WO2014083875A1 - Film électroconducteur et boîtier de composant électronique - Google Patents

Film électroconducteur et boîtier de composant électronique Download PDF

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Publication number
WO2014083875A1
WO2014083875A1 PCT/JP2013/067864 JP2013067864W WO2014083875A1 WO 2014083875 A1 WO2014083875 A1 WO 2014083875A1 JP 2013067864 W JP2013067864 W JP 2013067864W WO 2014083875 A1 WO2014083875 A1 WO 2014083875A1
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Prior art keywords
resin
resin layer
film
conductive
conductive particles
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PCT/JP2013/067864
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English (en)
Japanese (ja)
Inventor
晃祐 織田
隆 障子口
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三井金属鉱業株式会社
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Publication of WO2014083875A1 publication Critical patent/WO2014083875A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a conductive film having conductivity, an electronic component package using the same, and a method for manufacturing the same.
  • thermocompression bonding As a method of mounting a semiconductor chip and a printed wiring board, a conductive film is sandwiched between the electrodes (pads) of the semiconductor chip and the board wiring electrodes, and thermocompression bonding is performed.
  • a flip chip mounting technique is known in which electrical conduction is made by conductive particles in a conductive film.
  • an electromagnetic shielding film as a conductive film is attached to a printed wiring board, or an electromagnetic shielding film is mounted between a transmission system circuit and a reception system circuit mounted on a printed circuit board to couple the two. It is also done to prevent.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-298285
  • a conductive adhesive layer and, if necessary, a metal thin film are formed on one side of a cover film.
  • a reinforced shield film having a shield layer composed of layers, in which an adhesive layer and a releasable reinforcing film are sequentially laminated on the other surface.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-273577 discloses a shield film having a shield layer and a base film made of an aromatic polyamide resin.
  • a method for forming a resonance circuit using the shield film Several through holes are opened in the cover lay of the flexible printed wiring board and processed so that the ground circuit (earth circuit) is exposed, and then the conductive adhesive layer of the shield film and the cover lay are attached by hot press.
  • a method of forming a resonance circuit between the ground of the circuit and the silver deposition layer by forming a joint portion between the ground circuit and the conductive adhesive layer after being combined is disclosed.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2007-189091 discloses an isotropic conductive adhesive sheet including a release film and an isotropic conductive adhesive layer containing conductive particles and a binder.
  • an adhesive sheet with a release film is temporarily fixed to a circuit board, then the release film is peeled off, a reinforcing plate is superimposed on the surface of the conductive adhesive layer, and press working (130 to 190 ° C., 1 to 4 MPa), and a method of electrically connecting the reinforcing plate and the electrode via the low melting point metal powder is disclosed.
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2009-191099 includes a conductive adhesive layer formed in a film shape having a large number of conductive particles and a binder in which these conductive particles are dispersed, and has tackiness.
  • a conductive adhesive sheet having a tacky resin layer is disclosed.
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2009-289840 discloses a peelable film, an insulating layer made of a film-like curable insulating polyurethane polyurea resin composition (II), and a curable conductive polyurethane polyurea adhesive (A electromagnetic wave shielding adhesive film in which a conductive adhesive layer made of I) and a peelable film are sequentially laminated is disclosed.
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2010-168518 discloses an adhesive material made of a thermoplastic elastomer resin, an acrylic resin, or the like formed in a sheet shape, Ag coated Cu powder dispersed in the adhesive material, It has a conductive adhesive layer composed of a composition having conductive particles such as Ag-coated Ni powder, and the average value of the thickness of the adhesive substance with respect to the average particle diameter of the conductive particles is There is disclosed a conductive pressure-sensitive adhesive sheet that is in the range of 0.8 times to 1.4 times, and the content of the conductive particles is in the range of 15 to 25% by weight of the entire conductive adhesive layer.
  • Patent Document 7 Japanese Patent Laid-Open No. 2011-66329
  • a conductive member provided with a metal layer for connection to an external ground member and a conductive adhesive layer containing conductive particles in contact is heated and pressurized.
  • a shield film comprising: a cover film formed with a thin layer thickness; and a cover film adhered to the conductive adhesive layer; and a metal thin film layer and an adhesive layer sequentially laminated on the cover film.
  • a ground connection method using this a metal layer connected to an external ground member and a conductive adhesive layer containing conductive particles are used.
  • the conductive member provided in the touch state is pressed while being heated at a temperature at which the resin is softened to bond the conductive adhesive layer and the cover film, thereby projecting longer than the layer thickness of the cover film.
  • a ground connection method for a shield film is disclosed in which conductive particles reach the metal thin film layer to be grounded.
  • Patent Document 8 Japanese Patent Laid-Open No. 2011-166100 discloses an electromagnetic wave shielding adhesive film comprising a curable insulating layer, a conductive film, and a curable conductive adhesive layer in this order.
  • the conductive coating is a coating formed from a dispersion containing coated conductive particles having an average particle diameter of 0.001 to 0.5 ⁇ m, in which conductive particles are coated with a protective substance, and the curable conductive adhesive
  • An electromagnetic wave shielding adhesive film is disclosed, wherein the agent layer contains a curable insulating resin and a metal powder having an average particle diameter of 1 to 50 ⁇ m.
  • the curable conductive adhesive layer is superimposed on an adherend such as a printed wiring board and heated to cure the curable conductive adhesive layer and the curable insulating layer. It becomes possible to shield the adherend from electromagnetic waves.
  • Patent Document 9 Japanese Patent Application Laid-Open No. 2011-187895 discloses an electromagnetic wave shielding film in which a protective layer is laminated on a conductive layer made of (A) metal powder and (B) a binder resin. ) Conductive material containing flaky metal powder having an average thickness of 50 to 300 nm and an average particle diameter of 3 to 10 ⁇ m, and (b) acicular or dendritic metal powder (especially silver-coated copper powder) having an average particle diameter of 3 to 10 ⁇ m. What is formed from an adhesive paste is disclosed.
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2011-1715273 discloses an electromagnetic wave shielding adhesive film comprising an insulating film having no curability, a conductive coating, and a curable conductive adhesive layer in this order.
  • the conductive coating is a coating formed from a dispersion containing coated conductive particles having an average particle diameter of 0.001 to 0.5 ⁇ m, in which conductive particles are coated with a protective substance,
  • An electromagnetic wave shielding adhesive film is disclosed in which the conductive adhesive layer contains a curable insulating resin and a metal powder having an average particle diameter of 1 to 50 ⁇ m.
  • the adhesiveness of the film to a printed wiring board is one of the problems.
  • conventionally for example, means for roughening the surface of the printed wiring board to be adhered has been adopted.
  • it is difficult to obtain sufficient adhesiveness only by roughening the adherend surface and it is possible that it will be difficult to roughen the adherend surface itself as further miniaturization progresses. .
  • the manufacturing method of the electronic component package after mounting the electronic component on the circuit board and sealing the electronic component with a mold resin, half-cut dicing is performed to remove the mold resin between the electronic components and provide a groove portion. After applying a conductive paste from above the mold resin and filling the groove with the conductive paste, dicing along the central portion of the groove and dividing the package into electronic packages is produced. The way is done.
  • the manufacturing process of the electronic component package can be further simplified.
  • the problem is the adhesion between the conductive film and the mold resin.
  • the present invention relates to a conductive film (including an electromagnetic wave shielding film), which not only has excellent conductivity but also exhibits excellent press adhesion, that is, excellent adhesion when heated and pressurized.
  • a new conductive film is to be provided.
  • the present invention provides a conductive film for press bonding, comprising a resin layer A containing conductive particles having a rod shape (referred to as “bar-shaped conductive particles”) in a resin layer in a B-stage state. suggest.
  • the conductive film for press bonding proposed by the present invention includes, for example, a printed wiring board having a configuration in which an electronic component is mounted and the electronic component is sealed with a mold resin, particularly on the mold resin of the present invention.
  • the resin layer A side of the conductive film for press bonding proposed is stacked, and the resin of the resin layer A, the resin of the resin layers A and B, or the resin of the resin layers A and C is softened by heating.
  • the resin layer A is firmly adhered to at least the mold resin. Can be manufactured.
  • the conductive film for press bonding proposed by the present invention can exhibit excellent press adhesiveness, that is, excellent adhesiveness when heated and pressurized. Therefore, in the process where the conductive film is heated and softened and pressed, and further heated to cure the softened resin, the tip of the rod-like portion of the rod-like conductive particles in the resin layer A pierced the mold resin. In order to exert the anchor effect, excellent adhesiveness can be exhibited.
  • the conductive film for press bonding proposed by the present invention is not only excellent in conductivity but also can exhibit excellent press adhesiveness.
  • the conductive film according to the present embodiment includes a resin layer A containing rod-like conductive particles in a B-stage resin layer, and a release film. It is the electroconductive film of the structure provided. However, the release film may be provided as necessary.
  • the B stage state means an intermediate state of curing of the thermosetting resin having adhesiveness or tackiness, and can maintain a film shape or a sheet shape, and when heated, the resin softens or melts, It means a state of being cured when heated.
  • the conductive film 1 may include one or more layers other than the resin layer A and the release film.
  • the resin composition which comprises the resin layer A should just be a resin composition which can be in a B stage state.
  • this type of base resin is generally a thermosetting resin.
  • a thermoplastic resin mixed with a thermosetting resin may be used.
  • the resin mainly constituting the resin composition that can be in the B-stage state (referred to as “base resin”) is not particularly limited.
  • base resin epoxy resin, polydimethylsiloxane resin, acrylic resin, other organic functional polysiloxane resin, polyimide resin, fluorocarbon resin, benzocyclobutene resin, fluorinated polyallyl ether, polyamide resin, polyimide amide resin, phenol cresol resin
  • An aromatic polyester resin, a polyphenylene ether (PPE) resin, a bismaleimide triazine resin, a fluororesin, and the like can be used, and one or a mixture of two or more of these may be used.
  • epoxy resins acrylic resins, polydimethylsiloxane resins that can be crosslinked by free radical polymerization, atom transfer, radical polymerization, ring opening polymerization, ring opening metathesis polymerization, anionic polymerization, or cationic polymerization. Or one or more of other organofunctional polysiloxane resins may be blended.
  • the resin composition constituting the resin layer A is preferably a resin having a minimum melt viscosity of 10,000 Pa ⁇ s to 1,000,000 Pa ⁇ s at 100 to 150 ° C., and more preferably a resin composition of 100,000 Pa ⁇ s or more. (For example, the resin composition indicated by the solid line in FIG. 3)
  • the resin composition constituting the resin layer A can be formed from an epoxy resin, an epoxy curing agent, an organic solvent, a silane coupling agent, a surfactant, and the like.
  • a B-stage state can also be achieved by a polymer blend of an acrylic resin and an epoxy resin.
  • the resin composition can be brought into a B-stage state by volatilizing the solvent.
  • thermosetting examples include organic peroxides, isocyanate compounds, thermosetting agents such as epoxy compounds and amine compounds.
  • the conductive particles contained in the resin layer A are conductive particles such as silver powder particles, copper powder particles and iron powder particles, or particles made of an arbitrary material, for example, a part of these surfaces using the conductive particles as a core material.
  • cover all with different electroconductive materials for example, gold
  • the present invention is not limited to these, and any material having conductivity can be arbitrarily adopted.
  • the conductive particles in the resin layer A is occupied by “rod-like conductive particles”, particularly 70% by number or more. It is preferable that the rod-like conductive particles occupy a ratio exceeding 100% (including 100%).
  • the “rod-like conductive particles” mean conductive particles having a shape having a rod-like portion including a needle-like portion and a protrusion-like portion.
  • dendritic conductive particles FIG. 4 (A )
  • Acicular conductive particles see FIG. 4B
  • protruding conductive particles see FIGS. 4D and 4E
  • the “needle-like conductive particles” are particles composed of only a rod-like portion, and the “dendritic conductive particles” are rod-shaped when observed with an optical microscope or an electron microscope (500 to 20,000 times).
  • dendritic conductive particles include those in which wide leaves gather to form a pinecone shape, or those having a shape in which a large number of needle-like portions do not have a main shaft and extend radially. Absent.
  • the “protruded granular conductive particles” are provided with protrusions on the surface of granular particles such as spherical, substantially spherical, elliptical granular, substantially elliptical spherical, bowl-shaped (see FIG. 4C), and prismatic. It is the meaning of the electroconductive particle which exhibits a shape.
  • “needle-like conductive particles” such as needle-like conductive particles and dendrite-like conductive particles are preferable from the viewpoint of anchor effect, and among them, electromagnetic shielding properties are taken into account. Then, dendritic conductive particles are particularly preferable.
  • the “needle-like conductive particles” mean conductive particles having a shape having a needle-like portion, and examples thereof include needle-like conductive particles and dendrite-like conductive particles.
  • conductive particles exhibiting protrusion-like particles having sharp protrusions on the surface of the granular particles are particularly preferable.
  • wire-like conductive particles have a characteristic of being in the range of 1.2 to 2.5 when expressed as a ratio of average longest diameter / average equivalent circle diameter, and more than 1.2 or 2.0 or less is preferable, and 1.4 or more or 1.9 or less is particularly preferable among them.
  • the “average longest diameter” is the average value of the longest diameters of all particles observed in the field of view of a scanning electron micrograph (SEM photograph, 500 times or 2000 times).
  • Average equivalent circle diameter means the equivalent circle diameter of all the particles observed in the field of view of a scanning electron micrograph (SEM photograph, 500 times or 2000 times), that is, when the projected area of each particle approximates a circle It is an average value of the longest diameters of all particles having a diameter of.
  • the shape of the conductive particles other than the rod-like conductive particles contained in the resin layer A is not particularly limited.
  • a spherical shape, a bowl-like shape, or a scale-like shape can be mentioned.
  • the average equivalent circle diameter of the conductive particles contained in the resin layer A is preferably from 0.1 ⁇ m to 30 ⁇ m, since the viscosity of the paint may increase and the coating property may decrease. 0.5 ⁇ m to 20 ⁇ m, more preferably 1.0 ⁇ m or more or 10 ⁇ m or less.
  • the content of the conductive particles in the resin layer A is preferably adjusted appropriately because the required amount varies depending on the use of the conductive film 1, the ratio of the rod-like conductive particles, and the like.
  • the rod-like conductive particles can obtain conductivity even in a smaller amount than the spherical conductive particles, for example, 50% by number or more of the conductive particles in the resin layer A are rod-like conductive particles.
  • the content of the conductive particles in the resin layer A is 50 to 95% by mass of the entire resin layer A, particularly 60% by mass or more and 90% by mass or less, and more preferably 80% by mass or more. preferable.
  • the thickness of the resin layer A is not particularly limited. However, even if it is too thick, the anchor effect does not increase and the material is useless. On the other hand, if it is too thin, it becomes difficult to follow the unevenness of the adherend surface, and the resin layer A can ensure stable conductivity. Since it becomes difficult, the thickness of the resin layer A is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.5 ⁇ m or more or 80 ⁇ m or less, and particularly preferably 1.0 ⁇ m or more or 50 ⁇ m or less.
  • release film examples include a polyester-type, polypropylene-type, polyethylene-type or polytetrafluoroethylene-type cast film or stretched film obtained by applying a silicone resin to a release treatment, or release paper. .
  • the conductive film 1 is heated by overlapping the resin layer A on the adherend surface of the adherend and bringing a press hot plate or the like into contact with the surface of the release film. Then, the resin of the resin layer A is softened, and the surface of the release film is pressed with the press hot plate or the like, in other words, the surface of the release film is pressed (pressed) in the direction of the adherend as a pressed surface, Further, the conductive film 1 can be bonded to the adherend by curing the resin softened by heating.
  • FIG. 1 (B) By hot pressing the conductive film 1 in this way, as shown in FIG. 1 (B), the rod-like portion tip of the rod-like conductive particles in the resin layer A pierces the adherend surface and has an anchor effect. Since it exhibits, it can be firmly bonded without being peeled off and not shifted laterally.
  • the resin layer A side of the conductive film 1 is After superposing the mold resin, for example, by heating a heat plate or the like to heat the resin layer A, the resin of the resin layer A is softened. By pressing to the side and then further heating to cure the softened resin, the resin of the resin layer A covers the mold resin portion and enters and fills the cut groove, Electronic component packages can be manufactured.
  • the conductive film (referred to as “the present conductive film 2”) according to the second embodiment of the present invention is a resin layer containing rod-like conductive particles in the resin layer A, that is, a B-stage resin.
  • the release film should just be provided as needed.
  • the present conductive film 2 may include one or more layers other than the resin layer A, the resin layer B, and the release film.
  • the resin layer A and the release film are the same as those in the present conductive film 1.
  • the resin composition of the resin layer B may be the same as or different from the resin composition of the resin layer A. From the viewpoint of difficulty in peeling between the resin layer A and the resin layer B, it is preferable that the resin composition is made of the same base resin.
  • the thickness of the resin layer B is not particularly limited. However, if the thickness is too thick, the effect is not increased and the material is wasted. On the other hand, if the thickness is too thin, it becomes difficult to follow the unevenness of the adherend surface. Therefore, the thickness of the resin layer B is preferably 5 to 500 ⁇ m. Of these, it is more preferably 20 ⁇ m or more and 200 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 150 ⁇ m or less.
  • the resin layer A is preferably a layer that becomes the adherend surface. That is, it is preferable to laminate the release film, the resin layer B, and the resin layer A in this order.
  • a curing agent, a coupling agent, a corrosion inhibitor, or the like is mixed with the resin composition that can be in a B-stage state, if necessary, applied onto a release film, and the solvent is volatilized. It is preferable that the resin layer B in the B stage state is formed by primary curing.
  • conductive particles are mixed into a resin composition that can be in a B-stage state, and mixed with a curing agent, a coupling agent, a corrosion inhibitor, etc., if necessary, and dispersed without breaking the shape of the conductive particles. Kneaded and coated on the resin layer B, and first cured by volatilizing the solvent to form the B-stage resin layer A. The release film, the resin layer B, and the resin layer A It is preferable to produce this conductive film 2 which is laminated in order.
  • the conductive film 2 has the resin layer A overlaid on the adherend surface of the adherend, and a press hot plate or the like is brought into contact with the surface of the release film to heat the resin of the resin layer A and the resin layer B. After softening, the surface of the release film is pressed with the press hot plate or the like, in other words, the surface of the release film is pressed (pressed) as a pressed surface, and then further heated to be softened as described above. By curing the resin, the conductive film 2 can be joined to the adherend. Since the conductive film 2 is hot pressed in this way, the tip of the rod-shaped portion of the rod-like conductive particles in the resin layer A pierces the adherend surface and exhibits an anchor effect.
  • the resin layer B can be pushed by the resin layer A, break through the resin layer A, flow into a cut groove formed by, for example, half dicing, and bury the cut groove without a gap. Further, by providing the resin layer B, it is possible to enjoy benefits such as easy laser marking, weather resistance and prevention of discoloration over time.
  • the resin layer A side of the conductive film 2 is provided.
  • the resin layer A and the resin layer B are softened by heating, for example, by contacting a hot plate or the like on the mold resin, and then press-bonding with the surface of the release film as the pressed surface
  • the conductive film is pressed to the substrate side and then heated to cure the softened resin, so that the resin of the resin layer A covers the mold resin portion, and the resin of the resin layer B is the resin layer A.
  • the cut groove can be filled and filled with the resin of the resin layer A and the resin of the resin layer B, and an electronic component package can be manufactured.
  • the periphery of the electronic component sealed with the mold resin can be covered with a coating layer containing conductive particles, and the end of the coating layer penetrates into the cut groove and joins to the ground. Therefore, conduction can be obtained.
  • this electroconductive film 2 can be used conveniently as an electromagnetic wave shield film.
  • the conductive film (referred to as “the present conductive film 3”) according to the third embodiment of the present invention is a resin containing rod-like conductive particles in the resin layer A, that is, the B-stage resin.
  • This is a conductive film having a configuration including a layer A, a resin layer C containing conductive particles in a B-stage resin, and a release film.
  • the release film should just be provided as needed.
  • the present conductive film 3 may include one or more layers other than the resin layer A, the resin layer C, and the release film.
  • the resin layer A and the release film are the same as those in the present conductive film 1.
  • the conductive particles contained in the resin layer C are conductive particles such as silver powder particles, copper powder particles, and iron powder particles, or particles made of an arbitrary material, for example, a part of these surfaces using the conductive particles as a core material.
  • cover all with different electroconductive materials for example, gold
  • the present invention is not limited to these, and any material having conductivity can be arbitrarily adopted.
  • the resin layer C contains 50% by number or more
  • the resin layer C is softened or softened. Even when melted, the flow of the resin is hindered by these conductive particles, and the embedding into, for example, a cut groove formed by half dicing is prevented. Therefore, from the viewpoint of excellent fluidity, in other words, embedding property, it is preferable that the granular conductive particles occupy 50% by number or more of the conductive particles in the resin layer C. It is preferable that the granular conductive particles occupy a ratio exceeding the number%.
  • examples of the “granular conductive particles” include a spherical shape, a substantially spherical shape, an elliptical granular shape, a substantially elliptic spherical shape, a bowl shape, and a prismatic shape.
  • grains with a protrusion provided with the sharp protrusion part on the surface of these granular particles are also included.
  • a spherical shape or a substantially spherical shape is particularly preferable in terms of excellent fluidity, in other words, excellent embedding property in the groove.
  • the conductive particles in the resin layer C preferably have an average longest diameter / average equivalent circle diameter ratio of 1.0 to 2.0. .5 or less, preferably 1.3 or less.
  • the content of the conductive particles in the resin layer C is preferably adjusted according to the use of the conductive film 3 and the like.
  • the content of the conductive particles in the resin layer C is 50 to 95% by mass of the entire resin layer C, especially 65% by mass or 90% by mass, and more preferably 80% by mass or more and 90% by mass or less. Preferably there is.
  • the resin composition of the resin layer C may be the same as or different from the resin composition of the resin layer A. From the viewpoint of difficulty in peeling between the resin layer A and the resin layer C, a resin composition made of the same base resin is preferable.
  • the resin composition of the resin layer C and the resin is preferably different, and at least resin layer C preferably has lower viscoelasticity at 100 to 150 ° C.
  • the resin composition constituting the resin layer C is preferably a resin having a minimum melt viscosity of 100000 Pa ⁇ s or less at 100 to 150 ° C., more preferably 50000 Pa ⁇ s or less, and more preferably 30000 Pa ⁇ s or less. Even more preferable (for example, a resin composition indicated by a dotted line below in FIG. 3).
  • the thickness of the resin layer C is not particularly limited.
  • the resin layer C flows into a cut groove formed by half dicing and works to fill the groove portion. Therefore, the thickness of the resin layer C is appropriately adjusted according to the size of the groove portion. Is preferred.
  • the resin layer A is preferably a layer that becomes the adherend surface. That is, the release film, the resin layer C, and the resin layer A are preferably laminated in this order.
  • the conductive film 3 is heated by placing the resin layer A on the adherend surface and bringing a press hot plate or the like into contact with the surface of the release film. After softening the resin of the resin layer A and the resin layer C, the surface of the release film is pressed with the press hot plate or the like, in other words, the surface of the release film is pressed (pressed) as a pressed surface, The conductive film 3 can be bonded to the adherend by heating and curing the softened resin. By hot pressing the conductive film 3 in this way, as shown in FIG. 2 (B), the rod-like portion tip of the rod-like conductive particles in the resin layer A pierces the adherend surface and has an anchor effect.
  • the resin layer C has high fluidity because the conductive particles do not hinder the fluidity, so that the resin layer C breaks through the resin layer A and flows into the incision groove formed by half dicing so that the incision groove has no gap. Can be embedded. It should be noted that these effects can be obtained particularly effectively when the resin layer A is located on the bonding surface side.
  • the electronic component is sealed with a mold resin, and a cut groove is provided by half dicing, as shown in FIG.
  • the resin layer A side of the conductive film 3 is overlaid on the mold resin and heated by, for example, contacting a hot plate or the like, the resin of the resin layer A and the resin layer C is softened, and then the release film
  • the conductive film for press bonding is pressed to the substrate side with the surface of the substrate as the pressed surface, and then heated to cure the softened resin.
  • the resin of A covers the mold resin portion, and the resin of the resin layer C breaks through the resin layer A and enters the cut groove, so that the cut groove is embedded with the resin of the resin layer A and the resin of the resin layer C.
  • Filling with Can it is possible to manufacture the electronic component package.
  • the periphery of the electronic component sealed with the mold resin can be covered with a coating layer containing conductive particles, and the end of the coating layer is, for example, in a cut groove formed by half dicing. Since it penetrates into and is joined to the ground, conduction can be obtained.
  • this electroconductive film 3 can be used conveniently as an electromagnetic wave shield film.
  • any of the conductive films 1-3 can be used as conductive films such as an electromagnetic wave suppressing sheet, an electromagnetic wave absorbing sheet, an electromagnetic wave shielding film, a bonding film for connecting a circuit board and a circuit board, and an antistatic film.
  • the present conductive film containing dendritic conductive particles can be particularly preferably used as an electromagnetic shielding film.
  • Silver-coated copper powder A A silver-coated copper powder having a D50 of 13 ⁇ m and particles having a dendrite shape exceeding 80% by number when observed with an electron microscope (2000 times).
  • Silver-coated copper powder B A silver-coated copper powder having a D50 of 5 ⁇ m and particles having a dendrite shape of more than 80% by number when observed with an electron microscope (2000 times).
  • Silver-coated copper powder C Silver-coated copper powder having a D50 of 12 ⁇ m and particles exceeding 80% by number when observed with an electron microscope (2,000 times).
  • Silver-coated copper powder D Silver coating having a D50 of 5 ⁇ m, and particles having a protruding portion on the surface of the spherical particles, the particles exceeding 80% by number when observed with an electron microscope (2000 times) Copper powder.
  • Copper powder E A copper powder having a D50 of 5 ⁇ m and particles having a protrusion-shaped sphere in which more than 80% by number of particles have a protruding portion on the surface of the spherical particle when observed with an electron microscope (2000 magnifications).
  • Silver-coated copper powder F Silver-coated copper powder having a D50 of 5.5 ⁇ m and more than 80% by number, when observed with an electron microscope (2000 times), exhibits spherical particles.
  • the above D50 is a value obtained as follows. Take a small amount of conductive powder in a beaker, add 2 or 3 drops of 3% Triton X solution (Kanto Chemical), blend in with the powder, then add 50 mL of 0.1% SN Dispersant 41 solution (San Nopco) After that, a measurement sample was prepared by performing a dispersion treatment for 2 minutes using an ultrasonic dispersing device TIP ⁇ 20 (manufactured by Nippon Seiki Seisakusho). The volume accumulation standard D50 of this measurement sample was measured using a laser diffraction / scattering particle size distribution analyzer MT3300 (manufactured by Nikkiso).
  • Epoxy resin X Minimum melt viscosity at 100 to 150 ° C. is 25000 Pa ⁇ s at 110 ° C.
  • Epoxy resin Y minimum melt viscosity at 100 to 150 ° C. is 500,000 Pa ⁇ s at 110 ° C.
  • the minimum melt viscosity of the resin is 5 mm in thickness of the sample, using a viscosity measuring device (“HAAKE Rheo Stress 600” manufactured by Thermo ELECTRON CORPORATION), and the frequency (angular velocity) at a heating rate of 2 ° C./min. ) was adjusted appropriately.
  • HAAKE Rheo Stress 600 manufactured by Thermo ELECTRON CORPORATION
  • Example 1-5 and Comparative Example 1> Add 11 parts by mass of the epoxy resin X to 63 parts by mass of the silver-coated copper powders A to D or copper powder E shown in Table 1 in a proportion of 26 parts by mass of an organic solvent, and add a stirrer (Awatori Netaro (trade name)) After kneading for 3 minutes at a rotational speed of 2000 rpm, the coating film was applied on a 25 ⁇ m-thick release film (trade name “Aflex”, manufactured by Asahi Glass Co., Ltd.) using an applicator to a thickness of 50 ⁇ m. And heated in an oven at 150 ° C. for 3 minutes to produce a conductive film having the B-stage resin layer A on the release film.
  • the resin layer A of the conductive film obtained above is formed into a module substrate (an element is mounted on the substrate, further sealed with an epoxy resin mold resin, the surface is grooved by half dicing, and cut into the package substrate.
  • the film was softened (120 ° C.) by heating at a temperature rising rate of 3 ° C./min using a vacuum press, and the surface of the release film was covered. Pressed (pressed) in the direction of the adherend as a pressing surface at a pressure of 30 kgf / cm 2 , further heated to 180 ° C. to cure the softened resin, and bonded the film to the substrate, using semi-automatic dicing And then dicing into full pieces.
  • Example 6> The silver-coated copper powder A shown in Table 1 is added to 11 parts by mass of the epoxy resin X at a ratio of 63 parts by mass and 26 parts by mass of the organic solvent, and a rotational speed of 2000 rpm using a stirrer (Aritori Nertaro (trade name)). After being kneaded for 3 minutes, an applicator was used to form a coating film on a 25 ⁇ m thick release film (trade name “Aflex” manufactured by Asahi Glass Co., Ltd.) to form a coating film. On the prepared coating film, an epoxy resin X is applied to a thickness of 100 ⁇ m using an applicator to form a coating film, heated in an oven at 150 ° C. for 3 minutes, and B on the release film. A conductive film obtained by sequentially laminating the resin layer B and the resin layer A in a stage state was produced.
  • the resin layer A of the conductive film obtained above is formed into a module substrate (an element is mounted on the substrate, further sealed with an epoxy resin mold resin, the surface is grooved by half dicing, and cut into the package substrate.
  • the film was softened (120 ° C.) by heating at a temperature rising rate of 3 ° C./min using a vacuum press, and the surface of the release film was covered. Pressed (pressed) in the direction of the adherend as a pressing surface at a pressure of 30 kgf / cm 2 , further heated to 180 ° C. to cure the softened resin, and bonded the film to the substrate, using semi-automatic dicing And then dicing into full pieces.
  • Example 7-8> To 11 parts by mass of epoxy resin X or Y, 63 parts by mass of silver-coated copper powder A or D shown in Table 1 is added in a proportion of 26 parts by mass of organic solvent, and a stirrer (Awatori Kentaro (trade name)) is used. After kneading for 3 minutes at a rotational speed of 2000 rpm, a coating film is formed on a 25 ⁇ m-thick release film (trade name “Aflex”, manufactured by Asahi Glass Co., Ltd.) using an applicator to a thickness of 50 ⁇ m. did.
  • the silver-coated copper powder D shown in Table 1 is added in an amount of 63 parts by mass and 26 parts by mass of an organic solvent to 11 parts by mass of the epoxy resin X, and a rotational speed of 2000 rpm using a stirrer (Aritori Nertaro (trade name)). After kneading for 3 minutes, a coating film is formed on the prepared coating film using an applicator to a thickness of 100 ⁇ m, and heated in an oven at 150 ° C. for 3 minutes to form a release film. A conductive film was produced by sequentially laminating a resin layer C and a resin layer A in a B-stage state thereon.
  • the resin layer A of the conductive film obtained above is formed into a module substrate (an element is mounted on the substrate, further sealed with an epoxy resin mold resin, the surface is grooved by half dicing, and cut into the package substrate.
  • the film was softened (120 ° C.) by heating at a temperature rising rate of 3 ° C./min using a vacuum press, and the surface of the release film was covered. Pressed (pressed) in the direction of the adherend as a pressing surface at a pressure of 30 kgf / cm 2 , further heated to 180 ° C. to cure the softened resin, and bonded the film to the substrate, using semi-automatic dicing And then dicing into full pieces.
  • the average longest diameter was determined by observing the films obtained in Examples and Comparative Examples using a scanning electron microscope (2000 times), and determining the longest diameter of all particles observed in the field of view by using scanning electron From the micrograph, image analysis software (open source free software “ImageJ”) was used to calculate from the value of Ferret's Diameter of SetMeasurement, and the average longest diameter was obtained as the average value of all the particles.
  • image analysis software open source free software “ImageJ”
  • At least the resin layer A contains conductive particles having a rod-like shape from the viewpoint of improving the adhesion of the film in the module. It was. Among these, it has been found that dendritic particles are particularly preferable. It can be considered that such an effect is due to exerting an anchor effect because the tip of the rod-like portion of the rod-like conductive particles in the resin layer A pierces the adherend surface when the film is hot pressed. it can. Among these rod-like conductive particles, from the viewpoint of film adhesion, particles having a ratio of average longest diameter / average equivalent circle diameter in the range of 1.2 to 2.5 are preferable.
  • the resin of the resin layer A covers the mold resin portion and enters into the cut groove formed by half dicing, and the groove is filled with the resin. I was able to confirm that.
  • a resin layer A containing conductive particles having a rod-shaped shape and a resin layer C containing conductive particles having a dendritic shape or a projection-shaped granular shape. Can be firmly attached, and the resin of the resin layer A covers the mold resin portion, while the resin of the resin layer C breaks through the resin layer A and is in a cut groove formed by half dicing. It has been found that the groove can be filled and filled with the resin of the resin layers A and C without gaps.
  • the conductive particles contained in the resin layer C are preferably granular particles such as protruding granular particles and protruding non-particle particles rather than dendritic particles.
  • the conductive particles are 1.0 to 2.0, more preferably 1.5 or less, and most preferably 1.3 or less. It has been found that it is even more preferable that the particles are conductive particles.
  • the resin composition constituting the resin layer A has a minimum melt viscosity at 100 to 150 ° C., such as epoxy resin X (25000 Pa ⁇ s at 110 ° C.) and epoxy resin Y (500,000 Pa ⁇ s at 110 ° C.). It was found that the viscosity was preferably 10,000 Pa ⁇ s to 1,000,000 Pa ⁇ s, and above all, it was found that it was even more preferable to be 100,000 Pa ⁇ s or more like epoxy resin Y (500,000 Pa ⁇ s at 110 ° C.). On the other hand, the resin composition constituting the resin layers B and C is preferably a resin having a minimum melt viscosity at 100 to 150 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne un film électroconducteur (film de protection contre les ondes électromagnétiques y compris), ce nouveau film électroconducteur présentant non seulement une conductivité excellente mais aussi une plus forte adhérence. L'invention concerne également un film électroconducteur collé sous pression et comportant une couche de résine (A) dans laquelle des particules électroconductrices qui ont des tiges sont contenues dans une couche de résine de niveau B.
PCT/JP2013/067864 2012-11-30 2013-06-28 Film électroconducteur et boîtier de composant électronique WO2014083875A1 (fr)

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JP2012262678A JP6025532B2 (ja) 2012-11-30 2012-11-30 導電性フィルム及び電子部品パッケージ
JP2012-262678 2012-11-30

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