WO2016031787A1 - 導電性粘着シート - Google Patents

導電性粘着シート Download PDF

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Publication number
WO2016031787A1
WO2016031787A1 PCT/JP2015/073766 JP2015073766W WO2016031787A1 WO 2016031787 A1 WO2016031787 A1 WO 2016031787A1 JP 2015073766 W JP2015073766 W JP 2015073766W WO 2016031787 A1 WO2016031787 A1 WO 2016031787A1
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WIPO (PCT)
Prior art keywords
adhesive
conductive
conductive layer
resin
mass
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PCT/JP2015/073766
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English (en)
French (fr)
Japanese (ja)
Inventor
貴洋 植田
翔 大高
大雅 松下
香織 松下
宮田　壮
Original Assignee
リンテック株式会社
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Priority to KR1020177004810A priority Critical patent/KR102390524B1/ko
Priority to CN201580045648.3A priority patent/CN106795395B/zh
Priority to JP2016545532A priority patent/JP6500905B2/ja
Publication of WO2016031787A1 publication Critical patent/WO2016031787A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C09J121/00—Adhesives based on unspecified rubbers
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • 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
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive

Definitions

  • the present invention relates to a conductive adhesive sheet.
  • Conductive substances such as copper powder, silver powder, nickel powder, aluminum powder, and other metal powders are used for the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet. Are widely used in which they are dispersed in an adhesive resin.
  • Patent Document 1 discloses a conductive pressure-sensitive adhesive in which at least one of a carbon nanotube and a carbon microcoil is dispersed in a pressure-sensitive adhesive as a conductive substance, and a conductive pressure-sensitive adhesive sheet using the conductive pressure-sensitive adhesive. ing.
  • An object of the present invention is to provide a conductive pressure-sensitive adhesive sheet having good adhesive strength and excellent antistatic properties and conductivity.
  • the inventors have at least an adhesive conductive layer and a non-adhesive conductive layer, and each surface resistivity of the adhesive conductive layer and the non-adhesive conductive layer alone, and the surface resistivity of these two layers. It has been found that a conductive adhesive sheet in which the ratio is adjusted within a predetermined range can solve the above problems, and the present invention has been completed. That is, the present invention provides the following [1] to [16].
  • a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y),
  • the surface resistivity ( ⁇ SX ) of the adhesive conductive layer (X) alone is 1.0 ⁇ 10 2 to 1.0 ⁇ 10 10 ⁇ / ⁇
  • the non-adhesive conductive layer (Y) has a single surface resistivity ( ⁇ SY ) of 1.0 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 8 ⁇ / ⁇ , and Equation (1): 0 ⁇ satisfies the log 10 ( ⁇ SX / ⁇ SY ) ⁇ 6.0, the conductive adhesive sheet.
  • the adhesive resin (x1) contained in the adhesive composition is selected from the group consisting of acrylic resins, urethane resins, rubber resins, styrene resins, polyester resins, and polyolefin resins.
  • the above [4] wherein the content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass with respect to 100 parts by mass of the adhesive resin (x1).
  • the non-adhesive conductive layer (Y) is a layer containing one or more conductive materials selected from the group consisting of conductive polymers, carbon-based fillers, and metal oxides.
  • the non-adhesive conductive layer (Y) is a layer containing one or more conductive materials selected from the group consisting of polythiophene, PEDOT-PSS, carbon nanomaterials, and ITO (indium tin oxide).
  • the conductive pressure-sensitive adhesive sheet of the present invention has a good adhesive force and is excellent in antistatic properties and conductivity.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • surface resistivity of the conductive adhesive sheet means a surface resistivity measured from the surface side of the adhesive conductive layer (X) of the conductive adhesive sheet, unless otherwise specified.
  • the values of the surface resistivity and volume resistivity of each layer are values measured in accordance with JIS K 7194, and specifically mean values measured by the method described in the examples. To do.
  • the conductive adhesive sheet of the present invention has at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y).
  • the conductive adhesive sheet of the present invention can significantly reduce the surface resistivity of the adhesive conductive layer (X) and improve antistatic properties and conductivity. it can.
  • the conductive adhesive sheet of the present invention has good adhesive force.
  • “adhesive conductive layer (X)” and “non-adhesive conductive layer (Y)” are distinguished by the presence or absence of stickiness, and the presence or absence of stickiness is determined by the probe tack on the surface of each conductive layer. Judging from the peak top value. That is, in the present invention, if the value of the peak top of the probe tack with respect to the surface of the target conductive layer is 0.1 N or more, it is determined that the conductive layer has adhesiveness, and “adhesive conductive” “Layer (X)”.
  • the value of the probe tack peak top with respect to the surface of the target conductive layer is less than 0.1 N, it is determined that the conductive layer is non-adhesive, and “non-adhesive conductive layer (Y) "are categorized.
  • the value of the peak top of the probe tack with respect to the surface of the target conductive layer is a value measured according to JIS Z 0237 (1991), and specifically, by the method described in the examples described later. Means the measured value.
  • the conductive adhesive sheet of the present invention is not particularly limited as long as it has at least the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), and may have other layers other than these. .
  • the conductive adhesive sheet of one embodiment of the present invention may have a configuration in which another layer is provided between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y). From the viewpoint of reducing the surface resistivity of the pressure-sensitive adhesive sheet and improving antistatic properties and electrical conductivity, it is preferable that the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) are directly laminated.
  • FIG. 1 is a cross-sectional view of a conductive pressure-sensitive adhesive sheet with a base material, which is a preferred embodiment of the conductive pressure-sensitive adhesive sheet of the present invention.
  • a conductive adhesive sheet of one embodiment of the present invention for example, a substrate 13, a non-adhesive conductive layer (Y) 12, and an adhesive conductive layer (X) 11 as shown in FIG. 1 A of conductive adhesive sheets which have the structure laminated
  • This conductive adhesive sheet 1A has a two-layer body 21 composed of a non-adhesive conductive layer (Y) 12 and an adhesive conductive layer (X) 11 on one surface of a substrate.
  • a non-adhesive electroconductive layer (Y) and adhesive electroconductivity are shown on both surfaces of a base material as shown, for example in FIG.1 (c), (d). It may be a conductive pressure-sensitive adhesive sheet having two layers 21a and 21b each composed of the layer (X). That is, the conductive adhesive sheet 2A shown in FIG.
  • first non-adhesive conductive layer (YI) 12a and the first adhesive conductive layer (X -I) a first two-layer body 21a composed of 11a, and a second non-adhesive conductive layer (Y-II) 12b and a second adhesive conductive layer on the other surface of the substrate 13;
  • a second bilayer body 21b composed of the layer (X-II) 11b is included.
  • the conductive adhesive sheet 2B shown in FIG. 1 (d) is different from the configuration of the conductive adhesive sheet 2A on the first adhesive conductive layer (XI) 11a and the second adhesive conductive layer.
  • Each of the release sheets 14a and 14b is laminated on the (X-II) 11b.
  • FIG. 2 is sectional drawing of the electroconductive adhesive sheet without a base material which is a structure of the suitable one aspect
  • the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention may be a substrate-less conductive pressure-sensitive adhesive sheet.
  • the conductive adhesive sheet 3 which has the structure which pinched
  • the conductive adhesive sheet of one embodiment of the present invention as shown in FIG.
  • the conductive adhesive sheet 4 may have a configuration in which the three-layer body 22 in which the second adhesive conductive layer (X-II) 11b is laminated in this order is sandwiched between the two release sheets 14a and 14b.
  • the conductive adhesive sheet of one embodiment of the present invention having a configuration other than the above is composed of an adhesive conductive layer (X) and a non-adhesive conductive layer (Y) on one side of a release sheet that has been subjected to release treatment on both sides.
  • the conductive adhesive sheet etc. which have the structure which rolled what was provided so that adhesive electroconductive layer (X) may express the two-layer body rolled may be mentioned.
  • the first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (XI-II) 11b described above may be layers formed of the same adhesive composition and have different adhesive properties. It may be a layer formed from the composition.
  • the first non-adhesive conductive layer (YI) 12a and the second non-adhesive conductive layer (Y-II) 12b may be layers formed of the same forming material. It may be a layer formed from different forming materials.
  • the configurations of the first adhesive conductive layer (XI) and the second adhesive conductive layer (X-II) are the same as those of the adhesive conductive layer (X).
  • the configuration of the non-adhesive conductive layer (YI) and the second non-adhesive conductive layer (Y-II) is the same as that of the non-adhesive conductive layer (Y).
  • the adhesive conductive layer (X) has adhesiveness (the peak top value of the above-mentioned probe tack is 0.1 N or more), and the electrical conductivity (volume resistivity ( ⁇ VX ) of the layer alone is 1.0. ⁇ 10 8 ⁇ ⁇ cm or less).
  • the non-adhesive conductive layer (Y) is a non-adhesive layer (the probe tack has a peak top value of less than 0.1 N) and is conductive (volume resistivity ( ⁇ ) of the layer alone. VY ) is 1.0 ⁇ 10 8 ⁇ ⁇ cm or less).
  • the surface resistivity ( ⁇ SX ) of the adhesive conductive layer (X) alone is 1.0 ⁇ 10 2 to 1.0 ⁇ 10 10 ⁇ / ⁇ , preferably 1.0 ⁇ 10 2 to 1.0 ⁇ 10 8 ⁇ / ⁇ , more preferably 1.0 ⁇ 10 2 to 1.0 ⁇ 10 7 ⁇ / ⁇ , still more preferably 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 ⁇ / ⁇ is there.
  • the surface resistivity ( ⁇ SX ) it is necessary to contain a large amount of a conductive material, so the adhesive strength of the adhesive conductive layer (X) is reduced.
  • the surface resistivity ( ⁇ SY ) of the non-adhesive conductive layer (Y) alone is 1.0 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 8 ⁇ / ⁇ , preferably 1.0 ⁇ 10 ⁇ 2.
  • ⁇ SY surface resistivity of the non-adhesive conductive layer
  • a non-adhesive conductive layer (Y) having a surface resistivity ( ⁇ SY ) of less than 1.0 ⁇ 10 ⁇ 2 ⁇ / ⁇ or exceeding 1.0 ⁇ 10 8 ⁇ / ⁇ is provided, the conductive adhesive sheet It is difficult to express the effect of reducing the surface resistivity.
  • the value of the surface resistivity ( ⁇ SX ) of the adhesive conductive layer (X) alone and the value of the surface resistivity ( ⁇ SY ) of the non-adhesive conductive layer (Y) alone are as follows: It is necessary to satisfy the formula (1).
  • Formula (1) 0 ⁇ log 10 ( ⁇ SX / ⁇ SY ) ⁇ 6.0
  • the value of log 10 ( ⁇ SX / ⁇ SY ) exceeds 6.0, the surface resistivity of the conductive pressure-sensitive adhesive sheet is not sufficiently lowered, and the antistatic property and the conductivity tend to be inferior.
  • the value of log 10 ( ⁇ SX / ⁇ SY ) is preferably 5.0 or less, more preferably 4.5 or less, still more preferably 4.0 or less, and still more preferably 3.7 or less. is there.
  • the value of log 10 ( ⁇ SX / ⁇ SY ) needs to be a value larger than 0 as shown in the above formula (1). That is, in the present invention, from the viewpoint of effectively reducing the surface resistivity of the conductive adhesive sheet, the surface resistivity ( ⁇ SY ) of the non-adhesive conductive layer (Y) alone is the adhesive conductive layer (X) alone. It is a value smaller than the surface resistivity ( ⁇ SX ).
  • the volume resistivity ( ⁇ VX ) of the adhesive conductive layer (X) alone is preferably 1.0 ⁇ from the viewpoint of a conductive adhesive sheet with good adhesive force and effectively reduced surface resistivity. 10 0 to 1.0 ⁇ 10 8 ⁇ ⁇ cm, more preferably 1.0 ⁇ 10 0 to 1.0 ⁇ 10 6 ⁇ ⁇ cm, more preferably 1.0 ⁇ 10 0 to 1.0 ⁇ 10 5 ⁇ ⁇ Cm, more preferably 1.0 ⁇ 10 0 to 1.0 ⁇ 10 4 ⁇ ⁇ cm.
  • the volume resistivity ( ⁇ VY ) of the non-adhesive conductive layer (Y) alone is preferably 1.0 ⁇ 10 ⁇ 4 to 1 from the viewpoint of obtaining a conductive adhesive sheet with effectively reduced surface resistivity.
  • 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 2 ⁇ ⁇ cm still more preferably 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 1 ⁇ ⁇ cm, still more preferably 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 0 ⁇ ⁇ cm.
  • the volume resistivity ( ⁇ VY ) of the non-sticky conductive layer (Y) alone is the pressure-sensitive conductive layer ( X)
  • a value smaller than a single volume resistivity ( ⁇ VX ) is preferable.
  • the thickness (t X ) of the adhesive conductive layer (X) is appropriately adjusted depending on the application and the like, but is preferably 1 to 1200 ⁇ m, more preferably 2 to 600 ⁇ m, more preferably 3 to 300 ⁇ m, and still more preferably.
  • the thickness is 5 to 250 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 15 to 150 ⁇ m.
  • the thickness (t X) is 1 ⁇ m or more, it is possible to express the good adhesion which does not depend on the kind of the adherend.
  • the thickness (t X) is less than or equal to 1200 [mu] m, the conductivity of the conductive adhesive sheet obtained becomes good.
  • the adhesive conductive layer (X) protrudes from an end portion of the wound body or a winding shift due to deformation of the adhesive conductive layer (X). Can be suppressed.
  • the thickness (t Y ) of the non-adhesive conductive layer (Y) is appropriately adjusted depending on the application and the like, but is preferably 0.01 to 200 ⁇ m, more preferably 0.1 to 160 ⁇ m, still more preferably 0.00.
  • the thickness is 5 to 130 ⁇ m, more preferably 1.0 to 100 ⁇ m.
  • the thickness (t Y) is 0.01 ⁇ m or more, it is possible to lower the surface resistivity of the non-adhesive electrically conductive layer (Y) effectively.
  • the thickness (t Y ) is 200 ⁇ m or less
  • the conductive pressure-sensitive adhesive sheet when used as a wound body, winding deviation due to deformation of the non-adhesive conductive layer (Y) or the end of the wound body The adverse effect that the non-adhesive conductive layer (Y) protrudes from the portion can be suppressed.
  • it can be set as the electroconductive adhesive sheet which is easy to apply to a small electronic device by making the total thickness of an electroconductive adhesive sheet small.
  • the adhesive conductive layer (X) is preferably a layer formed from an adhesive composition containing an adhesive resin (x1) and a carbon-based filler (x2).
  • the said adhesive composition may contain a general purpose additive other than a crosslinking agent, a tackifier, and these according to the kind of adhesive resin (x1).
  • a general purpose additive other than a crosslinking agent, a tackifier, and these according to the kind of adhesive resin (x1).
  • the adhesive resin (x1) contained in the adhesive composition that is a material for forming the adhesive conductive layer (X) means an adhesive resin having a mass average molecular weight of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin (x1) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000 from the viewpoint of improving the adhesive strength of the conductive adhesive sheet.
  • the content of the pressure-sensitive adhesive resin (x1) in the pressure-sensitive adhesive composition is preferably 60.0 to 99.99% by mass, more preferably 70.75%, based on the total amount (100% by mass) of the pressure-sensitive adhesive composition. It is 0 to 99.9% by mass, more preferably 80.0 to 99.5% by mass, and still more preferably 90.0 to 99.0% by mass.
  • the adhesive resin (x1) an acrylic resin, a urethane resin, a polyisobutylene resin, a styrene resin, from the viewpoint of improving the adhesive strength of the conductive adhesive sheet and improving the antistatic property and conductivity, It is preferable to include at least one adhesive resin selected from the group consisting of polyester resins and polyolefin resins, and selected from the group consisting of acrylic resins, urethane resins, polyisobutylene resins, and styrene resins. It is more preferable to include one or more adhesive resins, and it is even more preferable to include one or more adhesive resins selected from the group consisting of acrylic resins and urethane resins.
  • acrylic resin examples include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a (meth) acrylate having a cyclic structure. And a polymer having a structural unit derived from.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,300,000, still more preferably 250,000 to 1,100,000, still more preferably 350,000 to 900,000. .
  • the structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “monomer (a1 ′)”), and a functional group
  • An acrylic copolymer having a structural unit (a2) derived from the containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) is preferable.
  • the said acryl-type copolymer may have the structural unit (a3) derived from other monomers (a3 ') other than a monomer (a1') and (a2 ').
  • the form of copolymerization of the acrylic copolymer is not particularly limited. That is, the acrylic copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 12, more preferably 4 to 8, and further preferably 4 to 6, from the viewpoint of improving the adhesive property.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate.
  • butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, and still more preferably based on all the structural units (100% by mass) of the acrylic copolymer. Is 70 to 97% by mass, more preferably 80 to 95% by mass.
  • Examples of the monomer (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. .
  • a carboxy group-containing monomer is preferable.
  • Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and (meth) acrylic acid is preferred.
  • the content of the structural unit (a2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably based on all the structural units (100% by weight) of the acrylic copolymer. Is 5 to 30% by mass, more preferably 7 to 20% by mass.
  • Examples of the monomer (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl.
  • Examples include (meth) acrylates having a cyclic structure such as (meth) acrylates and imide (meth) acrylates, vinyl acetate, acrylonitrile, and styrene.
  • the content of the structural unit (a3) is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and still more preferably 0 to 0% with respect to all the structural units (100% by weight) of the acrylic copolymer.
  • the amount is 10% by mass, more preferably 0 to 5% by mass.
  • the monomers (a1 ′) to (a3 ′) described above may be used alone or in combination of two or more.
  • the urethane resin that can be used as the adhesive resin (x1) is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in the main chain and / or side chain.
  • the urethane resin used in one embodiment of the present invention preferably includes a urethane polymer having a polyoxyalkylene skeleton.
  • the mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, and still more preferably 20,000 to 70,000.
  • polyol used as a raw material for the urethane-based prepolymer ( ⁇ ) examples include polyol compounds such as alkylene diol, polyether-type polyol, polyester-type polyol, and polycarbonate-type polyol.
  • the polyol is not particularly limited. It may be a bifunctional diol or a trifunctional triol. Among these polyols, diols are preferable from the viewpoints of availability, reactivity, and the like.
  • diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, and ethylene.
  • alkylene glycols such as glycol, propylene glycol, diethylene glycol and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol, and polyoxyalkylene glycols such as polytetramethylene glycol.
  • a glycol having a mass average molecular weight of 1000 to 3000 is preferable from the viewpoint of suppressing gelation in the reaction.
  • Examples of the polyvalent isocyanate compound that is a raw material for the urethane prepolymer ( ⁇ ) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxyly
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca.
  • HMDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodeca examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.
  • IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • the polyvalent isocyanate compound may be a modified product of a compound (polyisocyanate) selected from the above-mentioned aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specifically, it may be a trimethylolpropane adduct modified product of the compound, a burette modified product obtained by reacting the compound with water, or an isocyanurate modified product containing the isocyanurate ring in the compound.
  • polyvalent isocyanate compounds 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesiveness.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is more preferable.
  • the isocyanate group content (NCO%) in the urethane-based prepolymer ( ⁇ ) is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass, as measured according to JIS K 1603. is there.
  • chain extender a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.
  • the compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
  • aliphatic diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
  • alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
  • Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
  • Examples of bisphenol include bisphenol A and the like.
  • Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
  • Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino-2,3-propanediol, and 1-methyl.
  • Examples include amino alcohols such as amino-2,3-propanediol and N- (2-hydroxypropylethanolamine), and ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine.
  • the polyisobutylene resin (hereinafter also referred to as “PIB resin”) that can be used as the adhesive resin (x1) is a resin having a polyisobutylene skeleton in the main chain or side chain.
  • the cohesive force of the obtained pressure-sensitive adhesive composition can be sufficiently obtained, and the adhesive force of the conductive pressure-sensitive adhesive sheet can be improved, and the adherend can be prevented from being contaminated.
  • Mw mass average molecular weight
  • the cohesive force of the obtained pressure-sensitive adhesive composition can be sufficiently obtained, and the adhesive force of the conductive pressure-sensitive adhesive sheet can be improved, and the adherend can be prevented from being contaminated.
  • it is preferably 30,000 to 1,000,000, more preferably 50,000 to 800,000, and even more preferably 70,000 to 60. Ten thousand.
  • PIB resin examples include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers.
  • examples thereof include halogenated butyl rubber that has been brominated or chlorinated.
  • the structural unit derived from isobutylene is contained most in all the structural units.
  • the content of the structural unit derived from isobutylene is preferably 80 to 100% by mass, more preferably based on the total structural unit (100% by mass) of the PIB resin. Is 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass.
  • These PIB-based resins may be used alone or in combination of two or more.
  • the adhesive conductive layer (X) to be formed has a dense molecular structure when polymerized and has a polymerizable double bond in the main chain and side chain. What does not exist and contains many structural units derived from isobutylene is preferable.
  • the content of the structural unit derived from isobutylene having no polymerizable double bond in the main chain and side chain is the total structural unit of the PIB resin ( 100 to 100% by mass), preferably 80 to 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass.
  • the PIB resin used in one embodiment of the present invention includes a PIB resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter also referred to as “PIB resin (p1)”). It is preferable to use together a PIB resin (p2) having a mass average molecular weight of 50,000 to 250,000 (hereinafter also referred to as “PIB resin (p2)”).
  • the PIB resin (p1) having a high mass average molecular weight contributes to improving the durability and weather resistance of the adhesive conductive layer (X) formed from the resulting adhesive composition and improving the adhesive strength.
  • the PIB resin (p2) having a low mass average molecular weight is well compatible with the PIB resin (p1), and can appropriately plasticize the PIB resin (p1).
  • X) increases the wettability of the adherend and contributes to improving the physical properties of the adhesive, flexibility, and the like.
  • the mass average molecular weight (Mw) of the PIB resin (p1) is preferably from 270,000 to 600,000, more preferably from 290,000 to 480,000, still more preferably from 310,000 to 450,000, and even more preferably from the above viewpoint. 10,000 to 400,000.
  • the mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 18 It is 10,000 to 210,000.
  • the content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and even more.
  • the amount is preferably 8 to 20 parts by mass.
  • the content ratio of the PIB resin (p2) is 5 parts by mass or more, the PIB resin (p1) can be sufficiently plasticized, and the adhesive conductive layer (X) to be formed is wet with respect to the adherend. The adhesiveness can be improved while improving the property.
  • the content ratio of the PIB-based resin (p2) is 55 parts by mass or less, the adhesive force, holding force, and durability of the formed adhesive conductive layer (X) can be improved.
  • the styrene resin that can be used as the adhesive resin (x1) is a polymer having a structural unit derived from styrene.
  • the content of the structural unit derived from styrene is preferably 5 to 50% by mass, more preferably based on the total structural unit (100% by mass) of the styrene resin. Is 10 to 40% by mass, more preferably 15 to 35% by mass.
  • the mass average molecular weight (Mw) of the styrene-based resin is preferably 10,000 to 400,000, more preferably 20,000 to 300,000, and still more preferably 25,000-, from the viewpoint of improving the adhesive strength of the conductive adhesive sheet. 200,000.
  • the softening point of the styrene resin is preferably 80 to 200 ° C., more preferably 90 to 160 ° C., still more preferably 100 to 140 ° C., and still more preferably 105 from the viewpoint of improving the adhesive strength of the conductive adhesive sheet. ⁇ 135 ° C.
  • the softening point of the styrene-based resin means a value measured in accordance with JIS K2531.
  • styrenic resins examples include styrene-butadiene-styrene triblock copolymers (hereinafter also referred to as “SBS”), styrene-block- (ethylene-co-butylene) -block-styrene triblock copolymers (hereinafter referred to as “SBS”).
  • SBS styrene-butadiene-styrene triblock copolymers
  • SBS styrene-block- (ethylene-co-butylene) -block-styrene triblock copolymers
  • SEBS styrene-block- (ethylene-co-butylene) -block diblock copolymer
  • SEB styrene-butadiene diblock copolymer
  • SEB styrene-isoprene diblock Copolymer
  • SEB styrene-isoprene diblock Copolymer
  • SEB styrene-isoprene triblock copolymer
  • styrene-block- (butadiene-co-isoprene) -block diblock copolymer styrene-block- (butadiene-co-isoprene) -block-styrene tri Block copolymer, etc.
  • a copolymer of aromatic vinyl compounds such as styrene and ⁇ - methyl styrene.
  • Said styrenic resin may be used independently and may be used in combination of 2 or more type. Among these styrene resins, SBS, SEBS, and SEB are preferable, and SBS and SEBS are more preferable.
  • the form of copolymerization is not specifically limited. That is, the styrenic resin may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the polyester-based resin that can be used as the adhesive resin (x1) is a copolymer obtained by a polycondensation reaction between an acid component and a diol component or a polyol component, and includes a modified product of the copolymer.
  • the polycondensation reaction is performed by a general polyesterification reaction such as a direct esterification method or a transesterification method.
  • the form of copolymerization of the polyester resin is not particularly limited. That is, the polyester resin may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the acid component examples include terephthalic acid, isophthalic acid, phthalic anhydride, ⁇ -naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or esters thereof, pimelic acid, suberic acid, and azelain.
  • examples thereof include aliphatic dicarboxylic acids such as acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid or esters thereof; and alicyclic dicarboxylic acids such as 1,4-cyclohexahydrophthalic anhydride.
  • diol component or polyol component examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc.
  • Alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic glycols such as bisphenol A.
  • polyester resin may be used independently and may be used in combination of 2 or more type.
  • the polyolefin resin that can be used as the adhesive resin (x1) is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
  • polyolefin resins include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other ⁇ -olefins.
  • Copolymers copolymers, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers (ethylene -Vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.).
  • the polyolefin resin is a copolymer
  • the form of copolymerization is not specifically limited. That is, the polyolefin resin may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • Examples of the ethylenically unsaturated monomer include vinyl acetate, (meth) acrylic acid, alkyl (meth) acrylate, vinyl alcohol, and the like.
  • polypropylene resins containing a structural unit derived from propylene such as polypropylene, a copolymer of ethylene and propylene, and a copolymer of propylene and other ⁇ -olefin are preferable.
  • said polyolefin resin may be used independently and may be used in combination of 2 or more type.
  • Carbon filler (x2) As the carbon-based filler (x2) contained in the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive conductive layer (X) together with the pressure-sensitive resin (x1), a carbon-based filler having an average aspect ratio of 1.5 or more is preferable.
  • a carbon-based filler having an average aspect ratio of 1.5 or more the surface resistivity of the adhesive conductive layer (X) to be formed is lowered, and further the conductivity by providing the non-adhesive conductive layer (Y). The effect of reducing the surface resistivity of the adhesive sheet can be sufficiently exhibited. Moreover, the adhesive force of the adhesive conductive layer (X) can also be improved.
  • the average aspect ratio of the carbon filler (x2) is preferably 1.5 or more, more preferably 2 to 10,000, more preferably 3 to 5000, more preferably 4 to 1000, still more preferably 5 to 500, more preferably 6 to 400, still more preferably 10 to 300.
  • the “aspect ratio” is the ratio of the long side length (H) to the short side length (L) of the target carbon-based filler, that is, “long side length (H) / short. This is a value calculated from “length of side (L)”. Further, the “average aspect ratio” is an average value of the “aspect ratio” calculated by 10 carbon fillers to be processed.
  • the length (H) of the long side of the carbon-based filler (x2) means the length in the height direction (longitudinal direction) of the target carbon-based filler.
  • the length (L) of the short side of the carbon-based filler (x2) is a cut surface perpendicular to the height direction (longitudinal direction) of the target carbon-based filler if the cross section is a circle or an ellipse. If the cross section is a polygon, it means the diameter of the circumscribed circle of the polygon.
  • the length (H) of the long side of the carbon-based filler (x2) is preferably 0.01 to 2000 ⁇ m, more preferably 0.05 to 1000 ⁇ m, still more preferably 0.07 to 500 ⁇ m, still more preferably 0.8. 10 to 100 ⁇ m.
  • the average value of the long side lengths of 10 carbon-based fillers arbitrarily selected is regarded as the value of the “long-side length (H) of the carbon-based filler (x2)”. You can also.
  • the length (L) of the short side of the carbon filler (x2) is preferably 1 to 1000 nm, more preferably 2 to 750 nm, more preferably 3 to 500 nm, still more preferably 5 to 100 nm, and still more preferably 7 ⁇ 50 nm.
  • the average value of the short side lengths of 10 carbon-based fillers arbitrarily selected is regarded as the value of the “short-side length (L) of the carbon-based filler (x2)”. You can also.
  • Examples of the shape of the carbon-based filler (x2) include a columnar shape, a cylindrical shape, a weight shape, a fiber shape, an oblate shape (sphericity is usually 0.7 or less), and a shape obtained by combining these.
  • these shapes from the viewpoint of forming an adhesive conductive layer (X) having good conductivity, one type selected from a columnar carbon-based filler, a cylindrical carbon-based filler, and a fibrous carbon-based filler. The above is preferable.
  • the content of the carbon-based filler (x2) in the adhesive composition is preferably 0.01 to 15 parts by mass, more preferably 0.02 to 10 parts per 100 parts by mass of the adhesive resin (x1). Parts by mass, more preferably 0.30 to 7.0 parts by mass, still more preferably 0.40 to 5.0 parts by mass, still more preferably 0.50 to 4.5 parts by mass, and even more preferably 0.70 to 3.8 parts by mass. If the content of the carbon-based filler (x2) is 0.01 parts by mass or more, the surface resistivity of the formed adhesive conductive layer (X) alone is lowered, and the non-adhesive conductive layer (Y) is further reduced. The effect of reducing the surface resistivity of the conductive pressure-sensitive adhesive sheet due to the provision can be sufficiently exhibited.
  • the adhesive strength of the adhesive conductive layer (X) to be formed becomes good.
  • the conductive adhesive sheet of the present invention exhibits excellent antistatic properties and conductivity even when the content of the carbon-based filler (x2) in the adhesive conductive layer (X) is small, It is not necessary to add a large amount of filler (x2).
  • the content of the carbon-based filler (x2) relative to the total amount (100% by mass) of the adhesive composition is usually 0.01 to 10% by mass, preferably 0.30 to 7.0% by mass. More preferably, the content is 0.40 to 5.0% by mass, still more preferably 0.50 to 4.5% by mass, and still more preferably 0.70 to 3.8% by mass.
  • Examples of the carbon-based filler (x2) include carbon nanomaterials, carbon black, milled carbon fiber, and graphite. However, the carbon-based filler (x2) reduces the surface resistivity of the adhesive conductive layer (X) to be formed and has adhesive strength. From the viewpoint of improving the carbon, a carbon nanomaterial is preferable.
  • the carbon nanomaterial is composed of a material including a graphite sheet having a six-membered ring arrangement as a main structure, but the graphite structure may contain elements other than carbon such as boron and nitrogen.
  • the material may be in a form including another substance, and further, the carbon nanomaterial may be modified with another conductive substance.
  • Examples of the carbon nanomaterial include carbon nanotube (CNT), carbon nanofiber, carbon nanohorn, carbon nanocone, fullerene, and the like, and carbon nanotube is preferable.
  • the carbon nanotube is a cylindrical carbon polyhedron having a structure in which a graphite (graphite) sheet mainly having a carbon 6-membered ring structure is closed in a cylindrical shape.
  • the carbon nanotube includes a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape, a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape, and a three-layered graphite sheet
  • a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape
  • a three-layered graphite sheet There are multi-walled carbon nanotubes having a multi-layered structure concentrically closed as described above, and any two or more of these can be used in combination.
  • the adhesive composition which is a material for forming the adhesive conductive layer (X), may further contain a crosslinking agent.
  • a crosslinking agent especially an acrylic copolymer having the above-described structural unit (a2)
  • the adhesive conductive layer (X) to be formed is used.
  • the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent.
  • These crosslinking agents may be used alone or in combination of two or more. Among these, from the viewpoint of improving the adhesive strength of the conductive adhesive sheet, an isocyanate-based crosslinking agent is preferable.
  • isocyanate-based crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanate compounds such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate Is mentioned.
  • the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the adhesive resin (x1). Part.
  • the adhesive composition which is a material for forming the adhesive conductive layer (X) may further contain a tackifier.
  • a tackifier when the above-mentioned urethane resin, PIB resin, and styrene resin are used as the adhesive resin (x1), from the viewpoint of improving the adhesive strength of the adhesive conductive layer (X) to be formed, It is preferable to contain an imparting agent.
  • the mass average molecular weight (Mw) of this tackifier is usually less than 10,000, and is distinguished from the above-mentioned adhesive resin (x1).
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to 4000, more preferably 800 to 1500, from the viewpoint of improving the adhesive strength of the adhesive conductive layer (X) to be formed.
  • the softening point of the tackifier is preferably 110 ° C. or higher, more preferably 110 to 180 ° C., still more preferably 115 to 175 ° C., and still more preferably 120 to 170 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • tackifier examples include rosin resins such as rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, terpene phenols Terpene resins such as pentene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerization of C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 petroleum resin obtained and hydrogenated petroleum resin of this C5 petroleum resin; obtained by copolymerization of C9 fraction such as indene, vinyltoluene, ⁇ - or ⁇ -methylstyrene generated by thermal decomposition of petroleum naphtha C9 petroleum resin and hydrogenated petroleum resin of this C9 petroleum resin.
  • the content of the tackifier is preferably 1 to 200 parts by mass, more preferably 5 to 160 parts by mass, and still more preferably 10 to 120 parts by mass with respect to 100 parts by mass of the adhesive resin (x1).
  • the adhesive resin (x1) contains an acrylic resin
  • the content of the tackifier is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the acrylic resin. Part, more preferably 10 to 40 parts by weight.
  • the adhesive resin (x1) contains a urethane resin
  • the content of the tackifier is preferably 5 to 200 parts by mass, more preferably 40 to 160 parts by mass, with respect to 100 parts by mass of the urethane resin. More preferably, it is 80 to 120 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the PIB resin. More preferably, it is 15 to 40 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the styrene resin. More preferably, it is 25 to 60 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the polyester resin. More preferably, it is 25 to 60 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 25 to 60 parts by mass.
  • Examples of such general-purpose additives include ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, curing agents, curing aids, catalysts, and the like.
  • the amount of each general-purpose additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin (x1). 2 parts by mass.
  • the total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100% by mass) of the adhesive composition that is the material for forming the adhesive conductive layer (X) is preferably 20% by mass. As mentioned above, More preferably, it is 30 mass% or more.
  • the adhesive resin (x1) which has acrylic resin as a main component
  • the sum total content of the adhesive resin (x1) and carbon-type filler (x2) in the whole quantity (100 mass%) of an adhesive composition is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more.
  • the total content of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition is The total content of the adhesive resin (x1), the carbon-based filler (x2), and the tackifier is preferably 35% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more. Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
  • the total content of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition is The total content of the adhesive resin (x1), the carbon-based filler (x2), and the tackifier is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
  • the total content of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition is The amount is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
  • the notation “adhesive resin (x1) mainly composed of ZZ-based resin” means that “the content of ZZ-based resin is the largest among the resins included in the adhesive resin (x1)”. I mean.
  • the specific content of the ZZ resin in the description is usually 50% by mass or more, preferably 65 to 100% by mass, more preferably 75%, based on the total amount (100% by mass) of the adhesive resin (x1). To 100 mass%, more preferably 85 to 100 mass%.
  • the method for forming the adhesive conductive layer (X) is not particularly limited, and the adhesive conductive layer (X) can be produced by a known method. Examples thereof include the following methods (X-1) and (X-2). Method (X-1): An organic solvent solution of the pressure-sensitive adhesive composition is prepared, the solution is applied onto a release sheet described later by a known coating method to form a coating film, and the coating film is dried. A method for forming the adhesive conductive layer (X).
  • Method (X-2) After preparing a composite by heating and kneading the adhesive resin (x1) and the carbon-based filler (x2), the composite is molded into a sheet by a known molding method, and adhesive A method of forming the conductive layer (X).
  • Method (X-1) is a suitable forming method when an acrylic resin, a urethane resin, a PIB resin, or the like is used as the adhesive resin (x1).
  • the organic solvent used include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol, dimethylformamide, N-methyl.
  • examples include pyrrolidone and dimethyl sulfoxide.
  • the carbon-based filler (x2) is preferably blended with the adhesive resin (x1) in the form of a dispersion liquid dispersed in a solvent. Since the carbon filler (x2) can be mixed with the adhesive resin (x1) in a low-viscosity state by blending the carbon filler (x2) in the form of a dispersion, the carbon fillers (x2) are likely to be close to each other. By forming the network, the surface resistivity and volume resistivity of the formed adhesive conductive layer (X) are likely to be lowered. Examples of the solvent used for the preparation of the carbon filler (x2) dispersion include water and the above-mentioned organic solvents, and organic solvents are preferable.
  • Examples of the method for preparing the dispersion liquid of the carbon-based filler (x2) include a method in which the carbon-based filler (x2) is added to a solvent and vibration is applied for a certain period of time using ultrasonic waves or the like.
  • the solid concentration of the carbon filler (x2) dispersion is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 3% by mass.
  • examples of the method for applying the solution of the adhesive composition onto the release sheet include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating. Method, blade coating method, die coating method, gravure coating method and the like.
  • the coating layer after the drying treatment is applied for 7 days to 30 days, for example, in an environment of 23 ° C. and 50% RH (relative humidity). It is preferable that the coating layer is sufficiently cross-linked by allowing it to stand to a certain extent.
  • Method (X-2) is a preferable forming method when a resin that can be durable to heat kneading, such as a styrene resin, is used as the adhesive resin (x1).
  • the heating and kneading apparatus include a single screw extruder, a twin screw extruder, a roll mill, a plast mill, a Banbury mixer, an intermix, and a pressure kneader.
  • Examples of a method for molding the composite obtained by the heat kneading apparatus include a melt extrusion method, a calendar method, a compression molding method, and the like, and a compression molding method is preferable.
  • a sheet-like adhesive conductive layer (X) can be molded by sandwiching the prepared composite between two release sheets and heat-compressing with a hot press machine or the like.
  • a composite prepared by the base material and the release sheet may be sandwiched to form the sheet-like adhesive conductive layer (X).
  • the non-adhesive conductive layer (Y) is selected from the group consisting of a conductive polymer, a carbon-based filler, and a metal oxide from the viewpoint of sufficiently expressing the effect of reducing the surface resistivity of the conductive adhesive sheet. It is preferably a layer containing at least one conductive material, more preferably at least one conductive material selected from the group consisting of polythiophene, PEDOT-PSS, carbon nanomaterial, and ITO (indium tin oxide), It is further preferable to include one or more conductive materials selected from the group consisting of polythiophene, PEDOT-PSS, and carbon nanomaterials.
  • the density of the conductive material contained in the non-adhesive conductive layer (Y) is preferably from 0.8 to 2.5 g / cm 3 , more preferably from 0.8 to 2.5 from the viewpoint of reducing the weight of the conductive adhesive sheet. It is 2.0 g / cm 3 , more preferably 0.8 to 1.7 g / cm 3 .
  • the conductive material constituting the non-adhesive conductive layer (Y) will be described.
  • conductive polymer examples include polythiophene, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)), polyaniline, polypyrrole, polyquinoxaline, and the like. Among these, polythiophene and PEDOT-PSS are preferable.
  • the non-adhesive conductive layer (Y) containing a conductive polymer preferably contains a non-adhesive resin together with the conductive polymer.
  • the non-adhesive resin include acrylic resins, urethane resins, and PIB resins. And at least one non-adhesive resin selected from styrene-based resins.
  • the content of the conductive polymer is preferably 4 to 100% by mass, more preferably relative to the total amount (100% by mass) of the non-adhesive conductive layer (Y). 8 to 100% by mass.
  • the solution of the organic solvent containing a conductive polymer is prepared, and the said solution is used as a base material or a peeling sheet.
  • a method of forming the coating film by coating by a known coating method and drying the coating film may be mentioned.
  • the type of organic solvent used in the method and the method for applying the solution are the same as those described for “Method (X-1)”, which is the method for forming the adhesive conductive layer (X).
  • the non-adhesive conductive layer (Y) containing a carbon-based filler preferably contains a non-adhesive resin together with the carbon-based filler.
  • the non-adhesive resin include acrylic resins, urethane resins, PIB resins, and One or more non-adhesive resins selected from styrene resins are preferred.
  • the content of the carbon-based filler is preferably 0.1 to 20% by mass, more preferably based on the total amount (100% by mass) of the non-adhesive conductive layer (Y) Is 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, and still more preferably 2.0 to 7% by mass.
  • the non-adhesive electroconductive layer (Y) containing a carbon-type filler there is no restriction
  • the dispersion liquid of a carbon-type filler and the solution of the organic solvent of non-adhesive resin are mixed, and resin After preparing the solution of a composition, the said solution is apply
  • Method (X-1) which is a method for forming the above-mentioned adhesive conductive layer (X) Same as described.
  • a composite is prepared by heating and kneading a carbon-based filler and a non-adhesive resin, and then the composite is formed into a sheet by a known molding method.
  • the method obtained by making it into a shape may be sufficient.
  • the heating kneader and composite molding method used in the method are the same as those described for “Method (X-2)”, which is a method for forming the above-mentioned adhesive conductive layer (X).
  • ⁇ Metal oxide> Examples of the metal oxide include ITO (indium tin oxide), ZnO (zinc oxide), IZO (indium zinc oxide), AZO (zinc aluminum oxide), GZO (zinc gallium oxide), IGZO (indium gallium zinc oxide), and ATO ( Tin antimony oxide).
  • ITO indium tin oxide
  • a metal oxide as a conductive material, it is preferable that a non-adhesive conductive layer (Y) is a layer which consists only of the said metal oxide.
  • the method of forming by vapor deposition with respect to a base material is preferable.
  • the base material used for the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately selected according to the use of the conductive pressure-sensitive adhesive sheet, but may be an insulating base material including an insulating material, such as a metal. It may be a conductive substrate containing a conductive material.
  • an insulating substrate refers to a substrate having a surface resistivity of 1.0 ⁇ 10 14 ⁇ / ⁇ or more (preferably 1.0 ⁇ 10 16 ⁇ / ⁇ or more).
  • the insulating base material include various types of paper such as fine paper, art paper, coated paper, glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; Material: Polyolefin resin such as polyethylene resin and polypropylene resin, Polybutylene terephthalate resin, Polyester resin such as polyethylene terephthalate resin, Plastic film or sheet made of acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc .; Mixture of these resins A plastic film or sheet comprising: a plastic film or sheet comprising a laminate of these plastic films or sheets.
  • the base material such as a plastic film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral.
  • these insulating base materials may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant, and the like. Good.
  • the conductive substrate for example, a metal foil, a film or sheet obtained by laminating a metal foil with a resin or the like that forms the above-described insulating substrate, a film obtained by performing metal vapor deposition on the surface of the above-described insulating substrate, or Examples thereof include a sheet, a film or sheet obtained by performing antistatic treatment on the surface of the above-described insulating substrate, and a sheet in which a metal wire is knitted in a mesh shape.
  • a metal used for an electroconductive base material aluminum, copper, silver, gold
  • the thickness of the substrate is not particularly limited, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoint of ease of handling.
  • the base material is a plastic film or sheet
  • an oxidation method, an unevenness method, or the like is performed on the surface of the base material as necessary. It is preferable to perform the surface treatment.
  • the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • corrugated method For example, a sandblasting method, a solvent processing method, etc. are mentioned.
  • These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the non-adhesive conductive layer (Y) and the operability.
  • primer treatment can also be performed.
  • release sheet used for the conductive adhesive sheet of one embodiment of the present invention
  • a release sheet subjected to a double-sided release process a release sheet subjected to a single-sided release process, or the like is used, and a release agent is formed on the base for the release sheet.
  • coated are mentioned.
  • Examples of the release sheet base material include paper base materials such as glassine paper, coated paper, and high-quality paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, or polyethylene terephthalate resin, polybutylene terephthalate. Examples thereof include plastic films such as resins, polyester resin films such as polyethylene naphthalate resin, and polyolefin resin films such as polypropylene resin and polyethylene resin.
  • Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release sheet is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • the conductive adhesive sheet of one embodiment of the present invention is manufactured by appropriately bonding the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) formed by the above-described forming method, and a base material or a release sheet. can do.
  • the value of the peak top of the probe tack with respect to the surface of the adhesive conductive layer (X) of the conductive adhesive sheet of one embodiment of the present invention is preferably 0.1 N or more, more preferably 0.1 to 49 N, still more preferably Is 0.5 to 49N, and more preferably 1.0 to 49N.
  • the value of the peak top of the probe tack means a value measured by the method described in the examples.
  • the peak top value of the probe tack is a physical property value that is an index of the adhesive strength of the conductive adhesive sheet, and the larger the value, the higher the adhesive strength.
  • the surface resistivity ( ⁇ S ) measured from the surface side of the adhesive conductive layer (X) of the conductive adhesive sheet of one embodiment of the present invention is preferably 9.0 ⁇ 10 4 ⁇ / ⁇ or less, more preferably It is 1.0 ⁇ 10 4 ⁇ / ⁇ or less, more preferably 5.0 ⁇ 10 3 ⁇ / ⁇ or less, and still more preferably 2.0 ⁇ 10 3 ⁇ / ⁇ or less.
  • the value of the above-mentioned “surface resistivity measured from the surface side of the adhesive conductive layer (X) of the conductive adhesive sheet” is that at least the adhesive conductive layer (X) and the non-adhesive conductive layer (Y).
  • ⁇ Probe tack> It measured based on JIS Z0237 (1991). Specifically, after leaving a test piece having a size of 10 mm ⁇ 10 mm in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, the surface of the measurement target layer of the test piece is exposed. Then, using a tacking tester (manufactured by Rigaku Corporation, product name “PROBE TACK TESTER”), the probe tack value for the surface of the layer was measured.
  • a tacking tester manufactured by Rigaku Corporation, product name “PROBE TACK TESTER”
  • the probe tack value is determined by contacting a probe made of stainless steel having a diameter of 5 mm for 1 second with a contact load of 0.98 N / cm 2 at a speed of 600 mm / second after contacting the surface of the layer to be measured. The force required to separate from the surface was taken as the probe tack value of the surface of the layer. Further, the peak top of the probe tack value was measured for the surface of the non-adhesive conductive layer. Moreover, the peak top and integral value of the probe tack value were measured with respect to the surface of the adhesive conductive layer (X) of the conductive adhesive sheet. Further, when the surface of the layer to be measured is not sticky and the peak top of the probe tack value is not measurable, the value of the peak top is set to “0 (N)”.
  • ⁇ Surface resistivity, volume resistivity> The measurement was performed according to JIS K 7194. Specifically, after leaving a test piece having a size of 20 mm ⁇ 40 mm in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, the surface of the measurement target layer of the test piece is exposed. Then, the surface resistivity and the volume resistivity were measured using a low resistivity meter (product name “Loresta GP MCP-T610 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The above measurement was performed 3 times for the surface resistivity, the above measurement was performed 5 times for the volume resistivity, and Tables 1 and 2 list the average values of the measured values obtained in each measurement.
  • the conductive material prepared in Examples and Comparative Examples in which the base material, the non-adhesive conductive layer, the adhesive conductive layer (X), and the release sheet were laminated in this order.
  • the adhesive sheet was used as a test piece, the release sheet of the test piece was removed, and only the surface resistivity value was measured with respect to the surface of the exposed adhesive conductive layer (X).
  • Production Example 1 (Preparation of substrate with non-adhesive conductive layer (Y-1)) A polythiophene solution (Soken Chemical Co., Ltd.) on a 50 ⁇ m thick polyethylene terephthalate (PET) film (trade name “Lumirror”, surface resistivity: 1.18 ⁇ 10 18 ⁇ / ⁇ , manufactured by Toray Industries, Inc.) used as a substrate.
  • PET polyethylene terephthalate
  • a substrate with (Y-1) was obtained.
  • Production Example 2 (Preparation of substrate with non-adhesive conductive layer (Y-2)) Poly (3,4-ethylenedioxythiophene) -poly for 100 parts by mass (solid content) of an acrylic water-soluble polymer (trade name “Tamanori G-37”, polyacrylic acid, manufactured by Arakawa Chemical Industries, Ltd.) A solution containing 10 parts by mass (solid content ratio) of a dispersion of (styrenesulfonic acid) (PEDOT-PSS) (trade name “Orgacon S305” manufactured by Agfa) and 10 parts by mass of ethylene glycol was prepared.
  • PDOT-PSS dispersion of (styrenesulfonic acid)
  • Orgacon S305 manufactured by Agfa
  • Multi-walled carbon nanotubes (trade name “NC7000”, manufactured by Nanosil Co., Ltd., details will be described later) with respect to 100 parts by mass (solid content) of styrene resin (Clayton, trade name “1726M”, SEBS) 10 parts by mass (solid content ratio) was added, and the mixture was kneaded using a heating kneader (manufactured by Toyo Seiki Seisakusho, product name “30C150”) at 100 ° C. and 50 rpm to obtain a composite.
  • styrene resin Ciyton, trade name “1726M”, SEBS
  • a heating kneader manufactured by Toyo Seiki Seisakusho, product name “30C150”
  • the composite is sandwiched between the same PET film as used in Production Example 1 and a 75 ⁇ m-thick release sheet (trade name “SP-PET751031” manufactured by Lintec Corporation), and a hot press machine (Tester Sangyo) Using a product name “SA-302” manufactured by Co., Ltd., hot pressing was performed at 130 ° C. and 10 MPa for 10 minutes. After hot pressing, the release sheet was removed to obtain a base material with a non-adhesive conductive layer (Y-3) containing SEBS and CNT (10 parts by mass) having a thickness of 100.0 ⁇ m.
  • Y-3 non-adhesive conductive layer
  • Production Example 4 (Preparation of substrate with non-adhesive conductive layer (Y-4)) A non-adhesive conductive layer (Y-4) containing SEBS and CNT (4 parts by mass) having a thickness of 100.0 ⁇ m was prepared in the same manner as in Production Example 3 except that the blending amount of the multi-walled carbon nanotube was changed to “4 parts by mass”. ) To obtain a substrate.
  • Substrate with non-adhesive conductive layer (YA) made of ITO trade name “ITO-polyethylene terephthalate” (manufactured by Oike Kogyo Co., Ltd.)
  • Substrate with non-adhesive conductive layer (YB) made of copper trade name “Nikaflex” (manufactured by Nikkan Kogyo Co., Ltd.)
  • Base material with non-adhesive conductive layer (YC) made of aluminum Trade name “Metal Me # 50” (manufactured by Toray Film Processing Co., Ltd., 50 ⁇ m thick PET film (surface resistivity: 1.18 ⁇ 10 18) ⁇ / ⁇ ) on which an aluminum film having a thickness of 10.0 ⁇ m is deposited.
  • Table 1 shows various physical properties of the non-adhesive conductive layer of the substrate with the non-adhesive conductive layer used in the present examples and comparative examples.
  • Examples 1 to 15 and Comparative Examples 1 to 8 (1) Formation of adhesive conductive layer (X) Carbon filler (x2) of the type and blending amount (solid content ratio with respect to 100 parts by mass (adhesive content) of adhesive resin) shown in Table 2 was added to ethyl acetate. A dispersion of carbon-based filler (x2) having a solid content concentration of 0.5% by mass was prepared in advance by applying ultrasonic vibration (42 kHz, 125 W) for 1 hour with an ultrasonic cleaner. Next, a dispersion of the carbon-based filler (x2) is added to 100 parts by mass (solid content) of the type of adhesive resin (x1) shown in Table 2, and the types and blending amounts (solid content ratio) shown in Table 2 are further added.
  • a cross-linking agent and a tackifier were added as necessary. Then, it diluted suitably with ethyl acetate and stirred until it became uniform, and the solution of the adhesive composition was prepared. Then, the solution of the pressure-sensitive adhesive composition prepared as described above was peeled off from a release sheet (trade name “SP-PET 381031”, manufactured by Lintec Corporation, thickness: 38 ⁇ m, polyethylene terephthalate film whose surface was subjected to silicone release treatment). A coating film was formed by coating on the surface and dried to form a coating layer. Next, a release sheet of the same type as described above is separately laminated on the coating layer, and after standing for 14 hours in an environment of 23 ° C.
  • the coating layer is sufficiently cross-linked.
  • a laminate was obtained in which only the adhesive conductive layer (X) having the thickness shown in 2 was sandwiched between two release sheets.
  • Example 16 (1) Formation of adhesive conductive layer (X) Styrenic resin (trade name “P-907Y” manufactured by Toyo Adre Co., Ltd., details will be described later) per 100 parts by mass (solid content) of multi-walled carbon nanotube (CNT) (trade name “NC7000”, manufactured by Nanosil Co., Ltd., details will be described later) was added at the blending amount (solid content ratio) shown in Table 2, and a heat kneader (manufactured by Toyo Seiki Seisakusho, product name “ 30C150 ”) and kneaded at 100 ° C. and 50 rpm to obtain a composite.
  • X adhesive conductive layer
  • CNT multi-walled carbon nanotube
  • the composite is sandwiched between two release sheets (product name “SP-PET751031”, thickness: 75 ⁇ m, manufactured by Lintec Corporation), and hot press machine (product name “SA-302, manufactured by Tester Sangyo Co., Ltd.). )) For 10 minutes under conditions of 130 ° C. and 10 MPa to obtain a laminate in which only the adhesive conductive layer (X) was sandwiched between two release sheets.
  • (2) Production of conductive adhesive sheet Adhesive conductive layer (X) containing a styrene-based resin exposed by removing one release sheet of the laminate and a base with a non-adhesive conductive layer (Y-2) The material was bonded to a non-adhesive conductive layer to produce a conductive adhesive sheet.
  • PIB resin 90.9 parts by mass (solid content ratio) of PIB resin (trade name “Opanol B50", manufactured by BASF) with Mw of 340,000, and PIB resin (product manufactured by BASF, product of Mw 200,000) Name “Opanol B30”) 9.1 parts by mass (solid content ratio).
  • NC7000 trade name, manufactured by Nanosil Corporation, cylindrical multi-walled carbon nanotube, average aspect ratio (H / L): 150, long side length (H): 1.5 ⁇ m, short side length (L ): 10 nm.
  • AMC trade name, manufactured by Ube Industries, Ltd., cylindrical multi-walled carbon nanotube, average aspect ratio (H / L): 100, long side length (H): 1.1 ⁇ m, short side length (L): 11 nm.
  • (Crosslinking agent) -"Coronate L" a brand name, the Tosoh Corporation make, isocyanate type crosslinking agent, solid content concentration: 75 mass%.
  • (Tackifier) “Alcon P-125”: trade name, manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin, softening point: 125 ° C.
  • YS Polystar K125 trade name, manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point: 125 ° C.
  • Examples 17-23 Commercially available conductive double-sided tape (manufactured by Nissin EM Co., Ltd., trade name “conductive carbon double-sided tape 7311”, having a structure in which an adhesive layer containing an acrylic resin and carbon powder is sandwiched between two release sheets.
  • the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet was used as the pressure-sensitive conductive layer (X).
  • Adhesive conductive layer (X) exposed by removing one release sheet of the above-mentioned commercially available conductive double-sided tape, and a non-adhesive conductive layer (Y-1) of the type shown in Table 3 ) Or a non-adhesive conductive layer of a substrate with a non-adhesive conductive layer (Y-4) was bonded to produce a conductive adhesive sheet.
  • Comparative Example 9 An adhesive layer (adhesive conductive layer (X)) expressing one release sheet of the above-mentioned commercially available conductive double-sided tape and a PET film having a thickness of 50 ⁇ m (trade name “Lumirror” manufactured by Toray Industries, Inc.) Were bonded together to produce a conductive adhesive sheet.
  • adhesive conductive layer (X) expressing one release sheet of the above-mentioned commercially available conductive double-sided tape and a PET film having a thickness of 50 ⁇ m (trade name “Lumirror” manufactured by Toray Industries, Inc.) Were bonded together to produce a conductive adhesive sheet.
  • Table 2 and Table 3 show various physical property values measured based on the above method for the conductive adhesive sheet produced as described above.
  • the conductive adhesive sheets of Examples 1 to 23 have good adhesive strength, and have a lower surface resistivity and antistatic properties as compared with the conductive adhesive sheets of Comparative Examples 1 to 9. And it turns out that it is excellent in electroconductivity.
  • the conductive pressure-sensitive adhesive sheet of the present invention is excellent in antistatic property and conductivity because of having good adhesive force and low surface resistivity. Therefore, the conductive pressure-sensitive adhesive sheet of the present invention prevents, for example, ignition due to sparks generated from static electricity such as electromagnetic shielding materials for containers for storing electronic devices such as computers and communication devices, grounding wires for electrical components, and even triboelectricity. It is suitable as a joining member used for members such as materials.

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