WO2012164925A1 - Feuille électroconductrice et son procédé de fabrication, et composant électronique - Google Patents

Feuille électroconductrice et son procédé de fabrication, et composant électronique Download PDF

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Publication number
WO2012164925A1
WO2012164925A1 PCT/JP2012/003541 JP2012003541W WO2012164925A1 WO 2012164925 A1 WO2012164925 A1 WO 2012164925A1 JP 2012003541 W JP2012003541 W JP 2012003541W WO 2012164925 A1 WO2012164925 A1 WO 2012164925A1
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Prior art keywords
conductive
conductive layer
layer
fine particles
dendritic
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PCT/JP2012/003541
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English (en)
Japanese (ja)
Inventor
祐司 西山
冨永　浩史
邦広 古川
英宣 小林
和規 松戸
孝洋 松沢
晟 瞿
Original Assignee
東洋インキＳｃホールディングス株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=47258797&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012164925(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 東洋インキＳｃホールディングス株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Priority to KR1020187009342A priority Critical patent/KR101931274B1/ko
Priority to CN201280026529.XA priority patent/CN103597551B/zh
Priority to KR1020137033789A priority patent/KR101846474B1/ko
Priority to JP2013517880A priority patent/JP6064903B2/ja
Publication of WO2012164925A1 publication Critical patent/WO2012164925A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • 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
    • C09J2301/40—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

Definitions

  • the present invention relates to a conductive sheet that can be used by being attached to an adherend such as a printed wiring board, and a method for manufacturing the same. Moreover, it is related with the electronic component containing the above-mentioned electroconductive sheet.
  • Patent Document 1 discloses a thermosetting conductive adhesive sheet having a three-layer structure in which a conductive layer is sandwiched between adhesive layers made of a thermosetting adhesive.
  • the conductive layer constituting this sheet has a protruding portion raised in the surface direction.
  • the protruding portion of the conductive layer is in direct electrical contact with the adherend through the adhesive layer by thermocompression bonding the adhesive layer to the adherend. Thereby, it functions as a conductive adhesive sheet.
  • Patent Document 2 discloses a conductive adhesive film containing a thermoplastic resin having a glass transition temperature of ⁇ 10 ° C. or higher and 50 ° C. or lower, and silver powder.
  • the silver powder it is usually described that at least two kinds of silver powder, spherical, fine sphere and flake are used in combination.
  • Patent Document 3 discloses an electromagnetic wave shielding adhesive film comprising a polyurethane polyurea resin, an epoxy resin having two or more epoxy groups, and a conductive filler.
  • the conductive adhesive sheet disclosed in Patent Document 1 employs a structure in which a conductive layer made of a metal foil such as copper, iron, and aluminum is sandwiched between adhesive layers, the thickness of the printed wiring board is reduced. There is a problem that it is not suitable for thinning. Further, since the metal foil has low flexibility, it has been difficult to use it for a flexible printed wiring board in which a conductive adhesive sheet is repeatedly bent.
  • the conductive adhesive film disclosed in Patent Document 2 is not suitable for use in a high temperature environment because the heat resistance of the thermoplastic resin is low.
  • the present invention has been made in view of the above-mentioned background, and the object of the present invention is to minimize the seepage of the conductive layer in a hot press process in which a conductive sheet is adhered to an adherend such as a printed wiring board. It is to provide a conductive sheet having good processability, a method for producing the same, and an electronic component.
  • the conductive sheet according to the present invention comprises a conductive layer containing at least the thermosetting resin (A) and dendritic conductive fine particles (B), and the thickness of the conductive layer is (i) 150 ° C., The thickness after heat pressing under the conditions of 2 MPa for 30 minutes, when the thickness of the conductive layer before heat pressing is 100, is in the range of 30 to 95, and (ii) the dendritic conductivity the average particle diameter D 90 of fine particles (B) is 0.5 times or more the thickness of the conductive layer, those in the range of 3 times or less, at least one of met, the dendritic conductive fine particles (B) And having an average particle diameter D 50 of 3 ⁇ m or more and 50 ⁇ m or less, and containing the dendritic conductive fine particles (B) in the conductive layer in a range of 50 wt% or more and 90 wt% or less. It is.
  • the electronic component according to the present invention is one in which the conductive sheet of the above aspect is stuck.
  • the method for producing a conductive sheet according to the present invention comprises a conductive resin composition comprising dendritic conductive fine particles (B) having an average particle diameter D 50 of 3 ⁇ m or more and 50 ⁇ m or less, and a thermosetting resin (A). Then, it is applied to a peelable sheet to form a conductive layer containing the dendritic conductive fine particles (B) in a range of 50 wt% or more and 90 wt% or less, and the conductive layer is 2.5 MPa or more and 50 MPa. It includes a step of applying the following pressure.
  • a conductive layer containing a large amount of voids is formed before hot pressing, so that, for example, heat flowing when a conductive sheet is hot pressed on a printed wiring board. It became possible to absorb a plastic resin etc. in the said space
  • electronic parts such as a printed wiring board using the conductive sheet have a good yield due to a significant reduction in the number of defective products derived from seepage. Furthermore, the short circuit of the circuit of electronic parts, such as a printed wiring board, and ion migration could be reduced significantly.
  • a conductive sheet having good workability capable of reducing the seepage of the conductive layer to a minimum in the hot press step of sticking the conductive sheet to an adherend such as a printed wiring board, and its production
  • an adherend such as a printed wiring board
  • FIG. 2B is a cross-sectional view taken along the line IIB-IIB in FIG. 2A.
  • FIG. 2C is a cross-sectional view taken along the line IIC-IIC in FIG. 2A.
  • It is explanatory drawing of the circuit for measuring the connection resistance value A and is a schematic plan view of the flexible printed wiring board after heat-pressing a conductive sheet and a stainless steel plate.
  • FIG. 2D is a sectional view taken along the line IIE-IIE in FIG. 2D.
  • FIG. 2D is a cross-sectional view taken along the line IIF-IIF in FIG. 2D.
  • FIG. 3B is a cross-sectional view taken along the line IIIB-IIIB in FIG. 3A.
  • 3C is a cross-sectional view taken along the line IIIC-IIIC in FIG. 3A. It is explanatory drawing of the circuit for measuring the connection resistance value B, and the typical top view after laminating
  • FIG. 3D is a cross-sectional view taken along the line IIIE-IIIE of FIG. 3D.
  • FIG. 3D is a cross-sectional view taken along the line IIIF-IIIF of FIG. 3D.
  • any number A to any number B means a range larger than the numbers A and A but smaller than the numbers B and B.
  • the conductive sheet of the present invention has at least a conductive layer.
  • the conductive sheet may be composed of a single conductive layer, or may be a laminate of a plurality of conductive layers.
  • a layer other than the conductive layer for example, a support layer, an insulating layer, a protective layer, an adhesive layer
  • the electroconductive sheet as used in this specification does not need to have an electroconductive characteristic in the whole sheet, and should just have an electroconductive characteristic in an electroconductive layer at least.
  • the conductive characteristics of the conductive layer can be appropriately set according to the application and needs, and are not particularly limited.
  • the example comprised from one conductive layer is demonstrated as one embodiment of an electroconductive sheet.
  • the conductive layer of the conductive sheet according to the first embodiment includes a thermosetting resin (A) and dendritic conductive fine particles (B) as essential components.
  • A thermosetting resin
  • B dendritic conductive fine particles
  • the thickness after the heat press is 30 or more when the thickness of the conductive layer before the heat press is 100, The range is 95 or less.
  • the “conductive layer before hot pressing” refers to a conductive layer immediately before being attached to an adherend such as a printed wiring board.
  • the adherend is a general object to which the conductive sheet is attached, and examples thereof include a printed wiring board and a flexible board.
  • the thickness of the conductive layer after hot pressing under the above conditions of the conductive layer of the conductive sheet is more preferably 40 or more, and further preferably 45 or more. Further, the thickness of the conductive layer after the hot pressing is more preferably 90 or less, and further preferably 85 or less. Particularly preferred is the range of 60-80. When the thickness after hot pressing is greater than 95, it is assumed that there are few voids in the conductive layer before hot pressing, so there is little change in thickness before and after hot pressing, and the thermosetting resin (A ) May increase.
  • the conductive layer is assumed to have too many voids, so the thickness change before and after the hot pressing is large, and the voids remain even with the hot press, achieving the desired conductivity. It tends to be difficult.
  • the “bleed out” as used in this specification includes bleeding of a low molecular weight component and protrusion of a conductive layer flowing.
  • the void formed by using dendritic conductive fine particles (B) in the conductive layer is filled by hot pressing under conditions of a temperature of 150 ° C., a time of 30 minutes, and a pressure of 2 MPa. It is something that can be done.
  • the conditions at the time of adhering the electroconductive sheet of 1st Embodiment to adherends, such as a printed wiring board explain the example performed on the said heat press conditions, a different heat press process is employ
  • a sheet may be formed. For example, heating conditions, pressing conditions, and the like can be adjusted according to the type of thermoplastic resin used.
  • the conductive sheet of the first embodiment is laminated so that the conductive layer side of the conductive sheet of the first embodiment is in contact with an adherend such as a printed wiring board, and the adherend is subjected to the heating press step.
  • a conductive sheet can be attached to the substrate.
  • the thermoplastic resin since the thermoplastic resin is contained, adhesiveness with a to-be-adhered body can be kept favorable.
  • the adhesive layer different from a conductive layer is provided in a conductive sheet according to a use and needs, and the aspect which joins an adhesive layer and a to-be-adhered body It is good.
  • thermosetting resin (A) used in the first embodiment is not particularly limited as long as it does not depart from the gist of the present invention, but acrylic, phenolic, epoxy, urethane, melamine, alkyd resins, etc. Is preferred. Furthermore, when the adhesive is bonded in the hot press step and is used after being attached like a flexible printed wiring board, an acrylic resin and a urethane resin having both heat resistance and flexibility are more preferable. In addition, a thermosetting resin (A) may use one type, or may mix and use two or more types.
  • a curing agent in combination with the thermosetting resin (A).
  • the curing agent a known compound corresponding to the functional group of the resin to be used can be used.
  • the resin contains a carboxyl group
  • a resin contains a hydroxyl group, an isocyanate hardening
  • FIG. 1A shows an SEM image of an example of dendritic conductive fine particles (B) suitable for the conductive layer of the first embodiment.
  • the dendritic shape is generally called a dendritic shape and means a shape like a tree branch.
  • the material of the dendritic conductive fine particles (B) is a conductive metal such as gold, silver, copper, nickel, zinc or iron or an alloy thereof, a conductive organic compound such as polyaniline, polythiophene, or polyacetylene, or a conductive compound composed of these. Can be exemplified.
  • conductive fine particles in which a metal, an organic compound, or an inorganic compound is used as a nucleus and the surface of the nucleus is covered with a conductive material are also preferable examples.
  • the conductive fine particles having a conductive coating layer particles having a coating layer formed on the surface with respect to a core serving as a core are preferable examples.
  • the core include metals such as copper, nickel, and cadmium, conductive organic compounds such as polyaniline, polythiophene, and polyacetylene, or ordinary non-conductive organic compounds.
  • money, silver, copper is mentioned.
  • more preferable examples include conductive fine particles in which a coating layer is formed of silver with copper as a nucleus.
  • a dendritic electroconductive fine particle (B) may use a single type, and may mix and use multiple types.
  • the proportion of the coating layer in the conductive fine particles having a conductive coating layer is preferably 1% by weight to 40% by weight, more preferably 5% by weight to 20% by weight in 100% by weight of the dendritic conductive fine particles (B). .
  • the thickness of the conductive sheet changes before and after the heating press because the voids are likely to exist in the conductive layer mainly due to the presence of the bulky dendritic conductive fine particles (B), and the thermosetting resin (A) is changed by the heating press. It is speculated that this is due to the flow and filling the gap.
  • the voids of the dendritic conductive fine particles (B) are more easily affected by the relationship between the average particle diameter D 50 and the average particle diameter D 90 of the dendritic conductive fine particles (B) used. And a thickness change becomes large, so that there are many space
  • the dendritic conductive fine particles (B) preferably have an average particle diameter D 50 of 3 ⁇ m to 50 ⁇ m and an average particle diameter D 90 of 1.5 to 5 times the average particle diameter D 50 .
  • the average particle size D 50 is more preferably 3 ⁇ m to 40 ⁇ m, and further preferably 5 ⁇ m to 25 ⁇ m.
  • Mean By particle diameter D 50 is equal to or greater than 3 [mu] m, easily can voids in the conductive layer, it can be reduced exudation. On the other hand, the average particle diameter D 50 is 50 ⁇ m or less, it becomes easy to form the conductive layer of the appropriate thickness.
  • the average particle diameter D 90 of the dendrite conductive fine particles (B) is preferably from 1.5 to 5 times the average particle diameter D 50, 2-fold to 3.5-fold and more preferably.
  • the value of the average particle diameter D 90 tends to depend on the average particle diameter of the average particle diameter D 50 , but is preferably 4.5 ⁇ m to 250 ⁇ m.
  • the average particle diameter D 90 is not more than 5 times the average particle diameter D 50 , the width of the particle diameter distribution is not too wide, and the dendritic conductive fine particles (B) in the conductive layer are appropriately filled. Tend to be. Furthermore, the presence of huge dendritic particles makes it difficult for the huge dendritic particles to protrude from the conductive layer after heat pressing.
  • the dendrite-like conductive fine particles (B) preferably have a tap density (hereinafter also referred to as “TD”) of 0.8 g / cm 3 to 2.5 g / cm 3 .
  • TD tap density
  • the conductive fine particles can be more densely packed in the conductive layer.
  • the TD is 2.5 g / cm 3 or less, the conductive fine particles in the conductive layer are less likely to be overfilled and the film thickness before and after the heating press tends to be maintained at a large state. It is possible to reduce the ejection more.
  • the dendritic conductive fine particles (B) preferably have an apparent density (hereinafter also referred to as “AD”) of 0.4 g / cm 3 to 1.5 g / cm 3 .
  • AD apparent density
  • the conductive fine particles can be more densely packed in the conductive layer.
  • the TD is 1.5 g / cm 3 or less, the conductive fine particles in the conductive layer are less likely to be overfilled and the film thickness before and after the heating press tends to be maintained at a large state. It is possible to reduce the ejection more.
  • the dendritic conductive fine particles (B) By making the values of the apparent density AD and the tap density TD of the dendritic conductive fine particles (B) appropriate, voids can be formed more appropriately in the conductive layer. That is, the dendritic conductive fine particles (B) preferably have an AD / TD ratio (AD / TD) of 0.3 to 0.9. By setting AD / TD to 0.3 or more, the numerical values of AD and TD become more appropriate, and the change in film thickness after hot pressing tends not to be too large. On the other hand, by making AD / TD 0.9 or less, the numerical values of AD and TD become more appropriate, and the change in film thickness after hot pressing tends not to be too small.
  • the proportion of the dendritic conductive fine particles (B) used in the conductive layer is preferably 50% to 90% by weight and more preferably 60% to 80% by weight in 100% by weight of the conductive layer.
  • the amount used is 50% by weight or more, desired conductivity tends to be easily obtained.
  • the amount is 90% by weight or less, the amount of resin for forming a sheet tends to be easily secured.
  • the dendrite-like conductive fine particles (B) are shaped like tree branches as compared with spherical conductive fine particles or flaky conductive fine particles (see FIG. 1B). Easy to form. Therefore, when a conductive layer is formed using dendritic conductive fine particles (B), voids are likely to occur. By using the dendritic conductive fine particles (B), it is possible to stain in the horizontal direction compared to the case where conductive sheets using spherical conductive particles or flaky conductive fine particles as the main component are heated and pressed under the same conditions. It is possible to reduce the ejection more.
  • thermosetting resin (A) and the dendritic conductive fine particles (B) can be included.
  • additives can be included.
  • silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants and the like can be included.
  • a conductive resin composition (C) is prepared by mixing at least a thermosetting resin (A) and dendritic conductive fine particles (B).
  • the mixing method is not particularly limited, but preferred examples include a method using a mixer, a dissolver, a Hoover Mahler, a three-roll mill, a sand mill, and the like.
  • the conductive resin composition (C) for example, it is coated on a release sheet to form a conductive layer coating.
  • the coating method is not particularly limited, and a conventionally known method can be used without limitation. For example, gravure coating, kiss coating, die coating, lip coating, comma coating, blade coating, roll coating, knife coating, spray coating, bar coating, spin coating, dip coating, etc. A film is formed.
  • the thickness of the conductive layer before being hot-pressed can be appropriately set according to the use, but is preferably 5 ⁇ m to 100 ⁇ m.
  • the thickness is a value measured according to JISB7503 (dial gauge).
  • the film thickness of the conductive sheet of the first embodiment after hot pressing is preferably 0.25 to 10 times the average particle diameter D 50 of the dendritic conductive fine particles (B), preferably 0.5 to 5 times is more preferable.
  • the application of the conductive sheet of the first embodiment is not particularly limited, and can be used for all applications in which a conductive sheet is desired to be used.
  • it can be used for the purpose of attaching an electromagnetic wave shield to a printed wiring board, or for grounding a circuit formed on the printed wiring board.
  • it can be used by being attached to various electronic devices such as home appliances such as a microwave oven.
  • the conductive sheet of the first embodiment even if only one layer is used instead of a three-layer structure, an adhesive force to an adherend can be expressed by using a thermoplastic resin. it can. As a result, there is an excellent merit that it can be used for thin film applications. Moreover, since the electroconductive layer which uses a thermoplastic resin and dendritic electroconductive fine particles as an essential component is used without using metal foil like patent document 1, it is excellent in flexibility. Therefore, it can be suitably applied to flexible printed wiring boards and the like. Further, by using dendritic conductive fine particles as the conductive fine particles, voids or the like can be formed in the conductive layer, and the seepage during heat pressing can be absorbed by the voids.
  • the seepage of the conductive layer can be minimized.
  • the use of dendritic conductive fine particles can effectively suppress the seepage of the conductive layer.
  • the conductive sheet of the present invention it can be suitably used as an application used under severe conditions such as high temperature and high humidity.
  • the conductive sheet according to the second embodiment is a conductive sheet with an insulating layer in which an insulating layer and the conductive layer of the first embodiment are stacked.
  • the insulating layer used in the conductive sheet of the second embodiment is not particularly limited as long as it does not depart from the spirit of the present invention.
  • the raw material of an insulating layer is not specifically limited, For example, it is preferable to use resin which has insulation, such as the thermosetting resin (A) which can be used with a conductive layer.
  • resin which has insulation such as the thermosetting resin (A) which can be used with a conductive layer.
  • plastic films such as polyester, a polycarbonate, a polyimide, polyphenylene sulfide, can also be used.
  • the insulating layer contains a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling adjusting agent, a filler, a flame retardant and the like as necessary. You can also.
  • the use of the conductive sheet of the second embodiment is not particularly limited, for example, the conductive layer side can be attached to the outer main surface of the printed wiring board and used as an electromagnetic wave shielding film.
  • a well-known method can be used for the formation method of the insulating layer of the electroconductive sheet of 2nd Embodiment, and the lamination
  • a conductive layer can be formed on a previously formed insulating layer, or can be formed on the insulating layer by the same manufacturing method as the conductive layer described in the first embodiment.
  • the thickness of the insulating layer varies depending on the application, but is preferably 5 ⁇ m to 50 ⁇ m, for example.
  • the conductive layer is the same as that of the first embodiment, the same effect as that of the first embodiment can be obtained. Moreover, by using a laminated body with an insulating layer, it is possible to increase the mechanical strength of the conductive sheet or to impart insulating characteristics to the surface.
  • the layer for laminating the conductive layer is not particularly limited, and layers having various functions are used depending on the purpose.
  • stacked optical films such as a support layer, a semiconductor layer, a protective film, and an antireflection film, may be sufficient.
  • the method for manufacturing a conductive sheet according to the third embodiment is different from the method for manufacturing a conductive sheet according to the first embodiment in that a press process is included before the hot pressing described in the first embodiment.
  • a press process is included before the hot pressing described in the first embodiment.
  • the conductive sheet of the third embodiment is formed after applying and forming a conductive layer, and before performing a heat press when adhering to the adherend, a pressurizing step (hereinafter referred to as adherend and conductive).
  • adherend and conductive a pressurizing step
  • adherend and conductive a pressurizing step
  • it is manufactured by performing a “pre-pressurization step”.
  • the pre-pressurization step can be appropriately changed depending on the application, it is preferable to apply a pressure of 2.5 MPa to 50 MPa (25 kg / cm 2 to 510 kg / cm 2.
  • the temperature does not exclude heating. It is not intended to induce deformation or breakage of the dendritic conductive fine particles (B) and to promote the flow of the thermoplastic resin. Therefore, it is preferable that the heating is not performed or the temperature is not higher than the temperature that promotes the flow of the thermoplastic resin. .
  • pressure is applied to the conductive sheet in advance to deform the dendritic conductive fine particles (B) or fold the dendritic particles, thereby dendritic conductive fine particles (B)
  • the contact between each other becomes dense, and the conductive properties of the conductive layer can be further improved.
  • a method for applying pressure to the conductive sheet there is a method using a flat plate press, a roll press or the like. Among these, a roll press machine that can easily increase the pressure (increase the linear pressure) is preferable.
  • rolls having different surface hardnesses such as a metal roll and a resin roll can be used.
  • the conductive layer of the third embodiment performs a pre-pressurization step.
  • the thickness after the heat pressing under the above conditions needs to be in the range of 30 or more and 95 or less when the thickness of the conductive layer before the heat pressing is 100. That is, the thickness of the conductive layer before joining to the adherend after the pre-pressurization step is heated under the above conditions (150 ° C., 2 MPa, heated for 30 minutes).
  • the change needs to be included in the above range (a range of 30 or more and 95 or less when the thickness of the conductive layer is 100).
  • a film thickness may change in a pre-pressurization process. Even if the film thickness changes in the pre-pressurization step, the adherend and the conductive sheet can be removed if there is a gap for absorbing the movement of the thermoplastic resin composition or the bleed low molecular weight component. This is because even if heat-pressing at the time of joining, the seepage of the conductive layer can be effectively suppressed.
  • the conductive sheet having the same conductive layer as in the first embodiment since the same effect as in the first embodiment can be obtained.
  • the conductive layer is pressed in advance and the dendritic conductive fine particles (B) are crushed before the printed wiring board and the conductive sheet are heated and pressed, there is a merit that the conductive characteristics can be effectively extracted. is there.
  • the pre-pressurization step of the third embodiment can be suitably added.
  • the conductive sheet is a conductive sheet with an insulating layer
  • the timing of performing the pre-pressurization step is not limited, but it is more preferable to perform the pre-pressurization step before laminating the insulating layer.
  • the pre-pressurization process is performed on the conductive layer, the surface of the conductive layer becomes smoother.
  • the thickness accuracy of the insulating layer is improved. It becomes easy to obtain characteristics.
  • the conductive sheet according to the fourth embodiment includes a single conductive layer.
  • the conductive layer of the conductive sheet according to the fourth embodiment includes a thermosetting resin (A) and dendritic conductive fine particles (B) as essential components, and dendritic conductive fine particles (B the average particle diameter D 90 of) is intended for a film thickness of the conductive layer is in the range of 0.5 to 3 times.
  • the thickness of the conductive layer specified in the first embodiment is 150 ° C., 2 MPa, and the thickness of the conductive layer after 30 minutes is 30 minutes, the thickness of the conductive layer before the hot press is 100. It is not always necessary to be in the range of 30 or more and 95 or less. This is for a film thickness of the conductive layer, by an average particle diameter D 90 of the dendrite conductive fine particles (B) to 3 times or less, the tip of the fine particles, not easily protrude from the conductive layer when applying the heat press Because it becomes a tendency. Further, the average particle diameter D 90 by more than 0.5 times, because the gap in the conductive layer is less likely excessively occur.
  • the thickness of the conductive layer before hot pressing is 100 Further, it is more preferable to satisfy the condition of being in the range of 30 to 95.
  • the conductive sheet of the fourth embodiment is laminated so that the conductive layer side of the conductive sheet of the fourth embodiment is in contact with an adherend such as a printed wiring board, and is subjected to the heat press step described in the first embodiment.
  • a conductive sheet can be stuck on a to-be-adhered body.
  • the electroconductive sheet of 4th Embodiment since the thermoplastic resin is contained in the electroconductive layer, adhesiveness with a to-be-adhered body can be maintained favorable.
  • the conditions of a heat press can be arbitrarily set according to the use and needs of a conductive layer (for example, according to the electroconductive characteristic calculated
  • the adherend and the conductive sheet may be joined via an adhesive layer, for example, without performing the heat press step.
  • the method through the adhesive layer is not particularly limited.
  • an adhesive layer different from the conductive layer is provided on the conductive sheet, or an adhesive layer is provided on the adherend side and the adhesive layer is attached via the adhesive layer. The method of joining the body is mentioned.
  • thermoplastic resin (A) constituting the conductive layer are as described in the first embodiment.
  • thermoplastic resin (A) for the conductive layer it is preferable to use a curing agent in combination with the thermoplastic resin (A) for the conductive layer. Examples of the curing agent are also as described in the first embodiment.
  • dendritic conductive fine particles (B) those described in the first embodiment can be suitably applied.
  • the dendritic conductive fine particles (B) preferably have an average particle diameter D 50 of 3 ⁇ m to 50 ⁇ m and an average particle diameter D 90 of 1.5 to 5 times the average particle diameter D 50 .
  • the average particle size D 50 is more preferably 3 ⁇ m to 40 ⁇ m, and further preferably 5 ⁇ m to 25 ⁇ m.
  • Mean By particle diameter D 50 is equal to or greater than 3 [mu] m, easily can voids in the conductive layer, it can be reduced exudation. On the other hand, the average particle diameter D 50 is 50 ⁇ m or less, it becomes easy to form the conductive layer of the appropriate thickness.
  • the average particle diameter D 90 of the dendrite conductive fine particles (B) is preferably from 1.5 to 5 times the average particle diameter D 50, 2-fold to 3.5-fold and more preferably.
  • the value of the average particle diameter D 90 tends to depend on the average particle diameter of the average particle diameter D 50 , but is preferably 4.5 ⁇ m to 250 ⁇ m. The reason is as described in the first embodiment.
  • the dendrite-like conductive fine particles (B) preferably have a tap density (hereinafter also referred to as “TD”) of 0.8 g / cm 3 to 2.5 g / cm 3 .
  • the dendritic conductive fine particles (B) preferably have an apparent density (hereinafter also referred to as “AD”) of 0.4 g / cm 3 to 1.5 g / cm 3 .
  • AD apparent density
  • the dendritic conductive fine particles (B) have an AD / TD ratio (AD / TD) of 0.3 to 0.9.
  • the thickness of the conductive sheet of the fourth embodiment is not particularly limited, but is preferably 5 ⁇ m to 100 ⁇ m, and more preferably 10 ⁇ m to 50 ⁇ m.
  • the thickness is a value measured according to JISB7503 (dial gauge).
  • JISB7503 dial gauge
  • the proportion of the dendritic conductive fine particles (B) used in the conductive layer is preferably 50% to 90% by weight and more preferably 60% to 80% by weight in 100% by weight of the conductive layer.
  • the reason is as described in the first embodiment.
  • an additive can be added as necessary, and examples thereof include the additives described in the first embodiment.
  • the manufacturing method of an electroconductive sheet is as having described in 1st Embodiment.
  • the same effect as in the first embodiment can be obtained.
  • a dendrite-like conductive fine particle (B) in the conductive layer having an average particle diameter D 90 in the range of 0.5 to 3 times the thickness of the conductive layer is used as the thickness of the conductive layer.
  • the conductive sheet of the fifth embodiment is a laminate of the insulating layer and the conductive layer of the fourth embodiment.
  • the electromagnetic wave shielding film may be laminated with other layers (for example, a protective layer and an adhesive layer) other than the insulating layer and the conductive layer.
  • the material used for the insulating layer is not particularly limited, but preferred examples include those described in the second embodiment.
  • silane coupling agents, antioxidants, pigments, dyes, tackifier resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc., as necessary Can also be included.
  • the method for forming the insulating layer is as described in the second embodiment.
  • the thickness of the insulating layer is preferably 50 to 200 when the thickness of the conductive layer is 100. By making the thickness within the above range, it becomes easy to balance the physical properties of the electromagnetic wave shielding film.
  • the conductive layer of the conductive sheet of the fifth embodiment does not necessarily need to undergo a heating process, and the film thickness of the conductive layer indicates a film thickness when actually used, and before the heating process. Even after the heating process.
  • the adherend to which the electromagnetic wave shielding film can be attached is not particularly limited, and for example, a flexible printed wiring board that is repeatedly bent can be given as a representative example.
  • the present invention can be applied to various substrates such as rigid printed wiring boards, home appliances such as microwave ovens that require electromagnetic shielding, general electronic devices, and general members that want to shield electromagnetic waves.
  • the average particle diameter D 50 and the average particle diameter D 90 were measured using a Microtrac MT3300 manufactured by Nikkiso Co., Ltd.
  • the apparent density was determined by an apparent density test method for metal powder defined in JIS Z 2504: 2000.
  • the tap density was determined by JIS Z 2512: Metal powder-tap density measurement method.
  • a conductive sheet was prepared using the materials shown in Table 1A as the dendritic conductive fine particles, and using a urethane resin (manufactured by Toyochem) as the thermosetting resin.
  • the ratio of dendritic conductive fine particles (B) to thermosetting resin (A) was 250 parts by weight of dendritic conductive fine particles (B) with respect to 100 parts by weight of resin solids.
  • Examples 6 to 10 Using a urethane resin (manufactured by Toyochem Co., Ltd.) as an insulating layer on one side of the conductive sheets obtained in Examples 1 to 5, coating and drying to a dry film thickness of 10 ⁇ m, an insulating layer having a total thickness of 20 ⁇ m An attached conductive sheet was obtained.
  • a urethane resin manufactured by Toyochem Co., Ltd.
  • Example 11 The surface of the conductive sheet obtained in Example 2 was pre-pressurized using a roll press so that a pressure of 3 MPa was applied. Then, a conductive sheet with an insulating layer having a total thickness of 20 ⁇ m is obtained by applying and drying urethane resin (manufactured by Toyochem) as an insulating layer on the pre-pressurized conductive sheet surface so that the dry film thickness becomes 10 ⁇ m. It was.
  • urethane resin manufactured by Toyochem
  • Example 12 and 13 A conductive sheet with an insulating layer was obtained in the same manner as in Example 11 except that the prepressurizing pressure was changed to 10 MPa and 40 MPa, respectively.
  • the evaluation criteria are as follows. ⁇ : The amount of exudation of the conductive sheet is less than 0.01 mm. ⁇ : The amount of exudation of the conductive sheet is 0.01 mm or more and less than 0.05 mm. ⁇ : The amount of exudation of the conductive sheet is 0.05 mm or more.
  • connection resistance value A Samples having a width of 20 mm and a length of 50 mm were prepared for the conductive sheets of Examples 1 to 5 and Comparative Examples 1 and 2, and the connection resistance value A was measured using a separately prepared flexible printed wiring board. Specifically, as shown in FIGS. 2A to 2F, a circuit 2 made of copper foil having a thickness of 18 ⁇ m and not electrically connected is formed on a polyimide film 1 having a thickness of 12.5 ⁇ m. A flexible printed wiring board was prepared by laminating a cover film 3 having a through hole 4 having a thickness of 37.5 ⁇ m and a diameter of 0.8 mm, with an adhesive.
  • a conductive sheet 5 is placed on the cover film 3, and a 200 ⁇ m thick stainless steel plate 6 whose surface is treated with 0.1 ⁇ m thick nickel is placed on the conductive sheet 5 at 150 ° C., Heat pressing was performed for 30 minutes under the condition of 2.0 MPa. Thereafter, the resistance value in the vertical direction between the circuit 2 and the stainless steel plate 6 was measured using a four-point probe of “Lorester GP” manufactured by Mitsubishi Chemical Corporation.
  • the evaluation criteria are as follows. ⁇ : Less than 200 m ⁇ ⁇ : 200 m ⁇ or more, less than 500 m ⁇ x: 500 m ⁇ or more
  • connection resistance value B For the conductive sheets with insulating layers of Examples 6 to 13 and Comparative Examples 3 and 4, samples having a width of 20 mm and a length of 50 mm were prepared, and the connection resistance value B was measured using a separately prepared flexible printed wiring board. Specifically, as shown in FIGS. 3A to 3F, circuits 2A and 2B made of copper foil having a thickness of 18 ⁇ m and not electrically connected are formed on a polyimide film 1 having a thickness of 12.5 ⁇ m. A flexible printed wiring board was prepared in which a cover film 3 having a through hole 4 having a thickness of 37.5 ⁇ m and a diameter of 0.8 mm was laminated on the circuit 2A.
  • a conductive sheet 5 is placed on the cover film 3, and a 200 ⁇ m thick insulating layer 7 whose surface is treated with 0.1 ⁇ m thick nickel is placed on the conductive sheet 5 at 150 ° C. Heating and pressing was performed for 30 minutes under the condition of 2.0 MPa, and the resistance value between the circuit 2A and the circuit 2B was measured using a four-point probe of “Lorestar GP” manufactured by Mitsubishi Chemical Corporation.
  • the evaluation criteria are as follows. ⁇ : Less than 300 m ⁇ ⁇ : 300 m ⁇ or more, less than 500 m ⁇ x: 500 m ⁇ or more
  • the evaluation criteria are as follows. ⁇ : 3000 times or more ⁇ : 2500 times or more and less than 3000 times ⁇ : less than 2500 times
  • an average particle diameter D 50 was prepared a conductive layer by a silver 13 .mu.m.
  • the thermosetting resin a urethane resin (manufactured by Toyochem) is used, and the ratio of the dendritic conductive fine particles (B) to the thermosetting resin is 250 parts by weight of the dendritic conductive fine particles with respect to 100 parts by weight of the resin. Then, it was coated on a polyethylene terephthalate film having a surface of 100 ⁇ m peel-treated so that the dry film thickness was 10 ⁇ m using a bar coater, and dried at 100 ° C.
  • a conductive layer for 3 minutes to obtain a conductive layer.
  • an urethane resin manufactured by Toyochem Co., Ltd.
  • coating and drying were performed so that the dry film thickness was 15 ⁇ m, and an electromagnetic wave shielding film having an insulating layer with a total thickness of 25 ⁇ m was obtained. .
  • Examples 15 to 17 were carried out in the same manner as in Example 1 except that the conductive fine particles, the average particle diameter D 90, and the average particle diameter D 50 were replaced with the raw materials shown in Table 2A to obtain an electromagnetic wave shielding film. .
  • a conductive layer was prepared using the materials shown in Table 2A as the dendritic conductive fine particles (B) and a urethane resin (manufactured by Toyochem) as the thermosetting resin (A).
  • the ratio of the dendritic conductive fine particles (B) to the thermosetting resin (A) is such that the dendritic conductive fine particles are 250 parts by weight with respect to 100 parts by weight of the resin, and the thickness is 100 ⁇ m so that the dry film thickness is 10 ⁇ m.
  • coating was performed using a bar coater and dried at 100 ° C. for 3 minutes to obtain a conductive sheet.
  • an electromagnetic field film having an insulating layer with a total thickness of 18 ⁇ m is obtained. It was.
  • thermosetting resin a urethane resin (manufactured by Toyochem) is used, and the ratio of the dendritic conductive fine particles (B) to the thermosetting resin is 250 parts by weight of the dendritic conductive fine particles with respect to 100 parts by weight of the resin. Then, it was coated on a polyethylene terephthalate film having a 100 ⁇ m thick surface peel-treated so that the dry film thickness was 10 ⁇ m, and dried at 100 ° C. for 3 minutes to obtain a conductive sheet.
  • the thermosetting resin a urethane resin (manufactured by Toyochem) is used, and the ratio of the dendritic conductive fine particles (B) to the thermosetting resin is 250 parts by weight of the dendritic conductive fine particles with respect to 100 parts by weight of the resin. Then, it was coated on a polyethylene terephthalate film having a 100 ⁇ m thick surface peel-treated so that the dry film thickness was 10 ⁇ m, and dried at 100 °
  • a urethane resin (manufactured by Toyochem Co., Ltd.) was used as an insulating layer on one side of the conductive sheet, and a dry film thickness of 25 ⁇ m was provided to obtain an electromagnetic wave shielding film having an insulating layer with a total thickness of 35 ⁇ m.
  • Example 20 The surface of the conductive sheet obtained in Example 18 was pre-pressurized using a roll press so that a pressure of 3 MPa was applied. After that, a conductive sheet with an insulating layer having a total thickness of 20 ⁇ m is formed by applying and drying urethane resin (manufactured by Toyochem) as an insulating layer on the pre-pressurized conductive sheet surface so that the dry film thickness becomes 10 ⁇ m. Obtained.
  • urethane resin manufactured by Toyochem
  • Example 21 and 22 A conductive sheet with an insulating layer was obtained in the same manner as in Example 20 except that the prepressurizing pressure was changed to 10 MPa and 40 MPa, respectively.
  • dendrite silver dendrite copper powder, flaky silver, and spherical silver in Tables 2A and 2B, those manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. were used.
  • the dendrite silver-coated copper powders in Tables 2A and 2B use dendrite copper powders manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., and are coated with silver under the following conditions. A 10% by weight dendrite silver-coated copper powder was obtained.
  • the electromagnetic shielding films of the example of 6 mm width and 120 mm length and the comparative example were evaluated by the same method as the refractive evaluation described in Examples 1 to 13 and Comparative Examples 1 to 4. Evaluation criteria were the same as those described above. It is as follows.
  • ⁇ Insulation reliability> The electromagnetic wave shielding films of Examples 11 to 16 and Comparative Examples 11 to 15 having a width of 100 mm and a length of 100 mm were prepared and subjected to heat press treatment at 150 ° C. for 30 minutes and 2.0 MPa. After 1 minute when contact was made for 1 minute under the condition that the printing voltage was 100V, using HIPE-UP (MCP-HT450) surface resistance tester TYPE URS made by Mitsubishi Chemical Co., Ltd. The insulation reliability was evaluated. The evaluation criteria are as follows.
  • the average particle diameter D 90 of the dendritic conductive fine particles is specified within the range of 0.5 to 3 times the film thickness of the conductive layer, so that the conductive fine particles of the conventional shape are obtained. It can be seen that there is less seepage of the conductive layer in the lateral direction after hot pressing. Moreover, it was confirmed that it showed excellent flexibility and high insulation reliability.
  • An electromagnetic wave shielding film having at least an insulating layer and a conductive layer,
  • the conductive layer contains at least a thermosetting resin (A) and dendritic conductive fine particles (B), and the average particle diameter D90 of the dendritic conductive fine particles (B) is 0.5 to 0.5 with respect to the thickness of the conductive layer.
  • An electromagnetic wave shielding film characterized by being in a range of 3 times.
  • the dendritic conductive fine particles (B) include a nucleus containing copper and a silver coating layer, Item 4.
  • (Appendix 5) 5.
  • the conductive sheet according to the present invention can reduce the seepage of the conductive layer to a minimum in a process such as a heating process, the conductive sheet is attached to all adherends such as printed wiring boards and flexible printed boards. It can be suitably applied to applications that are used at least. In particular, it is particularly effective for sticking to the use of electronic parts where the bleeding of the conductive sheet is a problem.
  • the conductive sheet according to the present invention can be used by being laminated with an insulating layer, a support layer, an adhesive layer, a film having another function, or the like.

Abstract

La présente invention concerne une feuille électroconductrice possédant une bonne aptitude au traitement. Avec ladite feuille, il devient possible de réduire le lessivage d'une couche électroconductrice dans une étape de pressage à chaud permettant de faire adhérer ladite feuille à un objet d'intérêt, tel qu'une carte de circuits imprimés ; un procédé permettant de fabriquer ladite feuille ; et analogues. Cette feuille électroconductrice concerne une couche électroconductrice comprenant au moins une résine thermodurcissable (A) et des microparticules dendritiques électroconductrices (B). L'épaisseur de la couche électroconductrice satisfait aux exigences (i) et/ou (ii) suivantes : (i) l'épaisseur de la couche électroconductrice devient 30 à 95 après un pressage à chaud dans les conditions suivantes : 150 °C, 2 MPa et 30 minutes, lorsque l'épaisseur de la couche électroconductrice avant le pressage à chaud est définie à 100 ; et (ii) le diamètre de particule moyen (D90) des microparticules dendritiques électroconductrices (B) devient 0,5 à 3 fois l'épaisseur de la couche électroconductrice. Les microparticules dendritiques électroconductrices (B) présentent un diamètre de particule moyen (D50) de 3 à 50 µm inclus et sont contenues à hauteur de 50 à 90 % en poids inclus dans la couche électroconductrice.
PCT/JP2012/003541 2011-05-31 2012-05-30 Feuille électroconductrice et son procédé de fabrication, et composant électronique WO2012164925A1 (fr)

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CN201280026529.XA CN103597551B (zh) 2011-05-31 2012-05-30 导电性片及其制造方法以及电子零件
KR1020137033789A KR101846474B1 (ko) 2011-05-31 2012-05-30 도전성 시트 및 그 제조 방법, 및 전자 부품
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JP2016094511A (ja) * 2014-11-12 2016-05-26 デクセリアルズ株式会社 熱硬化性接着組成物、及び熱硬化性接着シート
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JP2019163419A (ja) * 2018-03-20 2019-09-26 タツタ電線株式会社 導電性接着剤層
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JP6431998B1 (ja) * 2018-03-20 2018-11-28 タツタ電線株式会社 導電性接着剤層
JP2019041132A (ja) * 2018-12-13 2019-03-14 東洋インキＳｃホールディングス株式会社 導電性樹脂組成物、導電性接着シート、電磁波シールドシートおよびプリント配線板
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CN103597551B (zh) 2016-04-06
KR101931274B1 (ko) 2018-12-20
JPWO2012164925A1 (ja) 2015-02-23
KR20180036806A (ko) 2018-04-09

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