WO2013015304A1 - 導電性粒子、導電材料及び接続構造体 - Google Patents
導電性粒子、導電材料及び接続構造体 Download PDFInfo
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- WO2013015304A1 WO2013015304A1 PCT/JP2012/068800 JP2012068800W WO2013015304A1 WO 2013015304 A1 WO2013015304 A1 WO 2013015304A1 JP 2012068800 W JP2012068800 W JP 2012068800W WO 2013015304 A1 WO2013015304 A1 WO 2013015304A1
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- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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- 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
- H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
- H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/156—Material
- H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
- H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
Definitions
- the present invention relates to conductive particles in which a conductive layer is disposed on the surface of base particles, and more particularly to conductive particles that can be used for electrical connection between electrodes, for example.
- the present invention also relates to a conductive material and a connection structure using the conductive particles.
- Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
- anisotropic conductive materials conductive particles are dispersed in a binder resin.
- the anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.
- Patent Document 1 discloses a conductive material in which a nickel conductive layer or a nickel alloy conductive layer is formed on the surface of spherical base particles having an average particle diameter of 1 to 20 ⁇ m by an electroless plating method. Sex particles are disclosed. The conductive particles have minute protrusions of 0.05 to 4 ⁇ m on the outermost layer of the conductive layer. The conductive layer and the protrusion are substantially continuously connected.
- Patent Document 2 discloses conductive particles having base particles and a conductive layer formed on the surface of the base particles.
- a divinylbenzene-ethylvinylbenzene mixture is used as part of the monomer to form the substrate particles.
- the compression elastic modulus is 2.5 ⁇ 10 9 N / m 2 or less
- the compression deformation recovery rate is 30% or more
- the fracture strain is 30% or more. is there.
- Patent Document 2 describes that when the electrodes of the substrate are electrically connected using the conductive particles, the connection resistance is reduced and the connection reliability is increased.
- connection resistance between the electrodes may increase.
- the resin component between the electrodes and the conductive particles may not be sufficiently eliminated. For this reason, the connection resistance between the electrodes connected by the conductive particles contained in the anisotropic conductive material may increase.
- a conductive layer containing nickel and phosphorus is formed.
- an oxide film is formed on the surfaces of the electrodes connected by the conductive particles and the conductive layer of the conductive particles.
- the conductive layer containing nickel and phosphorus is relatively soft. It may not be sufficiently eliminated, and the connection resistance may increase.
- connection target member or the substrate may be damaged by the conductive particles.
- connection resistance tends to increase.
- conduction reliability between the electrodes is lowered.
- a plurality of conductive particles may aggregate.
- a short circuit between the electrodes may occur.
- the oxide film may not be sufficiently removed, or damage to the connection target member or the substrate may not be suppressed. For this reason, even when the conductive particles described in Patent Document 2 are used, it is difficult to sufficiently reduce the connection resistance between the electrodes.
- An object of the present invention is to suppress the aggregation of a plurality of conductive particles, and further to reduce the connection resistance between electrodes when used for connection between electrodes, and the conductive particles It is to provide a conductive material and a connection structure used.
- a limited object of the present invention is that when used for connection between electrodes, the conductive particles that can effectively eliminate the oxide film on the surface of the electrode and conductive particles, and can reduce the connection resistance between the electrodes. And providing a conductive material and a connection structure using the conductive particles.
- the limited object of the present invention is to provide a conductive material that can effectively eliminate the resin component between the electrode and the conductive particles and reduce the connection resistance between the electrodes when used for connection between the electrodes. And providing a connection structure.
- a conductive material is disposed on the surface of the substrate particle and includes nickel, boron, and at least one metal component of tungsten and molybdenum. Conductive particles having a layer are provided.
- the content of the boron in 100% by weight of the entire conductive layer is 0.05% by weight or more and 4% by weight or less.
- the content of the metal component in 100% by weight of the entire conductive layer is 0.1% by weight or more and 30% by weight or less.
- the content of the metal component in the entire conductive layer of 100% by weight exceeds 5% by weight and is 30% by weight or less.
- the metal component contains tungsten.
- the compression modulus when the conductive particles and 10% compressive deformation is 5000N / mm 2 or more and 15000 N / mm 2 or less.
- the compression recovery rate is 5% or more and 70% or less.
- the metal component contains molybdenum.
- the said conductive layer contains nickel and molybdenum, and content of nickel is 70 weight% or more and 99.9 weight% in the whole 100 weight% of the said conductive layer.
- the molybdenum content is 0.1 wt% or more and 30 wt% or less.
- the compression elastic modulus when compressed by 5% is 7000 N / mm 2 or more, and 10% of the particle size of the conductive particles before compression in the compression direction. And when the conductive particles are compressed at 25% or less, the conductive layer is cracked.
- the thickness of the conductive layer is 0.05 ⁇ m or more and 0.5 ⁇ m or less.
- the conductive layer has a protrusion on the outer surface.
- the conductive material according to the present invention includes the above-described conductive particles and a binder resin.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection
- the part is formed of the above-described conductive particles, or is formed of a conductive material including the conductive particles and a binder resin.
- a conductive layer containing nickel, boron, and at least one metal component of tungsten and molybdenum is disposed on the surface of the base particle, and thus a plurality of conductive The aggregation of the conductive particles can be suppressed. Furthermore, when the electrodes are connected using the conductive particles according to the present invention, the connection resistance can be lowered.
- FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
- FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
- FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
- FIG. 5 is a schematic cross-sectional view for explaining a state when the conductive particles are compressed.
- FIG. 6 is a schematic diagram illustrating an example of the relationship between the compression load value and the compression displacement when a crack occurs in the conductive layer when the conductive particles are compressed.
- the conductive particle according to the present invention is a conductive particle that is disposed on the surface of the substrate particle, nickel, boron, and at least one metal component of tungsten and molybdenum. And having a layer.
- the conductive layer is a nickel-boron-tungsten / molybdenum conductive layer.
- at least one metal component of tungsten and molybdenum may be referred to as a metal component M.
- the conductive layer containing nickel, boron, and the metal component M may be referred to as a conductive layer X.
- the connection resistance between the electrodes is lowered.
- the content of nickel in 100% by weight of the entire conductive layer X in the conductive particles according to the present invention is 50% by weight or more, the connection resistance between the electrodes becomes considerably low. Accordingly, the content of nickel is preferably 50% by weight or more in the entire conductive layer X of 100% by weight.
- the connection resistance may increase.
- the oxide film on the surfaces of the electrodes and the conductive particles cannot be sufficiently removed, and the connection resistance tends to be high.
- the connection resistance tends to increase, and when it is 1% by weight or more, the connection resistance tends to further increase.
- connection target member or the substrate may be damaged by the conductive particles.
- connection resistance between the electrodes can be lowered.
- the oxide film on the surfaces of the electrodes and the conductive particles can be eliminated, and the connection resistance can be lowered.
- the conductive layer X includes not only boron but also at least one metal component M of tungsten and molybdenum. Therefore, the conductive layer X including boron and the metal component M is included. Can be quite stiff. For this reason, the oxide film on the surface of the electrode and the conductive particles can be sufficiently eliminated, and the connection resistance can be considerably reduced. Particularly when the conductive layer X contains the metal component M and the conductive layer X has protrusions on the outer surface, the oxide film on the surface of the electrode and conductive particles can be more effectively eliminated, and the connection resistance can be reduced. It can be made even lower.
- the conductive layer X contains the metal component M, the conductive layer X is considerably hardened. As a result, even if an impact is applied to the connection structure connecting the electrodes by the conductive particles, a conduction failure occurs. It becomes difficult. That is, the impact resistance of the connection structure can be increased.
- the surface of the conductive layer of the conventional conductive particles may be highly magnetic, and the surface of the conductive layer containing nickel and boron is highly magnetic. Therefore, when the electrodes are electrically connected, Due to the influence of the agglomerated conductive particles, the electrodes adjacent in the horizontal direction tend to be easily connected.
- the conductive layer X contains the metal component M, the magnetic property of the surface of the conductive layer X is considerably low. For this reason, it can suppress that several electroconductive particle aggregates. Therefore, when the electrodes are electrically connected, it is possible to prevent the electrodes adjacent in the lateral direction from being connected by the aggregated conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.
- the content of nickel is 70% by weight or more and 99.9% by weight or less, and the content of the metal component M is 0.1% by weight or more and 30% by weight.
- the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer X is less than 1% by weight.
- the content of nickel is 70% by weight or more and 99.9% by weight or less, and the content of the metal component M is 0.1% by weight or more and 30% by weight or less. It is preferable that the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer X is less than 1% by weight.
- the conductive particles having this preferable configuration are used for the connection between the electrodes, the oxide film on the surfaces of the electrodes and the conductive particles can be effectively eliminated. For this reason, the connection resistance between the electrodes in the obtained connection structure can be further reduced. Moreover, since the content of nickel in the conductive particles having this preferable configuration is 70% by weight or more, the connection resistance between the electrodes becomes considerably low.
- the content of the metal component M in 100% by weight of the entire conductive layer X is 0.1% by weight or more and 30% by weight or less, compared with a conductive layer not containing the metal component M, The conductive layer X becomes considerably hard. For this reason, as a result of effectively eliminating the oxide film on the surfaces of the electrodes and the conductive particles, the connection resistance between the electrodes is further reduced.
- the resin component between the electrodes and the conductive particles can be effectively eliminated, so that the connection between the electrodes The resistance becomes even lower.
- the compression elastic modulus (10% K value) when the conductive particles according to the present invention are 10% compressively deformed is preferably 5000 N / mm 2 or more, more preferably 7000 N / mm 2 or more, preferably 15000 N / mm 2 or less. More preferably, it is 10,000 N / mm 2 or less.
- the compression elastic modulus (10% K value) is not less than the above lower limit, the oxide film on the surface of the electrode and the conductive particles can be more effectively eliminated, and the resin component between the electrode and the conductive particles can be further removed. As a result of more effective elimination, the connection resistance between the electrodes is further reduced.
- the compression elastic modulus (10% K value) can be measured as follows.
- the conductive particles are compressed under the conditions of a compression rate of 2.6 mN / sec and a maximum test load of 10 gf with a cylindrical indenter end face (diameter 50 ⁇ m, made of diamond).
- the load value (N) and compression displacement (mm) at this time are measured.
- the compression elastic modulus can be obtained by the following formula.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- K value (N / mm 2 ) (3/2 1/2 ) ⁇ F ⁇ S ⁇ 3 / 2 ⁇ R ⁇ 1/2
- F Load value when the conductive particles are 10% compressively deformed (N)
- S Compression displacement (mm) when the conductive particles are 10% compressively deformed
- R radius of conductive particles (mm)
- the compression recovery rate of the conductive particles is preferably 5% or more, more preferably 20% or more, preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less.
- the compression recovery rate is not less than the above lower limit and not more than the above upper limit, the oxide film on the surface of the electrode and the conductive particles can be more effectively eliminated, and the resin component between the electrode and the conductive particles is further more effective.
- the connection resistance between the electrodes can be further reduced.
- peeling is further less likely to occur at the interface between the cured product and the portion of the connection portion excluding the conductive particles and the conductive particles and the connection target member.
- the conductive material is difficult to peel from the substrate or the like. This also makes the connection resistance between the electrodes even lower.
- the compression recovery rate can be measured as follows.
- a load (reverse load value) is applied to the central direction of the conductive particle until the conductive particle is compressed and deformed by 30% using a micro compression tester. Thereafter, unloading is performed up to the origin load value (0.40 mN). The load-compression displacement during this period is measured, and the compression recovery rate can be obtained from the following equation.
- the load speed is 0.33 mN / sec.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- Compression recovery rate (%) [(L1-L2) / L1] ⁇ 100
- L1 Compression displacement from the load value for origin to the reverse load value when applying a load
- L2 Unloading displacement from the reverse load value to the load value for origin when releasing the load
- the compression elastic modulus and the compression recovery rate are the kind of the base particle, the particle diameter of the base particle, the content of nickel in 100% by weight of the whole conductive layer X, and the whole conductive layer X.
- the content of the metal component M in 100% by weight, the content of phosphorus in the whole 100% by weight of the conductive layer X, the content of boron in the whole 100% by weight of the conductive layer X, the content of the conductive layer X It can be appropriately adjusted depending on the thickness.
- the compression modulus (5% K value) when compressed by 5% is preferably 7000 N / mm 2 or more.
- the conductive layer is cracked when the conductive particles are compressed by more than 10% and 25% or less of the particle diameter of the conductive particles before compression in the compression direction. It is preferable. In other words, when the conductive particles according to the present invention are compressed, the conductive particles exceed 10% of the particle diameter of the conductive particles before compression in the compression direction and are compressed and displaced at 25% or less. It is preferable that a crack occurs in the conductive layer. That is, the compressive displacement of the conductive particles that cause cracks in the conductive layer is preferably more than 10% and 25% or less. For example, when the conductive particles are significantly compressed, the conductive layer is moderately partially broken.
- the conductive particles having such properties not only have a sufficiently high hardness at the initial stage of compression, but also crack when appropriately compressed. Since the conductive layer is cracked at the stage where the conductive particles are appropriately compressed during the connection between the electrodes, damage to the electrodes can be suppressed. As a result, the connection resistance between the electrodes in the obtained connection structure can be further reduced, and the conduction reliability between the electrodes can be further increased.
- the compression elastic modulus (5% K value) when compressed at 5% is 7000 N / mm 2 or more and the conductive particles according to the present invention are compressed
- the compression direction When the conductive particles are compressed at more than 10% and less than 25% of the particle diameter of the conductive particles before compression, it is preferable that the conductive layer is cracked.
- the connection resistance between the electrodes can be further reduced.
- the conductive particles in the initial stage of compression have sufficient hardness.
- the oxide film on the surface of the electrode and the conductive particles can be effectively eliminated at the initial stage of compression of the conductive particles at the time of connection between the electrodes.
- the electrode and the conductive layer in the conductive particles are effectively in contact, and the connection resistance between the electrodes can be further reduced.
- the electrodes are electrically connected using conductive particles having a compression modulus (5% K value) of less than 7000 N / mm 2 when compressed by 5%, the compression is 5%.
- the oxide film on the surfaces of the electrodes and the conductive particles There is a tendency that the elimination property of the electrode decreases, and the connection resistance between the electrodes tends to increase.
- the 5% K value is more preferably 8000 N / mm 2 or more, further preferably 9000 N / mm 2 or more.
- the upper limit of the 5% K value is not particularly limited.
- the 5% K value may be, for example, 15000 N / mm 2 or less or 10000 N / mm 2 or less.
- the compression elastic modulus (5% K value) can be measured as follows.
- the conductive particles are compressed under the conditions of a compression rate of 2.6 mN / sec and a maximum test load of 10 gf with a cylindrical indenter end face (diameter 50 ⁇ m, made of diamond).
- the load value (N) and compression displacement (mm) at this time are measured.
- the compression elastic modulus can be obtained by the following formula.
- the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
- the compression modulus (10% K value and 5% K value) represents the hardness of the conductive particles universally and quantitatively. By using the compression elastic modulus, the hardness of the conductive particles can be expressed quantitatively and uniquely.
- the compression displacement at which the conductive layer is cracked is more preferably 12% or more, and more preferably 20% or less.
- FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
- the conductive particle 1 includes a base particle 2, a conductive layer 3, a plurality of core substances 4, and a plurality of insulating substances 5.
- the conductive layer 3 is disposed on the surface of the base particle 2.
- the conductive layer 3 includes nickel, boron, and the metal component M.
- the conductive layer 3 is a nickel-boron-tungsten / molybdenum conductive layer.
- the conductive particle 1 is a coated particle in which the surface of the base particle 2 is coated with the conductive layer 3.
- the conductive particle 1 has a plurality of protrusions 1a on the surface.
- the conductive layer 3 has a plurality of protrusions 3a on the outer surface.
- a plurality of core substances 4 are arranged on the surface of the base particle 2.
- a plurality of core materials 4 are embedded in the conductive layer 3.
- the core substance 4 is disposed inside the protrusions 1a and 3a.
- the conductive layer 3 covers a plurality of core materials 4.
- the outer surface of the conductive layer 3 is raised by the plurality of core materials 4 to form protrusions 1a and 3a.
- the conductive particles 1 have an insulating material 5 disposed on the outer surface of the conductive layer 3. At least a part of the outer surface of the conductive layer 3 is covered with the insulating material 5.
- the insulating substance 5 is made of an insulating material and is an insulating particle.
- the electroconductive particle which concerns on this invention may have the insulating substance arrange
- the conductive particles according to the present invention do not necessarily have an insulating material.
- FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
- the conductive particles 11 shown in FIG. 2 include base material particles 2, a second conductive layer 12 (another conductive layer), a conductive layer 13 (first conductive layer), a plurality of core substances 4, and a plurality of And an insulating material 5.
- the conductive particles 1 and the conductive particles 11 are different only in the conductive layer. That is, the conductive particle 1 has a single-layered conductive layer, whereas the conductive particle 11 has a two-layered second conductive layer 12 and conductive layer 13.
- the conductive layer 13 is disposed on the surface of the base particle 2.
- a second conductive layer 12 (another conductive layer) is disposed between the base particle 2 and the conductive layer 13. Therefore, the second conductive layer 12 is disposed on the surface of the base particle 2, and the conductive layer 13 is disposed on the surface of the second conductive layer 12.
- the conductive layer 13 includes nickel, boron, and tungsten.
- the conductive layer 13 has a plurality of protrusions 13a on the outer surface.
- the conductive particles 11 have a plurality of protrusions 11a on the surface.
- FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
- the conductive particle 21 shown in FIG. 3 has the base particle 2 and the conductive layer 22.
- the conductive layer 22 is disposed on the surface of the base particle 2.
- the conductive layer 22 includes nickel, boron, and the metal component M.
- the conductive particles 21 do not have a core substance.
- the conductive particles 21 do not have protrusions on the surface.
- the conductive particles 21 are spherical.
- the conductive layer 22 has no protrusion on the surface.
- the electroconductive particle which concerns on this invention does not need to have a litigation
- the conductive particles 21 do not have an insulating material.
- the conductive particles 21 may have an insulating material disposed on the surface of the conductive layer 22.
- the nickel content is 70 wt% or more and 99.9 wt% or less in 100 wt% of the entire conductive layers 3, 13, and 22, and the content of the metal component M is Is preferably 0.1% by weight or more and 30% by weight or less.
- the conductive layers 3, 13, and 22 do not contain phosphorus, or the conductive layers 3, 13, and 22 contain phosphorus, and the total content of the conductive layers 3, 13, and 22 is 100% by weight. It is preferable that it is less than%.
- the 5% K value of the conductive particles 1, 11 and 21 is preferably 7000 N / mm 2 or more. Further, when the conductive particles 1, 11, 21 are compressed, the conductive particles 1, 11, 21 exceed 10% of the particle diameter of the conductive particles 1, 11, 21 before compression in the compression direction, 25 It is preferable that cracks occur in the conductive layers 3, 13, and 22 when they are compressed and displaced by less than or equal to%. That is, in the conductive particles 1, 11, and 21, when the particle diameter of the conductive particles 1, 11, 21 before compression in the compression direction is X, the particle diameter of the conductive particles 1, 11, 21 in the compression direction Is preferably 0.75X or more and less than 0.90X, it is preferable that the conductive layers 3, 13, and 22 are cracked.
- the particle diameter of the conductive particles 1, 11, 21 before compression in the compression direction is 5 ⁇ m
- the conductive particles 1, 11, 21 are compressed and the conductive particles 1, 11, 11 in the compression direction are compressed.
- the particle diameter of 21 is 3.75 ⁇ m or more and less than 4.5 ⁇ m, it is preferable that cracks occur in the conductive layers 3, 13, and 22. In the conductive particles 11, not only the conductive layer 13 but also the second conductive layer 12 may be cracked.
- the “crack” indicates the first (first) crack in the conductive layer. Therefore, in the electroconductive particle 1,11,21 which concerns on this embodiment, when the electroconductive particle 1,11,21 which has the electroconductive layer 3,13,22 without a crack is compressed, electroconductive particle 1,11,21 It is preferable that cracking occurs in the conductive layers 3, 13, and 22 when 21 exceeds 10% of the particle diameter of the conductive particles 1, 11 and 21 before compression in the compression direction and is 25% or less.
- the measurement of the compression displacement at which the conductive layers 3, 13, and 22 are cracked is performed as follows.
- the conductive particles 21 are used.
- the conductive particles 21 are placed on the base 71.
- a micro compression tester (“Fischerscope H-100” manufactured by Fischer)
- a cylinder (diameter 50 ⁇ m, made of diamond) is used as the compression member 72 under conditions of a compression speed of 0.33 mN / sec and a maximum test load of 10 mN.
- the smooth end surface 72a of the compression member 72 is lowered toward the conductive particles 21 in the direction indicated by the arrow A.
- the conductive particles 21 are compressed by the smooth end surface 72a.
- the compression is continued until the crack 22a is partially generated in the conductive layer 22 of the conductive particles 21. In the case of conductive particles 1 and 11, the same measurement is performed.
- the conductive layer cracks when the conductive particles are compressed and displaced by more than 10% of the particle diameter of the conductive particles before compression in the compression direction. It is preferable that the conductive layer is cracked at a compression displacement of 25% or less.
- the relationship between the compressive load value and the compressive displacement is, for example, as shown in FIG. In FIG. 6, the compression is started from the point A0, and the conductive layer is cracked at the point A1. As the conductive layer cracks, the compression displacement (particle diameter) of the conductive particles in the compression direction changes, and the compression displacement moves from the A1 point to the A2 point.
- a compressive load is applied to the conductive particles, and if the conductive layer cracks, the conductive particles are compressed with a relatively small compressive load. Therefore, the compression member that applies the compressive load to the conductive particles moves.
- the compression displacement (particle diameter) of the conductive particles in the compression direction changes.
- the slope of the line from point A0 to point A1 is relatively large.
- the 5% K value of the conductive particles 21 is 7000 N / mm 2 or more and the conductive particles 21 are relatively hard, the slope of the line from the A0 point to the A1 point becomes large.
- Examples of 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 particles, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
- the base material particles are preferably resin particles formed of a resin.
- the said electroconductive particle is compressed by crimping
- the substrate particles are resin particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction
- Examples of the resin for forming the resin particles include polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, and polyphenylene.
- Examples thereof include oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyethersulfone, divinylbenzene polymer, and divinylbenzene copolymer.
- Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer.
- the resin for forming the resin particles is obtained by polymerizing one or more polymerizable monomers having a plurality of ethylenically unsaturated groups.
- a polymer is preferred.
- Examples of the inorganic material for forming the inorganic particles include silica and carbon black.
- 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 particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 1.5 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and even more preferably. Is not more than 300 ⁇ m, more preferably not more than 50 ⁇ m, particularly preferably not more than 30 ⁇ m, and most preferably not more than 5 ⁇ m.
- the particle diameter of the substrate particles is equal to or greater than the above lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased, and the electrodes are connected via the conductive particles. The connection resistance between them becomes even lower.
- the particle diameter of the base particle indicates a diameter when the base particle is a true sphere, and indicates a maximum diameter when the base particle is not a true sphere.
- the particle diameter of the substrate particles is particularly preferably 2 ⁇ m or more and 5 ⁇ m or less.
- the particle diameter of the substrate particles is in the range of 2 to 5 ⁇ m, even when the distance between the electrodes is small and the conductive layer is thick, small conductive particles can be obtained.
- the electroconductive particle which concerns on this invention is arrange
- the conductive layer X may be directly laminated on the surface of the base particle, or may be disposed on the surface of the base particle via another conductive layer or the like. Furthermore, another conductive layer may be disposed on the surface of the conductive layer X. It is preferable that no other conductive layer is disposed on the outer surface of the conductive layer X. It is preferable that the outer surface of the conductive particles is a conductive layer X containing nickel. When the electrodes are connected by conductive particles having the conductive layer X containing nickel, the connection resistance is further reduced.
- the conductive layer X includes nickel, boron, at least one metal component M of tungsten and molybdenum.
- the conductive layer X is a nickel-boron-tungsten / molybdenum conductive layer.
- the conductive layer X preferably includes nickel, boron, and tungsten, preferably includes nickel, boron, and molybdenum, and preferably includes nickel, boron, tungsten, and molybdenum.
- the conductive layer X may be a nickel-boron-tungsten conductive layer or a nickel-boron-molybdenum conductive layer.
- the metal component M preferably contains tungsten, preferably contains molybdenum, and preferably contains tungsten and molybdenum.
- nickel, boron, and the metal component M may be alloyed.
- nickel and boron may be alloyed, nickel and the metal component M may be alloyed, or boron and the metal component M may be alloyed.
- chromium or seaborgium may be used in the conductive layer X.
- the hardness tends to be relatively low at the initial compression stage of the nickel conductive layer that does not contain both tungsten and molybdenum. For this reason, at the time of the connection between electrodes, the effect which eliminates the oxide film on the surface of an electrode and electroconductive particle becomes small, and there exists a tendency for the effect which makes connection resistance low.
- the thickness of the nickel conductive layer that does not contain both tungsten and molybdenum is increased in order to obtain the effect of lowering the connection resistance further, or to be suitable for applications in which a large current flows, conductive objects may cause connection.
- the member or the substrate tends to be easily damaged. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
- the conductive layer X contains nickel and at least one metal component M of tungsten and molybdenum, it is easy to set the 5% K value to the lower limit or more. Further, the conductive layer X may be appropriately cracked when the conductive particles exceed 10% of the particle diameter of the conductive particles before compression in the compression direction and are compressed at 25% or less. Easy. When cracks occur when compressed appropriately, damage to the electrodes is less likely to occur, and therefore the connection resistance between the electrodes is further reduced.
- the conductive layer X includes nickel and at least one metal component M of tungsten and molybdenum, the conductive layer X has an appropriate hardness, and therefore compresses the conductive particles.
- an appropriate indentation can be formed on the electrodes.
- the indentation formed on the electrode is a concave portion of the electrode formed by pressing the electrode with conductive particles.
- the conductive layer X preferably contains nickel as a main component. From the viewpoint of effectively reducing the initial connection resistance between the electrodes, it is better that the content of nickel in 100% by weight of the entire conductive layer X is larger. Therefore, the content of nickel is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and further preferably 75% by weight or more, in 100% by weight of the entire conductive layer X. Even more preferably, it is 80% by weight or more, particularly preferably 85% by weight or more, still more preferably 90% by weight or more, and most preferably 95% by weight or more.
- the content of nickel in 100% by weight of the entire conductive layer X may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
- the connection resistance between the electrodes is further reduced.
- there are few oxide films in the surface of an electrode or a conductive layer there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.
- the upper limit of the nickel content can be changed as appropriate according to the content of boron and the metal component M.
- the content of nickel in 100% by weight of the entire conductive layer X is preferably 99.9% by weight or less, more preferably 99.85% by weight or less, still more preferably 99.7% by weight or less, and particularly preferably 99.% by weight. Less than 45% by weight.
- Conductive particles having a nickel conductive layer that does not contain boron are relatively soft at the initial compression stage of the nickel conductive layer that does not contain boron, and the oxide film on the surface of the electrode and conductive particles is eliminated when the electrodes are connected. The effect tends to be small, and the effect of reducing the connection resistance tends to be small.
- the conductive layer may contain phosphorus instead of boron. In the conductive particles having a conductive layer containing nickel and phosphorus, the effect of eliminating the oxide film on the surface of the electrode and the conductive particles tends to be small, and the effect of reducing the connection resistance tends to be small.
- the thickness of the conductive layer not containing boron or the thickness of the conductive layer containing nickel and phosphorus is increased in order to obtain the effect of lowering the connection resistance or to be suitable for applications in which a large current flows. If the thickness is increased, the connection target member or the substrate tends to be easily damaged by the conductive particles. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
- the conductive layer X contains boron, it is easy to make the 5% K value equal to or more than the lower limit. Further, the conductive layer X may be appropriately cracked when the conductive particles exceed 10% of the particle diameter of the conductive particles before compression in the compression direction and are compressed at 25% or less. Easy. In addition, since the conductive layer X contains nickel, boron, and the metal component M, it is even easier to set the 5% K value to the lower limit or more. Furthermore, when the conductive particles are compressed at more than 10% of the particle diameter of the conductive particles before compression in the compression direction and less than 25%, the conductive layer X is more appropriately cracked. Is easy. When cracks occur when compressed appropriately, damage to the electrodes is less likely to occur, and therefore the connection resistance between the electrodes is further reduced.
- the conductive layer X contains boron
- the conductive layer X has an appropriate hardness, so that the electrodes are more unlikely to be damaged, and therefore the connection resistance between the electrodes is further reduced.
- the conductive layer X contains boron
- the conductive layer X has an appropriate hardness, so that when the conductive particles are compressed to connect the electrodes, an appropriate indentation can be formed on the electrodes.
- the conductive layer X contains nickel, boron, and the metal component M, it is possible to achieve a high compressive elastic modulus. For this reason, the oxide film on the surface of the electrode and the conductive particle can be effectively eliminated at the initial stage of compression of the conductive particle at the time of connection between the electrodes, and the conductive particle is appropriately compressed at the time of connection between the electrodes. In this stage, the conductive layer X is cracked, so that damage to the electrode can be suppressed. As a result, the connection resistance between the electrodes in the resulting connection structure can be reduced, and the conduction reliability between the electrodes can be increased.
- the content of boron in 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably 5% by weight. Below, more preferably 4% by weight or less, still more preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less.
- the boron content is not less than the above lower limit, the conductive layer X becomes harder, the oxide film on the surface of the electrode and conductive particles can be more effectively removed, and the connection resistance between the electrodes is further reduced. can do.
- the boron content is not more than the above upper limit, the content of nickel and the metal component M is relatively increased, so that the connection resistance between the electrodes is lowered.
- the surface of the conductive layer X containing nickel and boron has high magnetism, and when the electrodes are electrically connected, the electrodes adjacent to each other in the lateral direction are connected due to the influence of the conductive particles aggregated by magnetism. There is a tendency to be easily. Since the conductive layer X contains nickel, boron, and the metal component M, the magnetism of the surface of the conductive layer X is considerably low. For this reason, it can suppress that several electroconductive particle aggregates. Therefore, when the electrodes are electrically connected, it is possible to prevent the electrodes adjacent in the lateral direction from being connected by the aggregated conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.
- the conductive layer X contains the metal component M, the conductive layer X has an appropriate hardness. Therefore, when the conductive particles are compressed to connect the electrodes, an appropriate indentation is formed on the electrodes. it can. Furthermore, the conductive layer X contains at least one of tungsten and molybdenum, or contains boron, so that the conductive layer X is considerably hardened. As a result, the electrodes are connected by conductive particles. Even when an impact is applied to the structure, poor conduction is unlikely to occur. That is, the impact resistance of the connection structure can be increased.
- the content of the metal component M (total content of tungsten and molybdenum) in 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.1% by weight or more. More preferably, it is 0.2% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably more than 5% by weight, most preferably 10% by weight or more.
- the content of the metal component M is equal to or more than the lower limit, the hardness of the outer surface of the conductive layer is further increased.
- the oxide film on the surface of the electrode or the conductive layer can be effectively eliminated, and the resin component between the electrode and the conductive particles can be removed. It can be effectively eliminated, the connection resistance is lowered, and the impact resistance of the resulting connection structure is increased. Furthermore, when the content of the metal component M is equal to or more than the lower limit, the magnetism of the outer surface of the conductive layer X becomes weak and the plurality of conductive particles are difficult to aggregate. For this reason, the short circuit between electrodes can be suppressed effectively.
- the upper limit of the content of the metal component M in 100% by weight of the entire conductive layer X can be appropriately changed depending on the contents of nickel and boron.
- the content of the metal component M in the total 100% by weight of the conductive layer X is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight or less. It is.
- the content of tungsten in 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.1% by weight or more. More preferably 0.2% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably more than 5% by weight, most preferably 10% by weight or more, preferably 40% by weight. % Or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight or less.
- the content of molybdenum in the total 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably. Is 0.2% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably more than 5% by weight, most preferably 10% by weight or more, preferably 40% by weight or less. More preferably, it is 30% by weight or less, further preferably 25% by weight or less, and particularly preferably 20% by weight or less.
- the total content of the nickel and the metal component M in 100% by weight of the conductive layer X is larger. Therefore, the total content of nickel and the metal component M is preferably 75.1% by weight or more, more preferably 80.1% by weight or more, and still more preferably 85.% by weight in the total 100% by weight of the conductive layer X. 1% by weight or more, particularly preferably 90.1% by weight or more, most preferably 95.1% by weight or more.
- the total content of nickel and the metal component M in 100% by weight of the entire conductive layer X may be 97.1% by weight or more, 97.6% by weight or more, and 98. It may be 1% by weight or more.
- the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the conductive layer X as a whole. Is preferably less than 1% by weight. From the viewpoint of further reducing the connection resistance between the electrodes, the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the conductive layer X as a whole. Is more preferably less than 0.5% by weight.
- the content of phosphorus in 100% by weight of the entire conductive layer X is more preferably 0.3% by weight or less, still more preferably 0.1% by weight. % Or less.
- the phosphorus content is less than or equal to the above upper limit, the oxide film on the surfaces of the electrodes and the conductive particles can be more effectively eliminated when connecting the electrodes. As a result, the connection resistance between the electrodes can be lowered.
- the resin component between the electrode and the conductive particles can be effectively eliminated, the connection resistance between the electrodes is further reduced. Since the connection resistance between the electrodes becomes considerably low, the conductive layer X particularly preferably does not contain phosphorus.
- the conductive layer X includes the metal component M and the phosphorus content is not more than the upper limit, and the conductive layer X has protrusions on the outer surface, the surface of the electrode and the conductive particles The oxide film can be more effectively eliminated, the resin component between the electrode and the conductive particles can be effectively eliminated, and the connection resistance can be further reduced.
- the conductive layer X containing the metal component M and the phosphorus content being not more than the above upper limit, the conductive layer X is considerably hardened.
- the connection structure in which the electrodes are connected by conductive particles Even if an impact is applied to this, poor conduction is unlikely to occur. That is, the impact resistance of the connection structure can be increased.
- the method for measuring the contents of nickel, boron, tungsten, molybdenum and phosphorus in the conductive layer X is not particularly limited, and various known analytical methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer, or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.
- ICP emission analyzer When measuring the contents of nickel, boron, tungsten, molybdenum and phosphorus in the conductive layer X, it is preferable to use an ICP emission analyzer.
- ICP emission analyzers examples include ICP emission analyzers manufactured by HORIBA.
- an ICP-MS analyzer In measuring the contents of nickel, boron, tungsten, molybdenum and phosphorus in the conductive layer X, an ICP-MS analyzer may be used.
- the metal for forming the other conductive layer is not particularly limited.
- the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. And alloys thereof.
- the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.
- the metal constituting the other conductive layer preferably contains nickel.
- the method for forming a conductive layer (another conductive layer and conductive layer X) on the surface of the substrate particle is not particularly limited.
- a method for forming the conductive layer for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a paste containing metal powder or metal powder and a binder is used for base particles or other conductive layers.
- a method of coating the surface for example, since formation of a conductive layer is simple, the method by electroless plating is preferable.
- Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
- the particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and even more preferably. Is not more than 300 ⁇ m, more preferably not more than 100 ⁇ m, still more preferably not more than 50 ⁇ m, particularly preferably not more than 30 ⁇ m, still more particularly preferably not more than 20 ⁇ m, most preferably not more than 5 ⁇ m.
- the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
- the particle diameter of the conductive particles when used for a conductive material such as an anisotropic conductive material is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 20 ⁇ m or less.
- the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
- the particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
- the thickness of the conductive layer X is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.3 ⁇ m or less.
- the thickness of the conductive layer X 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 do not become too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Deform.
- the thickness of the conductive layer X is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably 0.5 ⁇ m or less. More preferably, it is 0.3 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
- the thickness of the conductive layer X is not less than the above lower limit and not more than the above upper limit, the coating with the conductive layer X can be made uniform, and the connection resistance between the electrodes becomes sufficiently low.
- the total thickness of the conductive layer including the conductive layer X is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, particularly It is preferably 0.1 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.3 ⁇ m or less, and still more preferably 0.1 ⁇ m or less.
- the thickness of the entire conductive layer is not less than the above lower limit and not more than the above upper limit, the covering of the entire conductive layer can be made uniform, and the connection resistance between the electrodes becomes sufficiently low.
- the thickness of the conductive layer X is particularly preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less. Furthermore, it is particularly preferable that the particle diameter of the base particle is 2 ⁇ m or more and 5 ⁇ m or less, and the thickness of the conductive layer X is 0.05 ⁇ m or more and 0.5 ⁇ m or less. The thickness of the conductive layer X is most preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less. Furthermore, it is most preferable that the particle diameter of the substrate particles is 2 ⁇ m or more and 5 ⁇ m or less, and the thickness of the conductive layer X is 0.05 ⁇ m or more and 0.3 ⁇ m or less.
- the conductive particles can be suitably used for applications in which a large current flows. Furthermore, when the conductive particles are compressed to connect the electrodes, it is possible to further suppress the electrodes from being damaged.
- the thickness of the conductive layer X and the thickness of the entire conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a method for controlling the content of nickel, tungsten, molybdenum, boron and phosphorus in the conductive layer X for example, a method of controlling the pH of the nickel plating solution when forming the conductive layer X by electroless nickel plating, When forming the conductive layer X by electroless nickel plating, a method for adjusting the concentration of the boron-containing reducing agent, a method for adjusting the tungsten concentration in the nickel plating solution, a method for adjusting the molybdenum concentration in the nickel plating solution, and nickel Examples include a method of adjusting the nickel salt concentration in the plating solution.
- a catalytic step and an electroless plating step are performed.
- an example of a method for forming an alloy plating layer containing at least one of nickel, tungsten, and molybdenum and boron on the surface of the resin particles by electroless plating will be described.
- a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
- the surface of the resin particles is activated with an acid solution or an alkali solution
- the reducing agent a boron-containing reducing agent is preferably used.
- a phosphorus-containing reducing agent such as sodium hypophosphite may be used as the reducing agent.
- a nickel plating bath containing a nickel salt, at least one of a tungsten-containing compound and a molybdenum-containing compound, and the boron-containing reducing agent is used.
- nickel By immersing the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and a conductive layer containing nickel, boron, and the metal component M can be formed. .
- Examples of the tungsten-containing compound include tungsten boride and sodium tungstate.
- Examples of the molybdenum-containing compound include molybdenum boride and sodium molybdate.
- Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, potassium borohydride, and the like.
- the conductive particles according to the present invention preferably have protrusions on the surface.
- the conductive layer including the conductive layer X preferably has protrusions on the outer surface, and the conductive layer X preferably has protrusions on the outer surface.
- An oxide film is often formed on the surface of the electrode connected by the conductive particles.
- an oxide film is often formed on the surface of the conductive layer of the conductive particles.
- the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusion between the conductive particles causes a gap between the conductive particles and the electrode. Resin can be effectively eliminated. For this reason, the conduction
- the number of protrusions on the outer surface of the conductive layer per one conductive particle is preferably 3 or more, more preferably 5 or more.
- the upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
- the core substance Since the core substance is embedded in the conductive layer, it is easy for the conductive layer to have a plurality of protrusions on the outer surface. However, in order to form protrusions on the surfaces of the conductive particles and the conductive layer, the core substance is not necessarily used.
- a core material is attached to the surface of the base particle, and then a conductive layer is formed by electroless plating, and a conductive layer is formed on the surface of the base particle by electroless plating. Thereafter, a method of attaching a core substance and further forming a conductive layer by electroless plating may be used.
- a method for disposing the core substance on the surface of the base particle for example, a conductive substance that becomes the core substance is added to the dispersion of the base particle, and the core substance is added to the surface of the base particle, for example, .
- Examples include a method of attaching a core substance.
- the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.
- Examples of the conductive substance constituting the core substance include metals, metal oxides, conductive nonmetals such as graphite, and conductive polymers.
- Examples of the conductive polymer include polyacetylene. Among them, metal is preferable because conductivity can be increased and connection resistance can be effectively reduced.
- the core substance is preferably metal particles.
- the metal examples include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead.
- examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, and tin-lead-silver alloys. Of these, nickel, copper, silver or gold is preferable.
- the metal constituting the core material may be the same as or different from the metal constituting the conductive layer.
- the metal constituting the core material preferably includes a metal constituting the conductive layer. It is preferable that the metal which comprises the said core substance contains nickel. It is preferable that the metal which comprises the said core substance contains nickel.
- the shape of the core substance is not particularly limited.
- the shape of the core substance is preferably a lump.
- Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
- the average diameter (average particle diameter) of the core substance is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the connection resistance between the electrodes can be effectively reduced.
- the “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter).
- the average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
- the conductive particles according to the present invention preferably include an insulating material disposed on the surface of the conductive layer.
- an insulating material disposed on the surface of the conductive layer.
- an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes.
- the insulating substance between the conductive layer of the conductive particles and the electrodes can be easily excluded. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be easily excluded.
- the insulating material is an insulating particle because the insulating material can be more easily removed when the electrodes are crimped.
- thermoplastic resin examples include vinyl polymers and vinyl copolymers.
- thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
- water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
- Examples of a method for disposing an insulating material on the surface of the conductive layer include a chemical method and a physical or mechanical method.
- Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
- Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. In particular, since the insulating substance is difficult to be detached, a method of disposing the insulating substance on the surface of the conductive layer through a chemical bond is preferable.
- the average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles and the use of the conductive particles.
- the average diameter (average particle diameter) of the insulating material is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the average diameter of the insulating material is not less than the above lower limit, the conductive layers of the plurality of conductive particles are difficult to contact when the conductive particles are dispersed in the binder resin.
- the average diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating material between the electrodes and the conductive particles when the electrodes are connected. There is no need for heating.
- the “average diameter (average particle diameter)” of the insulating material indicates a number average diameter (number average particle diameter).
- the average diameter of the insulating material is obtained using a particle size distribution measuring device or the like.
- the conductive material according to the present invention includes the conductive particles described above and a binder resin.
- the conductive particles according to the present invention are preferably added to a binder resin and used as a conductive material.
- the conductive material according to the present invention is preferably an anisotropic conductive material.
- the binder resin is not particularly limited.
- a known insulating resin is used.
- the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers.
- the said binder resin only 1 type may be used and 2 or more types may be used together.
- Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
- examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
- examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
- the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
- the curable resin may be used in combination with a curing agent.
- thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
- the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
- the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
- a filler for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
- Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
- the method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used.
- Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse
- distributing is mentioned.
- the conductive material according to the present invention can be used as a conductive paste and a conductive film.
- a film-like adhesive such as a conductive film
- a film-like adhesive containing no conductive particles is added to the film-like adhesive containing the conductive particles. It may be laminated.
- the conductive paste is preferably an anisotropic conductive paste.
- the conductive film is preferably an anisotropic conductive film.
- the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less.
- the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
- the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 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 conduction reliability between the electrodes is further enhanced.
- connection structure can be obtained by connecting the connection target members using the conductive particles of the present invention or using a conductive material containing the conductive particles and a binder resin.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection portion is a conductive member of the present invention. It is preferable that the connection structure be formed of conductive particles or formed of a conductive material containing the conductive particles and a binder resin. In the case where conductive particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
- the conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.
- FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
- connection portion 54 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 that connects the first and second connection target members 52 and 53.
- the connection portion 54 is formed by curing a conductive material including the conductive particles 1.
- the conductive particles 1 are schematically shown for convenience of illustration.
- the first connection target member 52 has a plurality of electrodes 52b on the upper surface 52a (front surface).
- the second connection target member 53 has a plurality of electrodes 53b on the lower surface 53a (front surface).
- the electrode 52 b and the electrode 53 b are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
- the manufacturing method of the connection structure is not particularly limited.
- the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
- the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
- the heating temperature is about 120 to 220 ° C.
- connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, and glass boards.
- the conductive material is preferably a conductive material for connecting electronic components.
- the conductive material is a paste-like conductive paste, and is preferably applied on the connection target member in a paste-like state.
- 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, and a tungsten electrode.
- the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
- the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum 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. Examples of the trivalent metal element include Sn, Al, and Ga.
- Example 1 Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium tungstate was prepared.
- the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) on the surface of the resin particles. It was.
- Example 2 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 1 except that the sodium tungstate concentration is changed to 0.12 mol / L. Obtained.
- Example 3 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 1 except that the sodium tungstate concentration is changed to 0.23 mol / L. Obtained.
- Example 4 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 1 except that the sodium tungstate concentration is changed to 0.35 mol / L. Obtained.
- Nickel-boron-tungsten was formed on the surface of the resin particles in the same manner as in Example 1 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium tungstate concentration was changed to 0.35 mol / L. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Example 6 Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Electroless nickel plating step In the same manner as in Example 1, conductive particles in which a nickel-boron-tungsten conductive layer (thickness: 0.1 ⁇ m) was disposed on the surface of the resin particles were obtained.
- Example 7 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 6 except that the sodium tungstate concentration is changed to 0.35 mol / L. Obtained.
- Example 8 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 6 10 g of the conductive particles obtained in Example 6 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 9 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 1 except that the sodium tungstate concentration is changed to 0.46 mol / L. Obtained.
- Example 10 In the same manner as in Example 1 except that the dimethylamine borane concentration was changed to 4.60 mol / L and the sodium tungstate concentration was changed to 0.23 mol / L, nickel-boron-tungsten was formed on the surface of the resin particles. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Comparative Example 2 A conductive layer (thickness: 0.1 ⁇ m) containing nickel and boron was disposed on the surface of the resin particles in the same manner as in Example 1 except that 0.01 mol / L of sodium tungstate in the nickel plating solution was not used. Conductive particles were obtained.
- Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium molybdate was prepared.
- the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to remove the particles, washed with water, and dried to obtain conductive particles in which a nickel-boron-molybdenum conductive layer (thickness 0.1 ⁇ m) is disposed on the surface of the resin particles. It was.
- Example 12 Conductive particles in which a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) is arranged on the surface of the resin particles are the same as in Example 11 except that the sodium molybdate concentration is changed to 0.12 mol / L. Obtained.
- Example 13 Conductive particles in which a nickel-boron-molybdenum conductive layer (thickness 0.1 ⁇ m) is arranged on the surface of the resin particles are the same as in Example 11 except that the sodium molybdate concentration is changed to 0.23 mol / L. Obtained.
- Example 14 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.35 mol / L. Obtained.
- Nickel-boron-molybdenum was formed on the surface of the resin particles in the same manner as in Example 11 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium molybdate concentration was changed to 0.35 mol / L. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Example 16 (1) Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Example 17 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 16 except that the sodium molybdate concentration was changed to 0.35 mol / L. Obtained.
- Example 18 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 16 10 g of the conductive particles obtained in Example 16 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 19 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.46 mol / L. Obtained.
- Nickel-boron-molybdenum was formed on the surface of the resin particles in the same manner as in Example 11 except that the dimethylamine borane concentration was changed to 4.60 mol / L and the sodium molybdate concentration was changed to 0.23 mol / L. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- the plating state of 50 conductive particles obtained was observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or plating peeling was observed. The case where the number of conductive particles in which plating unevenness was confirmed was 4 or less was judged as “good”, and the case where the number of conductive particles in which plating unevenness was confirmed was 5 or more was judged as “bad”.
- the obtained anisotropic conductive material was stored at 25 ° C. for 72 hours. After storage, it was evaluated whether or not the conductive particles aggregated in the anisotropic conductive material were settled. The case where the aggregated conductive particles were not settled was judged as “good”, and the case where the aggregated conductive particles were settled was judged as “bad”.
- connection resistance Fabrication of connection structure 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP” manufactured by HX3941) and 2 parts by weight of a silane coupling agent (“SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight.
- a resin composition was obtained by dispersing.
- the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
- the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
- the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
- a two-layer flexible printed board width 2 cm, length 1 cm having the same aluminum electrode was bonded after being aligned so that the electrodes overlap each other.
- the laminated body of this glass substrate and the two-layer flexible printed board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
- a two-layer flexible printed board in which an aluminum electrode is directly formed on a polyimide film was used.
- connection resistance measurement The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Further, the connection resistance was determined according to the following criteria.
- connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- Impact resistance was evaluated by dropping the connection structure obtained in the above (6) connection resistance evaluation from a position of 70 cm in height and confirming conduction. The case where the rate of increase in resistance value from the initial resistance value was 50% or less was determined as “good”, and the case where the rate of increase in resistance value from the initial resistance value exceeded 50% was determined as “bad”.
- the conductive particles of Examples 21 to 40 and Comparative Examples 4 to 6 were prepared separately from the conductive particles of Examples 1 to 20 and Comparative Examples 1 to 3.
- Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium tungstate was prepared.
- the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) on the surface of the resin particles. It was.
- Example 22 Conductive particles having a nickel-boron-tungsten conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 21 except that the sodium tungstate concentration was changed to 0.12 mol / L. Obtained.
- Example 23 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles were obtained in the same manner as in Example 21 except that the sodium tungstate concentration was changed to 0.23 mol / L. Obtained.
- Example 24 Conductive particles having a nickel-boron-tungsten conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 21 except that the sodium tungstate concentration was changed to 0.35 mol / L. Obtained.
- Nickel-boron-tungsten was formed on the surface of the resin particles in the same manner as in Example 21 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium tungstate concentration was changed to 0.35 mol / L. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Example 26 (1) Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Electroless nickel plating step In the same manner as in Example 21, conductive particles in which a nickel-boron-tungsten conductive layer (thickness: 0.1 ⁇ m) was disposed on the surface of the resin particles were obtained.
- Example 27 Conductive particles having a nickel-boron-tungsten conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 26 except that the sodium tungstate concentration is changed to 0.35 mol / L. Obtained.
- Example 28 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 26 10 g of the conductive particles obtained in Example 26 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 29 Conductive particles having a nickel-boron-tungsten conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles are the same as in Example 21 except that the sodium tungstate concentration is changed to 0.46 mol / L. Obtained.
- Example 30 In the same manner as in Example 21, except that the dimethylamine borane concentration was changed to 4.60 mol / L and the sodium tungstate concentration was changed to 0.23 mol / L, nickel-boron-tungsten was formed on the surface of the resin particles. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Example 4 In the same manner as in Example 21 except that 0.92 mol / L of dimethylamine borane in the nickel plating solution was changed to 0.5 mol / L of sodium hypophosphite, nickel, tungsten and phosphorus were added to the surface of the resin particles.
- positioned was obtained.
- the phosphorus content in the entire conductive layer of 100% by weight was 8.7% by weight.
- Example 5 A conductive layer (thickness 0.1 ⁇ m) containing nickel and boron was disposed on the surface of the resin particles in the same manner as in Example 21 except that 0.01 mol / L of sodium tungstate in the nickel plating solution was not used. Conductive particles were obtained.
- Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium molybdate was prepared.
- the nickel plating solution was gradually dropped into the suspension to perform electroless nickel plating. Thereafter, the suspension is filtered to remove the particles, washed with water, and dried to obtain conductive particles in which a nickel-boron-molybdenum conductive layer (thickness 0.1 ⁇ m) is disposed on the surface of the resin particles. It was.
- Example 32 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 31 except that the sodium molybdate concentration was changed to 0.12 mol / L. Obtained.
- Example 33 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 31 except that the sodium molybdate concentration was changed to 0.23 mol / L. Obtained.
- Example 34 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles were obtained in the same manner as in Example 31 except that the sodium molybdate concentration was changed to 0.35 mol / L. Obtained.
- Nickel-boron-molybdenum was formed on the surface of the resin particles in the same manner as in Example 31 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium molybdate concentration was changed to 0.35 mol / L. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- Example 36 (1) Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Example 37 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 36 except that the sodium molybdate concentration was changed to 0.35 mol / L. Obtained.
- Example 38 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 36 10 g of the conductive particles obtained in Example 36 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 39 Conductive particles having a nickel-boron-molybdenum conductive layer (thickness: 0.1 ⁇ m) disposed on the surface of the resin particles in the same manner as in Example 31 except that the sodium molybdate concentration was changed to 0.46 mol / L. Obtained.
- Example 40 In the same manner as in Example 31, except that the dimethylamine borane concentration was changed to 4.60 mol / L and the sodium molybdate concentration was changed to 0.23 mol / L, nickel-boron-molybdenum was formed on the surface of the resin particles. Conductive particles having a conductive layer (thickness 0.1 ⁇ m) were obtained.
- the plating state of 50 conductive particles obtained was observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or plating peeling was observed. The case where the number of conductive particles in which plating unevenness was confirmed was 4 or less was judged as “good”, and the case where the number of conductive particles in which plating unevenness was confirmed was 5 or more was judged as “bad”.
- the obtained anisotropic conductive material was stored at 25 ° C. for 72 hours. After storage, it was evaluated whether or not the conductive particles aggregated in the anisotropic conductive material were settled. The case where the aggregated conductive particles were not settled was judged as “good”, and the case where the aggregated conductive particles were settled was judged as “bad”.
- connection structure 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP” manufactured by HX3941) and 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight.
- a resin composition was obtained by dispersing.
- the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
- the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
- the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
- a two-layer flexible printed board (width 2 cm, length 1 cm) having the same aluminum electrode was aligned and aligned so that the electrodes overlapped.
- the laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
- a two-layer flexible printed board in which an aluminum electrode is directly formed on a polyimide film was used.
- connection resistance measurement The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. The initial connection resistance was determined according to the following criteria.
- connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 4.0 ⁇ or less ⁇ ⁇ : Connection resistance is 4.0 ⁇ Exceeding 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- connection resistance after high-temperature and high-humidity test The connection structure obtained by producing the connection structure (6) was allowed to stand for 100 hours under the conditions of 85 ° C and 85% humidity. The connection resistance between the electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measurement value was used as the connection resistance after the high temperature and high humidity test. Moreover, the connection resistance after a high temperature, high humidity test was determined according to the following criteria.
- connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 4.0 ⁇ or less ⁇ ⁇ : Connection resistance is 4.0 ⁇ Exceeding 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- connection structure obtained by the preparation of the connection structure (6) was dropped from a position of 70 cm in height, and the impact resistance was evaluated by confirming conduction. The case where the rate of increase in resistance value from the initial resistance value was 50% or less was determined as “good”, and the case where the rate of increase in resistance value from the initial resistance value exceeded 50% was determined as “bad”.
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Abstract
Description
F:導電性粒子が10%圧縮変形したときの荷重値(N)
S:導電性粒子が10%圧縮変形したときの圧縮変位(mm)
R:導電性粒子の半径(mm)
L1:負荷を与えるときの原点用荷重値から反転荷重値に至るまでのまでの圧縮変位
L2:負荷を解放するときの反転荷重値から原点用荷重値に至るまでの除荷変位
F:導電性粒子が5%圧縮変形したときの荷重値(N)
S:導電性粒子が5%圧縮変形したときの圧縮変位(mm)
R:導電性粒子の半径(mm)
上記基材粒子としては、樹脂粒子、金属粒子を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。上記基材粒子は、金属粒子を除く基材粒子であることが好ましく、樹脂粒子、金属粒子を除く無機粒子又は有機無機ハイブリッド粒子であることが好ましい。
本発明に係る導電性粒子は、基材粒子の表面上に配置されており、かつニッケルとボロンとタングステン及びモリブデンの内の少なくとも1種の金属成分Mとを含む導電層Xを有する。上記導電層Xは、基材粒子の表面に直接積層されていてもよく、他の導電層などを介して基材粒子の表面上に配置されていてもよい。さらに、上記導電層Xの表面上に他の導電層が配置されていてもよい。上記導電層Xの外側の表面上に他の導電層が配置されていないことが好ましい。導電性粒子の外表面がニッケルを含む導電層Xであることが好ましい。ニッケルを含む導電層Xを有する導電性粒子により電極間を接続した場合には、接続抵抗がより一層低くなる。
上記芯物質が上記導電層中に埋め込まれていることによって、上記導電層が外表面に複数の突起を有するようにすることが容易である。但し、導電性粒子及び導電層の表面に突起を形成するために、芯物質を必ずしも用いなくてもよい。
本発明に係る導電性粒子は、上記導電層の表面上に配置された絶縁物質を備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、2つの電極で導電性粒子を加圧することにより、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。導電性粒子が導電層の外表面に複数の突起を有するので、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。
本発明に係る導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。本発明に係る導電性粒子は、バインダー樹脂中に添加され、導電材料として用いられることが好ましい。本発明に係る導電材料は、異方性導電材料であることが好ましい。
本発明の導電性粒子を用いて、又は該導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
タングステン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにタングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例6と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
タングステン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を4.60mol/Lを変更したこと、並びにタングステン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケルとタングステンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。導電層の全体100重量%におけるリンの含有量は8.9重量%であった。
ニッケルめっき液におけるタングステン酸ナトリウム0.01mol/Lを用いなかったこと以外は実施例1と同様にして、樹脂粒子の表面にニッケルとボロンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
モリブデン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにモリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例16と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
モリブデン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を4.60mol/Lを変更したこと、並びにモリブデン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケルとモリブデンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。導電層の全体100重量%におけるリンの含有量は9.5重量%であった。
(1)導電性粒子の圧縮弾性率(5%K値)
得られた導電性粒子の圧縮弾性率(5%K値)を、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
台の上に導電性粒子を置いた。微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて、圧縮速度0.33mN/秒及び最大試験荷重10mNの条件で、円柱(直径50μm、ダイヤモンド製)を圧縮部材として、該圧縮部材の平滑端面を導電性粒子に向かって降下させた。平滑端面により導電性粒子を圧縮した。導電性粒子の導電層に割れが生じるまで圧縮を行った。圧縮方向における圧縮前の導電性粒子の粒子径に対して、導電層に割れが生じた導電性粒子の上記圧縮変位を下記の表1,2に示した。上記圧縮変位の評価結果については、3つの導電性粒子の測定値の平均値を下記の表1,2に示した。
60%硝酸5mLと37%塩酸10mLとの混合液に、導電性粒子5gを加え、導電層を完全に溶解させ、溶液を得た。得られた溶液を用いて、ニッケル、ボロン、リン、タングステン及びモリブデンの含有量をICP-MS分析器(日立製作所社製)により分析した。なお、実施例の導電性粒子における導電層はリンを含んでいなかった。
得られた導電性粒子50個のめっき状態を、走査型電子顕微鏡により観察した。めっき割れ又はめっき剥がれ等のめっきむらの有無を観察した。めっきむらが確認された導電性粒子が4個以下の場合を「良好」、めっきむらが確認された導電性粒子が5個以上の場合を「不良」と判定した。
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、異方性導電材料を得た。
接続構造体の作製:
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、樹脂組成物を得た。
得られた接続構造体の対向する電極間の接続抵抗を4端子法により測定した。また、接続抵抗を下記の基準で判定した。
○○:接続抵抗が2.0Ω以下
○:接続抵抗が2.0Ωを超え、3.0Ω以下
△:接続抵抗が3.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(6)接続抵抗の評価で得られた接続構造体を高さ70cmの位置から落下させ、導通を確認することにより耐衝撃性の評価を行った。初期抵抗値からの抵抗値の上昇率が50%以下の場合を「良好」、初期抵抗値からの抵抗値の上昇率が50%を超える場合を「不良」と判定した。
微分干渉顕微鏡を用いて、上記(6)接続抵抗の評価で得られた接続構造体のガラス基板側から、ガラス基板に設けられた電極を観察し、導電性粒子が接触した電極の圧痕の形成の有無を下記の基準で判定した。なお、電極の圧痕の形成の有無について、電極面積が0.02mm2となるように、微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数を算出した。任意の10箇所を微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数の平均値を算出した。
○○:電極0.02mm2あたりの圧痕が25個以上
○:電極0.02mm2あたりの圧痕が20個以上、25個未満
△:電極0.02mm2あたりの圧痕が5個以上、20個未満
×:電極0.02mm2あたりの圧痕が5個未満
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
タングステン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにタングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例26と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
タングステン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を4.60mol/Lを変更したこと、並びにタングステン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケル-ボロン-タングステン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例21と同様にして、樹脂粒子の表面にニッケルとタングステンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。導電層の全体100重量%におけるリンの含有量は8.7重量%であった。
ニッケルめっき液におけるタングステン酸ナトリウム0.01mol/Lを用いなかったこと以外は実施例21と同様にして、樹脂粒子の表面にニッケルとボロンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
モリブデン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにモリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例36と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
モリブデン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ジメチルアミンボラン濃度を4.60mol/Lを変更したこと、並びにモリブデン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケル-ボロン-モリブデン導電層(厚み0.1μm)が配置された導電性粒子を得た。
ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例31と同様にして、樹脂粒子の表面にニッケルとモリブデンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。導電層の全体100重量%におけるリンの含有量は9.5重量%であった。
(1)導電性粒子の圧縮弾性率(10%K値)
得られた導電性粒子の圧縮弾性率(10%K値)を、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
得られた導電性粒子を30%圧縮したときの圧縮回復率を、微小圧縮試験機(フィッシャー社製「フィッシャースコープH-100」)を用いて測定した。
60%硝酸5mLと37%塩酸10mLとの混合液に、導電性粒子5gを加え、導電層を完全に溶解させ、溶液を得た。得られた溶液を用いて、ニッケル、ボロン、リン、タングステン及びモリブデンの含有量をICP-MS分析器(日立製作所社製)により分析した。なお、実施例の導電性粒子における導電層はリンを含んでいなかった。
得られた導電性粒子50個のめっき状態を、走査型電子顕微鏡により観察した。めっき割れ又はめっき剥がれ等のめっきむらの有無を観察した。めっきむらが確認された導電性粒子が4個以下の場合を「良好」、めっきむらが確認された導電性粒子が5個以上の場合を「不良」と判定した。
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、異方性導電材料を得た。
接続構造体の作製:
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、樹脂組成物を得た。
得られた接続構造体の対向する電極間の接続抵抗を4端子法により測定した。また、初期の接続抵抗を下記の基準で判定した。
○○:接続抵抗が2.0Ω以下
○:接続抵抗が2.0Ωを超え、3.0Ω以下
△:接続抵抗が3.0Ωを超え、4.0Ω以下
△△:接続抵抗が4.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(6)接続構造体の作製で得られた接続構造体を、85℃及び湿度85%の条件で100時間放置した。放置後の接続構造体の電極間の接続抵抗を4端子法により測定し、得られた測定値を高温高湿試験後の接続抵抗とした。また、高温高湿試験後の接続抵抗を下記の基準で判定した。
○○:接続抵抗が2.0Ω以下
○:接続抵抗が2.0Ωを超え、3.0Ω以下
△:接続抵抗が3.0Ωを超え、4.0Ω以下
△△:接続抵抗が4.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(6)接続構造体の作製で得られた接続構造体を高さ70cmの位置から落下させ、導通を確認することにより耐衝撃性の評価を行った。初期抵抗値からの抵抗値の上昇率が50%以下の場合を「良好」、初期抵抗値からの抵抗値の上昇率が50%を超える場合を「不良」と判定した。
微分干渉顕微鏡を用いて、上記(6)接続構造体の作製で得られた接続構造体のガラス基板側から、ガラス基板に設けられた電極を観察し、導電性粒子が接触した電極の圧痕の形成の有無を下記の基準で判定した。なお、電極の圧痕の形成の有無について、電極面積が0.02mm2となるように、微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数を算出した。任意の10箇所を微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数の平均値を算出した。
○○:電極0.02mm2あたりの圧痕が25個以上
○:電極0.02mm2あたりの圧痕が20個以上、25個未満
△:電極0.02mm2あたりの圧痕が5個以上、20個未満
×:電極0.02mm2あたりの圧痕が1個以上、5個未満
××:電極0.02mm2あたりの圧痕が0個
1a…突起
2…基材粒子
3…導電層
3a…突起
4…芯物質
5…絶縁物質
11…導電性粒子
11a…突起
12…第2の導電層
13…導電層
13a…突起
21…導電性粒子
22…導電層
22a…割れ
51…接続構造体
52…第1の接続対象部材
52a…上面
52b…電極
53…第2の接続対象部材
53a…下面
53b…電極
54…接続部
71…台
72…圧縮部材
72a…平滑端面
Claims (14)
- 基材粒子と、
前記基材粒子の表面上に配置されており、かつニッケルと、ボロンと、タングステン及びモリブデンの内の少なくとも1種の金属成分とを含む導電層とを有する、導電性粒子。 - 前記導電層の全体100重量%中の前記ボロンの含有量が0.05重量%以上、4重量%以下である、請求項1に記載の導電性粒子。
- 前記導電層の全体100重量%中の前記金属成分の含有量が0.1重量%以上、30重量%以下である、請求項1又は2に記載の導電性粒子。
- 前記導電層の全体100重量%中の前記金属成分の含有量が5重量%を超え、30重量%以下である、請求項1又は2に記載の導電性粒子。
- 前記金属成分がタングステンを含む、請求項1~4のいずれか1項に記載の導電性粒子。
- 10%圧縮変形したときの圧縮弾性率が5000N/mm2以上、15000N/mm2以下である、請求項1~5のいずれか1項に記載の導電性粒子。
- 圧縮回復率が5%以上、70%以下である、請求項1~6のいずれか1項に記載の導電性粒子。
- 前記金属成分がモリブデンを含む、請求項1~7のいずれか1項に記載の導電性粒子。
- 前記導電層がニッケルとモリブデンとを含み、
前記導電層の全体100重量%中、ニッケルの含有量が70重量%以上、99.9重量%以下であり、モリブデンの含有量が0.1重量%以上、30重量%以下である、請求項1~8のいずれか1項に記載の導電性粒子。 - 5%圧縮されたときの圧縮弾性率が7000N/mm2以上であり、かつ、圧縮方向における圧縮前の導電性粒子の粒子径の10%を超え、25%以下で導電性粒子が圧縮されたときに、前記導電層に割れが生じる、請求項1~9のいずれか1項に記載の導電性粒子。
- 前記導電層の厚みが0.05μm以上、0.5μm以下である、請求項1~10のいずれか1項に記載の導電性粒子。
- 前記導電層が外表面に突起を有する、請求項1~11のいずれか1項に記載の導電性粒子。
- 請求項1~12のいずれか1項に記載の導電性粒子と、バインダー樹脂とを含む、導電材料。
- 第1の接続対象部材と、第2の接続対象部材と、前記第1,第2の接続対象部材を接続している接続部とを備え、
前記接続部が、請求項1~12のいずれか1項に記載の導電性粒子により形成されているか、又は前記導電性粒子とバインダー樹脂とを含む導電材料により形成されている、接続構造体。
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JP2013232408A (ja) * | 2011-12-21 | 2013-11-14 | Sekisui Chem Co Ltd | 導電性粒子、導電材料及び接続構造体 |
WO2014115467A1 (ja) * | 2013-01-24 | 2014-07-31 | 積水化学工業株式会社 | 基材粒子、導電性粒子、導電材料及び接続構造体 |
JP5571271B1 (ja) * | 2013-01-24 | 2014-08-13 | 積水化学工業株式会社 | 基材粒子、導電性粒子、導電材料及び接続構造体 |
JP2014207222A (ja) * | 2013-03-19 | 2014-10-30 | 積水化学工業株式会社 | 接続構造体の製造方法及び接続構造体 |
JP2015005503A (ja) * | 2013-05-22 | 2015-01-08 | 積水化学工業株式会社 | 接続構造体 |
JP2015028920A (ja) * | 2013-06-26 | 2015-02-12 | 積水化学工業株式会社 | 接続構造体 |
JP2015118933A (ja) * | 2013-11-18 | 2015-06-25 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP2019021635A (ja) * | 2013-11-18 | 2019-02-07 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP2015130328A (ja) * | 2013-12-03 | 2015-07-16 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
WO2015174195A1 (ja) * | 2014-05-12 | 2015-11-19 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP5996806B2 (ja) * | 2014-05-12 | 2016-09-21 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JPWO2015174195A1 (ja) * | 2014-05-12 | 2017-04-20 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
TWI665685B (zh) * | 2014-05-12 | 2019-07-11 | 日商積水化學工業股份有限公司 | Conductive particles, conductive materials, and connection structures |
Also Published As
Publication number | Publication date |
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CN103650063A (zh) | 2014-03-19 |
KR101626266B1 (ko) | 2016-05-31 |
TW201310467A (zh) | 2013-03-01 |
JP5216165B1 (ja) | 2013-06-19 |
CN103650063B (zh) | 2016-01-20 |
KR20140043305A (ko) | 2014-04-09 |
KR101962977B1 (ko) | 2019-03-27 |
KR20150052363A (ko) | 2015-05-13 |
JPWO2013015304A1 (ja) | 2015-02-23 |
TWI511166B (zh) | 2015-12-01 |
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