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WO2017104665A1 - Conductive adhesive tape - Google Patents

Conductive adhesive tape Download PDF

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Publication number
WO2017104665A1
WO2017104665A1 PCT/JP2016/087070 JP2016087070W WO2017104665A1 WO 2017104665 A1 WO2017104665 A1 WO 2017104665A1 JP 2016087070 W JP2016087070 W JP 2016087070W WO 2017104665 A1 WO2017104665 A1 WO 2017104665A1
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WO
WIPO (PCT)
Prior art keywords
conductive
particles
pressure
adhesive tape
meth
Prior art date
Application number
PCT/JP2016/087070
Other languages
French (fr)
Japanese (ja)
Inventor
桃子 伊達木
耕平 丸尾
徳之 内田
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201680046144.8A priority Critical patent/CN107849402A/en
Priority to JP2016575241A priority patent/JP6832161B2/en
Priority to KR1020187006261A priority patent/KR20180094836A/en
Publication of WO2017104665A1 publication Critical patent/WO2017104665A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a conductive adhesive tape in which an adhesive layer is disposed on the surface of a conductive substrate.
  • conductive adhesive tape is used for the purpose of shielding electromagnetic waves and grounding for preventing static electricity.
  • Patent Document 1 discloses a conductive adhesive tape having a total thickness of 30 ⁇ m or less.
  • This conductive pressure-sensitive adhesive tape includes a conductive base material and a conductive pressure-sensitive adhesive layer containing conductive particles.
  • the conductive particles have a particle diameter d85 of 5 to 9 ⁇ m.
  • the conductive adhesive layer has a thickness of 1 to 6 ⁇ m.
  • nickel particles that are entirely nickel metal are used as the conductive particles.
  • Patent Document 1 due to the use of nickel particles as conductive particles, it is difficult to form a thin film smoothly unless a pulverization process such as a jet mill is performed due to secondary aggregation of particles. is there.
  • the tackiness is likely to be lowered. If the content of the conductive particles in the conductive pressure-sensitive adhesive layer is reduced in order to suppress the decrease in adhesiveness, the electrical characteristics are likely to be lowered.
  • the conductive particles are likely to aggregate, the surface smoothness of the pressure-sensitive adhesive may be lowered, and the adhesiveness may be lowered. Further, when exposed to high temperature or high humidity after application, floating and peeling will occur. Is likely to occur.
  • An object of the present invention is to provide a conductive pressure-sensitive adhesive tape that can increase the adhesiveness while maintaining its electrical characteristics, and can hardly be lifted and peeled even when exposed to high temperature or high humidity after being attached. Is to provide.
  • a conductive substrate and a pressure-sensitive adhesive layer disposed on the surface of the substrate are provided, and the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles.
  • the conductive particles have base particles excluding metal particles, and conductive portions arranged on the surface of the base particles, and in the pressure-sensitive adhesive layer, 100 parts by weight of the pressure-sensitive adhesive, A conductive pressure-sensitive adhesive tape in which the content of the conductive particles is 20 parts by weight or less is provided.
  • the average thickness of the adhesive layer is 20 ⁇ m or less.
  • the base material particles are resin particles.
  • the substrate is a metal foil.
  • the CV value of the particle diameter of the conductive particles is 3% or less.
  • the conductive pressure-sensitive adhesive tape according to the present invention includes a base material having conductivity and a pressure-sensitive adhesive layer disposed on the surface of the base material, and the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles.
  • the conductive particles include base particles excluding metal particles and conductive portions arranged on the surface of the base particles, and in the pressure-sensitive adhesive layer, 100 parts by weight of the pressure-sensitive adhesive.
  • the content of the conductive particles is 20 parts by weight or less, it is possible to increase the adhesiveness while maintaining the electrical characteristics, and even if it is exposed to high temperature or high humidity after being attached, it can float and peel. Can be made difficult to occur.
  • FIG. 1 is a cross-sectional view schematically showing a conductive pressure-sensitive adhesive tape according to an embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing a conductive adhesive tape according to an embodiment of the present invention.
  • the base material 11 has conductivity.
  • the base material 11 is a conductive base material.
  • the pressure-sensitive adhesive layer 12 has adhesiveness.
  • the pressure-sensitive adhesive layer 12 is disposed on the surface of the substrate 11.
  • the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive 21 and a plurality of conductive particles 22.
  • the conductive particles 22 have base material particles 31 and conductive portions 32.
  • the base particle 31 is a particle excluding metal particles.
  • the conductive part 32 is, for example, a conductive layer.
  • the conductive portion 32 is disposed on the surface of the base particle 31.
  • the content of the conductive particles 22 is 20 parts by weight or less with respect to the content of the pressure-sensitive adhesive 21 of 100 parts by weight.
  • the conductive pressure-sensitive adhesive tape includes a base material having conductivity and a pressure-sensitive adhesive layer disposed on the surface of the base material.
  • the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles.
  • the said electroconductive particle has a base material particle except a metal particle, and the electroconductive part arrange
  • the content of the conductive particles is 20 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive (component excluding the solvent of the pressure-sensitive adhesive layer and the conductive particles).
  • the adhesiveness can be increased while maintaining the electrical characteristics. Furthermore, in the present invention, since the above-described configuration is provided, even if the film is exposed to high temperature or high humidity after pasting, it is possible to make it difficult for floating and peeling to occur. In the present invention, excellent electrical characteristics can be exhibited despite the relatively small content of conductive particles. In the present invention, it is not necessary to increase the thickness of the conductive pressure-sensitive adhesive tape and the pressure-sensitive adhesive layer so as to exhibit sufficient pressure-sensitive adhesive properties.
  • the average thickness of the pressure-sensitive adhesive layer is 20 ⁇ m or less, sufficient adhesive properties can be exhibited, and even if the average thickness of the pressure-sensitive adhesive layer is 10 ⁇ m or less, sufficient adhesive properties can be exhibited. it can.
  • the present inventors have used base particles excluding metal particles and conductive particles having a conductive portion arranged on the surface of the base particles, It has been found that secondary agglomeration is suppressed, dispersibility is improved, and stable electrical characteristics can be exhibited even with a content of conductive particles of 20 parts by weight or less.
  • the specific conductive particles the specific gravity can be made smaller than that of the metal particles, and in the specific conductive particles, it is easy to reduce the variation in the surface state as compared with the metal particles. For this reason, in this invention, it is easy to improve an electrical characteristic effectively.
  • the base material is a support for supporting the pressure-sensitive adhesive layer.
  • the substrate include metal foil and conductive resin material. From the viewpoint of further improving the electrical characteristics of the conductive adhesive tape, the substrate is preferably a metal foil.
  • the material of the metal foil examples include gold, silver, copper, nickel, iron, tin, aluminum, and a graphite sheet.
  • the metal foil is preferably a gold foil, a copper foil, or an aluminum foil, and more preferably a copper foil or an aluminum foil.
  • a copper foil is preferable.
  • an aluminum foil is preferable.
  • the thermal conductivity of the substrate is preferably 90 W / m ⁇ K or more, more preferably 100 W / m ⁇ K or more.
  • the content of the conductive particles is 20 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive.
  • conductive particles having base particles excluding metal particles and conductive portions arranged on the surface of the base particles are used as the conductive particles.
  • the effect of the present invention can be further enhanced as compared with the case of using conductive particles that are metal particles.
  • the conductive layer is electrically conductive with respect to 100 parts by weight of the adhesive.
  • the content of the conductive particles is preferably 0.1 parts by weight or more, more preferably 0.75 parts by weight or more, further preferably 1 part by weight or more, preferably 15 parts by weight or less, more preferably 10 parts by weight or less, More preferably, it is 5 parts by weight or less.
  • the average thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the pressure-sensitive adhesiveness is further increased.
  • the electrical characteristics are further enhanced.
  • an electrical property can fully be improved.
  • the average particle size of the conductive particles is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, preferably 40 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the electrical characteristics are further enhanced.
  • the adhesive property is further enhanced.
  • the particle diameter of the conductive particles means the maximum diameter.
  • the maximum diameter means a diameter.
  • the average particle diameter of the conductive particles is calculated by measuring arbitrarily selected 50 conductive particles using an electron microscope or an optical microscope, and calculating the average particle diameter of each conductive particle. Is preferred.
  • the CV value (coefficient of variation) of the particle diameter of the conductive particles is preferably 3% or less, more preferably 2% or less.
  • the lower limit of the CV value of the particle diameter of the conductive particles is not particularly limited.
  • the CV value of the particle diameter of the conductive particles may be 1% or more.
  • the CV value (coefficient of variation) of the particle diameter of the conductive particles is calculated by the following formula.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
  • the average thickness of the conductive part is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 3000 nm or less, more preferably 1000 nm or less, and even more preferably 800 nm or less. More preferably, it is 500 nm or less, particularly preferably 400 nm or less, and most preferably 300 nm or less.
  • the conductive part may be a single layer or a multilayer.
  • the average thickness of the conductive part is the total thickness of the multilayer conductive part when the conductive part is a multilayer.
  • the electrical characteristics are further improved, and the variation in the electrical characteristics is further suppressed.
  • the average thickness of the conductive portion is not more than the above upper limit, the aggregation of the conductive particles is further suppressed, and the occurrence of floating and peeling at a high temperature or high humidity is further suppressed.
  • the thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the pressure-sensitive adhesive layer may contain a solvent separately from the pressure-sensitive adhesive and the conductive particles.
  • the solvent can be removed by volatilization, for example, by heating at 100 ° C. or higher.
  • Adhesive examples include (meth) acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. From the viewpoint of suppressing an excessive increase in the adhesive strength at high temperatures, the pressure-sensitive adhesive is preferably a (meth) acrylic pressure-sensitive adhesive.
  • the above (meth) acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive obtained by adding a crosslinking agent, a tackifying resin, various stabilizers and the like to a (meth) acrylic polymer as necessary.
  • the (meth) acrylic polymer is not particularly limited, but (meth) acrylic copolymer obtained by copolymerizing a mixed monomer containing a (meth) acrylic acid ester monomer and another copolymerizable monomer. A polymer is preferred.
  • the (meth) acrylic acid ester monomer is not particularly limited, but is an esterification reaction product of a primary or secondary alkyl alcohol having 1 to 12 carbon atoms in the alkyl group and (meth) acrylic acid (
  • a (meth) acrylic acid ester monomer is preferable, and specific examples include ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the said (meth) acrylic acid ester monomer only 1 type may be used and 2 or more types may be used together.
  • Examples of the other copolymerizable polymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; Functionality such as isobornyl (meth) acrylate, glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid and fumaric acid Monomer.
  • the other copolymerizable polymerizable monomer only one kind may be used, or two or more kinds may be used in combination.
  • the crosslinking agent is not particularly limited, and for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent.
  • the said crosslinking agent only 1 type may be used and 2 or more types may be used together.
  • the tackifying resin is not particularly limited, and examples thereof include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, and alicyclic copolymers.
  • the tackifying resin may be a hydrogenated resin. As for the said tackifier resin, only 1 type may be used and 2 or more types may be used together.
  • the said electroconductive particle has a base material particle except a metal particle, and the electroconductive part arrange
  • the base particles include resin particles, inorganic particles excluding metal particles, and organic-inorganic hybrid particles.
  • the substrate particles are preferably resin particles or organic-inorganic hybrid particles.
  • the base particles may be core-shell particles.
  • the core may be an organic core, and the shell may be an inorganic shell.
  • the base material particles are preferably resin particles.
  • the substrate particles are preferably not glass beads (glass particles).
  • the resin that is the material of the resin particles examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Ketones, polyether sulfones, and polymers such as obtained by a variety of polymerizable monomer having
  • the resin for forming the resin particles has an ethylenically unsaturated group from the viewpoint of further improving the electrical characteristics, adhesiveness, and prevention of occurrence of floating and peeling under high temperature or high humidity.
  • a polymer obtained by polymerizing one or more polymerizable monomers is preferable.
  • the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
  • Oxygen atom-containing (meth) acrylate compounds Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
  • Nitrile-containing monomers such as (meth) acrylonitrile
  • Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether
  • Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stea
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-
  • (meth) acryl indicates acrylic and methacrylic.
  • (meth) acrylate refers to acrylate and methacrylate.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles
  • examples of the inorganic material that is the material of the substrate particles include silica and carbon black.
  • the inorganic substance is not a metal.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary.
  • grains obtained by performing are mentioned.
  • the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the 10% K value of the substrate particles is preferably 4000 N / mm 2 or less.
  • the base particles having the specific compression characteristics are relatively soft and flexible. When the base conductive pressure-sensitive adhesive tape is affixed, the base particles are flexible, so that they can be compressed and deformed, and the electrical characteristics can be further enhanced as compared with the case of using relatively hard base particles. Can do.
  • the 10% K value of the base particles used in the examples described later is below this upper limit.
  • the 10% K value of the substrate particles can be measured as follows.
  • the base particles are compressed under a condition that a smooth tester end face of a cylinder (diameter 50 ⁇ m, made of diamond) is loaded at 25 ° C. and a maximum test load 20 mN over 60 seconds.
  • the load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula.
  • the micro compression tester for example, “Fischer Scope H-100” manufactured by Fischer is used.
  • the material for the conductive part is not particularly limited.
  • the material of the conductive part is preferably a metal.
  • the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, tungsten, and molybdenum. , Silicon and alloys thereof.
  • the metal include tin-doped indium oxide (ITO) and solder. From the viewpoint of effectively improving the electrical characteristics, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.
  • Electrolytic copper foil (1) (average thickness 12 ⁇ m)
  • Adhesive layer material Adhesive solution (1): In a reactor equipped with a thermometer, a stirrer and a condenser, butyl acrylate 60 parts by weight, 2-ethylhexyl acrylate 36.9 parts by weight, acrylic acid 3 parts by weight, 2-hydroxyethyl acrylate 0. After 1 part by weight and 80 parts by weight of ethyl acetate were added and the atmosphere was replaced with nitrogen, the reactor was heated to start refluxing. Subsequently, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator in the reactor. The solution was refluxed at 70 ° C. for 5 hours to obtain a solution of the acrylic copolymer (a). About the obtained acrylic copolymer (a), the weight average molecular weight measured by GPC method using "2690 Separations Model" made from Water as a column was 1.4 million.
  • Conductive particles (1) Metal-coated particles, average particle size of 10 ⁇ m, particle size CV value of 1.3%, particles in which acrylic resin particles are coated with nickel conductive parts (thickness 100 nm)
  • Conductive particles (2) Metal-coated particles, average particle diameter of 6 ⁇ m, particle diameter CV value of 2.3%, particles in which acrylic resin particles are coated with nickel conductive parts (thickness 100 nm)
  • Conductive particles (X) nickel particles, average particle size 2.2 ⁇ m, particle size CV value 9.6%
  • Conductive particles (Z) particles coated with silver-coated glass powder, average particle diameter of 26 ⁇ m, silver conductive part (thickness 100 nm)
  • Examples 1 to 7 and Comparative Examples 1 to 7 The electroconductive particle shown in Table 1 was mix
  • the compounding quantity of electroconductive particle is a compounding quantity from which the content of electroconductive particle turns into the quantity shown in Table 1 with respect to 100 weight part of adhesives in the adhesive layer obtained.
  • a PET separator having a thickness of 25 ⁇ m was prepared, and the composition was applied to the release-treated surface of the separator and dried at 100 ° C. for 3 minutes to form an adhesive layer having a thickness of 10 ⁇ m.
  • this pressure-sensitive adhesive layer was formed to the base material shown in Table 1, a conductive pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer having an average thickness shown in Table 1 was obtained.
  • no substrate was used in Comparative Examples 5 and 6, no substrate was used.
  • Adhesion criteria ⁇ : Adhesive strength is 11 N / 25 mm or more ⁇ : Adhesive strength is 10 N / 25 mm or more and less than 11 N / 25 mm ⁇ : Adhesive strength is less than 10 N / 25 mm
  • Resistance value 1 ( ⁇ ) (electrical characteristics)
  • the obtained conductive adhesive tape was cut into a size of 10 mm ⁇ 10 mm, and the separator was peeled off to obtain a conductive adhesive tape piece.
  • the affixing area to each electrode was 1 mm ⁇ 10 mm.
  • the resistance value after pressure release was read 60 times every 5 seconds and averaged to evaluate the resistance value.
  • the resistance value was determined according to the following criteria. In addition, it is excellent in the electrical property, so that resistance value is low.
  • the resistance value “OL” means a state where the measurement value exceeds the measurement limit (1 G ⁇ ) and the resistance value cannot be measured.
  • Resistance value is 1 ⁇ or less ⁇ : Resistance value exceeds 1 ⁇ , 3.1 ⁇ or less ⁇ : Resistance value exceeds 3.1 ⁇ , or the result is “OL”
  • Resistance value 2 ( ⁇ ) (electrical characteristics)
  • the obtained conductive adhesive tape was cut into a size of 10 mm ⁇ 2 mm, and the separator was peeled off to obtain a conductive adhesive tape piece.
  • a piece of conductive adhesive tape was attached to an aluminum plate electrode having a width of 1 mm by applying a pressure of 3 kg / cm 2 for 5 seconds.
  • the affixing area to each electrode was 1 mm ⁇ 2 mm.
  • the resistance value after pressure release was read 60 times every 5 seconds and averaged to evaluate the resistance value.
  • the resistance value was determined according to the following criteria. In addition, it is excellent in the electrical property, so that resistance value is low.
  • the resistance value “OL” means a state where the measurement value exceeds the measurement limit (1 G ⁇ ) and the resistance value cannot be measured.
  • Resistance value is 10 ⁇ or less ⁇ : Resistance value exceeds 10 ⁇ , 25 ⁇ or less ⁇ : Resistance value exceeds 25 ⁇ , or the result is “OL”
  • the obtained conductive adhesive tape was cut into a size of 20 mm ⁇ 20 mm, and the separator was peeled off to obtain a conductive adhesive tape piece. From the adhesive layer side of the conductive adhesive tape piece, 5mm to the right from the starting point to the end point in the plan view, 2mm under the right angle, 13mm to the left bent at a right angle, and attached to a glass plate (thickness 2mm) As a result, a laminate was obtained.
  • the 5 mm ⁇ 20 mm attachment surface was cut to 1.5 mm ⁇ 20 mm (1) and 0.7 mm ⁇ 20 mm (2), and unnecessary portions cut were peeled off to obtain evaluation samples.
  • the 1.5 mm ⁇ 20 mm and 0.7 mm ⁇ 20 mm sticking surfaces of (1) and (2) were crimped by reciprocating a 2 kg rubber roller once. After leaving for 20 minutes in the same environment, the obtained laminate was left for 72 hours under the conditions of 60 ° C. and humidity 90% RH. After leaving, the floating and peeling of the conductive pressure-sensitive adhesive tapes (1) and (2) were observed, and the resilience resistance was determined according to the following criteria.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided is a conductive adhesive tape which can have improved adhesiveness while maintaining electrical characteristics, and is less likely to lift or peel even when being exposed to high temperature or high humidity after being attached. The conductive adhesive tape according to the present invention is provided with a conductive base, and an adhesive layer provided on a surface of the base, wherein the adhesive layer contains an adhesive agent and conductive particles, the conductive particles each have a base particle excluding a metal particle, and a conductive part provided on the surface of the base particle, and in the adhesive layer, the contained amount of the conductive particles is 20 parts by weight or less with respect to 100 parts by weight of the adhesive agent.

Description

導電性粘着テープConductive adhesive tape
　本発明は、導電性を有する基材の表面上に、粘着剤層が配置されている導電性粘着テープに関する。 The present invention relates to a conductive adhesive tape in which an adhesive layer is disposed on the surface of a conductive substrate.
　電子機器及び通信機器では、電磁波の遮蔽、及び静電気防止のグランド用途などを目的として、導電性粘着テープが用いられている。 In electronic devices and communication devices, conductive adhesive tape is used for the purpose of shielding electromagnetic waves and grounding for preventing static electricity.
　下記の特許文献１には、総厚みが３０μｍ以下である導電性粘着テープが開示されている。この導電性粘着テープは、導電性基材と、導電性粒子を含有する導電性粘着剤層とを備える。上記導電性粒子の粒子径ｄ８５は、５～９μｍである。上記導電性粘着剤層の厚みは、１～６μｍである。特許文献１の実施例では、上記導電性粒子として、全体がニッケル金属であるニッケル粒子が用いられている。 The following Patent Document 1 discloses a conductive adhesive tape having a total thickness of 30 μm or less. This conductive pressure-sensitive adhesive tape includes a conductive base material and a conductive pressure-sensitive adhesive layer containing conductive particles. The conductive particles have a particle diameter d85 of 5 to 9 μm. The conductive adhesive layer has a thickness of 1 to 6 μm. In the example of Patent Document 1, nickel particles that are entirely nickel metal are used as the conductive particles.
ＷＯ２０１５／０７６１７４ＡWO2015 / 076174A
　特許文献１では、導電性粒子としてニッケル粒子が用いられていることなどによって、粒子の二次凝集に起因して、ジェットミル等の粉砕処理をしなければ、平滑に薄膜化することが困難である。 In Patent Document 1, due to the use of nickel particles as conductive particles, it is difficult to form a thin film smoothly unless a pulverization process such as a jet mill is performed due to secondary aggregation of particles. is there.
　また、電気特性を高めるために、導電性粘着剤層における導電性粒子の含有量を多くすると、粘着性が低下しやすい。粘着性の低下を抑えるために、導電性粘着剤層における導電性粒子の含有量を少なくすると、電気特性が低くなりやすい。 Moreover, if the content of the conductive particles in the conductive pressure-sensitive adhesive layer is increased in order to enhance the electrical characteristics, the tackiness is likely to be lowered. If the content of the conductive particles in the conductive pressure-sensitive adhesive layer is reduced in order to suppress the decrease in adhesiveness, the electrical characteristics are likely to be lowered.
　特許文献１では、導電性粒子が凝集しやすく、粘着剤の表面の平滑性が低下して粘着性が低くなることがあり、更に貼り付け後に高温又は高湿下に晒されると、浮き及び剥離が発生しやすい。 In Patent Document 1, the conductive particles are likely to aggregate, the surface smoothness of the pressure-sensitive adhesive may be lowered, and the adhesiveness may be lowered. Further, when exposed to high temperature or high humidity after application, floating and peeling will occur. Is likely to occur.
　本発明の目的は、電気特性を維持したままで粘着性を高めることができ、更に貼り付け後に高温又は高湿下に晒されても、浮き及び剥離を生じ難くすることができる導電性粘着テープを提供することである。 An object of the present invention is to provide a conductive pressure-sensitive adhesive tape that can increase the adhesiveness while maintaining its electrical characteristics, and can hardly be lifted and peeled even when exposed to high temperature or high humidity after being attached. Is to provide.
　本発明の広い局面によれば、導電性を有する基材と、前記基材の表面上に配置された粘着剤層とを備え、前記粘着剤層は、粘着剤と、導電性粒子とを含み、前記導電性粒子は、金属粒子を除く基材粒子と、前記基材粒子の表面上に配置された導電部とを有し、前記粘着剤層において、前記粘着剤１００重量部に対して、前記導電性粒子の含有量が２０重量部以下である、導電性粘着テープが提供される。 According to a wide aspect of the present invention, a conductive substrate and a pressure-sensitive adhesive layer disposed on the surface of the substrate are provided, and the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles. The conductive particles have base particles excluding metal particles, and conductive portions arranged on the surface of the base particles, and in the pressure-sensitive adhesive layer, 100 parts by weight of the pressure-sensitive adhesive, A conductive pressure-sensitive adhesive tape in which the content of the conductive particles is 20 parts by weight or less is provided.
　本発明に係る導電性粘着テープのある特定の局面では、前記粘着剤層の平均厚みが２０μｍ以下である。 In a specific aspect of the conductive adhesive tape according to the present invention, the average thickness of the adhesive layer is 20 μm or less.
　本発明に係る導電性粘着テープのある特定の局面では、前記基材粒子が樹脂粒子である。 In a specific aspect of the conductive adhesive tape according to the present invention, the base material particles are resin particles.
　本発明に係る導電性粘着テープのある特定の局面では、前記基材が金属箔である。 In a specific aspect of the conductive adhesive tape according to the present invention, the substrate is a metal foil.
　本発明に係る導電性粘着テープのある特定の局面では、前記導電性粒子の粒子径のＣＶ値が３％以下である。 In a specific aspect of the conductive adhesive tape according to the present invention, the CV value of the particle diameter of the conductive particles is 3% or less.
　本発明に係る導電性粘着テープは、導電性を有する基材と、上記基材の表面上に配置された粘着剤層とを備え、上記粘着剤層は、粘着剤と、導電性粒子とを含み、上記導電性粒子は、金属粒子を除く基材粒子と、上記基材粒子の表面上に配置された導電部とを有し、上記粘着剤層において、上記粘着剤１００重量部に対して、上記導電性粒子の含有量が２０重量部以下であるので、電気特性を維持したままで粘着性を高めることができ、更に貼り付け後に高温又は高湿下に晒されても、浮き及び剥離を生じ難くすることができる。 The conductive pressure-sensitive adhesive tape according to the present invention includes a base material having conductivity and a pressure-sensitive adhesive layer disposed on the surface of the base material, and the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles. The conductive particles include base particles excluding metal particles and conductive portions arranged on the surface of the base particles, and in the pressure-sensitive adhesive layer, 100 parts by weight of the pressure-sensitive adhesive In addition, since the content of the conductive particles is 20 parts by weight or less, it is possible to increase the adhesiveness while maintaining the electrical characteristics, and even if it is exposed to high temperature or high humidity after being attached, it can float and peel. Can be made difficult to occur.
図１は、本発明の一実施形態に係る導電性粘着テープを模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing a conductive pressure-sensitive adhesive tape according to an embodiment of the present invention.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　図１は、本発明の一実施形態に係る導電性粘着テープを模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a conductive adhesive tape according to an embodiment of the present invention.
　図１に示す導電性粘着テープ１は、基材１１と、粘着剤層１２とを備える。基材１１は、導電性を有する。基材１１は、導電性基材である。粘着剤層１２は、粘着性を有する。粘着剤層１２は、基材１１の表面上に配置されている。 1 includes a base material 11 and an adhesive layer 12. The conductive adhesive tape 1 shown in FIG. The base material 11 has conductivity. The base material 11 is a conductive base material. The pressure-sensitive adhesive layer 12 has adhesiveness. The pressure-sensitive adhesive layer 12 is disposed on the surface of the substrate 11.
　粘着剤層１２は、粘着剤２１と、複数の導電性粒子２２を含む。導電性粒子２２は、基材粒子３１と導電部３２とを有する。基材粒子３１は、金属粒子を除く粒子である。導電部３２は、例えば導電層である。導電部３２は、基材粒子３１の表面上に配置されている。 The pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive 21 and a plurality of conductive particles 22. The conductive particles 22 have base material particles 31 and conductive portions 32. The base particle 31 is a particle excluding metal particles. The conductive part 32 is, for example, a conductive layer. The conductive portion 32 is disposed on the surface of the base particle 31.
　粘着剤層１２において、粘着剤２１の含有量１００重量部に対して、導電性粒子２２の含有量は２０重量部以下である。 In the pressure-sensitive adhesive layer 12, the content of the conductive particles 22 is 20 parts by weight or less with respect to the content of the pressure-sensitive adhesive 21 of 100 parts by weight.
　導電性粘着テープ１のように、本発明に係る導電性粘着テープは、導電性を有する基材と、上記基材の表面上に配置された粘着剤層とを備える。上記粘着剤層は、粘着剤と、導電性粒子とを含む。上記導電性粒子は、金属粒子を除く基材粒子と、上記基材粒子の表面上に配置された導電部とを有する。上記粘着剤（上記粘着剤層の溶剤及び上記導電性粒子を除く成分）１００重量部に対して、上記導電性粒子の含有量は２０重量部以下である。 Like the conductive pressure-sensitive adhesive tape 1, the conductive pressure-sensitive adhesive tape according to the present invention includes a base material having conductivity and a pressure-sensitive adhesive layer disposed on the surface of the base material. The pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles. The said electroconductive particle has a base material particle except a metal particle, and the electroconductive part arrange | positioned on the surface of the said base material particle. The content of the conductive particles is 20 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive (component excluding the solvent of the pressure-sensitive adhesive layer and the conductive particles).
　本発明では、上記の構成が備えられているので、電気特性を維持したままで粘着性を高めることができる。さらに、本発明では、上記の構成が備えられているので、貼り付け後に高温又は高湿下に晒されても、浮き及び剥離を生じ難くすることができる。本発明では、導電性粒子の含有量が比較的少ないにもかかわらず、優れた電気特性を発現させることができる。本発明では、十分な粘着特性を発揮させるために、導電性粘着テープ及び粘着剤層の厚みをさほど厚くする必要がない。例えば、粘着剤層の平均厚みが２０μｍ以下であっても、十分な粘着特性を発揮させることができ、粘着剤層の平均厚みが１０μｍ以下であっても、十分な粘着特性を発揮させることができる。 In the present invention, since the above-described configuration is provided, the adhesiveness can be increased while maintaining the electrical characteristics. Furthermore, in the present invention, since the above-described configuration is provided, even if the film is exposed to high temperature or high humidity after pasting, it is possible to make it difficult for floating and peeling to occur. In the present invention, excellent electrical characteristics can be exhibited despite the relatively small content of conductive particles. In the present invention, it is not necessary to increase the thickness of the conductive pressure-sensitive adhesive tape and the pressure-sensitive adhesive layer so as to exhibit sufficient pressure-sensitive adhesive properties. For example, even if the average thickness of the pressure-sensitive adhesive layer is 20 μm or less, sufficient adhesive properties can be exhibited, and even if the average thickness of the pressure-sensitive adhesive layer is 10 μm or less, sufficient adhesive properties can be exhibited. it can.
　上述した課題に対して、本発明者らは、鋭意検討した結果、金属粒子を除く基材粒子と、上記基材粒子の表面上に配置された導電部を有する導電性粒子を用いることで、二次凝集を抑制し、分散性を向上させ、２０重量部以下の導電性粒子の含有量においても安定した電気特性を発揮できることを見出した。上記の特定の導電性粒子では、金属粒子よりも比重を小さくすることが容易であり、上記の特定の導電性粒子では、金属粒子よりも表面状態のばらつきを少なくすることが容易である。このため、本発明では、電気特性を効果的に高めることが容易である。 As a result of intensive studies, the present inventors have used base particles excluding metal particles and conductive particles having a conductive portion arranged on the surface of the base particles, It has been found that secondary agglomeration is suppressed, dispersibility is improved, and stable electrical characteristics can be exhibited even with a content of conductive particles of 20 parts by weight or less. In the specific conductive particles, the specific gravity can be made smaller than that of the metal particles, and in the specific conductive particles, it is easy to reduce the variation in the surface state as compared with the metal particles. For this reason, in this invention, it is easy to improve an electrical characteristic effectively.
　以下、導電性粘着テープの他の詳細を説明する。 Hereinafter, other details of the conductive adhesive tape will be described.
　（基材）
　上記基材は、上記粘着剤層を支持するための支持体である。上記基材としては、金属箔及び導電性樹脂材等が挙げられる。導電性粘着テープの電気特性をより一層高める観点からは、上記基材は金属箔であることが好ましい。 (Base material)
The base material is a support for supporting the pressure-sensitive adhesive layer. Examples of the substrate include metal foil and conductive resin material. From the viewpoint of further improving the electrical characteristics of the conductive adhesive tape, the substrate is preferably a metal foil.
　上記金属箔の材質としては、金、銀、銅、ニッケル、鉄、錫、アルミニウム、及びグラファイトシート等が挙げられる。電気特性をより一層高める観点からは、上記金属箔は、金箔、銅箔又はアルミニウム箔であることが好ましく、銅箔又はアルミニウム箔であることがより好ましい。加工性をより一層高める観点からは、銅箔が好ましい。耐腐食性をより一層高める観点からは、アルミニウム箔が好ましい。 Examples of the material of the metal foil include gold, silver, copper, nickel, iron, tin, aluminum, and a graphite sheet. From the viewpoint of further improving the electrical characteristics, the metal foil is preferably a gold foil, a copper foil, or an aluminum foil, and more preferably a copper foil or an aluminum foil. From the viewpoint of further improving the workability, a copper foil is preferable. From the viewpoint of further increasing the corrosion resistance, an aluminum foil is preferable.
　電気特性をより一層高める観点からは、上記基材の熱伝導率は好ましくは９０Ｗ／ｍ・Ｋ以上、より好ましくは１００Ｗ／ｍ・Ｋ以上である。 From the viewpoint of further improving the electrical characteristics, the thermal conductivity of the substrate is preferably 90 W / m · K or more, more preferably 100 W / m · K or more.
　（粘着剤層）
　上記粘着剤層において、上記粘着剤１００重量部に対して、上記導電性粒子の含有量は２０重量部以下である。本発明では、導電性粒子の含有量が同じである場合に、導電性粒子として、金属粒子を除く基材粒子と上記基材粒子の表面上に配置された導電部を有する導電性粒子を用いることで、金属粒子である導電性粒子を用いた場合と比べて、本発明の効果をより一層高めることができる。電気特性、粘着性、及び、高温又は高湿下での浮き及び剥離の発生防止性をより一層バランスよく高める観点からは、上記粘着剤層において、上記粘着剤１００重量部に対して、上記導電性粒子の含有量は好ましくは０．１重量部以上、より好ましくは０．７５重量部以上、更に好ましくは１重量部以上であり、好ましくは１５重量部以下、より好ましくは１０重量部以下、更に好ましくは５重量部以下である。 (Adhesive layer)
In the pressure-sensitive adhesive layer, the content of the conductive particles is 20 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive. In the present invention, when the content of the conductive particles is the same, conductive particles having base particles excluding metal particles and conductive portions arranged on the surface of the base particles are used as the conductive particles. As a result, the effect of the present invention can be further enhanced as compared with the case of using conductive particles that are metal particles. From the viewpoint of further improving the electrical characteristics, adhesiveness, and prevention of occurrence of floating and peeling under high temperature or high humidity, the conductive layer is electrically conductive with respect to 100 parts by weight of the adhesive. The content of the conductive particles is preferably 0.1 parts by weight or more, more preferably 0.75 parts by weight or more, further preferably 1 part by weight or more, preferably 15 parts by weight or less, more preferably 10 parts by weight or less, More preferably, it is 5 parts by weight or less.
　上記粘着剤層の平均厚みは、好ましくは１μｍ以上、より好ましくは３μｍ以上であり、好ましくは４０μｍ以下、より好ましくは２０μｍ以下、更に好ましくは１５μｍ以下、特に好ましくは１０μｍ以下である。上記粘着剤層の平均厚みが上記下限以上であると、粘着性がより一層高くなる。上記粘着剤層の平均厚みが上記上限以下であると、電気特性がより一層高くなる。また、本発明では、上記粘着剤層の平均厚みが上記上限以下であっても、電気特性を十分に高めることができる。 The average thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more, more preferably 3 μm or more, preferably 40 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm or less. When the average thickness of the pressure-sensitive adhesive layer is not less than the above lower limit, the pressure-sensitive adhesiveness is further increased. When the average thickness of the pressure-sensitive adhesive layer is not more than the above upper limit, the electrical characteristics are further enhanced. Moreover, in this invention, even if the average thickness of the said adhesive layer is below the said upper limit, an electrical property can fully be improved.
　上記導電性粒子の平均粒子径は、好ましくは１μｍ以上、より好ましくは３μｍ以上であり、好ましくは４０μｍ以下、より好ましくは１５μｍ以下、更に好ましくは１０μｍ以下である。上記導電性粒子の平均粒子径が上記下限以上であると、電気特性がより一層高くなる。上記導電性粒子の平均粒子径が上記上限以下であると、粘着特性がより一層高くなる。 The average particle size of the conductive particles is preferably 1 μm or more, more preferably 3 μm or more, preferably 40 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. When the average particle diameter of the conductive particles is not less than the above lower limit, the electrical characteristics are further enhanced. When the average particle size of the conductive particles is not more than the above upper limit, the adhesive property is further enhanced.
　上記導電性粒子の粒子径は、最大径を意味する。導電性粒子が真球状である場合には、上記最大径は直径を意味する。上記導電性粒子の平均粒子径は、任意に選択された５０個の導電性粒子を電子顕微鏡又は光学顕微鏡を用いて測定し、各導電性粒子の粒子径を算術平均することにより、算出することが好ましい。 The particle diameter of the conductive particles means the maximum diameter. When the conductive particles are spherical, the maximum diameter means a diameter. The average particle diameter of the conductive particles is calculated by measuring arbitrarily selected 50 conductive particles using an electron microscope or an optical microscope, and calculating the average particle diameter of each conductive particle. Is preferred.
　電気特性をより一層高める観点からは、上記導電性粒子の粒子径のＣＶ値（変動係数）は、好ましくは３％以下、より好ましくは２％以下である。上記導電性粒子の粒子径のＣＶ値の下限は特に限定されない。上記導電性粒子の粒子径のＣＶ値は１％以上であってもよい。上記導電性粒子の粒子径のＣＶ値が上記上限以下であると、導電性粒子の凝集がより一層抑えられ、電気特性のばらつきがより一層抑えられる。 From the viewpoint of further improving the electrical characteristics, the CV value (coefficient of variation) of the particle diameter of the conductive particles is preferably 3% or less, more preferably 2% or less. The lower limit of the CV value of the particle diameter of the conductive particles is not particularly limited. The CV value of the particle diameter of the conductive particles may be 1% or more. When the CV value of the particle diameter of the conductive particles is not more than the above upper limit, the aggregation of the conductive particles is further suppressed, and the variation in electrical characteristics is further suppressed.
　上記導電性粒子の粒子径のＣＶ値（変動係数）は、下記式で算出される。 The CV value (coefficient of variation) of the particle diameter of the conductive particles is calculated by the following formula.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：導電性粒子の粒子径の標準偏差
　Ｄｎ：導電性粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
　上記導電部の平均厚みは、好ましくは５ｎｍ以上、より好ましくは１０ｎｍ以上、更に好ましくは２０ｎｍ以上、特に好ましくは５０ｎｍ以上であり、好ましくは３０００ｎｍ以下、より好ましくは１０００ｎｍ以下、より一層好ましくは８００ｎｍ以下、更に好ましくは５００ｎｍ以下、特に好ましくは４００ｎｍ以下、最も好ましくは３００ｎｍ以下である。上記導電部は、単層であってもよく、多層であってもよい。上記導電部の平均厚みは、導電部が多層である場合には、多層の導電部の全体の厚みである。上記導電部の平均厚みが上記下限以上であると、電気特性がより一層良好になり、電気特性のばらつきがより一層抑えられる。上記導電部の平均厚みが上記上限以下であると、導電性粒子の凝集がより一層抑えられ、高温又は高湿下での浮き及び剥離の発生がより一層抑えられる。 The average thickness of the conductive part is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more, particularly preferably 50 nm or more, preferably 3000 nm or less, more preferably 1000 nm or less, and even more preferably 800 nm or less. More preferably, it is 500 nm or less, particularly preferably 400 nm or less, and most preferably 300 nm or less. The conductive part may be a single layer or a multilayer. The average thickness of the conductive part is the total thickness of the multilayer conductive part when the conductive part is a multilayer. When the average thickness of the conductive part is not less than the above lower limit, the electrical characteristics are further improved, and the variation in the electrical characteristics is further suppressed. When the average thickness of the conductive portion is not more than the above upper limit, the aggregation of the conductive particles is further suppressed, and the occurrence of floating and peeling at a high temperature or high humidity is further suppressed.
　上記導電部の厚みは、例えば透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより測定できる。 The thickness of the conductive part can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
　上記粘着剤層は、上記粘着剤及び上記導電性粒子とは別に、溶剤を含んでいてもよい。上記溶剤は、例えば、１００℃以上の加熱により、揮発によって除去可能である。 The pressure-sensitive adhesive layer may contain a solvent separately from the pressure-sensitive adhesive and the conductive particles. The solvent can be removed by volatilization, for example, by heating at 100 ° C. or higher.
　粘着剤：
　上記粘着剤としては、（メタ）アクリル系粘着剤、ゴム系粘着剤、ウレタン系粘着剤、エポキシ系粘着剤及びシリコーン系粘着剤等が挙げられる。高温下での粘着力の過度な上昇を抑制する観点からは、上記粘着剤は、（メタ）アクリル系粘着剤であることが好ましい。 Adhesive:
Examples of the pressure-sensitive adhesive include (meth) acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. From the viewpoint of suppressing an excessive increase in the adhesive strength at high temperatures, the pressure-sensitive adhesive is preferably a (meth) acrylic pressure-sensitive adhesive.
　上記（メタ）アクリル系粘着剤は、（メタ）アクリル重合体に、必要に応じて架橋剤、粘着付与樹脂及び各種安定剤などを添加した粘着剤である。 The above (meth) acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive obtained by adding a crosslinking agent, a tackifying resin, various stabilizers and the like to a (meth) acrylic polymer as necessary.
　上記（メタ）アクリル重合体は、特に限定されないが、（メタ）アクリル酸エステルモノマーと、他の共重合可能な重合性モノマーとを含む混合モノマーを共重合して得られた（メタ）アクリル共重合体であることが好ましい。 The (meth) acrylic polymer is not particularly limited, but (meth) acrylic copolymer obtained by copolymerizing a mixed monomer containing a (meth) acrylic acid ester monomer and another copolymerizable monomer. A polymer is preferred.
　上記（メタ）アクリル酸エステルモノマーとしては、特に限定されないが、アルキル基の炭素数が１～１２の１級又は２級のアルキルアルコールと、（メタ）アクリル酸とのエステル化反応物である（メタ）アクリル酸エステルモノマーが好ましく、具体的には、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸－２－エチルヘキシル等が挙げられる。上記（メタ）アクリル酸エステルモノマーは、１種のみが用いられてもよく、２種以上が併用されてもよい。 The (meth) acrylic acid ester monomer is not particularly limited, but is an esterification reaction product of a primary or secondary alkyl alcohol having 1 to 12 carbon atoms in the alkyl group and (meth) acrylic acid ( A (meth) acrylic acid ester monomer is preferable, and specific examples include ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. As for the said (meth) acrylic acid ester monomer, only 1 type may be used and 2 or more types may be used together.
　上記他の共重合可能な重合性モノマーとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキル；（メタ）アクリル酸イソボルニル、グリセリンジメタクリレート、（メタ）アクリル酸グリシジル、２－メタクリロイルオキシエチルイソシアネート、（メタ）アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸及びフマル酸等の官能性モノマーが挙げられる。上記他の共重合可能な重合性モノマーは、１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the other copolymerizable polymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; Functionality such as isobornyl (meth) acrylate, glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, crotonic acid, maleic acid and fumaric acid Monomer. As the other copolymerizable polymerizable monomer, only one kind may be used, or two or more kinds may be used in combination.
　上記架橋剤としては、特に限定されず、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、アミン系架橋剤、及び多官能アクリレート等が挙げられる。上記架橋剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The crosslinking agent is not particularly limited, and for example, an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, a peroxide crosslinking agent, a urea crosslinking agent, a metal alkoxide crosslinking agent, a metal chelate crosslinking agent. Agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, amine crosslinking agents, and polyfunctional acrylates. As for the said crosslinking agent, only 1 type may be used and 2 or more types may be used together.
　上記粘着付与樹脂としては、特に限定されないが、例えば、脂肪族系共重合体、芳香族系共重合体、脂肪族－芳香族系共重合体及び脂環式系共重合体等の石油系樹脂；クマロン－インデン系樹脂；テルペン系樹脂；テルペンフェノール系樹脂；重合ロジン等のロジン系樹脂；フェノール系樹脂；キシレン系樹脂等が挙げられる。上記粘着付与樹脂は、水素添加された樹脂であってもよい。上記粘着付与樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。 The tackifying resin is not particularly limited, and examples thereof include petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic-aromatic copolymers, and alicyclic copolymers. Coumarone-indene resin; terpene resin; terpene phenol resin; rosin resin such as polymerized rosin; phenol resin; xylene resin. The tackifying resin may be a hydrogenated resin. As for the said tackifier resin, only 1 type may be used and 2 or more types may be used together.
　導電性粒子：
　上記導電性粒子は、金属粒子を除く基材粒子と、上記基材粒子の表面上に配置された導電部とを有する。 Conductive particles:
The said electroconductive particle has a base material particle except a metal particle, and the electroconductive part arrange | positioned on the surface of the said base material particle.
　上記基材粒子としては、樹脂粒子、金属粒子を除く無機粒子及び有機無機ハイブリッド粒子等が挙げられる。上記基材粒子は、樹脂粒子又は有機無機ハイブリッド粒子であることが好ましい。上記基材粒子は、コアシェル粒子であってもよい。上記コアが有機コアであってもよく、上記シェルが無機シェルであってもよい。 Examples of the base particles include resin particles, inorganic particles excluding metal particles, and organic-inorganic hybrid particles. The substrate particles are preferably resin particles or organic-inorganic hybrid particles. The base particles may be core-shell particles. The core may be an organic core, and the shell may be an inorganic shell.
　電気特性を効果的に高める観点からは、上記基材粒子は、樹脂粒子であることが好ましい。上記基材粒子は、ガラスビーズ（ガラス粒子）ではないことが好ましい。 From the viewpoint of effectively improving electrical characteristics, the base material particles are preferably resin particles. The substrate particles are preferably not glass beads (glass particles).
　上記樹脂粒子の材料である樹脂として、種々の有機物が好適に用いられる。上記樹脂粒子を形成するための樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂；ポリメチルメタクリレート及びポリメチルアクリレート等のアクリル樹脂；ポリアルキレンテレフタレート、ポリカーボネート、ポリアミド、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ポリスルホン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、及び、エチレン性不飽和基を有する種々の重合性単量体を１種もしくは２種以上重合させて得られる重合体等が挙げられる。電気特性、粘着性、及び、高温又は高湿下での浮き及び剥離の発生防止性をより一層バランスよく高める観点からは、上記樹脂粒子を形成するための樹脂は、エチレン性不飽和基を有する重合性単量体を１種又は２種以上重合させた重合体であることが好ましい。 Various organic substances are preferably used as the resin that is the material of the resin particles. Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Alkylene terephthalate, polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene Oxide, polyacetal, polyimide, polyamideimide, polyether ether Ketones, polyether sulfones, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. The resin for forming the resin particles has an ethylenically unsaturated group from the viewpoint of further improving the electrical characteristics, adhesiveness, and prevention of occurrence of floating and peeling under high temperature or high humidity. A polymer obtained by polymerizing one or more polymerizable monomers is preferable.
　上記樹脂粒子を、エチレン性不飽和基を有する重合性単量体を重合させて得る場合には、該エチレン性不飽和基を有する重合性単量体としては、非架橋性の単量体と架橋性の単量体とが挙げられる。 When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and And a crosslinkable monomer.
　上記非架橋性の単量体としては、例えば、スチレン、α－メチルスチレン等のスチレン系単量体；（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート化合物；２－ヒドロキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート化合物；（メタ）アクリロニトリル等のニトリル含有単量体；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル等のビニルエーテル化合物；酢酸ビニル、酪酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の酸ビニルエステル化合物；エチレン、プロピレン、イソプレン、ブタジエン等の不飽和炭化水素；トリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート、塩化ビニル、フッ化ビニル、クロルスチレン等のハロゲン含有単量体等が挙げられる。 Examples of the non-crosslinkable monomer include styrene monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc. Oxygen atom-containing (meth) acrylate compounds; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
　上記架橋性の単量体としては、例えば、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、（ポリ）テトラメチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート等の多官能（メタ）アクリレート化合物；トリアリル（イソ）シアヌレート、トリアリルトリメリテート、ジビニルベンゼン、ジアリルフタレート、ジアリルアクリルアミド、ジアリルエーテル、γ－（メタ）アクリロキシプロピルトリメトキシシラン、トリメトキシシリルスチレン、ビニルトリメトキシシラン等のシラン含有単量体等が挙げられる。 Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-containing monomers such as rate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane, etc. Can be mentioned.
　「（メタ）アクリル」の用語は、アクリルとメタクリルとを示す。「（メタ）アクリレート」の用語は、アクリレートとメタクリレートとを示す。 The term “(meth) acryl” indicates acrylic and methacrylic. The term “(meth) acrylate” refers to acrylate and methacrylate.
　上記エチレン性不飽和基を有する重合性単量体を、公知の方法により重合させることで、上記樹脂粒子を得ることができる。この方法としては、例えば、ラジカル重合開始剤の存在下で懸濁重合する方法、及び非架橋の種粒子を用いてラジカル重合開始剤とともに単量体を膨潤させて重合する方法等が挙げられる。 The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
　上記基材粒子が金属粒子を除く無機粒子又は有機無機ハイブリッド粒子である場合には、上記基材粒子の材料である無機物としては、シリカ及びカーボンブラック等が挙げられる。上記無機物は金属ではない。上記シリカにより形成された粒子としては特に限定されないが、例えば、加水分解性のアルコキシシリル基を２つ以上有するケイ素化合物を加水分解して架橋重合体粒子を形成した後に、必要に応じて焼成を行うことにより得られる粒子が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。 When the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles, examples of the inorganic material that is the material of the substrate particles include silica and carbon black. The inorganic substance is not a metal. The particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
　上記基材粒子の１０％Ｋ値は、４０００Ｎ／ｍｍ２以下であることが好ましい。上記の特定の圧縮特性を有する上記基材粒子は比較的軟らかく、柔軟性を有する。上記基導電性粘着テープが貼り付けられる際に、上記基材粒子は柔軟であるため、圧縮変形することができ、比較的硬い基材粒子を用いた場合と比べて電気特性をより一層高めることができる。後述する実施例で用いた基材粒子の１０％Ｋ値は、この上限以下である。 The 10% K value of the substrate particles is preferably 4000 N / mm 2 or less. The base particles having the specific compression characteristics are relatively soft and flexible. When the base conductive pressure-sensitive adhesive tape is affixed, the base particles are flexible, so that they can be compressed and deformed, and the electrical characteristics can be further enhanced as compared with the case of using relatively hard base particles. Can do. The 10% K value of the base particles used in the examples described later is below this upper limit.
　上記基材粒子の１０％Ｋ値は、以下のようにして測定できる。 The 10% K value of the substrate particles can be measured as follows.
　微小圧縮試験機を用いて、円柱（直径５０μｍ、ダイヤモンド製）の平滑圧子端面で、２５℃、最大試験荷重２０ｍＮを６０秒かけて負荷する条件下で基材粒子を圧縮する。このときの荷重値（Ｎ）及び圧縮変位（ｍｍ）を測定する。得られた測定値から、上記圧縮弾性率を下記式により求めることができる。上記微小圧縮試験機として、例えば、フィッシャー社製「フィッシャースコープＨ－１００」等が用いられる。 Using a micro-compression tester, the base particles are compressed under a condition that a smooth tester end face of a cylinder (diameter 50 μm, made of diamond) is loaded at 25 ° C. and a maximum test load 20 mN over 60 seconds. The load value (N) and compression displacement (mm) at this time are measured. From the measured value obtained, the compression elastic modulus can be obtained by the following formula. As the micro compression tester, for example, “Fischer Scope H-100” manufactured by Fischer is used.
　１０％Ｋ値（Ｎ／ｍｍ２）＝（３／２１／２）・Ｆ・Ｓ－３／２・Ｒ－１／２
　Ｆ：基材粒子が１０％圧縮変形したときの荷重値（Ｎ）
　Ｓ：基材粒子が１０％圧縮変形したときの圧縮変位（ｍｍ）
　Ｒ：基材粒子の半径（ｍｍ） 10% K value (N / mm 2 ) = (3/2 1/2 ) · F · S −3 / 2 · R −1/2
F: Load value (N) when the base material particle is 10% compressively deformed
S: Compression displacement (mm) when the substrate particles are 10% compressively deformed
R: radius of base particle (mm)
　上記導電部の材料は特に限定されない。上記導電部の材料は、金属であることが好ましい。上記金属としては、例えば、金、銀、パラジウム、銅、白金、亜鉛、鉄、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、タリウム、ゲルマニウム、カドミウム、タングステン、モリブデン、ケイ素及びこれらの合金等が挙げられる。また、上記金属としては、錫ドープ酸化インジウム（ＩＴＯ）及びはんだ等が挙げられる。電気特性を効果的に高める観点からは、錫を含む合金、ニッケル、パラジウム、銅又は金が好ましく、ニッケル又はパラジウムがより好ましい。 The material for the conductive part is not particularly limited. The material of the conductive part is preferably a metal. Examples of the metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, tungsten, and molybdenum. , Silicon and alloys thereof. Examples of the metal include tin-doped indium oxide (ITO) and solder. From the viewpoint of effectively improving the electrical characteristics, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　以下の材料を用意した。 The following materials were prepared.
　（基材）
　電解銅箔（１）（平均厚み１２μｍ） (Base material)
Electrolytic copper foil (1) (average thickness 12μm)
　（粘着剤層の材料）
　粘着剤溶液（１）：温度計、攪拌機及び冷却管を備えた反応器に、ブチルアクリレート６０重量部、２－エチルヘキシルアクリレート３６．９重量部、アクリル酸３重量部、２－ヒドロキシエチルアクリレート０．１重量部、及び、酢酸エチル８０重量部を加え、窒素置換した後、反応器を加熱して還流を開始した。続いて、上記反応器内に、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を添加した。７０℃で５時間還流させて、アクリル共重合体（ａ）の溶液を得た。得られたアクリル共重合体（ａ）について、カラムとしてＷａｔｅｒ社製「２６９０　Ｓｅｐａｒａｔｉｏｎｓ　Ｍｏｄｅｌ」を用いてＧＰＣ法により測定された重量平均分子量は、１４０万であった。 (Adhesive layer material)
Adhesive solution (1): In a reactor equipped with a thermometer, a stirrer and a condenser, butyl acrylate 60 parts by weight, 2-ethylhexyl acrylate 36.9 parts by weight, acrylic acid 3 parts by weight, 2-hydroxyethyl acrylate 0. After 1 part by weight and 80 parts by weight of ethyl acetate were added and the atmosphere was replaced with nitrogen, the reactor was heated to start refluxing. Subsequently, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator in the reactor. The solution was refluxed at 70 ° C. for 5 hours to obtain a solution of the acrylic copolymer (a). About the obtained acrylic copolymer (a), the weight average molecular weight measured by GPC method using "2690 Separations Model" made from Water as a column was 1.4 million.
　得られたアクリル共重合体（ａ）の溶液に含まれるアクリル共重合体（ａ）の固形分１００重量部に対して、重合ロジンエステル（軟化点１５０℃）１５重量部、ロジンエステル（軟化点１００℃）１０重量部、テルペンフェノール（軟化点１５０℃）１０重量部、酢酸エチル（不二化学薬品社製）３４４重量部、及び、イソシアネート系架橋剤（日本ポリウレタン社製「コロネートＬ４５」）１重量部を添加し、攪拌して、導電性粒子を含まない粘着剤溶液（１）（粘着剤と溶剤とを含む液）を得た。 15 parts by weight of polymerized rosin ester (softening point 150 ° C.), rosin ester (softening point) with respect to 100 parts by weight of the solid content of acrylic copolymer (a) contained in the resulting solution of acrylic copolymer (a) 10 parts by weight of 100 ° C.), 10 parts by weight of terpene phenol (softening point 150 ° C.), 344 parts by weight of ethyl acetate (Fuji Chemical Co., Ltd.), and isocyanate crosslinking agent (“Coronate L45” manufactured by Nippon Polyurethane) A part by weight was added and stirred to obtain a pressure-sensitive adhesive solution (1) containing no conductive particles (a liquid containing a pressure-sensitive adhesive and a solvent).
　導電性粒子（１）：金属被覆粒子、平均粒子径１０μｍ、粒子径のＣＶ値１．３％、アクリル樹脂粒子が、ニッケル導電部（厚み１００ｎｍ）により被覆された粒子 Conductive particles (1): Metal-coated particles, average particle size of 10 μm, particle size CV value of 1.3%, particles in which acrylic resin particles are coated with nickel conductive parts (thickness 100 nm)
　導電性粒子（２）：金属被覆粒子、平均粒子径６μｍ、粒子径のＣＶ値２．３％、アクリル樹脂粒子が、ニッケル導電部（厚み１００ｎｍ）により被覆された粒子 Conductive particles (2): Metal-coated particles, average particle diameter of 6 μm, particle diameter CV value of 2.3%, particles in which acrylic resin particles are coated with nickel conductive parts (thickness 100 nm)
　導電性粒子（Ｘ）：ニッケル粒子、平均粒子径２．２μｍ、粒子径のＣＶ値９．６％ Conductive particles (X): nickel particles, average particle size 2.2 μm, particle size CV value 9.6%
　導電性粒子（Ｙ）：ニッケル粒子、平均粒子径１０μｍ、粒子径のＣＶ値３．３％ Conductive particles (Y): Nickel particles, average particle size 10 μm, particle size CV value 3.3%
　導電性粒子（Ｚ）：銀コートガラス粉末、平均粒子径２６μｍ、銀導電部（厚み１００ｎｍ）により被覆された粒子 Conductive particles (Z): particles coated with silver-coated glass powder, average particle diameter of 26 μm, silver conductive part (thickness 100 nm)
　（基材粒子の１０％Ｋ値）：
　基材粒子の１０％Ｋ値を、上述した方法により算出した。 (10% K value of substrate particles):
The 10% K value of the base particles was calculated by the method described above.
　（実施例１～７及び比較例１～７）
　下記の表１に示す粘着剤溶液に、表１に示す導電性粒子を配合し、配合物を得た。なお、導電性粒子の配合量は、得られる粘着剤層において、粘着剤１００重量部に対して、導電性粒子の含有量が表１に示す量となる配合量である。 (Examples 1 to 7 and Comparative Examples 1 to 7)
The electroconductive particle shown in Table 1 was mix | blended with the adhesive solution shown in following Table 1, and the compounding was obtained. In addition, the compounding quantity of electroconductive particle is a compounding quantity from which the content of electroconductive particle turns into the quantity shown in Table 1 with respect to 100 weight part of adhesives in the adhesive layer obtained.
　厚み２５μｍのＰＥＴセパレーターを用意し、このセパレーターの離型処理面に配合物を塗布し、１００℃で３分間乾燥させることにより、厚み１０μｍの粘着剤層を形成した。この粘着剤層を、表１に示す基材と貼り合わせることで、表１に示す平均厚みの粘着剤層を形成した導電性粘着テープを得た。なお、比較例５及び６では、基材を用いなかった。 A PET separator having a thickness of 25 μm was prepared, and the composition was applied to the release-treated surface of the separator and dried at 100 ° C. for 3 minutes to form an adhesive layer having a thickness of 10 μm. By bonding this pressure-sensitive adhesive layer to the base material shown in Table 1, a conductive pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer having an average thickness shown in Table 1 was obtained. In Comparative Examples 5 and 6, no substrate was used.
　（評価）
　（１）粘着力
　ＪＩＳ　Ｚ０２３７に準拠して、得られた導電性粘着テープの１８０度剥離粘着力を測定した。具体的には、得られた導電性粘着テープを、２５ｍｍ×１００ｍｍに裁断し、セパレーターを剥離して導電性粘着テープ片を得た。導電性粘着テープ片を、被着体であるＪＩＳ　Ｇ４３０５の２８０番研磨ＳＵＳに、２３℃及び湿度６５％ＲＨ試験室において２ｋｇゴムローラーを１往復させ圧着し、貼り付けた。同様の環境下にて２０分放置した後、引張速度３００ｍｍ／ｍｉｎにて、導電性粘着テープ片をＳＵＳから１８０度方向に引き剥がし、その引き剥がしに要する力を測定することで、粘着力を評価した。粘着力を下記の基準で判定した。 (Evaluation)
(1) Adhesive strength Based on JIS Z0237, the 180 degree | times peeling adhesive force of the obtained electroconductive adhesive tape was measured. Specifically, the obtained conductive adhesive tape was cut into 25 mm × 100 mm, and the separator was peeled off to obtain a conductive adhesive tape piece. The conductive adhesive tape piece was attached to the adherend JIS G4305 No. 280 polishing SUS by reciprocating a 2 kg rubber roller once in a 23 ° C. and 65% humidity RH test chamber. After leaving in the same environment for 20 minutes, the conductive adhesive tape piece is peeled off from SUS in the direction of 180 degrees at a pulling speed of 300 mm / min, and the adhesive force is measured by measuring the force required for the peeling. evaluated. The adhesive strength was determined according to the following criteria.
　［粘着力の判定基準］
　○：粘着力が１１Ｎ／２５ｍｍ以上
　△：粘着力が１０Ｎ／２５ｍｍ以上、１１Ｎ／２５ｍｍ未満
　×：粘着力が１０Ｎ／２５ｍｍ未満 [Adhesion criteria]
○: Adhesive strength is 11 N / 25 mm or more Δ: Adhesive strength is 10 N / 25 mm or more and less than 11 N / 25 mm ×: Adhesive strength is less than 10 N / 25 mm
　（２）抵抗値１（Ω）（電気特性）
　得られた導電性粘着テープを、１０ｍｍ×１０ｍｍのサイズに裁断し、セパレーターを剥離して導電性粘着テープ片を得た。幅１ｍｍのアルミニウム板電極に３ｋｇ／ｃｍ２の加圧を５秒間かけて導電性粘着テープ片を貼り付けた。各電極への貼り付け面積を１ｍｍ×１０ｍｍとした。その後、２３℃及び湿度６５％ＲＨ試験室において、圧開放後の抵抗値を５秒毎６０回読み取り平均化することで、抵抗値を評価した。抵抗値を下記の基準で判定した。なお、抵抗値が低いほど、電気特性に優れている。抵抗値の「Ｏ．Ｌ．」は測定限界（１ＧΩ）を超え、抵抗値が測定できない状態を意味する。 (2) Resistance value 1 (Ω) (electrical characteristics)
The obtained conductive adhesive tape was cut into a size of 10 mm × 10 mm, and the separator was peeled off to obtain a conductive adhesive tape piece. Pasted conductive adhesive tape strips over 5 seconds pressurization of 3 kg / cm 2 to the aluminum plate electrodes of width 1 mm. The affixing area to each electrode was 1 mm × 10 mm. Thereafter, in the 23 ° C. and 65% humidity RH test room, the resistance value after pressure release was read 60 times every 5 seconds and averaged to evaluate the resistance value. The resistance value was determined according to the following criteria. In addition, it is excellent in the electrical property, so that resistance value is low. The resistance value “OL” means a state where the measurement value exceeds the measurement limit (1 GΩ) and the resistance value cannot be measured.
　［抵抗値の判定基準］
　○：抵抗値が１Ω以下
　△：抵抗値が１Ωを超え、３．１Ω以下
　×：抵抗値が３．１Ωを超える、又は、結果が「Ｏ．Ｌ．」 [Criteria of resistance value]
○: Resistance value is 1Ω or less Δ: Resistance value exceeds 1Ω, 3.1Ω or less ×: Resistance value exceeds 3.1Ω, or the result is “OL”
　（３）抵抗値２（Ω）（電気特性）
　得られた導電性粘着テープを、１０ｍｍ×２ｍｍのサイズに裁断し、セパレーターを剥離して導電性粘着テープ片を得た。幅１ｍｍのアルミニウム板電極に３ｋｇ／ｃｍ２の加圧を５秒間かけて導電性粘着テープ片を貼り付けた。各電極への貼り付け面積を１ｍｍ×２ｍｍとした。その後、２３℃及び湿度６５％ＲＨ試験室において、圧開放後の抵抗値を５秒毎６０回読み取り平均化することで、抵抗値を評価した。抵抗値を下記の基準で判定した。なお、抵抗値が低いほど、電気特性に優れている。抵抗値の「Ｏ．Ｌ．」は測定限界（１ＧΩ）を超え、抵抗値が測定できない状態を意味する。 (3) Resistance value 2 (Ω) (electrical characteristics)
The obtained conductive adhesive tape was cut into a size of 10 mm × 2 mm, and the separator was peeled off to obtain a conductive adhesive tape piece. A piece of conductive adhesive tape was attached to an aluminum plate electrode having a width of 1 mm by applying a pressure of 3 kg / cm 2 for 5 seconds. The affixing area to each electrode was 1 mm × 2 mm. Thereafter, in the 23 ° C. and 65% humidity RH test room, the resistance value after pressure release was read 60 times every 5 seconds and averaged to evaluate the resistance value. The resistance value was determined according to the following criteria. In addition, it is excellent in the electrical property, so that resistance value is low. The resistance value “OL” means a state where the measurement value exceeds the measurement limit (1 GΩ) and the resistance value cannot be measured.
　［抵抗値の判定基準］
　○：抵抗値が１０Ω以下
　△：抵抗値が１０Ωを超え、２５Ω以下
　×：抵抗値が２５Ωを超える、又は、結果が「Ｏ．Ｌ．」 [Criteria of resistance value]
○: Resistance value is 10Ω or less Δ: Resistance value exceeds 10Ω, 25Ω or less ×: Resistance value exceeds 25Ω, or the result is “OL”
　（４）耐反発性（高温及び高湿下での浮き及び剥離の発生）
　得られた導電性粘着テープを、２０ｍｍ×２０ｍｍのサイズに裁断し、セパレーターを剥離して導電性粘着テープ片を得た。導電性粘着テープ片の粘着剤層側から、平面視において貼り付け起点から貼り付け終点まで右に５ｍｍ、直角に曲げ下に２ｍｍ、直角に曲げ左に１３ｍｍ、ガラス板（厚さ２ｍｍ）に貼り付けて、積層体を得た。５ｍｍ×２０ｍｍの貼り付け面を１．５ｍｍ×２０ｍｍ（１）及び０．７ｍｍ×２０ｍｍ（２）となるよう裁断し、裁断した不必要な部分は剥ぎ取り、評価サンプルを得た。（１）、（２）の１．５ｍｍ×２０ｍｍ及び０．７ｍｍ×２０ｍｍの貼り付け面を、２ｋｇゴムローラーを１往復させ圧着した。同様の環境下にて２０分放置した後、得られた積層体を６０℃及び湿度９０％ＲＨの条件で７２時間放置した。放置後に、導電性粘着テープ（１），（２）の浮き及び剥離を観察し、耐反発性を下記の基準で判定した。 (4) Resilience resistance (occurrence of floating and peeling at high temperature and high humidity)
The obtained conductive adhesive tape was cut into a size of 20 mm × 20 mm, and the separator was peeled off to obtain a conductive adhesive tape piece. From the adhesive layer side of the conductive adhesive tape piece, 5mm to the right from the starting point to the end point in the plan view, 2mm under the right angle, 13mm to the left bent at a right angle, and attached to a glass plate (thickness 2mm) As a result, a laminate was obtained. The 5 mm × 20 mm attachment surface was cut to 1.5 mm × 20 mm (1) and 0.7 mm × 20 mm (2), and unnecessary portions cut were peeled off to obtain evaluation samples. The 1.5 mm × 20 mm and 0.7 mm × 20 mm sticking surfaces of (1) and (2) were crimped by reciprocating a 2 kg rubber roller once. After leaving for 20 minutes in the same environment, the obtained laminate was left for 72 hours under the conditions of 60 ° C. and humidity 90% RH. After leaving, the floating and peeling of the conductive pressure-sensitive adhesive tapes (1) and (2) were observed, and the resilience resistance was determined according to the following criteria.
　［耐反発性の判定基準］
　○：導電性粘着テープ（１）及び（２）の双方で、浮き及び剥離の双方が発生しない
　△：導電性粘着テープ（２）で、浮き及び剥離の双方が発生しない。導電性粘着テープ（１）で、浮き又は剥離が発生
　×：導電性粘着テープ（１）及び（２）の双方で、浮き又は剥離が発生 [Judgment criteria for rebound resistance]
○: Neither floating nor peeling occurs in both of the conductive adhesive tapes (1) and (2). Δ: Both floating and peeling do not occur in the conductive adhesive tape (2). Floating or peeling occurs with conductive adhesive tape (1) ×: Floating or peeling occurs with both conductive adhesive tapes (1) and (2)
　（５）二次凝集
　得られた配合物（粘着剤溶液に導電性粒子を配合した配合物）を、光学顕微鏡を用いて観察し、導電性粒子の凝集の有無を確認した。 (5) Secondary aggregation The obtained blend (mixture in which conductive particles were blended into an adhesive solution) was observed using an optical microscope to confirm the presence or absence of aggregation of the conductive particles.
　詳細及び結果を下記の表１に示す。 Details and results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１…導電性粘着テープ
　１１…基材
　１２…粘着剤層
　２１…粘着剤
　２２…導電性粒子
　３１…基材粒子
　３２…導電部 DESCRIPTION OF SYMBOLS 1 ... Conductive adhesive tape 11 ... Base material 12 ... Adhesive layer 21 ... Adhesive 22 ... Conductive particle 31 ... Base material particle 32 ... Conductive part

Claims (5)

  1. 　導電性を有する基材と、
    　前記基材の表面上に配置された粘着剤層とを備え、
    　前記粘着剤層は、粘着剤と、導電性粒子とを含み、
    　前記導電性粒子は、金属粒子を除く基材粒子と、前記基材粒子の表面上に配置された導電部とを有し、
    　前記粘着剤層において、前記粘着剤１００重量部に対して、前記導電性粒子の含有量が２０重量部以下である、導電性粘着テープ。     A conductive substrate;
    An adhesive layer disposed on the surface of the substrate;
    The pressure-sensitive adhesive layer includes a pressure-sensitive adhesive and conductive particles,
    The conductive particles have base particles excluding metal particles, and conductive portions arranged on the surface of the base particles.
    The said adhesive layer WHEREIN: The electroconductive adhesive tape whose content of the said electroconductive particle is 20 weight part or less with respect to 100 weight part of said adhesives.
  2. 　前記粘着剤層の平均厚みが２０μｍ以下である、請求項１に記載の導電性粘着テープ。 The conductive adhesive tape according to claim 1, wherein the average thickness of the adhesive layer is 20 μm or less.
  3. 　前記基材粒子が樹脂粒子である、請求項１又は２に記載の導電性粘着テープ。 The conductive adhesive tape according to claim 1 or 2, wherein the substrate particles are resin particles.
  4. 　前記基材が金属箔である、請求項１～３のいずれか１項に記載の導電性粘着テープ。 The conductive adhesive tape according to any one of claims 1 to 3, wherein the substrate is a metal foil.
  5. 　前記導電性粒子の粒子径のＣＶ値が３％以下である、請求項１～４のいずれか１項に記載の導電性粘着テープ。 The conductive adhesive tape according to any one of claims 1 to 4, wherein a CV value of a particle diameter of the conductive particles is 3% or less.
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