
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (2B) is the same as R in the above formula (1).
  • the molecular weight of the compound having at least one carboxyl group is preferably 10,000 or less, more preferably 1000 or less, and even more preferably 500 or less.
  • the molecular weight means a molecular weight that can be calculated from the structural formula when the compound having at least one carboxyl group is not a polymer and when the structural formula of the compound having at least one carboxyl group can be specified. Further, when the compound having at least one carboxyl group is a polymer, it means a weight average molecular weight.
  • the conductive particles may have a conductive particle main body and an anionic polymer disposed on the surface of the conductive particle main body.
  • the conductive particles are preferably obtained by surface-treating the conductive particle body with an anionic polymer or a compound that becomes an anionic polymer.
  • the conductive particles are preferably a surface treated product of an anionic polymer or a compound that becomes an anionic polymer.
  • the anion polymer and the compound used as the said anion polymer only 1 type may respectively be used and 2 or more types may be used together.
  • the anionic polymer is a polymer having an acidic group.
  • an anionic polymer for example, a (meth) acrylic polymer copolymerized with (meth) acrylic acid, synthesized from a dicarboxylic acid and a diol, and having carboxyl groups at both ends are used.
  • Polyester polymer having a carboxyl group at both ends obtained by intermolecular dehydration condensation reaction of dicarboxylic acid, polyester polymer synthesized from dicarboxylic acid and diamine and having carboxyl group at both ends, and modified poval having carboxyl group (Nippon Synthetic Chemical Co., Ltd. "GOHSEX T") etc., and the method of making the carboxyl group of an anionic polymer react with the hydroxyl group of the surface of an electroconductive particle main body is mentioned.
  • anion portion of the anionic polymer examples include the carboxyl group, and other than that, a tosyl group (p—H 3 CC 6 H 4 S ( ⁇ O) 2 —), a sulfonate ion group (—SO 3 —) ), And phosphate ion groups (—PO 4 ⁇ ) and the like.
  • a compound having a functional group that reacts with a hydroxyl group on the surface of the conductive particle main body and a functional group that can be polymerized by addition or condensation reaction is used as another method for the surface treatment.
  • the method of polymerizing on the surface of an electroconductive particle main body is mentioned.
  • the functional group that reacts with the hydroxyl group on the surface of the conductive particle body include a carboxyl group and an isocyanate group, and the functional group that polymerizes by addition and condensation reactions includes a hydroxyl group, a carboxyl group, an amino group, and (meta ) An acryloyl group is mentioned.
  • the weight average molecular weight of the anionic polymer is preferably 2000 or more, more preferably 3000 or more, preferably 10,000 or less, more preferably 8000 or less.
  • the weight average molecular weight is not less than the above lower limit and not more than the above upper limit, a sufficient amount of charge and flux properties can be introduced on the surface of the conductive particles. Thereby, the cohesiveness of electroconductive particle can be effectively improved at the time of conductive connection, and the oxide film on the surface of an electrode can be effectively removed at the time of connection of the connection object member.
  • the weight average molecular weight is not less than the above lower limit and not more than the above upper limit, it is easy to dispose an anionic polymer on the surface of the conductive particle body, and it is possible to effectively increase the cohesiveness of the solder particles at the time of conductive connection.
  • the conductive particles can be arranged more efficiently on the electrode.
  • the weight average molecular weight indicates a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the weight average molecular weight of the polymer obtained by surface-treating the conductive particle main body with a compound that becomes an anionic polymer is obtained by dissolving the solder in the conductive particles, and diluting the conductive particles with dilute hydrochloric acid that does not cause decomposition of the polymer. After removal, it can be determined by measuring the weight average molecular weight of the remaining polymer.
  • the acid value per 1 g of the conductive particles is preferably 1 mgKOH or more, more preferably 2 mgKOH or more, preferably 10 mgKOH or less, more preferably 6 mgKOH or less.
  • the acid value can be measured as follows. 1 g of conductive particles is added to 36 g of acetone and dispersed with an ultrasonic wave for 1 minute. Thereafter, phenolphthalein is used as an indicator and titrated with a 0.1 mol / L potassium hydroxide ethanol solution.
  • FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used as a conductive material.
  • the conductive particles 21 shown in FIG. 4 are solder particles.
  • the conductive particles 21 are entirely formed of solder.
  • the conductive particles 21 do not have base particles in the core and are not core-shell particles.
  • both the center part and the outer surface part of an electroconductive part are formed with the solder.
  • FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used as a conductive material.
  • the electroconductive particle 31 shown in FIG. 5 is equipped with the base material particle 32 and the electroconductive part 33 arrange
  • the conductive portion 33 covers the surface of the base particle 32.
  • the conductive particles 31 are coated particles in which the surface of the base particle 32 is covered with the conductive portion 33.
  • the conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion).
  • the conductive particle 31 includes a second conductive portion 33A between the base particle 32 and the solder portion 33B. Therefore, the conductive particles 31 are composed of the base particle 32, the second conductive portion 33A disposed on the surface of the base particle 32, and the solder portion 33B disposed on the outer surface of the second conductive portion 33A.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used as a conductive material.
  • the conductive portion 33 in the conductive particle 31 has a two-layer structure.
  • the conductive particle 41 shown in FIG. 6 has a solder part 42 as a single-layer conductive part.
  • the conductive particles 41 include base particles 32 and solder portions 42 disposed on the surfaces of the base particles 32.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably substrate particles excluding metal, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the substrate particles may be copper particles.
  • the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide , Polyacetal, polyimide, polyamideimide, polyether ether Tons, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer,
  • polyolefin resins such as polyethylene, polypropylene,
  • the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
  • the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
  • Oxygen atom-containing (meth) acrylate compounds Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
  • Nitrile-containing monomers such as (meth) acrylonitrile
  • Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether
  • Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stea
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • examples of inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the particles formed from the silica are not particularly limited.
  • firing may be performed as necessary.
  • grains obtained by performing are mentioned.
  • examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the metal particles are preferably copper particles.
  • the substrate particles are preferably not metal particles.
  • the method for forming the conductive part on the surface of the base particle and the method for forming the solder part on the surface of the base particle or the surface of the second conductive part are not particularly limited.
  • Examples of the method for forming the conductive portion and the solder portion include a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, And a method of coating the surface of the substrate particles with a paste containing metal powder or metal powder and a binder.
  • a method using electroless plating, electroplating, or physical collision is preferable.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like is used.
  • the melting point of the substrate particles is preferably higher than the melting point of the solder part.
  • the melting point of the substrate particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, and particularly preferably higher than 450 ° C.
  • the melting point of the substrate particles may be less than 400 ° C.
  • the melting point of the substrate particles may be 160 ° C. or less.
  • the softening point of the substrate particles is preferably 260 ° C. or higher.
  • the softening point of the substrate particles may be less than 260 ° C.
  • the conductive particles may have a single layer solder portion.
  • the conductive particles may have a plurality of layers of conductive parts (solder part, second conductive part). That is, in the conductive particles, two or more conductive portions may be stacked.
  • the solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower.
  • the solder part is preferably a metal layer (low melting point metal layer) having a melting point of 450 ° C. or lower.
  • the low melting point metal layer is a layer containing a low melting point metal.
  • the solder in the conductive particles is preferably metal particles having a melting point of 450 ° C. or lower (low melting point metal particles).
  • the low melting point metal particles are particles containing a low melting point metal.
  • the low melting point metal is a metal having a melting point of 450 ° C. or lower.
  • the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
  • the solder in the conductive particles preferably contains tin.
  • the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably. It is 70% by weight or more, particularly preferably 90% by weight or more.
  • the tin content is determined using a high-frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.
  • ICP-AES high-frequency inductively coupled plasma emission spectrometer
  • EDX-800HS fluorescent X-ray analyzer
  • the solder is melted and joined to the electrodes, and the solder conducts between the electrodes. For example, since the solder and the electrode are not in point contact but in surface contact, the connection resistance is lowered.
  • the use of conductive particles having solder on the outer surface of the conductive portion increases the bonding strength between the solder and the electrode, and as a result, the solder and the electrode are more unlikely to peel off, and the conduction reliability is effective. To be high.
  • the low melting point metal constituting the solder part and the solder particles is not particularly limited.
  • the low melting point metal is preferably tin or an alloy containing tin.
  • the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy.
  • the low melting point metal is preferably tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, or a tin-indium alloy because of its excellent wettability with respect 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. Of these, a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which is low-melting and lead-free is preferable. That is, the solder preferably does not contain lead, and is preferably a solder containing tin and indium or a solder containing tin and bismuth.
  • the solder in the conductive particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, molybdenum and palladium. Moreover, from the viewpoint of further increasing the bonding strength between the solder and the electrode, the solder in the conductive particles preferably contains nickel, copper, antimony, aluminum, or zinc.
  • the content of these metals for increasing the bonding strength is preferably 0% in 100% by weight of the solder in the conductive particles. 0.0001% by weight or more, preferably 1% by weight or less.
  • the melting point of the second conductive part is preferably higher than the melting point of the solder part.
  • the melting point of the second conductive part is preferably more than 160 ° C, more preferably more than 300 ° C, still more preferably more than 400 ° C, still more preferably more than 450 ° C, particularly preferably more than 500 ° C, most preferably Preferably it exceeds 600 degreeC. Since the solder part has a low melting point, it melts during conductive connection. It is preferable that the second conductive portion does not melt during conductive connection.
  • the conductive particles are preferably used by melting solder, preferably used by melting the solder part, and used without melting the solder part and melting the second conductive part. It is preferred that Since the melting point of the second conductive part is higher than the melting point of the solder part, it is possible to melt only the solder part without melting the second conductive part during conductive connection.
  • the absolute value of the difference between the melting point of the solder part and the melting point of the second conductive part exceeds 0 ° C, preferably 5 ° C or more, more preferably 10 ° C or more, still more preferably 30 ° C or more, particularly preferably Is 50 ° C. or higher, most preferably 100 ° C. or higher.
  • the second conductive part preferably contains a metal.
  • the metal which comprises the said 2nd electroconductive part is not specifically limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.
  • the second conductive part is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and even more preferably a copper layer.
  • the conductive particles preferably have a nickel layer, a palladium layer, a copper layer, or a gold layer, more preferably have a nickel layer or a gold layer, and still more preferably have a copper layer.
  • the thickness of the solder part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the thickness of the solder part is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. .
  • the thickness of the conductive part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 0.5 ⁇ m or less, Especially preferably, it is 0.3 micrometer or less.
  • the thickness of the conductive portion is the thickness of the entire conductive layer when the conductive portion is a multilayer. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not hardened, and the conductive particles are sufficiently deformed when connecting the electrodes. .
  • the thickness of the outermost conductive layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably Is 0.1 ⁇ m or less.
  • the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, corrosion resistance is sufficiently high, and the connection resistance between the electrodes is further increased. Lower.
  • the thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a field emission scanning electron microscope (FE-SEM).
  • FE-SEM field emission scanning electron microscope
  • the average particle size of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
  • the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrodes, and there are many solders in the conductive particles between the electrodes. It is easy to arrange and the conduction reliability is further enhanced.
  • the “average particle size” of the conductive particles indicates a number average particle size.
  • the average particle diameter of the conductive particles is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing laser diffraction particle size distribution measurement.
  • the shape of the conductive particles is not particularly limited.
  • the conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 10% by weight or more, particularly preferably 20% by weight or more, most preferably. It is 30% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrodes, and more solder in the conductive particles is arranged between the electrodes. It is easy to do and the conduction reliability is further increased. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
  • thermosetting compound is a compound that can be cured by heating.
  • examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
  • an epoxy compound or an episulfide compound is preferable from the viewpoint of further improving the curability and viscosity of the conductive material and further improving the connection reliability.
  • the said thermosetting compound only 1 type may be used and 2 or more types may be used together.
  • the thermosetting compound preferably includes a thermosetting compound having a triazine skeleton.
  • the thermosetting compound having a triazine skeleton include triazine triglycidyl ether and the like, and TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-L) manufactured by Nissan Chemical Industries PAS, TEPIC-VL, TEPIC-UC) and the like.
  • the above-mentioned epoxy compound includes an aromatic epoxy compound. Crystalline epoxy compounds such as resorcinol-type epoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, and benzophenone-type epoxy compounds are preferred.
  • An epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder is preferable. The melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher.
  • the content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
  • thermosetting agent thermosets the thermosetting compound.
  • 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 (thermal cation curing agent), and a thermal radical generator.
  • a thiol curing agent and an amine curing agent are used. From the viewpoint of efficiently arranging the solder in the conductive particles on the electrode, and from the viewpoint of increasing the heat resistance of the cured product, when using conductive particles having solder on the outer surface portion of the conductive part, The combined use with an amine curing agent has great significance.
  • curing agent only 1 type may be used respectively and 2 or more types may be used together.
  • the amine curing agent has an amino group.
  • the amine curing agent is not particularly limited, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5].
  • Undecane bis (4-aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine , Isophorone diamine, 1,3-bisaminomethylcyclohexane, norbornene diamine, 1,2-diaminocyclohexane, lalomine, diaminodiphenylmethane, benzylamine, adipic acid dihy Hydrazide, sebacic acid dihydrazide, dodecane geo hydrazide, isophthalic acid dihydrazide, salicylic acid hydrazide, polyoxypropylene diamine and polyoxypropylene triamine and the like.
  • the amine curing agent may be an amine curing agent having low reactivity at 25 ° C. preferable. Specifically, it is preferably an amine curing agent that requires 24 hours or more at 25 ° C. so that the degree of cure of the conductive material becomes 80% or more, and 25% because the degree of cure of the conductive material becomes 80% or more. More preferred is an amine curing agent that requires 48 hours or more at ° C.
  • the degree of cure of the conductive material can be measured as follows.
  • DSC differential scanning calorimeter
  • the thiol curing agent has a thiol group.
  • the thiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexakis-3-mercaptopropionate. It is done.
  • the thiol curing agent is preferably a primary thiol curing agent.
  • the thiol curing agent preferably has a plurality of thiol groups. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrodes and further improving the conduction reliability and insulation reliability between the electrodes, the thiol curing agent preferably has a polyether skeleton. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrodes and further improving the conduction reliability between the electrodes, the thiol curing agent preferably has four or more thiol groups.
  • the reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower.
  • the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrode.
  • the reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder in the conductive particles, and is preferably 5 ° C. or higher. Is more preferable, and it is still more preferable that it is 10 degreeC or more higher.
  • the reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
  • the total content of the thiol curing agent and the amine curing agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200
  • the amount is not more than parts by weight, more preferably not more than 100 parts by weight, still more preferably not more than 75 parts by weight.
  • 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 weight of the thiol curing agent and the amine curing agent in the conductive material is preferably 1: 1 to 100: 1, more preferably 2: 1 to 50: 1, and even more preferably 4: 1 to 15: 1.
  • 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 conductive particles, more preferably 5 ° C. or more, More preferably, it is 10 ° C. or higher.
  • the melting point of the flux is preferably higher than the reaction initiation temperature of the thermosetting agent, more preferably 5 ° C. or more, More preferably, it is 10 ° C. or higher.
  • the flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
  • the solder can be efficiently aggregated on the electrode portion. This is because, when heat is applied at the time of joining, when the electrode formed on the connection target member is compared with the portion of the connection target member around the electrode, the thermal conductivity of the electrode portion is that of the connection target member portion around the electrode. Due to the fact that it is higher than the thermal conductivity, the temperature rise of the electrode portion is fast. At the stage where the melting point of the solder is exceeded, the inside of the solder is dissolved, but the oxide film formed on the surface does not reach the melting point (activation temperature) of the flux and is not removed.
  • the flux is preferably a flux that releases cations by heating.
  • a flux that releases cations upon heating the solder can be placed more efficiently on the electrode.
  • thermal cation initiator thermal cation curing agent
  • 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 is made of insulating particles. It is preferable to contain. In the conductive material, the insulating particles may not be attached to the surface of the conductive particles. In the conductive material, the insulating particles may not be in contact with the surface of the conductive particles. In the conductive material, the insulating particles are preferably present away from the conductive particles.
  • the average particle diameter of the insulating particles is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 25 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the average particle diameter of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material, and between the connection target members connected by the solder in the conductive particles The interval becomes even more moderate.
  • the material for the insulating particles includes an insulating resin and an insulating inorganic substance.
  • said insulating resin the said resin quoted as resin for forming the resin particle which can be used as a base particle is mentioned.
  • As said insulating inorganic substance the said inorganic substance quoted as an inorganic substance for forming the inorganic particle which can be used as a base particle is mentioned.
  • the insulating resin that is the material of the insulating particles include 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. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
  • the content of the insulating particles is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. It is as follows.
  • the conductive material may not contain insulating particles. When the content of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material, and the interval between the connection target members connected by the solder in the conductive particles becomes even more reasonable.
  • the conductive material may be, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a lubricant as necessary.
  • various additives such as an antistatic agent and a flame retardant may be included.
  • connection structure includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided.
  • the connection portion is formed of the conductive material described above.
  • the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
  • the method for manufacturing the connection structure includes the step of disposing the conductive material on the surface of the first connection target member having at least one first electrode on the surface, using the conductive material described above, A second connection target member having at least one second electrode on the surface opposite to the first connection target member side of the material, the first electrode and the second electrode A step of arranging the first connection target member and the second connection target member by connecting the first connection target member and the second connection target member by heating the conductive material to a temperature equal to or higher than the melting point of the solder in the conductive particles. Forming a portion with the conductive material, and electrically connecting the first electrode and the second electrode with a solder portion in the connection portion.
  • the conductive material is heated above the curing temperature of the thermosetting compound.
  • connection structure since a specific conductive material is used, solder in a plurality of conductive particles easily collects between the first electrode and the second electrode.
  • the solder can be efficiently arranged on the electrode (line).
  • a part of the solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved.
  • a conductive paste is used instead of a conductive film. It is preferable to use it.
  • the thickness of the solder part between the electrodes is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less.
  • Solder wet area on the surface of the electrode (area where the solder is in contact with 100% of the exposed area of the electrode, electrically connected to the first electrode and the first electrode before forming the connecting portion)
  • the area of contact of the solder part after forming the connecting part with respect to the exposed area of 100% with the second electrode is preferably 50% or more, more preferably 70% or more, preferably Is 100% or less.
  • connection target member in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the second connection is applied to the conductive material.
  • the weight of the target member is preferably added, and in the step of arranging the second connection target member and the step of forming the connection portion, the conductive material exceeds the weight force of the second connection target member. It is preferable that no pressure is applied. In these cases, the uniformity of the amount of solder can be further enhanced in the plurality of solder portions.
  • the thickness of the solder portion can be made even more effective, and a large amount of solder in a plurality of conductive particles tends to gather between the electrodes, and the solder in the plurality of conductive particles is more efficiently distributed on the electrode (line). Can be arranged. In addition, it is difficult for a part of the solder in the plurality of conductive particles to be disposed in the region (space) where the electrode is not formed, and the amount of solder in the conductive particle disposed in the region where the electrode is not formed is further increased. Can be reduced. Therefore, the conduction reliability between the electrodes can be further enhanced. In addition, the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
  • connection portion if the weight of the second connection target member is added to the conductive material without applying pressure, the connection portion is Solder arranged in a region (space) where no electrode is formed before it is formed is more likely to gather between the first electrode and the second electrode, and solder in a plurality of conductive particles can be Line) more efficiently.
  • a configuration in which a conductive paste is used instead of a conductive film and a configuration in which the weight of the second connection target member is added to the conductive paste without applying pressure are used in combination. This has a great meaning in order to obtain the effects of the present invention at a higher level.
  • WO2008 / 023452A1 describes that it is preferable to pressurize with a predetermined pressure at the time of bonding from the viewpoint of efficiently moving the solder powder to the electrode surface, and the pressurizing pressure further ensures the solder area.
  • the pressure is set to 0 MPa or more, preferably 1 MPa or more.
  • a predetermined pressure may be applied to the adhesive tape by its own weight.
  • WO2008 / 023452A1 it is described that the pressure applied intentionally to the adhesive tape may be 0 MPa, but there is no difference between the effect when the pressure exceeding 0 MPa is applied and when the pressure is set to 0 MPa. Not listed.
  • WO2008 / 023452A1 recognizes nothing about the importance of using a paste-like conductive paste instead of a film.
  • a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied.
  • the conductive film in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is.
  • the melt viscosity of the conductive film compared with the conductive paste, the melt viscosity of the conductive film cannot be sufficiently lowered at the melting temperature of the solder, and the aggregation of the solder tends to be hindered.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
  • connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3.
  • Part 4 The connection part 4 is formed of the conductive material described above.
  • the material of the connection part 4 is the conductive material described above.
  • the conductive material includes solder particles as conductive particles.
  • the connecting portion 4 includes a solder portion 4A in which a plurality of solder particles are gathered and joined to each other, and a cured product portion 4B in which a thermosetting component is thermally cured.
  • solder particles are used as the conductive particles in order to form the solder portion 4A.
  • both the central portion and the outer surface of the conductive portion are formed of solder.
  • the first connection object member 2 has a plurality of first electrodes 2a on the surface (upper surface).
  • the second connection target member 3 has a plurality of second electrodes 3a on the surface (lower surface).
  • the first electrode 2a and the second electrode 3a are electrically connected by the solder portion 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A.
  • no solder exists in a region (cured product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
  • connection structure 1 a plurality of solder particles gather between the first electrode 2 a and the second electrode 3 a, and after the plurality of solder particles melt, After the electrode surface wets and spreads, it solidifies to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. That is, by using solder particles, the solder portion 4A, the first electrode 2a, and the solder as compared with the case where the outer surface portion of the conductive portion is made of conductive particles such as nickel, gold or copper are used. The contact area between the portion 4A and the second electrode 3a increases. For this reason, the conduction
  • the conductive material may contain a flux. When the flux is used, the flux is generally deactivated gradually by heating.
  • connection structure 1 shown in FIG. 1 all of the solder portions 4A are located in the facing region between the first and second electrodes 2a and 3a.
  • the connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection portion 4X.
  • the connection part 4X has the solder part 4XA and the hardened
  • most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a are opposed to each other, and a part of the solder portion 4XA is first and second. You may protrude to the side from the area
  • the solder part 4XA protruding laterally from the region where the first and second electrodes 2a and 3a are opposed is a part of the solder part 4XA and is not a solder separated from the solder part 4XA.
  • the amount of solder away from the solder portion can be reduced, but the solder away from the solder portion may exist in the cured product portion.
  • connection structure 1 If the amount of solder particles used is reduced, the connection structure 1 can be easily obtained. If the amount of the solder particles used is increased, it becomes easy to obtain the connection structure 1X.
  • the first electrode 2a and the second electrode 2a are arranged in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a.
  • the solder portions 4A and 4XA in the connection portions 4 and 4X are preferably disposed at 70% or more, particularly preferably 80% or more, and most preferably 90% or more.
  • the portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is seen.
  • the solder portion in the connection portion is preferably disposed.
  • the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode.
  • the portion where the first electrode and the second electrode face each other is 70% or more (more preferably 80% or more, more preferably 90%) of the solder portion in the connection portion. In particular, it is preferable that 95% or more, most preferably 99% or more) is disposed.
  • connection structure 1 using the conductive material Next, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
  • the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared.
  • a conductive material 11 including a thermosetting component 11B and a plurality of solder particles 11A is disposed on the surface of the first connection target member 2 (first Process).
  • the conductive material used includes a thermosetting compound, a thiol curing agent, and an amine curing agent as the thermosetting component 11B.
  • the conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the conductive material 11 is disposed, the solder particles 11A are disposed both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
  • the arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by an inkjet device.
  • the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared.
  • the 2nd connection object member 3 is arrange
  • the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
  • the conductive material 11 is heated to a temperature equal to or higher than the melting point of the solder particles 11A (third step).
  • the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder).
  • the solder particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect).
  • the thermosetting component 11B is thermoset. As a result, as shown in FIG.
  • connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11.
  • the connection part 4 is formed of the conductive material 11
  • the solder part 4A is formed by joining a plurality of solder particles 11A
  • the cured part 4B is formed by thermosetting the thermosetting component 11B.
  • pressurization may be performed as long as the interval between the first electrode and the second electrode can be secured.
  • insulating particles spacers
  • insulating particles spacers
  • at least one, preferably three or more insulating particles are disposed between the electrodes. You can do so.
  • 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 even more preferably 200 ° C. or lower.
  • the first connection target member or the second connection target member is peeled from the connection portion for the purpose of correcting the position or redoing the manufacturing. can do.
  • the heating temperature for performing this peeling is preferably not lower than the melting point of the solder, more preferably not lower than the melting point (° C.) of the solder + 10 ° C.
  • the heating temperature for performing this peeling may be the melting point of solder (° C.) + 100 ° C. or less.
  • a heating method in the third step a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the solder and the curing temperature of the thermosetting compound, or a connection structure The method of heating only the connection part of these is mentioned.
  • instruments used in the method of locally heating include a hot plate, a heat gun that applies hot air, a soldering iron, and an infrared heater.
  • the metal directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin.
  • the upper surface of the hot plate is preferably formed.
  • the first and second connection target members are not particularly limited. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor
  • the first and second connection target members are preferably electronic components.
  • At least one of the first connection target member and the second connection target member is 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 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 glycidyl ether and 30 parts by weight of a 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
  • Thermosetting compound 3 Epoxy compound, “TEPIC-SS” manufactured by Nissan Chemical Industries, epoxy equivalent 100 g / eq
  • Thermosetting compound 4 epoxy compound, “TEPIC-VL” manufactured by Nissan Chemical Industries, epoxy equivalent 135 g / eq
  • Thermosetting agent 1 Trimethylolpropane tris (3-mercaptopropinate), “TMMP” manufactured by SC Organic Chemical Co., Ltd.
  • Thermosetting agent 2 Pentaerythritol tetrakis-3-mercaptopropionate, “PEMP” manufactured by SC Organic Chemical Co., Ltd.
  • Thermosetting agent 3 Dipentaerythritol hexakis-3-mercaptopropionate, “DPMP” manufactured by SC Organic Chemical Co., Ltd.
  • Latent epoxy thermosetting agent 1 T & K TOKA's “Fujicure 7000”
  • Latent epoxy thermosetting agent 2 “HXA-3922HP” manufactured by Asahi Kasei E-Materials
  • Latent epoxy thermosetting agent 3 polyoxypropylene diamine, “Jeffamine D-230” manufactured by Huntsman Corporation
  • Latent epoxy thermosetting agent 4 polyoxypropylene triamine, “Jeffamine T-403” manufactured by Huntsman Corporation
  • Flux 1 Glutaric acid, Wako Pure Chemical Industries, melting point 96 ° C
  • Insulating particles average particle size 30 ⁇ m, CV value 5%, softening point 330 ° C., Sekisui Chemical Co., Ltd., divinylbenzene crosslinked particles
  • Solder particles A (SnBi solder particles, melting point 139 ° C., “ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter 5 ⁇ m))
  • Solder particles 1 to 3 Method for producing solder particles 1: SnBi solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 5 ⁇ m) and glutaric acid (a compound having two carboxyl groups, “glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.) By using a catalyst p-toluenesulfonic acid and stirring for 8 hours while dehydrating in a toluene solvent at 90 ° C., solder particles 1 in which a carboxyl group-containing group is covalently bonded to the surface of the solder were obtained.
  • SnBi solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 5 ⁇ m) and glutaric acid (a compound having two carboxyl groups, “glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.)
  • glutaric acid a compound having two carboxyl groups, “glutaric
  • the molecular weight of the polymer formed on the solder surface 0.1N hydrochloric acid was used, the solder was dissolved, the polymer was recovered by filtration, and the weight average molecular weight was determined by GPC.
  • the obtained solder particles 1 had a CV value of 20% and a molecular weight Mw of the polymer constituting the surface of 2000.
  • Method for producing solder particles 2 200 g of SnBi solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 5 ⁇ m), 10 g of a silane coupling agent having an isocyanate group (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.), and 70 g of acetone Were weighed into a three-necked flask. While stirring at room temperature, 0.25 g of dibutyltin laurate, which is a reaction catalyst between the hydroxyl group on the solder particle surface and the isocyanate group, 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.
  • SnBi solder particles (“ST-5” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (media
  • 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.
  • ester group of monoethyl adipate was reacted with the silanol group derived from the silane coupling agent by a transesterification reaction to form a covalent bond.
  • adipic acid was added and reacted at 60 ° C. for 1 hour to add adipic acid to the remaining ethyl ester group that had not reacted with the silanol group of monoethyl adipate.
  • solder particles 2 were obtained.
  • the CV value was 20%
  • the molecular weight Mw of the polymer constituting the surface was 9800.
  • solder particles 3 In the step of obtaining the solder particles 2, the solder particles 3 were obtained in the same manner except that monoethyl adipate was changed to monoethyl glutarate and adipic acid was changed to glutaric acid.
  • CV value of solder particles The CV value was measured with a laser diffraction particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.).
  • Examples 1 to 14 and Comparative Examples 1 and 2 (1) Preparation of anisotropic conductive paste The components shown in Tables 1 and 2 below were blended in the blending amounts shown in Tables 1 and 2 to obtain anisotropic conductive pastes.
  • connection structures of the types shown in Tables 1 and 2 below were produced as follows.
  • FR ⁇ glass epoxy substrate
  • a copper electrode pattern copper electrode thickness 12 ⁇ m
  • first connection object member glass epoxy substrate (FR ⁇ ) having a copper electrode pattern (copper electrode thickness 12 ⁇ m) with L / S of 40 ⁇ m / 40 ⁇ m and electrode length of 3 mm on the upper surface 4 substrates, thickness 0.6 mm) (first connection object member) was prepared.
  • a flexible printed circuit board (a second connection target member made of polyimide, having a thickness of 0.1 mm) having an L / S of 40 ⁇ m / 40 ⁇ m and an electrode length of 3 mm on a lower surface of a copper electrode pattern (copper electrode thickness 12 ⁇ m). 1 mm) was prepared.
  • the overlapping area of the glass epoxy substrate and the flexible printed circuit board was 1.5 cm ⁇ 3 mm, and the number of connected electrodes was 75 pairs.
  • the anisotropic conductive paste immediately after fabrication was applied on the upper surface of the glass epoxy substrate so as to have a thickness of 100 ⁇ m on the electrode of the glass epoxy substrate to form an anisotropic conductive paste layer.
  • the flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. At this time, no pressure was applied. The weight of the flexible printed board is added to the anisotropic conductive paste layer.
  • the anisotropic conductive paste layer was heated so that the temperature became 139 ° C. (melting point of the solder) 5 seconds after the start of temperature increase. Further, 15 seconds after the start of temperature increase, the anisotropic conductive paste layer was heated to 160 ° C. to cure the anisotropic conductive paste, and a connection structure was obtained.
  • Viscosity The viscosity ( ⁇ 25) at 25 ° C. of the anisotropic conductive paste was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
  • solder placement accuracy on electrode 1 In the obtained connection structure, when the portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is viewed, the first electrode The ratio X of the area where the solder part in the connection part is arranged in the area of 100% of the part where the part and the second electrode face each other was evaluated.
  • the solder placement accuracy 1 on the electrode was determined according to the following criteria.
  • Ratio X is 70% or more ⁇ : Ratio X is 60% or more and less than 70% ⁇ : Ratio X is 50% or more and less than 60% X: Ratio X is less than 50%
  • solder placement accuracy 2 In the obtained connection structure, when the portion where the first electrode and the second electrode face each other in the direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode is seen, The ratio Y of the solder part in the connection part arrange
  • the solder placement accuracy 2 on the electrode was determined according to the following criteria.
  • Ratio Y is 99% or more ⁇ : Ratio Y is 90% or more and less than 99% ⁇ : Ratio Y is 70% or more and less than 90% X: Ratio Y is less than 70%
  • connection resistance The average value of connection resistance is 10 14 ⁇ or more ⁇ : The average value of connection resistance is 10 8 ⁇ or more and less than 10 14 ⁇ ⁇ : The average value of connection resistance is 10 6 ⁇ or more and less than 10 8 ⁇ : The average value of the connection resistance is 10 5 ⁇ or more and less than 10 6 ⁇ ⁇ : The average value of the connection resistance is less than 10 5 ⁇
  • Misalignment is less than 15 ⁇ m ⁇ : Misalignment is 15 ⁇ m or more and less than 25 ⁇ m ⁇ : Misalignment is 25 ⁇ m or more and less than 40 ⁇ m ⁇ : Misalignment is 40 ⁇ m or more
  • Heat resistance heat-resistant yellowing
  • blends were prepared by blending components other than the solder particles in the conductive paste, and a cured sheet having a thickness of 0.6 mm was prepared. After exposure at 150 ° C. for 1000 hours, heat resistance (heat yellowing resistance) was evaluated by measuring transmittance at a measurement wavelength of 400 nm. The heat resistance was determined according to the following criteria.
  • Transmittance is 90% or more
  • Transmittance is 80% or more and less than 90%
  • Transmittance is 70% or more and less than 80%
  • Transmittance is less than 70%

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EP3597330A4 (en) * 2017-03-15 2020-11-25 Hitachi Chemical Company, Ltd. METAL PASTE FOR BONDING, BONDED BODY AS WELL AS A METHOD FOR MANUFACTURING THE SAME, AND A SEMICONDUCTOR DEVICE AS WELL AS A METHOD FOR MANUFACTURING THE SAME

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