WO2016076096A1 - Composition adhésive thermodurcissable - Google Patents

Composition adhésive thermodurcissable Download PDF

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Publication number
WO2016076096A1
WO2016076096A1 PCT/JP2015/079867 JP2015079867W WO2016076096A1 WO 2016076096 A1 WO2016076096 A1 WO 2016076096A1 JP 2015079867 W JP2015079867 W JP 2015079867W WO 2016076096 A1 WO2016076096 A1 WO 2016076096A1
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WIPO (PCT)
Prior art keywords
thermosetting adhesive
conductive filler
epoxy resin
mass
adhesive composition
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PCT/JP2015/079867
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English (en)
Japanese (ja)
Inventor
芳人 田中
稔城 名取
利之 峯岸
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デクセリアルズ株式会社
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Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to KR1020177011235A priority Critical patent/KR101941386B1/ko
Priority to CN201580059044.4A priority patent/CN107109161B/zh
Publication of WO2016076096A1 publication Critical patent/WO2016076096A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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

Definitions

  • the present invention relates to a conductive thermosetting adhesive composition for connecting and reinforcing a ground terminal of a flexible printed wiring board to a metal plate.
  • a flexible printed wiring board is bonded to a metal plate and reinforced, and a ground terminal is electrically connected to the metal plate to shield it.
  • a conductive thermosetting adhesive composition is used for bonding the flexible printed wiring board and the metal plate.
  • conventional techniques there are, for example, Japanese Patent Application Laid-Open Nos. 2011-79959 and 2013-41869.
  • the present invention has been proposed in view of such a conventional situation, and provides a thermosetting adhesive composition having conductivity and capable of suppressing resin seepage.
  • thermosetting adhesive composition includes an acrylic copolymer, a thermosetting epoxy resin in which an epoxy group remains in the molecule, and an epoxy resin curing that causes the thermosetting epoxy resin to undergo a curing reaction.
  • a resin component containing an agent, a dendritic conductive filler dispersed in the resin component, and a non-conductive filler dispersed in the resin component, and an average particle diameter of the non-conductive filler Is a thermosetting adhesive composition having a range of 3 ⁇ m to 15 ⁇ m.
  • the present invention is the thermosetting adhesive composition in which the non-conductive filler is contained in the range of 4 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer.
  • the present invention is a thermosetting adhesive composition in which the non-conductive filler is an organic filler.
  • the present invention is the thermosetting adhesive composition, wherein the non-conductive filler is an organic filler that is polyurethane resin particles.
  • the present invention provides an alkyl (meth) acrylate monomer in the range of 55 wt% or more and 80 wt% or less when the acrylic copolymer is 100 wt% of a monomer that generates the acrylic copolymer by a copolymerization reaction.
  • the present invention is the thermosetting adhesive composition, wherein the epoxy resin curing agent is an organic acid dihydrazide.
  • the liquid thermosetting epoxy resin which is the liquid epoxy resin, is 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
  • the solid thermosetting epoxy resin which is contained in the following range and is the solid epoxy resin, is contained in the range of 10 parts by mass to 50 parts by mass, and consists of the acrylic copolymer and the epoxy resin.
  • curing agent is a thermosetting adhesive composition contained in 1 to 50 mass parts with respect to 100 mass parts of raw material components.
  • the present invention is a thermosetting adhesive composition in which the average particle diameter of the dendritic conductive filler is in the range of 3 ⁇ m to 20 ⁇ m.
  • the present invention is a thermosetting adhesive composition formed into a film.
  • the present invention is a thermosetting adhesive composition in which the average particle size of the nonconductive filler is smaller than the average particle size of the dendritic conductive filler.
  • the non-conductive filler having a predetermined average particle diameter is entangled with the dendritic conductive filler, the flow of the resin component can be suppressed and the resin seepage can be suppressed.
  • FIG. 1 is a perspective view for explaining a connection method using a thermosetting adhesive sheet.
  • FIG. 2 is a cross-sectional view of a connection structure using a thermosetting adhesive sheet.
  • FIG. 3 is a cross-sectional view of a thermosetting adhesive sheet for explaining a connection method using the thermosetting adhesive sheet.
  • FIG. 4 is a view for explaining the shape of the dendritic filler.
  • thermosetting adhesive composition When a monomer that generates an acrylic resin by a polymerization reaction is called an acrylic monomer, the thermosetting adhesive composition of the present invention is an acrylic copolymer that is an acrylic polymer obtained by copolymerizing two or more types of acrylic monomers. (A) is contained. In addition, the thermosetting adhesive composition of the present invention contains a thermosetting epoxy resin (B) in which an epoxy group remains in the molecule and is classified as a prepolymer. The thermosetting epoxy resin (B) is a polymer having reactivity, and when the polymerization reaction is initiated by the reaction initiator, it is crosslinked to form a network polymer.
  • thermosetting adhesive composition of the present invention includes a resin component, an epoxy resin curing agent (C), and a tree branch.
  • a conductive filler (D) in a shape and a non-conductive filler (E) are contained.
  • the components (A) to (E) of the thermosetting adhesive composition will be described in detail.
  • the acrylic copolymer of the present invention imparts film-forming properties during film molding and imparts flexibility and toughness to the cured product.
  • (meth) acrylate means acrylate (acrylic acid ester) or methacrylate (methacrylic acid ester).
  • the alkyl (meth) acrylate can be appropriately selected from those used in conventional acrylic thermosetting adhesives applied in the field of electronic components, and can be used as a monomer.
  • An alkyl (meth) acrylate having 4 to 12 alkyl groups can be used.
  • the amount of acrylonitrile (AN) in all the monomers that produced the acrylic copolymer is too low, the heat resistance is lowered, and if it is too much, it tends to be difficult to dissolve in the solvent. 30 wt% or less.
  • the amount of glycidyl methacrylate (GMA) in all the monomers that produced the acrylic copolymer is too small, the heat resistance is lowered, and if too much, the peel strength tends to be lowered. It is 15 wt% or less.
  • the polymerization method of the acrylic copolymer is not particularly limited, but pearl polymerization is preferably used from the viewpoint of obtaining a high molecular weight.
  • the weight average molecular weight of the acrylic copolymer is too small, the heat resistance is lowered.
  • the weight average molecular weight is too large, the solution viscosity is increased and the coating property tends to be deteriorated. Therefore, it is preferably 500,000 to 700,000, more preferably 550000 or more. 650000 or less.
  • thermosetting epoxy resin forms a three-dimensional network structure and imparts good heat resistance and adhesiveness.
  • the thermosetting epoxy resin includes a solid thermosetting epoxy resin that is solid at room temperature and There is a liquid thermosetting epoxy resin that is liquid at room temperature, and the thermosetting epoxy resin contained in the present invention is a mixture of a solid thermosetting epoxy resin and a liquid thermosetting epoxy resin.
  • normal temperature means a temperature range of 5 ° C. to 35 ° C. (5 ° C. or more and 35 ° C. or less) defined by JIS Z 8703.
  • the liquid thermosetting epoxy resin is not particularly limited as long as it is liquid at room temperature, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac phenol type epoxy resin, and naphthalene type epoxy resin. Among these, one kind can be used alone, or two or more kinds can be used in combination. In particular, it is preferable to use a bisphenol A type epoxy resin or a bisphenol F type epoxy resin from the viewpoint of tackiness and flexibility of the film.
  • the content of the liquid thermosetting epoxy resin is preferably 5 masses per 100 parts by mass of the acrylic copolymer. Part or more and 30 parts by mass or less, and more preferably 15 parts by mass or more and 25 parts by mass or less.
  • the solid thermosetting epoxy resin is not particularly limited as long as it is compatible with a liquid thermosetting epoxy resin and is solid at room temperature.
  • a polyfunctional epoxy resin, a dicyclopentadiene (DCPD) type epoxy resin, A novolak phenol type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, and the like are listed, and one of these can be used alone, or two or more can be used in combination. Among these, it is preferable to use a DCPD type epoxy resin.
  • the content of the solid thermosetting epoxy resin is too small, the heat resistance is lowered, and if it is too much, the adhesiveness tends to be lowered. Therefore, 10 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer.
  • the range of not more than part by mass is preferable, and the range of not less than 30 parts by mass and not more than 50 parts by mass is more preferable.
  • curing agent the well-known hardening
  • one can be used alone, or two or more can be used in combination.
  • the organic acid dihydrazide Since the organic acid dihydrazide is solid at room temperature, it can improve the room temperature storage property of the thermosetting adhesive composition.
  • the organic acid dihydrazide include adipic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, iminodiacetic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide dihydrazide, sebacic acid dihydrazide dihydrazide, , Maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4′-bisbenzenedi
  • the average particle diameter of the organic acid dihydrazide is preferably in the range of 0.5 ⁇ m to 15 ⁇ m, and more preferably in the range of 1 ⁇ m to 5 ⁇ m. If the average particle size is too small, the organic acid dihydrazide particles tend to dissolve and the storage stability at normal temperature decreases when an organic solvent is used for application of the thermosetting adhesive composition, and if the average particle size is too large Since the applicability of the thermosetting adhesive composition is reduced and the particle size is large, it becomes difficult to sufficiently mix with an acrylic copolymer or a thermosetting epoxy resin.
  • the content of the epoxy resin curing agent is too small, unreacted epoxy groups remain and crosslinking is not sufficient, so heat resistance and adhesiveness are lowered, and if too much, excessive curing agent remains unreacted, Since heat resistance and adhesiveness tend to decrease, it is preferably used in the range of 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the acrylic copolymer and the thermosetting epoxy resin. It is more preferable to use in the range of not less than 30 parts by mass.
  • the dendritic shape is also called a dendrite.
  • “dendritic shape” means a shape like a branch of a tree, and the dendritic conductive filler 21 includes a main branch 31 and side branches. 32, 33.
  • the main branch 31 and the side branches 32 and 33 are easily entangled with each other. Even electrical connection can be maintained.
  • the tap density is measured by a method defined in JISJZ 2512. Specifically, a specified amount of powder is put in a container, and a tapping device is used to tap until the volume of the powder does not decrease any more, and the mass of the powder is divided by the powder volume after tapping.
  • the dendritic conductive filler 21 can be obtained by forming the main branch 31 and the side branches 32 and 33 on the metal powder by, for example, an electrolytic method, a liquid phase reduction method, or the like.
  • the metal powder include copper powder, silver powder, and nickel powder.
  • the main branch 31 and the side branches 32 and 33 include copper, silver, and gold. That is, examples of the dendritic conductive filler 21 include copper-coated copper powder, silver-coated copper powder, gold-coated copper powder, silver-coated nickel powder, and gold-coated nickel powder. Among these, silver-coated copper powder is used. It is preferable to use it.
  • the average particle diameter of the dendritic conductive filler 21 is preferably in the range of 3 ⁇ m to 20 ⁇ m, and more preferably in the range of 5 ⁇ m to 15 ⁇ m. If the average particle size is too small, it is difficult to form the main branches 31 and the side branches 32 and 33, and if the average particle size is too large, it is difficult to reduce the film thickness.
  • the average particle diameter of the dendritic conductive filler 21 is, for example, a particle diameter D50 that is 50% of the total sieve fraction calculated from the particle diameter distribution measurement result by a laser diffraction scattering method.
  • the addition amount of the dendritic conductive filler 21 is preferably used in the range of 100 to 300 parts by mass, and in the range of 150 to 250 parts by mass with respect to 100 parts by mass of the acrylic copolymer. More preferably, it is used. If the addition amount is too small, the conductivity and the resin flow tend to deteriorate, and if the addition amount is too large, the conduction stability in a high temperature environment or a high temperature and high humidity environment tends to decrease.
  • a non-dendritic conductive filler such as a spherical shape, a flake shape, or a filament shape may be added.
  • the proportion of the dendritic conductive filler in the conductive filler is preferably 40 wt% or more and 100 wt% or less, preferably 60 wt% or more and 100 wt% or less. It is more preferable to use within a range.
  • the ratio of the dendritic conductive filler 21 is too small, the conduction stability in a high temperature environment or a high temperature and high humidity environment tends to be lowered.
  • the average particle diameter of the non-conductive filler is preferably in the range of 3 ⁇ m to 15 ⁇ m, and more preferably in the range of 5 ⁇ m to 15 ⁇ m. If the average particle size is too small, the effect of suppressing the amount of resin seepage tends to be small, and if the average particle size is too large, the resistance value tends to increase.
  • the average particle diameter of a conductive filler be the particle diameter D50 of 50% of the sieving integrated fraction calculated from the particle diameter distribution measurement result by the laser diffraction scattering method.
  • the addition amount of a nonelectroconductive filler in the range of 4 to 120 mass parts with respect to 100 mass parts of acrylic copolymers, and to use in the range of 10 to 100 mass parts. It is more preferable. If the amount added is too small, the effect of suppressing the amount of the resin oozing out tends to be small, and if the amount added is too large, the adhesive strength tends to decrease.
  • an organic filler or an inorganic filler can be used as the non-conductive filler.
  • the organic filler include polyurethane resin particles, polyimide resin particles, benzoguanamine resin particles, and epoxy resin particles.
  • the inorganic filler include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and the like.
  • organic fillers are preferable, and polyurethane resin particles are preferably used among organic fillers as an example.
  • the polyurethane resin particles can be produced by suspension polymerization, and in particular, the adhesive strength of the thermosetting adhesive composition can be increased due to the property that the glass transition temperature is low.
  • the average particle size of the non-conductive filler is the average particle size of the dendritic conductive filler or the thermosetting although it depends on the thickness of the adhesive sheet, it is preferably in the range of 3 ⁇ m to 15 ⁇ m in the case of organic filler, and in the range of 3 ⁇ m to 10 ⁇ m in the case of inorganic filler.
  • blending monomers such as thermal conductive particles, film-forming resins, various acrylic monomers, fillers, softeners, colorants, flame retardants, thixotropic agents, silane coupling agents, etc. May be.
  • the average particle diameter of the non-conductive filler is smaller than the average particle diameter of the dendritic conductive filler contained in the thermosetting adhesive composition. Then, the non-conductive filler having a predetermined average particle diameter becomes entangled with the dendritic conductive filler, the flow of the resin component is suppressed, and the resin seepage is also suppressed. Moreover, adhesive strength can be improved by using an organic filler as a nonelectroconductive filler.
  • thermosetting adhesive sheet made of a thermosetting adhesive composition formed into a sheet shape comprises an acrylic copolymer (A), a thermosetting epoxy resin (B), and an epoxy resin curing agent (C). Dendritic conductive filler (D) and non-conductive filler (E) are dispersed in the resin component to be contained. Since the components (A) to (E) are the same as those of the thermosetting adhesive composition described above, the description thereof is omitted here.
  • thermosetting adhesive composition having a desired composition.
  • the prepared thermosetting adhesive composition is applied on a base film by a bar coater or roll coater so that the dry thickness is in the range of 10 ⁇ m or more and 60 ⁇ m or less, and is dried by a conventional method.
  • a thermosetting adhesive sheet having a layer of the adhesive composition can be produced.
  • a base material film a base material such as a polyethylene terephthalate film or a polyimide film, which is a base material that is peel-treated with silicone or the like as required, can be used.
  • FIG. 1 to 3 are diagrams showing connection examples using a thermosetting adhesive sheet.
  • Reference numeral 8 in FIG. 2 indicates a connection structure in which the flexible printed wiring board 10 and the metal plate 30 are bonded together by the thermosetting adhesive sheet 20 using a thermosetting adhesive sheet.
  • connection structure 8 will be described.
  • the base material 12, the wiring 13, the adhesive layer 14, and the protective layer 15 are laminated in this order, and the terminal 11 is provided at the end.
  • the flexible printed wiring board 10 is made of, for example, polyimide as the base material 12, copper as the wiring 13, epoxy resin as the adhesive layer 14, polyimide as the protective layer 15, and the surface of the terminal 11 is gold-plated.
  • FIG. 3 shows that the uncured thermosetting adhesive sheet 20 is peeled from the base film as shown in FIG. 1, and the flexible printed wiring board 10 and the metal plate 30 are peeled off. The surface and the back surface of the layer of the thermosetting composition are exposed.
  • thermosetting adhesive sheet 20 is brought into contact with the protective layer 15 on the surface of the flexible printed wiring board 10 and the surface of the terminal 11 exposed on the bottom surface of the opening 18, and the opposite side is brought into contact with the metal plate 30, While heating the plate 10 and the metal plate 30, one or both of the metal plate 30 and the flexible printed wiring board 10 are pressed against the thermosetting adhesive sheet 20.
  • thermosetting adhesive sheet 20 is heated by heat conduction from the heated metal plate 30 or the heated flexible printed wiring board 10, heated up, and softened. At this time, the flow of the resin component is suppressed by the non-conductive filler 22 and the dendritic conductive filler 21 dispersed in the resin component.
  • thermosetting adhesive sheet 20 is heated while being in contact with the metal plate 30, the protective layer 15 of the flexible printed wiring board 10, and the terminals 11.
  • the temperature of the thermosetting adhesive sheet 20 rises to a predetermined temperature
  • the epoxy resin curing agent and the epoxy group in the thermosetting epoxy resin react to initiate the polymerization reaction of the thermosetting epoxy resin, thereby increasing the network structure.
  • a molecular epoxy resin is formed and thermoset.
  • thermosetting thermosetting adhesive sheet 20 is also in contact with the metal plate 30, the protective layer 15 of the flexible printed wiring board 10, and the terminals 11, and the tree branches dispersed in the thermosetting thermosetting adhesive sheet 20.
  • the conductive filler 21 is in contact with the adjacent dendritic conductive filler 21, and the thermosetting thermosetting adhesive sheet 20 is at least as thick as the plurality of dendritic conductive fillers 21 in contact with each other. It has electrical conductivity in the direction. In this example, the thermosetting adhesive sheet 20 also has electrical conductivity in the spreading direction.
  • the dendritic conductive filler 21 located on the surface of the heat-cured thermosetting adhesive sheet 20 is in contact with the terminal 11 on one side of the heat-cured thermosetting adhesive sheet 20 and on the metal plate 30 on the opposite surface. Therefore, the metal plate 30 and the terminal 11 are in contact with and electrically connected to a plurality of dendritic conductive fillers 21 in contact with each other located in the thermosetting adhesive sheet 20 that has been thermoset. Therefore, the metal plate 30 and the terminal 11 are electrically connected by the thermosetting thermosetting adhesive sheet 20.
  • the metal plate 30 When the metal plate 30 is sized to cover the wiring pattern of the flexible printed wiring board 10 and the terminal 11 is connected to the ground potential, the metal plate 30 is connected to the ground potential.
  • the wiring pattern 10 is shielded so that harmful electromagnetic waves do not enter the wiring pattern.
  • thermosetting adhesive sheet 20 is cured and the flexible printed wiring board 10 is bonded to the metal plate 30 to reinforce the flexible printed wiring board 10 and connect the terminals 11 of the flexible printed wiring board 10 to the metal plate. 30 can be electrically connected.
  • the flexible printed wiring board 10 can be shielded.
  • the terminal 11 connected to the metal plate 30 by the cured thermosetting adhesive sheet 20 can be connected to a potential other than the ground potential of the electronic circuit of the flexible printed wiring board 10.
  • thermosetting adhesive sheet was produced and it verified about the magnitude
  • the thermosetting adhesive sheet prepared the thermosetting adhesive composition using the following component.
  • the thermosetting adhesive composition is applied to a release-treated polyethylene terephthalate film (PET), dried in a drying oven at 50 to 130 ° C., and thermoset having a layer of 35 ⁇ m thick thermosetting adhesive composition.
  • An adhesive sheet was prepared.
  • the tap density of the dendritic conductive filler was measured by a method defined in JIS Z 2512. Specifically, a specified amount of powder was placed in a container, and a tapping device was used to tap until the powder volume did not decrease any further, and the density was obtained by dividing the mass of the powder by the powder volume after tapping. Moreover, the average particle diameter of the conductive filler was set to a particle diameter D50 of 50% of the integrated fraction under the sieve calculated from the particle diameter distribution measurement result by the laser diffraction scattering method.
  • the acrylic monomer contained 66 wt.% Of alkyl (meth) acrylate containing butyl acrylate (BA) and ethyl acrylate (EA). %, Acrylonitrile (AN) 24 wt%, and glycidyl methacrylate (GMA) 10 wt%, and an acrylic copolymer copolymerized was used.
  • thermosetting adhesive sheet is cut into strips (2 cm ⁇ 5 cm), and a layer of the thermosetting adhesive composition on one side is temporarily attached to a 1.5 cm ⁇ 40 cm gold-plated substrate with a laminator set at 140 ° C.
  • the release substrate was removed to expose the layer of the thermosetting adhesive composition on the other side.
  • a 50 ⁇ m-thick polyimide film of the same size is superimposed on the exposed layer of the thermosetting adhesive composition from above, and the temperature is measured using a vacuum press (product name “Vacuum Star”, manufactured by Mikado Technos Co., Ltd.). After hot pressing under the conditions of 185 ° C., pressure 4.0 MPa, vacuum holding time 10 seconds + press time 90 seconds, it was kept in an oven at 140 ° C. for 60 minutes. Thereafter, a 90 ° peel test was performed on the polyimide film at a peel rate of 50 mm / min, and the force required for peeling was measured as the peel strength.
  • the peel strength is desirably 12 N / cm or more.
  • thermosetting adhesive composition layer on one side of the thermosetting adhesive sheet was temporarily sticking to a 100 ⁇ m thick SUS plate (2 cm ⁇ 3 cm) with a laminator set at 140 ° C., the release substrate was removed and the other side was removed. The layer of the thermosetting adhesive composition on the surface was exposed, and the layer of the thermosetting adhesive composition was cut off to the same size as the SUS plate.
  • thermosetting adhesive composition on the SUS plate was temporarily attached to a 175 ⁇ m-thick polyimide film (5 cm ⁇ 5 cm) with a laminator set at 140 ° C., and then a vacuum press (product name “Vacuum Star”, Mikado Technos Co., Ltd.) was used for hot pressing under conditions of a temperature of 185 ° C., a pressure of 4.0 MPa, a vacuum holding time of 10 seconds and a pressing time of 90 seconds, and then held in an oven at 140 ° C. for 60 minutes. And the length which the layer of the thermosetting adhesive composition oozed out from the SUS edge part of a test piece was measured with the metal microscope as the amount of resin oozing-out. The amount of the resin oozing out is desirably 200 ⁇ m or less.
  • thermosetting adhesive sheet As shown in Table 1, 25 parts by mass of an acrylic copolymer, 5 parts by mass of a liquid thermosetting epoxy resin, 10 parts by mass of a solid thermosetting epoxy resin, 10 parts by mass of adipic acid dihydrazide, A thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing 50 parts by mass of copper powder and 6 parts by mass of polyurethane particles having an average particle size of 3.8 ⁇ m. This thermosetting adhesive sheet had (1) peel strength of 15.1 N / cm and (2) resin oozing amount of 188 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 6 parts by mass of polyurethane particles having an average particle diameter of 6.0 ⁇ m were blended as the nonconductive filler.
  • the thermosetting adhesive sheet had (1) a peel strength of 15.2 N / cm and (2) a resin oozing amount of 106 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 6 parts by mass of polyurethane particles having an average particle diameter of 15.0 ⁇ m were blended as the nonconductive filler.
  • the thermosetting adhesive sheet had (1) a peel strength of 15.3 N / cm and (2) a resin oozing amount of 95 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 12 parts by mass of silica particles having an average particle size of 3.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 12.4 N / cm and (2) resin oozing amount of 195 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 12 parts by mass of silica particles having an average particle size of 7.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 12.0 N / cm and (2) resin oozing amount of 98 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 12 parts by mass of silica particles having an average particle diameter of 10.0 ⁇ m were blended as the nonconductive filler.
  • the thermosetting adhesive sheet (1) had a peel strength of 12.5 N / cm, and (2) the resin oozing amount was 98 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that no non-conductive filler was added.
  • This thermosetting adhesive sheet had (1) peel strength of 12.1 N / cm, and (2) resin oozing amount was 254 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 6 parts by mass of polyurethane particles having an average particle size of 0.7 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 15.6 N / cm, and (2) resin oozing amount was 240 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 6 parts by mass of polyurethane particles having an average particle size of 2.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 14.8 N / cm and (2) resin oozing amount of 210 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 1 except that 12 parts by mass of silica particles having an average particle diameter of 0.7 ⁇ m was blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 12.2 N / cm and (2) resin oozing amount of 212 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 2 except that 50 parts by mass of filamentous nickel powder was used as the conductive filler instead of the dendritic copper powder.
  • the amount of the (2) resin oozing out of this thermosetting adhesive sheet was 249 ⁇ m.
  • the average particle size of the non-conductive filler was 3 to 15 ⁇ m as in Examples 1 to 6, the amount of the resin oozing was reduced and the peel strength was good.
  • the peel strength polyurethane particles that are organic fillers were better than silica particles that were inorganic fillers.
  • thermosetting adhesive sheet was produced in the same manner as in Example 2 except that 0.5 part by mass of polyurethane particles having an average particle diameter of 6.0 ⁇ m was blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 15.0 N / cm, and (2) resin oozing amount was 225 ⁇ m.
  • thermosetting adhesive sheet was prepared in the same manner as in Example 2 except that 1 part by mass of polyurethane particles having an average particle diameter of 6.0 ⁇ m was blended as the nonconductive filler.
  • the thermosetting adhesive sheet had (1) a peel strength of 15.1 N / cm and (2) a resin oozing amount of 198 ⁇ m.
  • thermosetting adhesive sheet was prepared in the same manner as in Example 2 except that 3 parts by mass of polyurethane particles having an average particle size of 6.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 14.9 N / cm and (2) resin oozing amount of 161 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 2 except that 10 parts by mass of polyurethane particles having an average particle diameter of 6.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 15.5 N / cm and (2) resin oozing amount of 86 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 2 except that 30 parts by mass of polyurethane particles having an average particle size of 6.0 ⁇ m were blended as the nonconductive filler.
  • This thermosetting adhesive sheet had (1) peel strength of 13.0 N / cm and (2) resin oozing amount of 66 ⁇ m.
  • Dendritic copper powder A tap density 0.89 g / cm 3 , average particle size 6 ⁇ m
  • Dendritic copper powder B tap density 1.18 g / cm 3 , average particle size 10 ⁇ m
  • Dendritic copper powder C tap density 1.60 g / cm 3 , average particle size 12 ⁇ m
  • Dendritic copper powder D tap density 3.28 g / cm 3 , average particle size 23 ⁇ m
  • each compounding component and evaluation item are the same as that of 1st Example, description is abbreviate
  • thermosetting adhesive sheet was prepared using a thermosetting adhesive composition containing This thermosetting adhesive sheet had a (1) peel strength of 15.1 N / cm and (2) a resin oozing amount of 194 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 11 except that 250 parts by mass of dendritic copper powder B having a tap density of 1.18 g / cm 3 as a conductive filler was blended. .
  • the thermosetting adhesive sheet had (1) a peel strength of 15.1 N / cm and (2) a resin oozing amount of 115 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 11 except that 250 parts by mass of dendritic copper powder C having a tap density of 1.60 g / cm 3 was blended as a conductive filler. .
  • This thermosetting adhesive sheet had (1) peel strength of 15.0 N / cm and (2) resin exudation amount of 112 ⁇ m.
  • thermosetting adhesive sheet was produced in the same manner as in Example 11 except that 250 parts by mass of dendritic copper powder D having a tap density of 3.28 g / cm 3 was blended as a conductive filler. .
  • the thermosetting adhesive sheet had (1) a peel strength of 12.1 N / cm and (2) a resin oozing amount of 94 ⁇ m.
  • thermosetting adhesive sheet exhibited adhesiveness on the surface at room temperature ( ⁇ adhesion '' includes tackiness), but the thermosetting adhesive sheet of the present invention adheres to the surface at room temperature. In order to adhere the metal plate and the flexible printed wiring board heating, the adhesiveness may be manifested when the temperature is increased by heating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une composition adhésive thermodurcissable qui ne subit pas d'exsudation d'une résine ; et une feuille adhésive thermodurcissable. La présente invention concerne une composition adhésive thermodurcissable, qui constitue une feuille 20 adhésive thermodurcissable et qui comprend un copolymère acrylique, une résine époxy thermodurcissable, un agent de durcissement de la résine, une charge conductrice dendritique 21 et une charge non conductrice 22 présentant un diamètre moyen de particule dans la plage de de 3 à 15 μm inclus, valeurs extrêmes incluses. Dans la composition adhésive thermodurcissable, la fluidisation du constituant de résine peut être empêchée, car la charge non conductrice 22 est enchevêtrée avec la charge conductrice dendritique 21. Par conséquent, la composition adhésive thermodurcissable peut connecter électriquement une plaque métallique 30 à une borne 11, tout en empêchant l'exsudation de la résine.
PCT/JP2015/079867 2014-11-12 2015-10-22 Composition adhésive thermodurcissable WO2016076096A1 (fr)

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KR20170063820A (ko) 2017-06-08
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JP2016102204A (ja) 2016-06-02
CN107109161B (zh) 2019-07-02
KR101941386B1 (ko) 2019-01-22
TWI699415B (zh) 2020-07-21
CN107109161A (zh) 2017-08-29

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