JP6357413B2 - Conductive material and connection structure - Google Patents

Description

  The present invention relates to a conductive material containing conductive particles and a binder resin. The present invention also relates to a connection structure using the conductive material.

  Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin.

  The anisotropic conductive material is used to electrically connect electrodes of various connection target members such as a flexible printed circuit (FPC), a glass substrate, a glass epoxy substrate, and a semiconductor chip to obtain a connection structure. ing. Moreover, as the conductive particles, conductive particles having base particles and a conductive layer disposed on the surface of the base particles may be used.

As an example of the anisotropic conductive material, the following Patent Document 1 discloses an anisotropic conductive material including conductive particles in which a conductive metal layer is formed on the surface of resin particles and a binder resin. Yes. The particle diameter of the resin particles is 1.0 μm to 2.5 μm. The 10% K value of the resin particles is 10000 N / mm ² or more. The ratio of the breaking point load (mN) of the resin particles to the average particle diameter (μm) of the resin particles (breaking point load (mN) / average particle diameter (μm)) is 4 or more.

  Patent Document 2 below discloses an anisotropic conductive film in which a conductive adhesive layer and an insulating adhesive layer are laminated. The conductive adhesive layer includes conductive particles and a binder resin. The binder resin contained in the conductive adhesive layer includes an epoxy resin, a phenoxy resin, and a curing agent. The insulating adhesive layer includes a binder resin. The binder resin contained in the insulating adhesive layer includes an epoxy resin, a phenoxy resin, and a curing agent. The melt viscosity when the binder component is connected is 500 poises or less. The insulating adhesive layer has a melt viscosity equivalent to that of the conductive adhesive layer.

  Patent Document 3 below discloses an anisotropic conductive material including conductive particles in which organic polymer particles (B) are covered with a conductive metal (C) and a binder resin. The organic polymer particles (B) are particles in which the shell is the inorganic compound (A), the core is the organic polymer (b), and the core is covered with the shell.

JP 2012-190560 A JP 2010-10142 A JP 2006-156068 A

  In recent years, connection target members such as substrates bonded by anisotropic conductive materials have been made thinner. Furthermore, a relatively soft resin substrate has been used as a connection target member. For this reason, when the electrodes of the connection target members are electrically connected using a conventional anisotropic conductive material, the conductive particles are pushed into the connection target members during compression, and the stress is easily dispersed. As a result, the resin component in the anisotropic conductive material between the conductive particles and the electrode may not be sufficiently excluded. For this reason, a resin component may be pinched | interposed between electroconductive particle and an electrode. Therefore, in the obtained connection structure, the connection resistance between electrodes may become high.

  In general, when the conductive particles are hardened, the resin component between the conductive particles and the electrode is highly excluded. However, when a thin substrate or a resin substrate is bonded, the conductive particles are excessively pushed into the substrate at the time of compression, so that cracks are likely to occur in the wiring, and the connection resistance between the electrodes tends to be high.

  If the viscosity of the adhesive is lowered in order to enhance the resin component exclusion, it is easy for the conductive particles to flow out, and in addition, air bubbles are likely to be included in the space, reducing the connection reliability, and in particular the moisture resistance. There is a disadvantage that the performance is lowered.

  The object of the present invention is to prevent the occurrence of cracks due to deformation of the substrate even when a thin substrate or a resin substrate is used, and to reliably eliminate the resin component, thereby reducing the connection resistance after connecting the electrodes. It is possible to provide a conductive material that can increase connection reliability by increasing moisture resistance. Another object of the present invention is to provide a connection structure using the conductive material.

According to a broad aspect of the present invention, the conductive particle includes a binder resin, and the conductive particle includes a base particle and a conductive layer disposed on a surface of the base particle, and the group The material particles are core-shell particles having a core and a shell disposed on the surface of the core, and the compressive elastic modulus when the conductive particles are compressed by 10% is 4000 N / mm ² or more, and the conductive The ratio of the compressive load value when the conductive particles are compressed by 40% to the compressive load value when the conductive particles are compressed by 10% is 5.5 or less, and the melt viscosity at 100 ° C. of the binder resin is 50 Pa · s. There is provided a conductive material that is at least 1000 Pa · s.

  In a specific aspect of the conductive material according to the present invention, the core is an organic core, and the shell is an inorganic shell.

  On the specific situation with the electrically-conductive material which concerns on this invention, the thickness of the said shell is 100 nm or more and 3 micrometers or less.

  On the specific situation with the electrically-conductive material which concerns on this invention, the said electroconductive particle is further equipped with the insulating substance arrange | positioned on the outer surface of the said electroconductive layer.

  On the specific situation with the electrically-conductive material which concerns on this invention, the said electroconductive particle has a processus | protrusion on the outer surface of the said conductive layer.

  According to a wide aspect of the present invention, a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the A connection portion connecting the second connection target member, the connection portion is formed of the conductive material described above, and the first electrode and the second electrode are the conductive A connection structure is provided that is electrically connected by particles.

  In a specific aspect of the connection structure according to the present invention, at least one of the first connection target member and the second connection target member is a resin substrate or a glass substrate.

  In a specific aspect of the connection structure according to the present invention, at least one of the first electrode and the second electrode, the metal constituting the electrode surface in contact with the conductive particles is tin-doped oxidation. Indium, titanium or molybdenum is included.

The conductive material according to the present invention includes conductive particles and a binder resin, and the conductive particles include base particles and a conductive layer disposed on the surface of the base particles. A core-shell particle having a core and a shell disposed on the surface of the core, the compressive elastic modulus when compressing the conductive particle by 10% is 4000 N / mm ² or more, and the conductive particle is 40 The ratio of the compressive load value when compressed to 10% to the compressive load value when the conductive particles are compressed by 10% is 5.5 or less, and the melt viscosity at 100 ° C. of the binder resin is 50 Pa · s or more and 1000 Pa. -Since it is below s, the connection resistance after connecting between electrodes can be made low.

FIG. 1 is a cross-sectional view showing an example of conductive particles contained in a conductive material according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a modification of the conductive particles. FIG. 3 is a cross-sectional view showing another modification of the conductive particles. FIG. 4 is a cross-sectional view schematically showing a connection structure using a conductive material including the conductive particles shown in FIG.

  Details of the present invention will be described below.

(Conductive material)
The conductive material according to the present invention includes conductive particles and a binder resin. The conductive particles include base particles and a conductive layer disposed on the surface of the base particles. The base particle is a core-shell particle having a core and a shell disposed on the surface of the core. The compression elastic modulus (10% K value) when the conductive particles are compressed by 10% is 4000 N / mm ² or more. Ratio of compressive load value (40% load value) when 40% of the conductive particles are compressed to compressive load value (10% load value) when the conductive particles are compressed 10% (40% load value / 10) % Load value) is 5.5 or less. The binder resin has a melt viscosity at 100 ° C. of 50 Pa · s or more and 1000 Pa · s or less.

  Since the conductive material according to the present invention has the above-described configuration, even when a thin substrate or a resin substrate is used, the generation of cracks due to the deformation of the substrate is prevented, and the resin component is reliably eliminated, so that the electrode It is possible to reduce the connection resistance after connecting the gaps, and it is possible to increase the connection reliability by increasing the moisture resistance. The conductive particles contained in the conductive material according to the present invention are relatively hard at the initial stage of compression and relatively flexible at the later stage of compression. Therefore, in the conductive material according to the present invention, even when a thin substrate or a resin substrate is connected, the member to be connected is deformed during compression, and the conductive particles are not easily pushed into the member to be connected. The resin component in the conductive material between the electrode and the electrode can be sufficiently removed. For this reason, in the obtained connection structure, the connection resistance between electrodes becomes low. Further, in the conductive material according to the present invention, since the melt viscosity of the binder resin is within the above-described range, the binder resin does not flow excessively when the bonding target member is bonded, and is disposed between the connection target members. A large amount of binder resin can be retained. For this reason, the adhesive force with respect to the connection object member of an electrically-conductive material can be raised.

  Hereinafter, the detail of the electroconductive particle and binder resin which are used for the electrically-conductive material which concerns on this invention is demonstrated.

[Conductive particles]
The conductive particles include base particles and a conductive layer disposed on the surface of the base particles. The base particle is a core-shell particle having a core and a shell disposed on the surface of the core.

The compression elastic modulus (10% K value) when the conductive particles are compressed by 10% is 4000 N / mm ² or more. The 10% K value is preferably 6000 N / mm ² or more. The 10% K value is preferably 15000 N / mm ² or less. When the 10% K value is equal to or more than the above lower limit, the binder resin is effectively excluded at the time of connection, and the conductive film or the oxide film on the surface of the electrode is effectively penetrated. Lower. When the 10% K value is less than or equal to the above upper limit, cracks are more unlikely to occur in the electrode.

  Ratio of compressive load value (40% load value) when 40% of the conductive particles are compressed to compressive load value (10% load value) when the conductive particles are compressed 10% (40% load value / 10) % Load value) is 5.5 or less. The ratio (40% load value / 10% load value) is preferably 4.5 or less. The ratio (40% load value / 10% load value) is preferably 0.10 or more. When the ratio (40% load value / 10% load value) is less than or equal to the above upper limit, the contact area between the electrode and the conductive particles is sufficiently large, the connection resistance between the electrodes is effectively reduced, and the electrode The connection reliability between them becomes even higher. When the ratio (40% load value / 10% load value) is equal to or higher than the lower limit, the exclusion property of the binder resin is further enhanced.

  The compressive elastic modulus (10% K value) and the compressive load value (10% load value and 40% load value) of the conductive particles can be measured as follows.

  Using a micro-compression tester, the conductive particles are compressed under the conditions of 25 ° C., compression speed of 0.3 mN / sec, and maximum test load of 20 mN on the end face of a cylindrical indenter (diameter: 100 μm, made of diamond). The load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.

10% 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 elastic modulus universally and quantitatively represents the hardness of the conductive particles. By using the compression elastic modulus, the hardness of the conductive particles can be expressed quantitatively and uniquely.

  The particle diameter of the core-shell particles is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 500 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 10 μm or less. is there. When the particle diameter of the core-shell particles is not less than the above lower limit and not more than the above upper limit, the 10% K value and the above ratio (40% load value / 10% load value) can easily exhibit suitable values, and can be electrically conductive. It becomes possible to use suitably for the connection use between the electrodes of particle | grains. For example, when the particle diameter of the core-shell particles is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes is sufficiently large, And it becomes difficult to form the agglomerated conductive particles when forming the conductive layer. 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 core-shell particle means a diameter when the core-shell particle is a spherical shape, and when the core-shell particle has a shape other than a true spherical shape, it is assumed to be a true sphere corresponding to the volume of the core-shell particle. It means the diameter of the case. Moreover, in this invention, a particle size means the average particle diameter which measured the core-shell particle with arbitrary particle size measuring apparatuses. For example, a particle size distribution measuring machine using a principle such as laser light scattering, change in electrical resistance value, image analysis after imaging, or a scanning electron microscope can be used.

  The base particle is a core-shell particle including a core and a shell disposed on the surface of the core. The core is preferably an organic core. The shell is preferably an inorganic shell. It is preferable that the core is an organic core and the shell is an inorganic shell. The substrate particles include an organic core and an inorganic shell disposed on the surface of the organic core, and are preferably core-shell particles, and are preferably core-shell type organic-inorganic hybrid particles. When the core is an organic core or the shell is an inorganic shell, the compression recovery rate is good, and the 10% K value and the ratio (40% load value / 10% load value) are the values described above. It is easy to satisfy

  The core is preferably an organic core, and is preferably an organic particle. Since the organic core and the organic particle are relatively soft compared to the inorganic core and the inorganic particle, a shell is formed on the surface of the relatively soft organic core. As a result, the ratio (40% load value / 10 % Load value) is easily satisfied.

  Various organic materials are suitably used as a material for forming the organic core. Examples of the material for forming the organic core include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, and various polymerizable monomers having an ethylenically unsaturated group are polymerized by one or more kinds. The resulting polymer is used. Easily design and synthesize base particles with any compression properties suitable for conductive materials by polymerizing one or more of various polymerizable monomers having ethylenically unsaturated groups It is.

  When the organic core is obtained by polymerizing a monomer having an ethylenically unsaturated group, the monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer. And a polymer.

  Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; oxygen such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate (Meth) acrylates; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether; vinyl acids such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate Esters; Unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; Halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene Is mentioned.

  Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanure And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane It is done.

  The organic core can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.

  From the viewpoint of suppressing the deformation of the core during the formation of the shell and the use of the base particles, the decomposition temperature of the core is preferably more than 200 ° C, more preferably more than 250 ° C, and still more preferably 300 ° C. Exceed. The decomposition temperature of the core may exceed 400 ° C., may exceed 500 ° C., may exceed 600 ° C., and may exceed 800 ° C.

  The base particles are core-shell particles. The shell is disposed on the surface of the core. The shell preferably covers the surface of the core. The shell is preferably an inorganic shell.

  The inorganic shell preferably contains 50% by weight or more of silicon atoms. In this case, the inorganic shell is an inorganic shell containing silicon atoms as a main component. The inorganic shell may contain a carbon atom, but even if it contains a carbon atom, if the non-carbon atom is the main component, for example, if the silicon atom is the main component, it is called an inorganic shell.

  The inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material. In the sol-gel method, it is easy to dispose a shell-like material on the surface of the core. In the case of performing the firing, in the base material particles, after the firing, the core remains without being removed by volatilization or the like. The said base particle is equipped with the said core after baking. If the core is removed by volatilization or the like after firing, the 10% K value becomes considerably low.

  As a specific method of the sol-gel method, an interfacial sol reaction is performed by coexisting an inorganic monomer such as tetraethoxysilane in a dispersion containing a core, a solvent such as water or alcohol, a surfactant, and a catalyst such as an aqueous ammonia solution. And a method in which a sol-gel reaction is performed with an inorganic monomer such as tetraethoxysilane coexisting with a solvent such as water or alcohol and an aqueous ammonia solution, and then the sol-gel reaction product is heteroaggregated in the core. In the sol-gel method, the metal alkoxide is preferably hydrolyzed and polycondensed.

  In the sol-gel method, it is preferable to use a surfactant. In the presence of a surfactant, the metal alkoxide is preferably made into a shell by a sol-gel method. The surfactant is not particularly limited. The surfactant is appropriately selected and used so as to form a good shell. Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among these, a cationic surfactant is preferable because a good inorganic shell can be formed.

  Examples of the cationic surfactant include quaternary ammonium salts and quaternary phosphonium salts. Specific examples of the cationic surfactant include hexadecyl ammonium bromide.

  In order to form the inorganic shell on the surface of the core, the shell-like material is preferably fired. The degree of crosslinking in the inorganic shell can be adjusted by the firing conditions. In addition, by performing the firing, the 10% K value and the ratio (40% load value / 10% load value) of the base material particles are more preferable values compared to the case where the firing is not performed. Become. In particular, the 10% K value is sufficiently increased by increasing the degree of crosslinking.

  The inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method and then firing the shell-like material at 100 ° C. or higher (firing temperature). The firing temperature is more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. When the firing temperature is equal to or higher than the lower limit, the degree of cross-linking in the inorganic shell becomes more appropriate, and the 10% K value and the ratio (40% load value / 10% load value) exhibit a more preferable value. The substrate particles can be used more suitably depending on the use of the conductive particles.

  The inorganic shell is formed on the surface of the core by forming a metal alkoxide into a shell-like material by a sol-gel method, and then firing the shell-like material at a temperature lower than the decomposition temperature (firing temperature) of the organic core. It is preferable. The firing temperature is preferably 10 ° C. or more lower than the decomposition temperature of the core, and more preferably 50 ° C. or more lower than the decomposition temperature of the core. The firing temperature is preferably 500 ° C. or lower, more preferably 300 ° C. or lower, and still more preferably 200 ° C. or lower. When the firing temperature is equal to or lower than the upper limit, it is possible to suppress thermal deterioration and deformation of the core, and conductive particles exhibiting a good value for the 10% K value and the ratio (40% load value / 10% load value). can get.

  Examples of the metal alkoxide include silane alkoxide, titanium alkoxide, zirconium alkoxide, and aluminum alkoxide. From the viewpoint of forming a good inorganic shell, the metal alkoxide is preferably a silane alkoxide, a titanium alkoxide, a zirconium alkoxide or an aluminum alkoxide, more preferably a silane alkoxide, a titanium alkoxide or a zirconium alkoxide, and a silane alkoxide. More preferably. From the viewpoint of forming a good inorganic shell, the metal atom in the metal alkoxide is preferably a silicon atom, a titanium atom, a zirconium atom or an aluminum atom, more preferably a silicon atom, a titanium atom or a zirconium atom. More preferably, it is a silicon atom. As for the said metal alkoxide, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of forming a good inorganic shell, the metal alkoxide is preferably a metal alkoxide represented by the following formula (1).

M (R1) _n (OR2) _4-n (1)

  In said formula (1), M is a silicon atom, a titanium atom, or a zirconium atom, R1 is a phenyl group, a C1-C30 alkyl group, a C1-C30 organic group which has a polymerizable double bond, or A C1-C30 organic group which has an epoxy group is represented, R2 represents a C1-C6 alkyl group, and n represents the integer of 0-2. When n is 2, the plurality of R1s may be the same or different. Several R2 may be the same and may differ.

  From the viewpoint of forming a good inorganic shell, the metal alkoxide is preferably a silane alkoxide represented by the following formula (1A).

Si (R1) _n (OR2) _4-n (1A)

  In the above formula (1A), R1 represents a phenyl group, an alkyl group having 1 to 30 carbon atoms, an organic group having 1 to 30 carbon atoms having a polymerizable double bond, or an organic group having 1 to 30 carbon atoms having an epoxy group. R2 represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. When n is 2, the plurality of R1s may be the same or different. Several R2 may be the same and may differ. In order to effectively increase the content of silicon atoms contained in the inorganic shell, n in the above formula (1A) preferably represents 0 or 1, and more preferably represents 0. When the content of silicon atoms contained in the inorganic shell is high, the effect of the present invention is more excellent.

  When R1 is an alkyl group having 1 to 30 carbon atoms, specific examples of R1 include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, n-hexyl group, cyclohexyl group, n-octyl group, And n-decyl group. This alkyl group preferably has 10 or less carbon atoms, more preferably 6 or less. The alkyl group includes a cycloalkyl group.

  Examples of the polymerizable double bond include a carbon-carbon double bond. When R1 is an organic group having 1 to 30 carbon atoms having a polymerizable double bond, specific examples of R1 include a vinyl group, an allyl group, an isopropenyl group, and a 3- (meth) acryloxyalkyl group. Etc. Examples of the (meth) acryloxyalkyl group include a (meth) acryloxymethyl group, a (meth) acryloxyethyl group, and a (meth) acryloxypropyl group. The carbon number of the organic group having 1 to 30 carbon atoms having a polymerizable double bond is preferably 2 or more, preferably 30 or less, more preferably 10 or less. The above “(meth) acryloxy” means methacryloxy or acryloxy.

  When R1 is an organic group having 1 to 30 carbon atoms having an epoxy group, specific examples of R1 include 1,2-epoxyethyl group, 1,2-epoxypropyl group, 2,3-epoxypropyl group, Examples include 3,4-epoxybutyl group, 3-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl) ethyl group. Carbon number of the C1-C30 organic group which has the said epoxy group becomes like this. Preferably it is 8 or less, More preferably, it is 6 or less. In addition, the C1-C30 organic group which has the said epoxy group is group containing the oxygen atom derived from an epoxy group in addition to a carbon atom and a hydrogen atom.

  Specific examples of R2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. In order to effectively increase the content of silicon atoms contained in the inorganic shell, R2 preferably represents a methyl group or an ethyl group.

  Specific examples of the silane alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxy. Examples include silane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, and diisopropyldimethoxysilane. Silane alkoxides other than these may be used.

  In order to effectively increase the content of silicon atoms contained in the inorganic shell, it is preferable to use tetramethoxysilane or tetraethoxysilane as the material of the inorganic shell. In 100% by weight of the inorganic shell material, the total content of tetramethoxysilane and tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient). In 100% by weight of the inorganic shell, the total content of the skeleton derived from tetramethoxysilane and the skeleton derived from tetraethoxysilane is preferably 50% by weight or more (or the total amount may be sufficient).

  Specific examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and the like. Titanium alkoxides other than these may be used.

  Specific examples of the zirconium alkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide and the like. Other zirconium alkoxides may be used.

  The metal alkoxide preferably includes a metal alkoxide having a structure in which four oxygen atoms are directly bonded to a metal atom. The metal alkoxide preferably includes a metal alkoxide represented by the following formula (1a).

M (OR2) ₄ (1a)

  In said formula (1a), M is a silicon atom, a titanium atom, or a zirconium atom, R2 represents a C1-C6 alkyl group. Several R2 may be the same and may differ.

  The metal alkoxide preferably includes a silane alkoxide having a structure in which four oxygen atoms are directly bonded to a silicon atom. In this silane alkoxide, generally, four oxygen atoms are bonded to a silicon atom by a single bond. The metal alkoxide preferably includes a silane alkoxide represented by the following formula (1Aa).

Si (OR2) ₄ (1Aa)

  In said formula (1Aa), R2 represents a C1-C6 alkyl group. Several R2 may be the same and may differ.

  From the viewpoint of effectively increasing the 10% K value and controlling the ratio (40% load value / 10% load value) to a more suitable value, the metal alkoxide 100 used for forming the inorganic shell 100 is used. In mol%, a metal alkoxide having a structure in which four oxygen atoms are directly bonded to the metal atom, a metal alkoxide represented by the formula (1a), and four oxygen atoms are directly bonded to the silicon atom. Each content of the silane alkoxide having a structure or the silane alkoxide represented by the above formula (1Aa) is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and even more preferably. Is 55 mol% or more, particularly preferably 60 mol% or more and 100 mol% or less. The total amount of metal alkoxide used to form the inorganic shell is a metal alkoxide having a structure in which four oxygen atoms are directly bonded to the metal atom, the metal alkoxide represented by the formula (1a), the silicon atom May be a silane alkoxide having a structure in which four oxygen atoms are directly bonded to each other, or a silane alkoxide represented by the above formula (1Aa).

  From the viewpoint of effectively increasing the 10% K value and controlling the ratio (40% load value / 10% load value) to a more suitable value, it is derived from the metal alkoxide contained in the inorganic shell. Ratio of the number of metal atoms in which four oxygen atoms are directly bonded in 100% of the total number of metal atoms, four —O—Si groups are directly bonded, and 4 in the four —O—Si groups The ratio of the number of silicon atoms to which two oxygen atoms are directly bonded is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55% or more, and particularly preferably 60%. % Or more.

  Further, from the viewpoint of appropriately increasing the 10% K value and controlling the ratio (40% load value / 10% load value) to a more suitable value, the metal atoms contained in the inorganic shell The ratio of the number of metal atoms in which four oxygen atoms are directly bonded to the total number of 100% is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more. It is. From the viewpoint of appropriately increasing the 10% K value and controlling the ratio (40% load value / 10% load value) to a more suitable value, the metal alkoxide is a silane alkoxide, and the inorganic shell. Of the silicon atoms in which four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded. The ratio of the number is preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, still more preferably 55% or more, and particularly preferably 60% or more.

  In addition, a silicon atom in which four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded is represented by, for example, the following formula (11). It is a silicon atom in the structure. Specifically, it is a silicon atom indicated by an arrow A in the structure represented by the following formula (11X).

  The oxygen atom in the above formula (11) generally forms a siloxane bond with the adjacent silicon atom.

  The ratio of the number of silicon atoms in which four -O-Si groups are directly bonded and the four oxygen atoms in the four -O-Si groups are directly bonded (the ratio of the number of Q4 (%)). As a measuring method, for example, using an NMR spectrum analyzer, Q4 (four -O-Si groups are directly bonded and four oxygen atoms in the four -O-Si groups are directly bonded). The peak area of silicon atoms) and Q1 to Q3 (1 to 3 —O—Si groups are directly bonded, and 1 to 3 oxygen atoms in 1 to 3 —O—Si groups are directly bonded to each other. And the peak area of silicon atoms). According to this method, in the total number of 100% of silicon atoms contained in the inorganic shell, four —O—Si groups are directly bonded and four oxygen atoms in the four —O—Si groups are directly bonded. The ratio of the number of bonded silicon atoms (the ratio of the number of Q4) can be determined.

  The thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, and particularly preferably 600 nm or less. When the thickness of the shell is not less than the above lower limit and not more than the above upper limit, the 10% K value and the above ratio (40% load value / 10% load value) exhibit a more preferable value, and the conductive particles are disposed between the electrodes. It can be suitably used for connection applications. The thickness of the shell is an average thickness per base particle. The thickness of the shell can be controlled by controlling the sol-gel method.

  In the present invention, the thickness of the shell is determined by observing the base particle and the core using a particle size distribution measuring machine using a principle such as laser light scattering, change in electric resistance value, image analysis after imaging, a scanning electron microscope, or the like. It can be obtained from the difference between the average value of the particle diameters of 50 base particles arbitrarily selected and the average value of the particle diameters of the cores. The particle diameter of the core means a diameter when the core is a perfect sphere, and means a maximum diameter when the core is a shape other than a true sphere.

  The aspect ratio of the substrate particles is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. The aspect ratio indicates a major axis / minor axis.

(Conductive particles)
The said electroconductive particle is equipped with the base material particle mentioned above and the conductive layer arrange | positioned on the surface of this base material particle.

  FIG. 1 is a sectional view showing conductive particles contained in a conductive material according to an embodiment of the present invention.

  The electroconductive particle 1 shown in FIG. 1 has the base material particle 11 and the electroconductive layer 2 arrange | positioned on the surface of the base material particle 11. FIG. The conductive layer 2 covers the surface of the base particle 11. The conductive particle 1 is a coated particle in which the surface of the base particle 11 is coated with the conductive layer 2.

  The base particle 11 includes a core 12 and a shell 13 disposed on the surface of the core 12. The shell 13 covers the surface of the core 12. The conductive layer 2 is disposed on the surface of the shell 13. The conductive layer 2 covers the surface of the shell 13.

  FIG. 2 is a sectional view showing a modification example of the conductive particles.

  The conductive particle 21 shown in FIG. 2 has the base particle 11 and the conductive layer 22 arranged on the surface of the base particle 11. The conductive layer 22 includes a first conductive layer 22A that is an inner layer and a second conductive layer 22B that is an outer layer. The base particle 11 and the shell 13 are in contact with the conductive layer 22 and the first conductive layer 22A. The first conductive layer 22 </ b> A is disposed on the surface of the base particle 11. A first conductive layer 22 </ b> A is disposed on the outer surface of the shell 13. A second conductive layer 22B is disposed on the surface of the first conductive layer 22A.

  FIG. 3 is a sectional view showing another modification example of the conductive particles.

  The conductive particles 31 shown in FIG. 3 include base material particles 11, a conductive layer 32, a plurality of core substances 33, and a plurality of insulating substances 34.

  The conductive layer 32 is disposed on the surface of the base particle 11. A conductive layer 32 is disposed on the surface of the shell 13.

  The conductive particles 31 have a plurality of protrusions 31a on the conductive surface. The conductive layer 32 has a plurality of protrusions 32a on the outer surface. Thus, the conductive particles may have protrusions on the conductive surface or may have protrusions on the outer surface of the conductive layer. A plurality of core substances 33 are arranged on the surface of the base particle 11. A plurality of core materials 33 are arranged on the outer surface of the shell 13. The plurality of core materials 33 are embedded in the conductive layer 32. The core substance 33 is disposed inside the protrusions 31a and 32a. The conductive layer 32 covers a plurality of core materials 33. The outer surface of the conductive layer 32 is raised by the plurality of core materials 33, and protrusions 31a and 32a are formed.

  The conductive particles 31 have an insulating material 34 disposed on the outer surface of the conductive layer 32. At least a part of the outer surface of the conductive layer 32 is covered with an insulating material 34. The insulating substance 34 is made of an insulating material and is an insulating particle. Thus, the said electroconductive particle may have the insulating substance arrange | positioned on the outer surface of a conductive layer.

  The metal for forming the conductive layer is not particularly limited. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and these. And the like. Examples of the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes can be made still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable.

  Like the conductive particles 1 and 31, the conductive layer may be formed of a single layer. Like the conductive particles 21, the conductive layer may be formed of a plurality of layers. That is, the conductive layer may have a stacked structure of two or more layers. When the conductive layer is formed of a plurality of layers, the outermost layer is preferably a gold layer, a nickel layer, a palladium layer, a copper layer, or an alloy layer containing tin and silver, and is a gold layer. Is more preferable. When the outermost layer is these preferred conductive layers, the connection resistance between the electrodes is further reduced. Moreover, when the outermost layer is a gold layer, the corrosion resistance is further enhanced.

  The method for forming the conductive layer on the surface of the substrate particles is not particularly limited. As 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 method of coating the surface of base particles with metal powder or a paste containing metal powder and a binder Etc. Especially, 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 0.5 μm or more, more preferably 1 μm or more, preferably 520 μm or less, more preferably 500 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 20 μm. It is as follows. When 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 electrode becomes 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. Further, when the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material. The particle diameter of the conductive particles is also preferably 5 μm or less.

  The particle diameter of the conductive particles means the diameter when the conductive particles are true spherical, and means the maximum diameter when the conductive particles have a shape other than the true spherical shape.

  The thickness of the conductive layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 0.3 μm or less. The thickness of the conductive layer is the thickness of the entire conductive layer when the conductive layer is a multilayer. When the thickness of the conductive layer is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting the electrodes. .

  When the conductive layer is formed of a plurality of layers, the thickness of the outermost conductive layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0. .1 μm or less. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating with the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes is further increased. Lower. Further, when the outermost layer is a gold layer, the thinner the gold layer, the lower the cost.

  The thickness of the conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).

  The conductive particles may have protrusions on the conductive surface. The conductive particles may have protrusions on the outer surface of the conductive layer. It is preferable that there are a plurality of the protrusions. An oxide film is often formed on the surface of the conductive layer and the surface of the electrode connected by the conductive particles. When conductive particles having protrusions are used, the oxide film is effectively eliminated by the protrusions by placing the conductive particles between the electrodes and pressing them. For this reason, an electrode and the conductive layer of electroconductive particle can be contacted still more reliably, and the connection resistance between electrodes can be made low. Furthermore, when the conductive particles are provided with an insulating material on the surface, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the conductive particles and the electrodes are separated by protrusions of the conductive particles. Insulating substances or binder resins in between can be effectively eliminated. For this reason, the conduction | electrical_connection reliability between electrodes can be improved.

  As a method of forming protrusions on the surface of the base particle, a method of forming a conductive layer by electroless plating after attaching a core substance to the surface of the base particle, and electroless on the surface of the base particle Examples include a method of forming a conductive layer by plating, attaching a core substance, and further forming a conductive layer by electroless plating. In addition, the core material may not be used to form the protrusion. When the core material is used, the core material is preferably disposed inside or inside the conductive layer.

  The conductive particles may include an insulating substance disposed on the outer surface of the conductive layer. In this case, when the conductive particles are used for connection between the electrodes, a short circuit between adjacent electrodes can be prevented. Specifically, when a plurality of conductive particles are in contact with each other, 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. In addition, the insulating substance between the conductive layer of an electroconductive particle and an electrode can be easily excluded by pressurizing electroconductive particle with two electrodes in the case of the connection between electrodes. When the conductive particles have protrusions on the surface of the conductive layer, the insulating substance between the conductive layer of the conductive particles and the electrode can be more easily eliminated. The insulating substance is preferably an insulating resin layer or insulating particles, and more preferably insulating particles. The insulating particles are preferably insulating resin particles.

  Examples of a method for disposing an insulating substance on the outer 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 outer surface of the conductive layer through a chemical bond is preferable.

  Each of the outer surface of the conductive layer and the surface of the insulating particles may be coated with a compound having a reactive functional group. The outer surface of the conductive layer and the surface of the insulating particles may not be directly chemically bonded, but may be indirectly chemically bonded by a compound having a reactive functional group. After introducing a carboxyl group into the outer surface of the conductive layer, the carboxyl group may be chemically bonded to a functional group on the surface of the insulating particle through a polymer electrolyte such as polyethyleneimine.

[Binder resin]
The binder resin has a melt viscosity at 100 ° C. of 50 Pa · s or more and 1000 Pa · s or less. From the viewpoint of further suppressing the excessive flow of the binder resin and further increasing the moisture resistance during the bonding of the bonding target member, the melt viscosity of the binder resin is preferably 80 Pa · s or more. From the viewpoint of further improving the exclusion property of the binder resin, the melt viscosity of the binder resin is preferably 800 Pa · s or less.

  For the measurement of the melt viscosity, “Digital Viscometer HV-8” manufactured by Reska Co., Ltd. is used.

  The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. As for 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 resins, ethylene-vinyl acetate copolymers, and polyamide resins. 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. Examples of the thermoplastic block copolymer 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 product of a styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

  The binder resin preferably contains a curable compound. The curable compound may be a photocurable compound or a thermosetting compound. The photocurable compound and the thermosetting compound may be used in combination. The curable compound is preferably a thermosetting compound. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  Known examples of the curable compound include epoxy resins, phenoxy resins, polyvinyl formal resins, polystyrene resins, polyvinyl butyral resins, polyester resins, polyamide resins, xylene resins, and polyurethane resins. The curable compound is appropriately selected and used so that the melt viscosity of the binder resin satisfies the above-described range. As for the said sclerosing | hardenable compound, only 1 type may be used and 2 or more types may be used together.

  The binder resin preferably contains a thermosetting agent or a photocuring initiator in order to cure the curable compound.

  The said thermosetting agent is not specifically limited. A conventionally known thermosetting agent can be used as the thermosetting agent. Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and acid anhydrides. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.

Since the conductive material can be cured more rapidly at a low temperature, the thermosetting agent is preferably an imidazole curing agent, a polythiol curing agent, or an amine curing agent. Moreover, since the storage stability of the said electrically-conductive material can be improved, a latent hardening agent is preferable.
The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent, or a latent amine curing agent. The thermosetting agent may be coated with a polymer material such as polyurethane resin or polyester resin.

  The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.

  The polythiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

  The amine curing agent is not particularly limited, and hexamethylene diamine, octamethylene diamine, decamethylene diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 30 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the curable compound. is there. When the content of the thermosetting agent is not less than the lower limit and not more than the upper limit, the conductive material is sufficiently thermoset.

  The photocuring initiator is not particularly limited. Conventionally known photocuring initiators can be used as the photocuring initiator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.

  The photocuring initiator is not particularly limited, and examples thereof include acetophenone photocuring initiator, benzophenone photocuring initiator, thioxanthone, ketal photocuring initiator, halogenated ketone, acyl phosphinoxide, and acyl phosphonate. .

  Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photocuring initiator include benzyldimethyl ketal.

  The content of the photocuring initiator is not particularly limited. The content of the photocuring initiator is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 2 parts by weight or less, more preferably 100 parts by weight of the curable compound. Is 1 part by weight or less. When the content of the photocuring initiator is not less than the lower limit and not more than the upper limit, the conductive material is appropriately photocured.

  In 100% by weight of the conductive material, 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. When 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.

  In 100% by weight of the conductive material, the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, More preferably, it is 40% by weight or less, further preferably 20% by weight or less, and particularly preferably 10% by weight or less. When 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.

  In addition to the conductive particles and the binder resin, 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. 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, kneaded and dispersed 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 is preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material. The conductive material can be used as a conductive paste and a conductive film. When the conductive material according to the present invention is a conductive film, a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles. From the viewpoint of further enhancing the exclusion of the resin component, it is preferable that the melt viscosity of the binder resin constituting the film not containing conductive particles is lower than the melt viscosity of the binder resin constituting the conductive film. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.

(Connection structure)
A connection structure can be obtained by connecting the connection target members using the conductive material described above.

  The connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the connection portion. Is preferably a connection structure formed of the conductive material described above. The conductive material used for obtaining the connection structure is preferably an anisotropic conductive material.

  The first connection target member preferably has a first electrode on the surface. The second connection target member preferably has a second electrode on the surface. It is preferable that the first electrode and the second electrode are electrically connected by the conductive particles.

  FIG. 4 is a cross-sectional view schematically showing a connection structure using a conductive material including the conductive particles 1 shown in FIG.

  The connection structure 51 shown in FIG. 4 is a connection that connects the first connection target member 52, the second connection target member 53, and the first connection target member 52 and the second connection target member 53. Part 54. The connection part 54 is formed of a conductive material containing the conductive particles 1 and a binder resin. In FIG. 4, the conductive particles 1 are schematically shown for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 21 and 31 may be used.

  The first connection target member 52 has a plurality of first electrodes 52a on the surface (upper surface). The second connection target member 53 has a plurality of second electrodes 53a on the surface (lower surface). The first electrode 52 a and the second electrode 53 a 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. As an example of a method of manufacturing a connection structure, a method of placing the conductive material between a first connection target member and a second connection target member to obtain a laminate, and then heating and pressurizing the laminate Etc. The pressure of the said pressurization is about 9.8 * 10 < ⁴ > -4.9 * 10 < ⁶ > Pa. The temperature of the said heating is about 120-220 degreeC. The pressure of the pressurization for connecting the electrode of the flexible printed board, the electrode arranged on the resin film, and the electrode of the touch panel is about 9.8 × 10 ^{4 to} 1.0 × 10 ⁶ Pa.

  Specific examples of the connection target member include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. The conductive material is preferably a conductive material for connecting electronic components. The conductive paste is a paste-like conductive material, and is preferably applied on the connection target member in a paste-like state.

  By using the conductive material according to the present invention, the effect of reducing the connection resistance due to the exclusion of the resin component can be effectively obtained. Therefore, at least one of the first connection target member and the second connection target member. One is preferably a resin substrate or a glass substrate, and it is preferable that both the first connection target member and the second connection target member are resin substrates or glass substrates. It is more preferable that at least one of the first connection target member and the second connection target member is a resin substrate, and both the first connection target member and the second connection target member are A resin substrate is particularly preferable. The material of the resin substrate is resin, and the resin substrate is formed of resin.

  Examples of the electrodes provided on the connection target member include gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, and metal electrodes such as tungsten electrodes and titanium electrodes. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of 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.

  By using the conductive material according to the present invention, the effect of reducing the connection resistance accompanying the exclusion of the resin component can be effectively obtained. Therefore, at least one of the first electrode and the second electrode, It is preferable that the metal which comprises the electrode surface which contacts electroconductive particle contains a tin dope indium oxide (ITO), titanium, or molybdenum. More preferably, the metal constituting the electrode surface in contact with the conductive particles in both the first electrode and the second electrode contains tin-doped indium oxide (ITO), titanium, or molybdenum. The electrode is preferably an ITO electrode, a titanium electrode, or a molybdenum electrode.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

Example 1
(1) Production of base particles Production of core particles
Monomer mixed solution, 20 parts by weight of benzoyl peroxide is added to a mixed liquid in which 600 parts by weight of divinylbenzene (purity 96%) and 400 parts by weight of isobornyl acrylate are mixed in advance, and stirred until it is uniformly dissolved. Got. 4000 parts by weight of a 2% by weight aqueous polyvinyl alcohol solution in which polyvinyl alcohol having a molecular weight of about 1700 was dissolved in pure water was prepared and placed in a reaction kettle. The above-mentioned monomer mixed solution was put into this, and the particle size was adjusted by stirring for 2 to 4 hours so that the monomer droplets had a predetermined particle size. Thereafter, the reaction was carried out in a nitrogen atmosphere at 85 ° C. for 9 hours, and a monomer droplet polymerization reaction was carried out to obtain polymer particles. After the obtained particles were washed several times with hot water, classification operation was performed to collect several kinds of particles having different particle diameters.

  In Example 1, the recovered polymer particles (organic core) had an average particle size of 3.00 μm and a CV value of 3.0%.

Preparation of core-shell particles)
30 parts by weight of the particles (organic core), 12 parts by weight of a surfactant hexadecyl ammonium bromide, and 24 parts by weight of a 25% by weight aqueous ammonia solution were mixed in 540 parts by weight of methanol and 60 parts by weight of pure water. A core particle dispersion was prepared. 120 parts by weight of tetraethoxysilane was added to this dispersion, and a condensation reaction by a sol-gel reaction was performed. Condensed tetraethoxysilane was deposited on the surface of the core particles, and core-shell type particles were formed. The obtained particles were washed several times with ethanol and dried to obtain core-shell particles. When the particle diameter of the core-shell particles was measured, it was 4.02 μm and the CV value was 3.2%. From the difference in particle diameter, the thickness of the shell was calculated to be 0.51 μm.

(2) Production of conductive particles After washing and drying the obtained base particles, a nickel layer was formed on the surface of the obtained base particles by electroless plating to produce conductive particles. . The nickel layer had a thickness of 0.1 μm.

(3) Production of conductive material (anisotropic conductive film) 65 parts by weight of bisphenol A type epoxy resin (“Epicoat 828” manufactured by Mitsubishi Chemical Corporation) and phenoxy resin (weight average molecular weight of about 25000) (“PKHA” manufactured by Union Carbide) ] 35 parts by weight, 200 parts by weight of methyl ethyl ketone, 2 parts by weight of a 50% by weight ethyl acetate solution of p-acetoxyphenylbenzylmethylsulfonium salt, and 2 parts by weight of a silane coupling agent (“SH6040” manufactured by Toray Dow Corning Silicone) The conductive particles were added and dispersed so that the content was 3% by weight to obtain a resin composition.

  The obtained resin composition was applied to a 50 μm-thick PET (polyethylene terephthalate) film whose one surface was released from the mold, 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 μm.

(Example 2)
Of the particles classified and recovered in Example 1, a particle size of 2.50 μm was used as the core particles, and 540 parts by weight of isopropyl alcohol was used instead of 540 parts by weight of methanol when preparing the core-shell particles, tetraethoxy Conductive particles and a conductive material were produced in the same manner as in Example 1 except that the amount of silane used was changed from 120 parts by weight to 140 parts by weight.

(Example 3)
Of the particles classified and collected in Example 1, the particle size of 2.25 μm was used as the core particles, and 540 parts by weight of isopropyl alcohol was used instead of 540 parts by weight of methanol when preparing the core-shell particles, tetraethoxy Conductive particles and a conductive material were produced in the same manner as in Example 1 except that the amount of silane used was changed from 120 parts by weight to 310 parts by weight.

Example 4
Of the particles classified and collected in Example 1, a particle size of 2.00 μm was used as the core particles, and 540 parts by weight of isopropyl alcohol was used instead of 540 parts by weight of methanol when preparing the core-shell particles, tetraethoxy Conductive particles and a conductive material were produced in the same manner as in Example 1 except that the amount of silane used was changed from 120 parts by weight to 250 parts by weight.

(Example 5)
(1) Production of base particles Production of core particles
To 1000 parts by weight of divinylbenzene (purity 96%), 40 parts by weight of benzoyl peroxide was added and stirred until evenly dissolved to obtain a monomer mixture. About 4000 parts by weight of a 2% by weight polyvinyl alcohol aqueous solution in which polyvinyl alcohol having a molecular weight of about 1700 was dissolved in pure water was prepared and placed in a reaction kettle. The above-mentioned monomer mixed solution was put into this, and the particle size was adjusted by stirring for 2 to 4 hours so that the monomer droplets had a predetermined particle size. Thereafter, the reaction was carried out in a nitrogen atmosphere at 85 ° C. for 9 hours, and a monomer droplet polymerization reaction was carried out to obtain polymer particles. After the obtained particles were washed several times with hot water, classification operation was performed to collect several kinds of particles having different particle diameters.

  In Example 5, the polymer particles (organic core) collected among them had an average particle diameter of 2.50 μm and a CV value of 3.1%.

Preparation of core-shell particles)
30 parts by weight of the particles (organic core), 12 parts by weight of hexadecylammonium bromide as a surfactant, and 24 parts by weight of a 25% by weight aqueous ammonia solution are mixed in 540 parts by weight of isopropyl alcohol and 60 parts by weight of pure water. Then, a dispersion of core particles was prepared. To this dispersion, 140 parts by weight of tetraethoxysilane was added, and a condensation reaction by a sol-gel reaction was performed. Condensed tetraethoxysilane was deposited on the surface of the core particles, and core-shell type particles were formed. The obtained particles were washed several times with ethanol and dried to obtain core-shell particles. When the particle diameter of the core-shell particles (base material particles) was measured, it was 3.01 μm and the CV value was 3.2%. From the difference in particle diameter, the thickness of the shell was calculated to be 0.26 μm. The conductive particles and the conductive material were produced in the same manner as in Example 1.

(Example 6)
Of the particles classified and recovered in Example 5, the particle diameter of 2.25 μm was used as the core particle, and the amount of tetraethoxysilane used was changed from 140 parts by weight to 310 parts by weight when preparing the core-shell particles. In the same manner as in Example 4, conductive particles and a conductive material were produced.

(Example 7)
The same operation as in Example 4 was performed except that 1000 parts by weight of divinylbenzene (purity 96%) was changed to 800 parts by weight of divinylbenzene (96% purity) and 200 parts by weight of acrylonitrile at the time of preparation of the core particles. It was. Thereafter, the same operation as in Example 4 was performed to produce core-shell particles. Using the obtained core-shell particles as base particles, conductive particles and conductive materials were produced in the same manner as in Example 5.

(Example 8)
When forming a nickel layer on the surface of the obtained base particle by electroless plating method, by adding Ni powder with an average particle diameter of 150 nm, the surface has an uneven shape, and a plurality of protrusions are formed. Conductive particles and a conductive material were produced in the same manner as in Example 1 except that the nickel layer was formed.

Example 9
The surface of the conductive particles prepared in Example 8 was coated with resin particles (insulating particles) having an average particle diameter of 360 nm, and conductive particles having insulating particles attached to the outer surface of the conductive layer were prepared. A conductive material was produced in the same manner as in Example 1 except that this conductive particle was used.

(Example 10)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 60 parts by weight and the amount of phenoxy resin was changed from 45 parts by weight to 40 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Example 11)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 55 parts by weight and the amount of phenoxy resin was changed from 35 parts by weight to 45 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Example 12)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 45 parts by weight and the amount of phenoxy resin was changed from 35 parts by weight to 55 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Example 13)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 35 parts by weight and the amount of phenoxy resin was changed from 35 parts by weight to 65 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Comparative Example 1)
(1) Production of base particles Production of core)
950 parts by weight of 1,4-butanediol diacryl and 50 parts by weight of ethylene glycol dimethacrylate were mixed to obtain a mixed solution. 20 parts by weight of benzoyl peroxide was added to the obtained mixed solution and stirred until it was uniformly dissolved to obtain a monomer mixed solution. 4000 parts by weight of a 2% by weight aqueous polyvinyl alcohol solution obtained by dissolving polyvinyl alcohol having a molecular weight of about 1700 in pure water was placed in a reaction kettle. Into this, the obtained monomer mixture was put and stirred for 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size. Thereafter, the reaction was performed in a nitrogen atmosphere at 85 ° C. for 9 hours, and the polymerization reaction of the monomer droplets was performed to obtain particles. The obtained particles were washed several times with hot water, and then classified to recover polymer particles (organic cores) having several different particle sizes.

  In Comparative Example 1, polymer particles (organic core) having a particle size of 2.49 μm were prepared from the polymer particles recovered by the classification operation.

Preparation of core-shell particles)
30 parts by weight of the obtained polymer particles (organic core), 12 parts by weight of hexadecylammonium bromide as a surfactant, 24 parts by weight of a 25% by weight aqueous ammonia solution, 540 parts by weight of isopropyl alcohol and 60 parts of pure water. It put in the weight part and mixed, and the dispersion liquid of the polymer particle was obtained. To this dispersion, 140 parts by weight of tetraethoxysilane was added, and a condensation reaction by a sol-gel reaction was performed. A condensate of tetraethoxysilane was deposited on the surface of the polymer particles to form a shell, thereby obtaining particles. The obtained particles were washed several times with ethanol and dried to obtain core-shell particles (base material particles). The obtained core-shell particles had a particle size of 3.01 μm. From the core particle size and the core-shell particle size, the thickness of the shell was calculated to be 0.26 μm. Using the core-shell particles as base particles, conductive particles and a conductive material were produced in the same manner as in Example 1.

(Comparative Example 2)
(1) Production of base particles Production of core particles
700 parts by weight of styrene and 300 parts by weight of divinylbenzene (purity 57%) were mixed to obtain a mixed solution. 40 parts by weight of benzoyl peroxide was added to the obtained mixed solution and stirred until it was uniformly dissolved to obtain a monomer mixed solution. About 4000 parts by weight of a 2% by weight polyvinyl alcohol aqueous solution in which polyvinyl alcohol having a molecular weight of about 1700 was dissolved in pure water was prepared and placed in a reaction kettle. The above-mentioned monomer mixed solution was put into this, and the particle size was adjusted by stirring for 2 to 4 hours so that the monomer droplets had a predetermined particle size. Thereafter, the reaction was carried out in a nitrogen atmosphere at 85 ° C. for 9 hours, and a monomer droplet polymerization reaction was carried out to obtain polymer particles. After the obtained particles were washed several times with hot water, classification operation was performed to collect several kinds of particles having different particle diameters.

  In Comparative Example 2, the recovered polymer particles had an average particle diameter of 2.98 μm and a CV value of 3.1%. Using the polymer particles as base particles, conductive particles and a conductive material were produced in the same manner as in Example 1.

(Comparative Example 3)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 75 parts by weight and the amount of phenoxy resin was changed from 45 parts by weight to 25 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Comparative Example 4)
Implemented except that the amount of bisphenol A epoxy resin used was changed from 65 parts by weight to 25 parts by weight and the amount of phenoxy resin was changed from 45 parts by weight to 75 parts by weight when producing the conductive material. In the same manner as in Example 1, a conductive material was produced.

(Evaluation)
(1) Particle size of base material particle, core particle size and shell layer thickness, and conductive particle size For the obtained base material particle, a particle size distribution measuring device (“Mutizer 3” manufactured by Beckman Coulter, Inc.) is used. Used, about 10,000 particle diameters were measured, and the average particle diameter and standard deviation were measured. The particle size of the core particles used when producing the base particles was also measured by the same method as described above. The thickness of the inorganic shell was determined from the difference between the particle size of the substrate particles and the particle size of the core particles.

  Moreover, the particle diameter of the obtained conductive particles was also measured by the same method as described above.

(2) Compression characteristics of conductive particles (10% K value, 10% load value, and 40% load value)
The above-mentioned compression elastic modulus (10% K value, 10% load value and 40% load value) of the obtained conductive particles was measured by the above-described method under the condition of 23 ° C. (“Fischer” manufactured by Fischer). Scope H-100 ").

(3) Melt viscosity Using a rheometer (“RS150” manufactured by HAAKE), the melt viscosity at 100 ° C. of the component excluding the conductive particles of the conductive material, that is, the melt viscosity at 100 ° C. of the binder resin is the condition at a frequency of 1 Hz. The temperature was measured from 60 ° C. to 120 ° C. at a heating rate of 5 ° C./min.

(4) Connection resistance The obtained anisotropic conductive film was cut into a size of 5 mm × 5 mm. On the cut anisotropic conductive film, a polyimide substrate (width 3 cm, length 3 cm) provided with an ITO electrode (height 0.2 μm, L / S = 20 μm / 20 μm) having a resistance measurement lead wire on one side. ) Was attached to the center of the ITO electrode. A polyimide substrate provided with a copper electrode (width 2 cm, length 1 cm) was aligned and bonded so that the electrodes overlap each other. The laminated body of the polyimide substrate and the polyimide substrate was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.

  The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. Connection resistance was determined according to the following criteria.

[Evaluation criteria for connection resistance]
◯: Connection resistance is 3.0Ω or less ○: Connection resistance exceeds 3.0Ω, 4.0Ω or less △: Connection resistance exceeds 4.0Ω, 5.0Ω or less ×: Connection resistance exceeds 5.0Ω

(5) Evaluation of connection reliability The connection structure produced in the above (4) evaluation of connection resistance was left under conditions of 85 ° C. and relative humidity of 85%. After 100 hours from the start of standing, the connection resistance between the electrodes was measured by the 4-terminal method in the same manner as described above. When the average connection resistance (after leaving) is less than 150% compared to the average value of the connection resistance (before leaving) at the time of the above continuity evaluation, “○” indicates that the average value of the connection resistance (after leaving) is The case where it rose by 150% or more was judged as “x”.

  The results are shown in Table 1 below.

  Moreover, when obtaining a connection structure by evaluation of (4) and (5) using the electrically conductive material of Example 1, evaluation which changed the polyimide substrate into the glass substrate was implemented. Even in this case, the connection resistance and the connection reliability were good results (connection resistance ○, connection reliability ○). Furthermore, when the connection structure was obtained in the evaluations (4) and (5) using the conductive material of Example 1, evaluation was performed by changing the ITO electrode to a titanium electrode. Even in this case, the connection resistance and the connection reliability were good results (connection resistance ○, connection reliability ○). Further, in Examples 8 and 9, since the protrusion was formed on the outer surface of the conductive layer, the measured value of connection resistance was lower than that in Example 1. Moreover, in Example 9, since the insulating particles adhered to the outer surface of the conductive layer, the insulation reliability was excellent.

DESCRIPTION OF SYMBOLS 1 ... Conductive particle 2 ... Conductive layer 11 ... Base particle 12 ... Core 13 ... Shell 21 ... Conductive particle 22 ... Conductive layer 22A ... 1st conductive layer 22B ... 2nd conductive layer 31 ... Conductive particle 31a ... Projection 32 ... Conductive layer 32a ... Protrusion 33 ... Core material 34 ... Insulating material 51 ... Connection structure 52 ... First connection object member 52a ... First electrode 53 ... Second connection object member 53a ... Second electrode 54. Connection part

Claims (8)

Containing conductive particles and a binder resin,
The conductive particles comprise base particles and a conductive layer disposed on the surface of the base particles,
The base particle is a core-shell particle having a core and a shell disposed on a surface of the core;
The compressive elastic modulus when compressing the conductive particles by 10% is 4000 N / mm ² or more,
The ratio of the compressive load value when the conductive particles are compressed by 40% to the compressive load value when the conductive particles are compressed by 10% is 5.5 or less,
The electrically conductive material whose melt viscosity in 100 degreeC of the said binder resin is 50 Pa.s or more and 1000 Pa.s or less. The core is an organic core;
The conductive material according to claim 1, wherein the shell is an inorganic shell.   The conductive material according to claim 1, wherein the shell has a thickness of 100 nm or more and 3 μm or less.   The conductive material according to claim 1, wherein the conductive particles further include an insulating material disposed on an outer surface of the conductive layer.   The conductive material according to claim 1, wherein the conductive particles have protrusions on an outer surface of the conductive layer. A first connection object member having a first electrode on its surface;
A second connection target member having a second electrode on its surface;
A connection portion connecting the first connection target member and the second connection target member;
The connection portion is formed of the conductive material according to any one of claims 1 to 5,
A connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.   The connection structure according to claim 6, wherein at least one of the first connection target member and the second connection target member is a resin substrate or a glass substrate.   The metal constituting the electrode surface in contact with the conductive particles of at least one of the first electrode and the second electrode includes tin-doped indium oxide, titanium, or molybdenum. The connection structure described.

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