TWI683871B - Conductive adhesive sheet - Google Patents

Conductive adhesive sheet Download PDF

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TWI683871B
TWI683871B TW104128147A TW104128147A TWI683871B TW I683871 B TWI683871 B TW I683871B TW 104128147 A TW104128147 A TW 104128147A TW 104128147 A TW104128147 A TW 104128147A TW I683871 B TWI683871 B TW I683871B
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adhesive
conductive layer
conductive
resin
mass
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TW201619324A (en
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植田貴洋
大高翔
松下大雅
松下香織
宮田壮
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日商琳得科股份有限公司
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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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

本發明提供一種導電性黏著薄片，其為至少具有黏著性導電層(X)及非黏著性導電層(Y)之導電性黏著薄片，黏著性導電層(X)之表面電阻率(ρSX)之值為1.0×102~1.0×1010Ω/□，非黏著性導電層(Y)之表面電阻率(ρSY)之值為1.0×10-2~1.0×108Ω/□，且，滿足式(1)：0<log10(ρSX/ρSY)≦6.0。該導電性黏著薄片，於具有良好黏著力的同時，亦具有優良之抗靜電性及導電性。 The invention provides a conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), and a surface resistivity (ρ SX ) of the adhesive conductive layer (X) The value is 1.0×10 2 ~1.0×10 10 Ω/□, and the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) is 1.0×10 -2 ~1.0×10 8 Ω/□, and , Satisfying formula (1): 0<log 10 (ρ SX /ρ SY )≦6.0. The conductive adhesive sheet not only has good adhesion, but also has excellent antistatic properties and electrical conductivity.

Description

導電性黏著薄片 Conductive adhesive sheet

本發明為有關導電性黏著薄片者。 The present invention relates to a conductive adhesive sheet.

以往，放置電腦、通信機器等電子機器的容器之電磁遮蔽材料、電氣零件等接地線，甚至因摩擦靜電等靜電所產生之火花的抗發火材料等的各種接合中，多使用具有簡易接著性的導電性黏著薄片。 In the past, in various joints such as electromagnetic shielding materials for containers of electronic devices such as computers and communication equipment, grounding wires for electrical parts, and even anti-ignition materials such as sparks generated by static electricity such as friction and static electricity, many have used simple adhesion Conductive adhesive sheet.

導電性黏著薄片所具有的黏著劑層所使用的黏著劑組成物中，為賦予抗靜電性及導電性等目的，多使用將銅粉、銀粉、鎳粉、鋁粉等金屬粉等之導電性物質分散於黏著性樹脂中所得者。 In the adhesive composition used in the adhesive layer of the conductive adhesive sheet, for the purpose of imparting antistatic properties and electrical conductivity, the conductivity of metal powders such as copper powder, silver powder, nickel powder, aluminum powder, etc. is often used. The substance is dispersed in the adhesive resin.

例如，專利文獻1中，揭示使用於黏著劑中分散有作為導電性物質之碳奈米管及碳微線圈中之至少一者的導電性黏著劑，及使用該導電性黏著劑之導電性黏著薄片等內容。 For example, Patent Document 1 discloses a conductive adhesive in which at least one of a carbon nanotube and a carbon microcoil dispersed as a conductive substance is dispersed in the adhesive, and conductive adhesive using the conductive adhesive Contents such as flakes.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]特開2001-172582號公報 [Patent Document 1] JP 2001-172582

但，上述就提高具有導電性黏著薄片的黏著劑層之導電性的目的上，作為黏著劑層的形成材料之黏著劑組成物中必須大量添加導電性物質，使導電性物質粒子更緊密地接觸。 However, for the purpose of improving the conductivity of the adhesive layer having a conductive adhesive sheet, a large amount of conductive substance must be added to the adhesive composition as a material for forming the adhesive layer, so that the particles of the conductive substance are in closer contact .

但是，黏著劑組成物中，添加大量的導電性物質時，會有造成該黏著劑組成物所形成之黏著劑層的黏著力降低之傾向。另一方面，為提高黏著力之目的，而降低黏著劑層中之導電性物質的含量時，將會造成黏著劑層之導電性降低，而會有無法兼顧之問題產生。 However, when a large amount of conductive material is added to the adhesive composition, the adhesive force of the adhesive layer formed by the adhesive composition tends to decrease. On the other hand, for the purpose of improving the adhesive force, when the content of the conductive material in the adhesive layer is reduced, the conductivity of the adhesive layer will be reduced, and there will be problems that cannot be taken into account.

專利文獻1所揭示之導電性黏著薄片，就同時提高黏著力及導電性之觀點中，仍存在有不充分之問題。 The conductive adhesive sheet disclosed in Patent Document 1 still has a problem of insufficiency from the viewpoint of improving adhesion and conductivity at the same time.

本發明，以提供一種於具有良好的黏著力的同時，亦具有優良之抗靜電性及導電性的導電性黏著薄片為目的。 The present invention aims to provide a conductive adhesive sheet that has good adhesion and excellent antistatic properties and conductivity.

本發明者們，發現至少具有黏著性導電層及非黏著性導電層作為構成內容，與，將黏著性導電層及非黏著性導電層單獨之各表面電阻率，及該2層之表面電阻率之比率調整至特定範圍之導電性黏著薄片，即可解決上 述問題，因而完成本發明。 The present inventors found that at least the adhesive conductive layer and the non-adhesive conductive layer are included as constituents, and the surface resistivities of the adhesive conductive layer and the non-adhesive conductive layer alone, and the surface resistivities of the two layers The ratio can be adjusted to a specific range of conductive adhesive sheets to solve the problem This problem was completed, thus completing the present invention.

即，本發明為，提供下述〔1〕~〔16〕者。 That is, the present invention provides the following [1] to [16].

〔1〕一種導電性黏著薄片，其為至少具有黏著性導電層(X)及非黏著性導電層(Y)之導電性黏著薄片，其中，黏著性導電層(X)單獨之表面電阻率(ρSX)之值為1.0×102~1.0×1010Ω/□，非黏著性導電層(Y)單獨之表面電阻率(ρSY)之值為1.0×10-2~1.0×108Ω/□，且，滿足式(1)：0<log10(ρSX/ρSY)≦6.0。 [1] A conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), wherein the surface conductivity of the adhesive conductive layer (X) alone ( ρ SX ) is 1.0×10 2 ~1.0×10 10 Ω/□, and the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 -2 ~1.0×10 8 Ω /□, and satisfy formula (1): 0<log 10 (ρ SX /ρ SY )≦6.0.

〔2〕如上述〔1〕記載之導電性黏著薄片，其中，黏著性導電層(X)之厚度(tX)為1~1200μm。 [2] The conductive adhesive sheet described in [1] above, wherein the thickness (t X ) of the adhesive conductive layer ( X ) is 1 to 1200 μm.

〔3〕如上述〔1〕或〔2〕記載之導電性黏著薄片，其中，非黏著性導電層(Y)之厚度(tY)為0.01~200μm。 [3] The conductive adhesive sheet described in [1] or [2] above, wherein the thickness (t Y ) of the non-adhesive conductive layer ( Y ) is 0.01 to 200 μm.

〔4〕如上述〔1〕~〔3〕中任一項記載之導電性黏著薄片，其中，黏著性導電層(X)為，由含有黏著性樹脂(x1)及碳系填料(x2)之黏著性組成物所形成之層。 [4] The conductive adhesive sheet according to any one of [1] to [3] above, wherein the adhesive conductive layer (X) is composed of an adhesive resin (x1) and a carbon-based filler (x2) The layer formed by the adhesive composition.

〔5〕如上述〔4〕記載之導電性黏著薄片，其中，前述黏著性組成物中所含之黏著性樹脂(x1)為，含有由丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、苯乙烯系樹脂、聚酯系樹脂，及聚烯烴系樹脂所成之群所選出之1種以上的黏著性樹脂。 [5] The conductive adhesive sheet as described in [4] above, wherein the adhesive resin (x1) contained in the adhesive composition contains acrylic resin, urethane resin, rubber One or more adhesive resins selected from the group consisting of resins, styrene resins, polyester resins, and polyolefin resins.

〔6〕如上述〔4〕或〔5〕記載之導電性黏著薄片，其中，前述黏著性組成物中所含有之碳系填料(x2)的平均長徑比為1.5以上。 [6] The conductive adhesive sheet described in [4] or [5] above, wherein the average aspect ratio of the carbon-based filler (x2) contained in the adhesive composition is 1.5 or more.

〔7〕如上述〔4〕~〔6〕中任一項記載之導電性黏著薄片，其中，前述黏著性組成物中所含之碳系填料(x2)之含量，相對於黏著性樹脂(x1)100質量份，為0.01~15質量份。 [7] The conductive adhesive sheet according to any one of [4] to [6] above, wherein the content of the carbon-based filler (x2) contained in the adhesive composition is relative to the adhesive resin (x1 ) 100 parts by mass, 0.01 to 15 parts by mass.

〔8〕如上述〔4〕~〔7〕中任一項記載之導電性黏著薄片，其中，前述黏著性組成物中所含之碳系填料(x2)為碳奈米材料。 [8] The conductive adhesive sheet according to any one of [4] to [7] above, wherein the carbon-based filler (x2) contained in the adhesive composition is a carbon nanomaterial.

〔9〕如上述〔1〕~〔8〕中任一項記載之導電性黏著薄片，其中，非黏著性導電層(Y)為，含有由導電性高分子、碳系填料，及金屬氧化物所成之群所選出之1種以上的導電材料之層。 [9] The conductive adhesive sheet as described in any one of [1] to [8] above, wherein the non-adhesive conductive layer (Y) contains a conductive polymer, a carbon-based filler, and a metal oxide A layer of more than one conductive material selected by the group.

〔10〕如上述〔1〕~〔9〕中任一項記載之導電性黏著薄片，其中，非黏著性導電層(Y)為，含有由聚噻吩、PEDOT-PSS、碳奈米材料，及ITO(氧化銦錫)所成之群所選出之1種以上的導電材料之層。 [10] The conductive adhesive sheet as described in any one of [1] to [9] above, wherein the non-adhesive conductive layer (Y) is made of polythiophene, PEDOT-PSS, carbon nanomaterial, and A layer of more than one conductive material selected from the group of ITO (indium tin oxide).

〔11〕如上述〔9〕或〔10〕記載之導電性黏著薄片，其中，非黏著性導電層(Y)中所含之導電材料的密度為0.8~2.5g/cm3。 [11] The conductive adhesive sheet described in [9] or [10] above, wherein the density of the conductive material contained in the non-adhesive conductive layer (Y) is 0.8 to 2.5 g/cm 3 .

〔12〕如上述〔1〕~〔11〕中任一項記載之導電性黏著薄片，其為具有依基材、非黏著性導電層(Y)，及黏著性導電層(X)之順序層合之構成內容。 [12] The conductive adhesive sheet according to any one of the above [1] to [11], which has a sequential layer according to a substrate, a non-adhesive conductive layer (Y), and an adhesive conductive layer (X) Together constitute the content.

〔13〕如上述〔12〕記載之導電性黏著薄片，其於基材之兩面上，分別具有由非黏著性導電層(Y)及黏著性導電層(X)所構成之二層體。 [13] The conductive adhesive sheet as described in [12] above, which has two layers composed of a non-adhesive conductive layer (Y) and an adhesive conductive layer (X) on both sides of the substrate.

〔14〕如上述〔12〕或〔13〕記載之導電性黏著薄片，其中，前述基材為，表面電阻率為1.0×1014Ω/□以上之絕緣性基材。 [14] The conductive adhesive sheet according to [12] or [13] above, wherein the substrate is an insulating substrate having a surface resistivity of 1.0×10 14 Ω/□ or more.

〔15〕如上述〔1〕~〔11〕中任一項記載之導電性黏著薄片，其為具有，黏著性導電層(X)及非黏著性導電層(Y)所構成之二層體被2枚剝離薄片所挾夾之構成內容。 [15] The conductive adhesive sheet as described in any one of [1] to [11] above, which is a two-layer body consisting of an adhesive conductive layer (X) and a non-adhesive conductive layer (Y) The contents of the sandwich between the two peeling sheets.

〔16〕如上述〔1〕~〔11〕中任一項記載之導電性黏著薄片，其為具有，依第一黏著性導電層(X-I)、非黏著性導電層(Y)，及第二黏著性導電層(X-II)之順序層合而得之三層體被2枚剝離薄片所挾夾之構成內容。 [16] The conductive adhesive sheet according to any one of the above [1] to [11], which has a first adhesive conductive layer (XI), a non-adhesive conductive layer (Y), and a second The three-layer body obtained by laminating the adhesive conductive layer (X-II) in sequence is sandwiched by two peeling sheets.

本發明之導電性黏著薄片，於具有良好黏著力的同時，也具有優良之抗靜電性及導電性。 The conductive adhesive sheet of the present invention not only has good adhesion, but also has excellent antistatic properties and conductivity.

1A、1B、2A、2B、3、4‧‧‧導電性黏著薄片 1A, 1B, 2A, 2B, 3, 4‧‧‧‧ conductive adhesive sheet

11‧‧‧黏著性導電層(X) 11‧‧‧Adhesive conductive layer (X)

11a‧‧‧第一黏著性導電層(X-I) 11a‧‧‧The first adhesive conductive layer (X-I)

11b‧‧‧第二黏著性導電層(X-II) 11b‧‧‧Second adhesive conductive layer (X-II)

12‧‧‧非黏著性導電層(Y) 12‧‧‧non-adhesive conductive layer (Y)

12a‧‧‧第一非黏著性導電層(Y-I) 12a‧‧‧The first non-adhesive conductive layer (Y-I)

12b‧‧‧第二非黏著性導電層(Y-II) 12b‧‧‧Second non-adhesive conductive layer (Y-II)

13‧‧‧基材 13‧‧‧ Base material

14‧‧‧剝離薄片 14‧‧‧Peeling flakes

21‧‧‧二層體 21‧‧‧two-layer body

21a‧‧‧第一之二層體 21a‧‧‧The first two-layer body

21b‧‧‧第二之二層體 21b‧‧‧Second layer

22‧‧‧三層體 22‧‧‧Triple

[圖1]本發明之導電性黏著薄片之較佳態樣之一的構成內容，為附有基材之導電性黏著薄片的截面圖。 [FIG. 1] One of the preferred aspects of the conductive adhesive sheet of the present invention is a cross-sectional view of a conductive adhesive sheet with a substrate.

[圖2]本發明之導電性黏著薄片之較佳態樣之一的構成內容，為不具基材之導電性黏著薄片的截面圖。 [FIG. 2] The configuration content of one of the preferred aspects of the conductive adhesive sheet of the present invention is a cross-sectional view of the conductive adhesive sheet without a substrate.

本說明書中，「質量平均分子量(Mw)」為， 凝膠滲透色層分析(GPC)法所測定之標準聚苯乙烯換算之值，具體而言為基於實施例記載之方法所測定之值。 In this specification, "mass average molecular weight (Mw)" is, The value converted to the standard polystyrene measured by the gel permeation chromatography (GPC) method is specifically the value measured based on the method described in the Examples.

又，例如「(甲基)丙烯酸酯」係為表示「丙烯酸酯」及「甲基丙烯酸酯」等二者時所使用者，其他類似用語亦為相同之意義。 In addition, for example, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and other similar terms have the same meaning.

此外，「導電性黏著薄片之表面電阻率」，於無特別限定下，為表示由導電性黏著薄片所具有之黏著性導電層(X)的表面側所測定之表面電阻率之意。 In addition, "surface resistivity of the conductive adhesive sheet" means, without particular limitation, the surface resistivity measured from the surface side of the adhesive conductive layer (X) of the conductive adhesive sheet.

又，本發明中，各層之表面電阻率及體積電阻率之值，為使用JIS K 7194為基準所測定之值，具體而言，為依實施例記載之方法所測定之值之意。 In addition, in the present invention, the values of the surface resistivity and volume resistivity of each layer are the values measured using JIS K 7194 as a reference, and specifically, the values measured according to the methods described in the examples.

〔導電性黏著薄片〕 [Conductive adhesive sheet]

本發明之導電性黏著薄片，至少具有黏著性導電層(X)及非黏著性導電層(Y)。 The conductive adhesive sheet of the present invention has at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y).

本發明之導電性黏著薄片，因設有非黏著性導電層(Y)，故可大幅降低黏著性導電層(X)之表面電阻率、提高抗靜電性及導電性。其結果，因黏著性導電層(X)中無需含有大量之碳系填料，故本發明之導電性黏著薄片，具有良好的黏著力。 Since the conductive adhesive sheet of the present invention is provided with a non-adhesive conductive layer (Y), the surface resistivity of the adhesive conductive layer (X) can be greatly reduced, and the antistatic property and conductivity can be improved. As a result, since the adhesive conductive layer (X) does not need to contain a large amount of carbon-based filler, the conductive adhesive sheet of the present invention has good adhesion.

本發明中，「黏著性導電層(X)」與「非黏著性導電層(Y)」之區別，為以有無黏著性作為區別，黏著性之有無，為使用各導電層之表面的探針測試(probe tack)之峰頂(peak top)值進行判斷。 In the present invention, the difference between "adhesive conductive layer (X)" and "non-adhesive conductive layer (Y)" is based on the presence or absence of adhesion, and the presence or absence of adhesion is used to probe the surface of each conductive layer The peak value of the probe tack is judged.

即，本發明中，作為對象之導電層的表面之探針測試之峰頂值為0.1N以上時，該導電層則判斷為具有黏著性，而分類為「黏著性導電層(X)」。 That is, in the present invention, when the peak top value of the probe test on the surface of the target conductive layer is 0.1 N or more, the conductive layer is judged to be adhesive, and is classified as “adhesive conductive layer (X)”.

相反地，作為對象之導電層的表面之探針測試之峰頂值未達0.1N時，該導電層則判斷為非黏著性，而分類為「非黏著性導電層(Y)」。 Conversely, when the peak value of the probe test on the surface of the target conductive layer is less than 0.1N, the conductive layer is judged to be non-adhesive and is classified as "non-adhesive conductive layer (Y)".

又，作為對象之導電層的表面之探針測試之峰頂值，為依JIS Z 0237(1991)為基準所設定之值，具體而言，為依後述實施例記載之方法所測定之值之意。 Also, the peak top value of the probe test on the surface of the target conductive layer is a value set according to JIS Z 0237 (1991) as a reference, specifically, a value measured according to the method described in the embodiment described later meaning.

本發明之導電性黏著薄片，至少具有黏著性導電層(X)及非黏著性導電層(Y)構成者時，並未有特別之限定，其亦可具有上述以外的其他之層。 When the conductive adhesive sheet of the present invention has at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), it is not particularly limited, and it may have other layers than the above.

又，本發明之一態樣的導電性黏著薄片，可為於黏著性導電層(X)與非黏著性導電層(Y)之間設有其他之層的構成內容，但就降低導電性黏著薄片之表面電阻率、提高抗靜電性及導電性之觀點，以黏著性導電層(X)與非黏著性導電層(Y)直接層合之構成者為佳。 In addition, the conductive adhesive sheet according to one aspect of the present invention may be constituted by providing another layer between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), but the conductive adhesion is reduced From the viewpoint of the surface resistivity of the sheet, improvement of antistatic property and conductivity, it is preferable that the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) be directly laminated.

圖1為，本發明之導電性黏著薄片之較佳態樣之一的構成內容，為附有基材之導電性黏著薄片的截面圖。 FIG. 1 is a cross-sectional view of the structure of one of the preferred aspects of the conductive adhesive sheet of the present invention, which is a conductive adhesive sheet with a substrate.

本發明之一態樣的導電性黏著薄片，例如，圖1(a)所示般，具有依序層合基材13、非黏著性導電層(Y)12，及黏著性導電層(X)11所得之構成內容的導電性黏著薄片1A等。該導電性黏著薄片1A，於基材之一側之面上，具有 由非黏著性導電層(Y)12及黏著性導電層(X)11所構成之二層體21。 The conductive adhesive sheet of one aspect of the present invention, for example, as shown in FIG. 1(a), has a laminated substrate 13, a non-adhesive conductive layer (Y) 12, and an adhesive conductive layer (X) in this order 11. The resulting conductive adhesive sheet 1A and so on. The conductive adhesive sheet 1A has a surface on one side of the substrate A two-layer body 21 composed of a non-adhesive conductive layer (Y) 12 and an adhesive conductive layer (X) 11.

又，對於導電性黏著薄片1A之構成，可再於黏著性導電層(X)11上，層合剝離薄片14，而形成如圖1(b)所示之導電性黏著薄片1B者亦可。 In addition, for the configuration of the conductive adhesive sheet 1A, the peeling sheet 14 may be laminated on the adhesive conductive layer (X) 11 to form the conductive adhesive sheet 1B as shown in FIG. 1(b).

又，本發明之一態樣之導電性黏著薄片，例如，如圖1(c)、(d)所示般，可為於基材之兩面上，分別具有由非黏著性導電層(Y)及黏著性導電層(X)所構成之二層體21a、21b的導電性黏著薄片。 Moreover, the conductive adhesive sheet of one aspect of the present invention, for example, as shown in FIGS. And the conductive adhesive sheet of the two-layer body 21a, 21b composed of the adhesive conductive layer (X).

即，圖1(c)所示導電性黏著薄片2A為，於基材13之一側之面上，具有由第一非黏著性導電層(Y-I)12a及第一黏著性導電層(X-I)11a所構成之第一之二層體21a，於基材13之另一側之面上，具有由第二非黏著性導電層(Y-II)12b及第二黏著性導電層(X-II)11b所構成之第二之二層體21b。 That is, the conductive adhesive sheet 2A shown in FIG. 1(c) is provided with a first non-adhesive conductive layer (YI) 12a and a first adhesive conductive layer (XI) on one side of the substrate 13 The first two-layer body 21a composed of 11a has a second non-adhesive conductive layer (Y-II) 12b and a second adhesive conductive layer (X-II) on the other side of the substrate 13 ) The second two-layer body 21b composed of 11b.

又，圖1(d)所示之導電性黏著薄片2B為，相對於導電性黏著薄片2A之構成，具有再於第一黏著性導電層(X-I)11a上及第二黏著性導電層(X-II)11b上，分別層合剝離薄片14a、14b之構成。 In addition, the conductive adhesive sheet 2B shown in FIG. 1(d) has a structure that is further formed on the first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (X) with respect to the configuration of the conductive adhesive sheet 2A -II) A structure in which peeling sheets 14a and 14b are laminated on 11b, respectively.

又，圖2為，本發明之導電性黏著薄片之較佳態樣之一的構成內容，為不具基材之導電性黏著薄片的截面圖。 2 is a cross-sectional view of the structure of one of the preferred aspects of the conductive adhesive sheet of the present invention, which is a conductive adhesive sheet without a substrate.

本發明之一態樣之導電性黏著薄片，亦可為無基材之導電性黏著薄片，具體而言，如圖2(a)所示般，具有黏著 性導電層(X)11及非黏著性導電層(Y)12所構成之二層體21被2片剝離薄片14a、14b挾夾之構成的導電性黏著薄片3等。 The conductive adhesive sheet of one aspect of the present invention may also be a substrate-free conductive adhesive sheet. Specifically, as shown in FIG. 2(a), it has adhesion The two-layered body 21 composed of the conductive conductive layer (X) 11 and the non-adhesive conductive layer (Y) 12 is sandwiched by two peeling sheets 14a, 14b, a conductive adhesive sheet 3 and the like.

又，本發明之一態樣之導電性黏著薄片，亦可為如圖2(b)所示般，具有依第一黏著性導電層(X-I)11a、非黏著性導電層(Y)12，及第二黏著性導電層(X-II)11b之順序層合而得的三層體22被2片剝離薄片14a、14b挾夾之構成的導電性黏著薄片4亦可。 Moreover, the conductive adhesive sheet of one aspect of the present invention may also have a first adhesive conductive layer (XI) 11a and a non-adhesive conductive layer (Y) 12 as shown in FIG. 2(b). The three-layer body 22 formed by sequentially laminating the second adhesive conductive layer (X-II) 11b may be sandwiched by two peeling sheets 14a and 14b, and the conductive adhesive sheet 4 may be sandwiched.

具有上述以外之構成的本發明之一態樣之導電性黏著薄片，例如，兩面為經剝離處理之剝離薄片的一側面上，具有黏著性導電層(X)及非黏著性導電層(Y)所構成之二層體，以黏著性導電層(X)為外表之方式設置的滾筒狀捲曲而得的構成之導電性黏著薄片等。 The conductive adhesive sheet according to an aspect of the present invention having a structure other than the above, for example, has a tacky conductive layer (X) and a non-adhesive conductive layer (Y) on one side of the peeled sheet on both sides of which is peeled off The formed two-layer body is a conductive adhesive sheet composed of a roller-shaped curl formed with the adhesive conductive layer (X) as the outer surface.

上述第一黏著性導電層(X-I)11a及第二黏著性導電層(X-II)11b，可為由相同之黏著性組成物所形成之層亦可、相異之黏著性組成物所形成之層亦可。 The first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (X-II) 11b may be layers formed of the same adhesive composition, or may be formed of different adhesive compositions The layer can also be.

又，第一非黏著性導電層(Y-I)12a及第二非黏著性導電層(Y-II)12b，亦相同地，可為由相同之形成材料所形成之層亦可、相異之形成材料所形成之層亦可。 In addition, the first non-adhesive conductive layer (YI) 12a and the second non-adhesive conductive layer (Y-II) 12b are also the same, and may be formed of the same forming material or may be formed differently The layer formed by the material may also be used.

又，本發明中，第一黏著性導電層(X-I)及第二黏著性導電層(X-II)之構成，與黏著性導電層(X)為相同，第一非黏著性導電層(Y-I)及第二非黏著性導電層(Y-II)之構成，與非黏著性導電層(Y)為相同。 Furthermore, in the present invention, the first adhesive conductive layer (XI) and the second adhesive conductive layer (X-II) are the same as the adhesive conductive layer (X), and the first non-adhesive conductive layer (YI ) And the second non-adhesive conductive layer (Y-II) are the same as the non-adhesive conductive layer (Y).

黏著性導電層(X)為，具有黏著性(上述探針測 試之峰頂之值為0.1N以上)，且，具有導電性(層之單獨體積電阻率(ρVX)為1.0×108Ω．cm以下)之層。 The adhesive conductive layer (X) is adhesive (the value of the peak top measured by the above probe is 0.1 N or more), and is conductive (the individual volume resistivity (ρ VX ) of the layer is 1.0×10 8 Ω .Cm below) layer.

另一方面，非黏著性導電層(Y)為，非黏著性(上述探針測試之峰頂之值為0.1N未達)之層，且，具有導電性(層單獨之體積電阻率(ρVY)為1.0×108Ω．cm以下)之層。 On the other hand, the non-adhesive conductive layer (Y) is a layer that is non-adhesive (the value of the peak top measured by the above probe is less than 0.1N) and has conductivity (volume resistivity of the layer alone (ρ VY ) is a layer of 1.0×10 8 Ω·cm or less).

本發明中，黏著性導電層(X)單獨之表面電阻率(ρSX)為，1.0×102~1.0×1010Ω/□，較佳為1.0×102~1.0×108Ω/□、更佳為1.0×102~1.0×107Ω/□、特佳為1.0×102~1.0×106Ω/□。 In the present invention, the surface resistivity (ρ SX ) of the adhesive conductive layer (X) alone is 1.0×10 2 ~1.0×10 10 Ω/□, preferably 1.0×10 2 ~1.0×10 8 Ω/□ , More preferably, it is 1.0×10 2 ~1.0×10 7 Ω/□, and particularly preferably 1.0×10 2 ~1.0×10 6 Ω/□.

因表面電阻率(ρSX)未達1.0×102Ω/□時，多含有大量導電性物質，故容易造成黏著性導電層(X)之黏著力降低，且就經濟面而言亦不佳。 When the surface resistivity (ρ SX ) is less than 1.0×10 2 Ω/□, it contains a lot of conductive materials, so it is easy to cause the adhesion of the adhesive conductive layer (X) to decrease, and it is also not good in terms of economy .

另一方面，表面電阻率(ρSX)超過1.0×1010Ω/□時，即使設有非黏著性導電層(Y)，也極不容易發現導電性黏著薄片之表面電阻率降低之效果。 On the other hand, when the surface resistivity (ρ SX ) exceeds 1.0×10 10 Ω/□, even if the non-adhesive conductive layer (Y) is provided, the effect of lowering the surface resistivity of the conductive adhesive sheet is not easily found.

又，非黏著性導電層(Y)單獨之表面電阻率(ρSY)為，1.0×10-2~1.0×108Ω/□，較佳為1.0×10-2~1.0×107Ω/□、更佳為1.0×10-2~1.0×106Ω/□、特佳為1.0×10-2~1.0×105Ω/□、最佳為1.0×10-2~1.0×104Ω/□、最較佳為1.0×10-2~1.0×103Ω/□。 Moreover, the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 -2 ~1.0×10 8 Ω/□, preferably 1.0×10 -2 ~1.0×10 7 Ω/ □, better 1.0×10 -2 ~1.0×10 6 Ω/□, especially good 1.0×10 -2 ~1.0×10 5 Ω/□, best 1.0×10 -2 ~1.0×10 4 Ω /□, most preferably 1.0×10 -2 to 1.0×10 3 Ω/□.

表面電阻率(ρSY)為未達1.0×10-2Ω/□，或超過1.0×108Ω/□時，即使設有非黏著性導電層(Y)，也極不容易發現導電性黏著薄片之表面電阻率降低之效果。 When the surface resistivity (ρ SY ) is less than 1.0×10 -2 Ω/□, or exceeds 1.0×10 8 Ω/□, even if a non-adhesive conductive layer (Y) is provided, it is very difficult to find conductive adhesion The effect of reducing the surface resistivity of the sheet.

此外，本發明中，以黏著性導電層(X)單獨之 表面電阻率(ρSX)之值，與非黏著性導電層(Y)單獨之表面電阻率(ρSY)之值，必須滿足以下之式(1)之內容。 In addition, in the present invention, the value of the surface resistivity (ρ SX ) of the adhesive conductive layer (X) alone and the value of the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone must satisfy the following The content of formula (1).

式(1)：0<log10(ρSX/ρSY)≦6.0 Formula (1): 0<log 10 (ρ SX /ρ SY )≦6.0

上述log10(ρSX/ρSY)之值超過6.0時，將無法充分降低導電性黏著薄片之表面電阻率，而會造成抗靜電性及導電性劣化之傾向。 When the value of log 10 (ρ SX /ρ SY ) exceeds 6.0, the surface resistivity of the conductive adhesive sheet cannot be sufficiently reduced, which may cause the tendency of deterioration of antistatic properties and conductivity.

就上述之觀點而言，log10(ρSX/ρSY)之值，較佳為5.0以下，更佳為4.5以下，特佳為4.0以下，最佳為3.7以下。 From the above viewpoint, the value of log 10 (ρ SX /ρ SY ) is preferably 5.0 or less, more preferably 4.5 or less, particularly preferably 4.0 or less, and most preferably 3.7 or less.

另一方面，如上述式(1)所示般，log10(ρSX/ρSY)之值必須為大於0之值。 On the other hand, as shown in the above formula (1), the value of log 10 (ρ SX /ρ SY ) must be a value greater than 0.

即，本發明中，就可有效率地降低導電性黏著薄片之表面電阻率之觀點，非黏著性導電層(Y)單獨之表面電阻率(ρSY)，為較黏著性導電層(X)單獨之表面電阻率(ρSX)為更小之值。 That is, in the present invention, from the viewpoint of efficiently reducing the surface resistivity of the conductive adhesive sheet, the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone is the more adhesive conductive layer (X) The individual surface resistivity (ρ SX ) is a smaller value.

黏著性導電層(X)單獨之體積電阻率(ρVX)，就具有良好黏著力、可有效率地降低表面電阻率之導電性黏著薄片之觀點，較佳為1.0×100~1.0×108Ω．cm、更佳為1.0×100~1.0×106Ω．cm、特佳為1.0×100~1.0×105Ω．cm、最佳為1.0×100~1.0×104Ω．cm。 The volume resistivity (ρ VX ) of the adhesive conductive layer (X) alone is preferably 1.0×10 0 ~1.0×10 from the viewpoint of a conductive adhesive sheet that has good adhesion and can effectively reduce the surface resistivity 8 Ω. cm, more preferably 1.0×10 0 ~1.0×10 6 Ω. cm, especially good is 1.0×10 0 ~1.0×10 5 Ω. cm, the best is 1.0×10 0 ~1.0×10 4 Ω. cm.

非黏著性導電層(Y)單獨之體積電阻率(ρVY)，就為有效率地降低表面電阻率之導電性黏著薄片之觀點，較佳為1.0×10-4~1.0×106Ω．cm、更佳為1.0×10-4~1.0×104Ω．cm、特佳為1.0×10-4~1.0×103Ω．cm、特較佳為1.0×10-4 ~1.0×102Ω．cm、特更佳為1.0×10-4~1.0×101Ω．cm、最佳為1.0×10-4~1.0×100Ω．cm。 The volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone is preferably 1.0×10 -4 ~1.0×10 6 Ω from the viewpoint of the conductive adhesive sheet that efficiently reduces the surface resistivity. cm, more preferably 1.0×10 -4 ~1.0×10 4 Ω. cm, especially good is 1.0×10 -4 ~1.0×10 3 Ω. cm, particularly preferably 1.0×10 -4 ~1.0×10 2 Ω. cm, especially better is 1.0×10 -4 ~1.0×10 1 Ω. cm, the best is 1.0×10 -4 ~1.0×10 0 Ω. cm.

又，本發明之一態樣中，就可有效率地降低導電性黏著薄片之表面電阻率之觀點，非黏著性導電層(Y)單獨之體積電阻率(ρVY)，以較黏著性導電層(X)單獨之體積電阻率(ρVX)為更小之值為佳。 In addition, in one aspect of the present invention, from the viewpoint that the surface resistivity of the conductive adhesive sheet can be efficiently reduced, the volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone is conductive with a more adhesive The volume resistivity (ρ VX ) of the layer (X) alone is preferably smaller.

黏著性導電層(X)之厚度(tX)，可配合用途等作適當之調整，較佳為1~1200μm、更佳為2~600μm、更較佳為3~300μm、特佳為5~250μm、更特佳為10~200μm、最佳為15~150μm。 The thickness (t X ) of the adhesive conductive layer (X) can be adjusted appropriately according to the application, etc. It is preferably 1 to 1200 μm, more preferably 2 to 600 μm, more preferably 3 to 300 μm, and particularly preferably 5 to 250μm, more preferably 10~200μm, most preferably 15~150μm.

厚度(tX)為1μm以上時，無論被附著體之種類為何，皆具有良好之黏著力。另一方面，厚度(tX)為1200μm以下時，可使所得導電性黏著薄片具有良好的導電性。又，將該導電性黏著薄片作為捲繞體之際，可抑制黏著性導電層(X)因變形所產生之捲曲偏移，或由捲繞體之端部擠壓出黏著性導電層(X)等弊害。 When the thickness (t X ) is 1 μm or more, it has good adhesion regardless of the type of attached body. On the other hand, when the thickness (t X ) is 1200 μm or less, the obtained conductive adhesive sheet can have good conductivity. In addition, when this conductive adhesive sheet is used as a winding body, it is possible to suppress the curl deviation of the adhesive conductive layer (X) due to deformation, or to extrude the adhesive conductive layer (X) from the end of the winding body ) And other disadvantages.

非黏著性導電層(Y)之厚度(tY)，可配合用途等作適當之調整，較佳為0.01~200μm、更佳為0.1~160μm、特佳為0.5~130μm、最佳為1.0~100μm。 The thickness (t Y ) of the non-adhesive conductive layer (Y) can be adjusted appropriately according to the application, etc. It is preferably 0.01 to 200 μm, more preferably 0.1 to 160 μm, particularly preferably 0.5 to 130 μm, and most preferably 1.0 to 100μm.

厚度(tY)為0.01μm以上時，可有效率地降低非黏著性導電層(Y)之表面電阻率。 When the thickness (t Y ) is 0.01 μm or more, the surface resistivity of the non-adhesive conductive layer (Y) can be effectively reduced.

另一方面，厚度(tY)為200μm以下時，於導電性黏著薄片作為捲繞體之際，可抑制非黏著性導電層(Y)因變形所產生之捲曲偏移，或由捲繞體之端部擠出非黏著性導電 層(Y)等之弊害。又，將導電性黏著薄片之總厚度降低時，可作為容易適用於小型電子機器之導電性黏著薄片。 On the other hand, when the thickness (t Y ) is 200 μm or less, when the conductive adhesive sheet is used as the winding body, it is possible to suppress the curl deviation of the non-adhesive conductive layer (Y) due to deformation or the winding body Disadvantages of extruding non-adhesive conductive layer (Y) at the end In addition, when the total thickness of the conductive adhesive sheet is reduced, it can be used as a conductive adhesive sheet that can be easily applied to small electronic equipment.

〔黏著性導電層(X)之形成材料〕 [Forming material of adhesive conductive layer (X)]

黏著性導電層(X)，以由含有黏著性樹脂(x1)及碳系填料(x2)之黏著性組成物所形成之層為佳。 The adhesive conductive layer (X) is preferably a layer formed of an adhesive composition containing an adhesive resin (x1) and a carbon-based filler (x2).

又，該黏著性組成物，可配合黏著性樹脂(x1)之種類，再含有交聯劑或黏著賦予劑、該些以外之常用添加劑。 In addition, the adhesive composition can be blended with the type of the adhesive resin (x1), and further contains a crosslinking agent, an adhesion-imparting agent, and other common additives other than these.

以下，將對該黏著性組成物所含各成份進行說明。 Hereinafter, each component contained in the adhesive composition will be described.

<黏著性樹脂(x1)> <Adhesive resin (x1)>

作為黏著性導電層(X)之形成材料的黏著性組成物所含之黏著性樹脂(x1)，係指質量平均分子量為1萬以上之具有黏著性的樹脂之意。 The adhesive resin (x1) contained in the adhesive composition as the forming material of the adhesive conductive layer (X) means an adhesive resin having a mass average molecular weight of 10,000 or more.

黏著性樹脂(x1)之質量平均分子量(Mw)，就提高導電性黏著薄片之黏著力之觀點，較佳為1萬~200萬、更佳為2萬~150萬。 The mass average molecular weight (Mw) of the adhesive resin (x1) is preferably 10,000 to 2 million, and more preferably 20,000 to 1.5 million from the viewpoint of improving the adhesion of the conductive adhesive sheet.

黏著性組成物中之黏著性樹脂(x1)的含量，相對於該黏著性組成物之全量(100質量%)，較佳為60.0~99.99質量%、更佳為70.0~99.9質量%、特佳為80.0~99.5質量%、最佳為90.0~99.0質量%。 The content of the adhesive resin (x1) in the adhesive composition is preferably 60.0 to 99.99% by mass, more preferably 70.0 to 99.9% by mass, and particularly preferably the total amount of the adhesive composition (100% by mass). It is 80.0-99.5 mass%, and the best is 90.0-99.0 mass%.

黏著性樹脂(x1)，就提高導電性黏著薄片之黏著力，使抗靜電性及導電性良好之觀點，以含有由丙烯酸 系樹脂、胺基甲酸酯系樹脂、聚異丁烯系樹脂、苯乙烯系樹脂、聚酯系樹脂，及聚烯烴系樹脂所成之群所選出之1種以上的黏著性樹脂為佳，含有由丙烯酸系樹脂、胺基甲酸酯系樹脂、聚異丁烯系樹脂，及苯乙烯系樹脂所成之群所選出之1種以上的黏著性樹脂為較佳，含有由丙烯酸系樹脂，及胺基甲酸酯系樹脂所成之群所選出之1種以上的黏著性樹脂為更佳。 Adhesive resin (x1) improves the adhesion of the conductive adhesive sheet to improve antistatic properties and conductivity, and contains acrylic acid Resins, urethane resins, polyisobutylene resins, styrene resins, polyester resins, and polyolefin resins, preferably one or more adhesive resins selected from the group consisting of One or more adhesive resins selected from the group consisting of acrylic resins, urethane resins, polyisobutylene resins, and styrene resins are preferred, including acrylic resins, and amino resins One or more adhesive resins selected from the group of ester resins are more preferred.

(丙烯酸系樹脂) (Acrylic resin)

作為黏著性樹脂(x1)使用的丙烯酸系樹脂，例如，具有由具直鏈或支鏈之烷基的烷基(甲基)丙烯酸酯所產生之結構單位的聚合物、具有由具環狀構造之(甲基)丙烯酸酯所產生之結構單位的聚合物等。 The acrylic resin used as the adhesive resin (x1), for example, a polymer having a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, and having a cyclic structure The polymer of structural unit produced by (meth)acrylate.

丙烯酸系樹脂之質量平均分子量(Mw)，較佳為5萬~150萬、更佳為15萬~130萬、特佳為25萬~110萬、最佳為35萬~90萬。 The mass average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 1.5 million, more preferably 150,000 to 1.3 million, particularly preferably 250,000 to 1.1 million, and most preferably 350,000 to 900,000.

丙烯酸系樹脂之中，又以由具有碳數1~20之烷基的烷基(甲基)丙烯酸酯(a1’)(以下，亦稱為「單體(a1’)」)所產生之結構單位(a1)，及由具有含有官能基之單體(a2’)(以下，亦稱為「單體(a2’)」)所產生之結構單位(a2)的丙烯酸系共聚物為佳。 Among acrylic resins, a structure derived from an alkyl (meth)acrylate (a1') having an alkyl group having 1 to 20 carbon atoms (hereinafter, also referred to as "monomer (a1')") The unit (a1) and the acrylic copolymer of the structural unit (a2) produced by the monomer (a2') having a functional group (hereinafter, also referred to as "monomer (a2')") are preferred.

又，該丙烯酸系共聚物，亦可具有由單體(a1’)及(a2’)以外的其他單體(a3’)所產生之結構單位(a3)。 In addition, the acrylic copolymer may have a structural unit (a3) produced by monomers (a3') other than the monomers (a1') and (a2').

又，該丙烯酸系共聚物之共聚的形態，並未有特別之 限定。即，該丙烯酸系共聚物，可為嵌段共聚物、無規共聚物、接枝共聚物之任一者。 Moreover, the form of copolymerization of the acrylic copolymer is not particularly special limited. That is, the acrylic copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer.

單體(a1’)所具有之烷基的碳數，就提高黏著特性之觀點，較佳為1~12、更佳為4~8、特佳為4~6。 The carbon number of the alkyl group of the monomer (a1') is preferably from 1 to 12, more preferably from 4 to 8, and particularly preferably from 4 to 6, from the viewpoint of improving adhesion characteristics.

單體(a1’)，例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸硬脂酯等。 Monomer (a1'), for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.

該些單體(a1’)之中，又以(甲基)丙烯酸丁酯及(甲基)丙烯酸2-乙基己酯為佳、以(甲基)丙烯酸丁酯為較佳。 Among these monomers (a1'), butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are more preferred, and butyl (meth)acrylate is more preferred.

結構單位(a1)之含量，相對於上述丙烯酸系共聚物之全結構單位(100質量%)，較佳為50~99.5質量%、更佳為60~99質量%、特佳為70~97質量%、最佳為80~95質量%。 The content of the structural unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, and particularly preferably 70 to 97% relative to the total structural unit of the acrylic copolymer (100% by mass). %, the best is 80~95 mass%.

單體(a2’)，例如，含有羥基之單體、含有羧基之單體、含有環氧基之單體、含胺基物之單體、含有氰基之單體、含有酮基之單體、含有烷氧矽烷基之單體等。 Monomer (a2'), for example, monomer containing hydroxyl group, monomer containing carboxyl group, monomer containing epoxy group, monomer containing amine group, monomer containing cyano group, monomer containing ketone group , Monomers containing alkoxysilyl groups, etc.

該些單體(a2’)之中，又以含有羧基之單體為佳。 Among these monomers (a2'), those containing a carboxyl group are preferred.

含有羧基之單體，例如，(甲基)丙烯酸、馬來酸、富馬酸、衣康酸等等，又以(甲基)丙烯酸為佳。 The carboxyl group-containing monomers, for example, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, etc., are also preferably (meth)acrylic acid.

結構單位(a2)之含量，相對於上述丙烯酸系共聚物之全結構單位(100質量%)，較佳為0.5~50質量%、更佳為1~40質量%、特佳為5~30質量%、最佳為7~20質量%。 The content of the structural unit (a2) is preferably 0.5 to 50 mass%, more preferably 1 to 40 mass%, and particularly preferably 5 to 30 mass relative to the total structural unit (100 mass%) of the acrylic copolymer. %, the best is 7~20 mass%.

單體(a3’)，例如，環己基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、異莰基(甲基)丙烯酸酯、二環戊烷基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯基氧基(甲基)丙烯酸乙酯、醯亞胺(甲基)丙烯酸酯等，具有環狀構造的(甲基)丙烯酸酯、乙酸乙烯酯、丙烯腈、苯乙烯等。 Monomer (a3'), for example, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentenyloxy ethyl (meth)acrylate, amide imide (meth)acrylate, etc., (meth)acrylate, acetic acid with a cyclic structure Vinyl ester, acrylonitrile, styrene, etc.

結構單位(a3)之含量，相對於丙烯酸系共聚物之全結構單位(100質量%)，較佳為0~30質量%、更佳為0~20質量%、特佳為0~10質量%、最佳為0~5質量%。 The content of the structural unit (a3) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass relative to the total structural unit (100% by mass) of the acrylic copolymer. , The best is 0 ~ 5 mass%.

又，上述單體(a1’)~(a3’)，可各別單獨使用，或將2種以上組合使用。 In addition, the monomers (a1') to (a3') may be used alone or in combination of two or more.

(胺基甲酸酯系樹脂) (Urethane resin)

作為黏著性樹脂(x1)使用的胺基甲酸酯系樹脂，只要為主鏈及/或側鏈上，具有胺基甲酸酯鍵結及尿素鍵結中至少一者之聚合物時，並未有特別之限制，例如，聚醇與聚異氰酸酯化合物進行反應而得之胺基甲酸酯系預聚合物(α)，或該胺基甲酸酯系預聚合物(α)，再使用鏈延長劑進行鏈延長反應而得之胺基甲酸酯系聚合物(β)等。 The urethane resin used as the adhesive resin (x1), as long as the polymer has at least one of urethane linkage and urea linkage in the main chain and/or side chain, and There is no particular limitation, for example, the carbamate-based prepolymer (α) obtained by reacting a polyalcohol with a polyisocyanate compound, or the carbamate-based prepolymer (α), and then the chain A carbamate-based polymer (β) obtained by a chain extender undergoing a chain extension reaction.

該些之中，作為本發明之一態樣使用之胺基甲酸酯系樹脂，又以含有具有聚氧伸烷基骨架之胺基甲酸酯系聚合物為佳。 Among these, the urethane-based resin used as one aspect of the present invention is preferably a urethane-based polymer having a polyoxyalkylene skeleton.

胺基甲酸酯系樹脂之質量平均分子量(Mw)，較佳為1萬~20萬、更佳為1.2萬~15萬、特佳為1.5萬 ~10萬、最佳為2萬~7萬。 The mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, and particularly preferably 15,000 ~100,000, the best is 20,000~70,000.

作為胺基甲酸酯系預聚合物(α)之原料的聚醇，例如，伸烷二醇、聚醚型聚醇、聚酯型聚醇、聚碳酸酯型聚醇等聚醇化合物等，其只要為聚醇時，並未有特別之限制，其可為二官能基之二醇、三官能基之三醇。 Polyols as raw materials for the urethane-based prepolymer (α) include, for example, polyalcohol compounds such as alkylene glycols, polyether polyols, polyester polyols, and polycarbonate polyols. There is no particular limitation as long as it is a polyalcohol, and it may be a difunctional diol or a trifunctional triol.

該些聚醇之中，就取得之容易性、反應性等觀點，又以二醇為佳。 Among these polyalcohols, diols are preferred in terms of ease of acquisition and reactivity.

二醇，例如，1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,7-庚二醇等鏈烷二醇、乙二醇、丙二醇、二乙二醇、二丙二醇等烷二醇、聚乙二醇、聚丙二醇、聚丁二醇等聚烷二醇、聚四甲基二醇等聚氧烷基二醇等。又，該些之二醇，可單獨或將或2種以上組合使用。 Glycols, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, etc. Alkyl diols such as diol, ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and polyoxyalkylenes such as polytetramethyl glycol Glycol etc. In addition, these diols can be used alone or in combination of two or more.

該些二醇之中，於再與鏈延長劑進行反應之情形，就可抑制該反應中凝膠化之觀點，以質量平均分子量1000~3000之二醇為佳。 Among these diols, in the case of reacting with a chain extender again, the viewpoint of suppressing gelation in the reaction is preferable, and a diol having a mass average molecular weight of 1,000 to 3,000 is preferred.

作為胺基甲酸酯系預聚合物(α)之原料的聚異氰酸酯化合物，可列舉如，芳香族聚異氰酸酯、脂肪族聚異氰酸酯、脂環式聚異氰酸酯等。 Examples of the polyisocyanate compound as a raw material of the urethane-based prepolymer (α) include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.

芳香族聚異氰酸酯，例如，1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯(MDI)、2,4-伸甲苯基二異氰酸酯(2,4-TDI)、2,6-伸甲苯基二異氰酸酯(2,6-TDI)、4,4’-伸甲苯胺基二異氰酸酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、二伸胺基苯 甲醚二異氰酸酯、4,4’-二苯基醚二異氰酸酯、4,4’,4”-三苯基甲烷三異氰酸酯、1,4-四甲基二甲苯二異氰酸酯、1,3-四甲基二甲苯二異氰酸酯等。 Aromatic polyisocyanates, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-phenylene diisocyanate Isocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), 4,4'-tolyl diisocyanate, 2,4,6-triisocyanate toluene, 1, 3,5-triisocyanate benzene, diaminobenzene Dimethyl ether diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethyl Xylene diisocyanate, etc.

脂肪族聚異氰酸酯，例如，伸三甲基二異氰酸酯、四甲基二異氰酸酯、伸六甲基二異氰酸酯(HMDI)、伸五甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、2,3-伸丁基二異氰酸酯、1,3-伸丁基二異氰酸酯、伸十二烷甲基二異氰酸酯、2,4,4-伸三甲基伸六甲基二異氰酸酯等。 Aliphatic polyisocyanates, for example, trimethyl diisocyanate, tetramethyl diisocyanate, hexamethyl diisocyanate (HMDI), pentamethyl diisocyanate, 1,2-propylene diisocyanate, 2,3- Butyl diisocyanate, 1,3-butyl butyl diisocyanate, dodecyl methyl diisocyanate, 2,4,4-trimethyl hexamethyl diisocyanate, etc.

脂環式聚異氰酸酯，例如，3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯(IPDI)、1,3-環戊二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯、4,4’-伸甲基雙(環己基異氰酸酯)、1,4-雙(異氰酸酯甲基)環己烷、1,4-雙(異氰酸酯甲基)環己烷等。 Alicyclic polyisocyanate, for example, 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'-methylidene bis(cyclohexyl isocyanate), 1,4-bis(isocyanate methyl) cyclohexane, 1,4-bis(isocyanate methyl) cyclohexane, etc.

又，聚異氰酸酯化合物，可為由上述芳香族聚異氰酸酯、脂肪族聚異氰酸酯，及脂環式聚異氰酸酯所選出之化合物(聚異氰酸酯)之變性物。具體而言，可為，該化合物之三羥甲基丙烷加成物型變性物、該化合物與水進行反應而得之滴定管(burette)型變性物、該化合物含有異三聚氰酸酯環而得之異三聚氰酸酯型變性物亦可。 In addition, the polyisocyanate compound may be a denatured compound (polyisocyanate) selected from the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specifically, it may be a trimethylolpropane adduct-type denaturant of the compound, a burette-type denaturant obtained by reacting the compound with water, the compound containing an isocyanurate ring, and The obtained isocyanurate denatured substance may also be used.

該些聚異氰酸酯化合物之中，就可製得具有優良黏著性之胺基甲酸酯系聚合物之觀點，又以4,4’-二苯基甲烷二異氰酸酯(MDI)、2,4-伸甲苯基二異氰酸酯(2,4-TDI)、2,6-伸甲苯基二異氰酸酯(2,6-TDI)、伸六甲基 二異氰酸酯(HMDI)、3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯(IPDI)及該些之變性物所選出之1種以上者為佳，就耐候性之觀點，以由HMDI、IPDI及該些變性物所選出之1種以上者為較佳。 Among these polyisocyanate compounds, from the viewpoint of producing a carbamate-based polymer with excellent adhesion, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-extruded Tolyl diisocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), hexamethyl One or more selected from diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and these denatures are preferred. From the viewpoint of weather resistance, to One or more selected from HMDI, IPDI, and these denatures are preferred.

胺基甲酸酯系預聚合物(α)中之異氰酸酯基含量(NCO%)，於依JIS K 1603為基準測定之值中，較佳為0.5~12質量%、更佳為1~4質量%。 The isocyanate group content (NCO%) in the urethane-based prepolymer (α) is preferably 0.5 to 12% by mass, and more preferably 1 to 4 of the values measured according to JIS K 1603. %.

鏈延長劑，以至少具有2個之羥基及胺基中之至少一者的化合物，或，具有3個以上之羥基及胺基中之至少一者的化合物為佳。 The chain extender is preferably a compound having at least one of at least two hydroxyl groups and amine groups, or a compound having at least one of three or more hydroxyl groups and amine groups.

具有2個之羥基及胺基中之至少一者的化合物，以由脂肪族二醇、脂肪族二胺、烷醇胺、雙酚、芳香族二胺所成群所選出之至少1種的化合物為佳。 A compound having at least one of two hydroxyl groups and amine groups, at least one compound selected from the group consisting of aliphatic diol, aliphatic diamine, alkanolamine, bisphenol, and aromatic diamine Better.

脂肪族二醇，例如，1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,7-庚二醇等鏈烷二醇、乙二醇、丙二醇、二乙二醇、二丙二醇等烷二醇等。 Aliphatic diol, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, etc. Alkanediols such as alkanediol, ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.

脂肪族二胺，例如，伸乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺等。 Aliphatic diamines, for example, ethylene diamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.

烷醇胺，例如，單乙醇胺、單丙醇胺、異丙醇胺等。 Alkanolamines, for example, monoethanolamine, monopropanolamine, isopropanolamine, etc.

雙酚，例如，雙酚A等。 Bisphenol, for example, bisphenol A and the like.

芳香族二胺，例如，二苯基甲烷二胺、伸甲苯基二胺、二甲苯二胺等。 Aromatic diamines, for example, diphenylmethane diamine, tolyl diamine, xylene diamine, etc.

具有3個以上之羥基及胺基中之至少一者的化合物，例如，三羥甲基丙烷、二-三羥甲基丙烷、季戊 四醇、二季戊四醇等聚醇、1-胺基-2,3-丙二醇、1-甲基胺基-2,3-丙二醇、N-(2-羥基丙基乙醇胺)等胺基醇、四甲基二甲苯二胺之乙烯氧化物或丙烯氧化物附加物等。 Compounds with at least one of three or more hydroxyl groups and amine groups, for example, trimethylolpropane, di-trimethylolpropane, pentapentane Polyols such as tetraol and dipentaerythritol, 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, N-(2-hydroxypropylethanolamine) and other amino alcohols, tetramethyl Addition of ethylene oxide or propylene oxide based on xylene diamine.

(聚異丁烯系樹脂) (Polyisobutylene resin)

作為黏著性樹脂(x1)使用的聚異丁烯系樹脂(以下，亦稱為「PIB系樹脂」)，係指主鏈或側鏈具有聚異丁烯骨架之樹脂。 The polyisobutylene-based resin (hereinafter also referred to as "PIB-based resin") used as the adhesive resin (x1) refers to a resin having a polyisobutylene skeleton in the main chain or side chain.

PIB系樹脂之質量平均分子量(Mw)，就可使所得黏著性組成物具有充分凝集力、提高導電性黏著薄片之黏著力等觀點，及防止被附著體污染等觀點，較佳為2萬以上，再就對被附著體之濕潤性或對溶劑之溶解性之觀點，較佳為3萬~100萬、更佳為5萬~80萬、特佳為7萬~60萬。 The mass average molecular weight (Mw) of the PIB-based resin can provide the adhesive composition with sufficient cohesive force, improve the adhesive force of the conductive adhesive sheet, and prevent contamination by attachments. It is preferably at least 20,000. From the viewpoint of the wettability of the attached body or the solubility of the solvent, it is preferably 30,000 to 1 million, more preferably 50,000 to 800,000, and particularly preferably 70,000 to 600,000.

PIB系樹脂，例如，異伸丁基之均聚物的聚異丁烯、異伸丁基與異戊二烯的共聚物、異伸丁基與n-丁烯的共聚物、異伸丁基與丁二烯的共聚物，及該些共聚物經溴化或氯化等之後的鹵化丁基橡膠等。 PIB-based resins, for example, polyisobutylene of isobutylene homopolymer, copolymer of isobutylene and isoprene, copolymer of isobutylene and n-butene, isobutylene and butylene Copolymers of diene and halogenated butyl rubber after bromination or chlorination of these copolymers.

又，PIB系樹脂為共聚物之情形，由異伸丁基產生之結構單位，於全結構單位之中為含量最多者。 In addition, when the PIB-based resin is a copolymer, the structural unit derived from isobutyl group is the one with the largest content among all structural units.

本發明之一態樣所使用之PIB系樹脂中，由異伸丁基所產生之結構單位的含量，相對於該PIB系樹脂之全結構單位(100質量%)，較佳為80~100質量%、更佳為90~100質量%、特佳為95~100質量%、最佳為98~100質量%。 In the PIB-based resin used in one aspect of the present invention, the content of structural units derived from isobutyl groups is preferably 80 to 100 masses relative to the total structural units (100% by mass) of the PIB-based resin %, more preferably 90 to 100% by mass, particularly good 95 to 100% by mass, and most preferably 98 to 100% by mass.

該些之PIB系樹脂，可單獨使用亦可、將2種以上組合使用亦可。 These PIB-based resins may be used alone or in combination of two or more.

該些之中，就可提高所形成之黏著性導電層(X)之耐久性及耐候性之觀點，於聚合之際，又以含有大量具有緻密之分子構造、主鏈及側鏈不存在聚合性雙鍵，且由異伸丁基所產生之結構單位者為佳。 Among these, from the viewpoint of improving the durability and weather resistance of the adhesive conductive layer (X) formed, at the time of polymerization, it contains a large number of dense molecular structures, and the main chain and side chains do not have polymerization It is preferably a double bond and the structural unit produced by isobutyl butyl.

本發明之一態樣所使用之PIB系樹脂中，該些主鏈及側鏈不存在聚合性雙鍵、由異伸丁基所產生之結構單位的含量，相對於該PIB系樹脂之全結構單位(100質量%)，較佳為80~100質量%、更佳為90~100質量%、特佳為95~100質量%、最佳為98~100質量%。 In the PIB-based resin used in one aspect of the present invention, the content of structural units derived from isobutyl groups without polymerizable double bonds in these main chains and side chains is relative to the overall structure of the PIB-based resin The unit (100% by mass) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 98 to 100% by mass.

又，使用PIB系樹脂之情形，以將質量平均分子量較高之PIB系樹脂，與質量平均分子量較低之PIB系樹脂合併使用者為佳。 In addition, when using a PIB resin, it is preferable to combine a PIB resin with a higher mass average molecular weight with a PIB resin with a lower mass average molecular weight.

更具體而言，本發明之一態樣所使用之PIB系樹脂，為將質量平均分子量為27萬~60萬之PIB系樹脂(p1)(以下，亦稱為「PIB系樹脂(p1)」)，與質量平均分子量為5萬~25萬之PIB系樹脂(p2)(以下，亦稱為「PIB系樹脂(p2)」)合併使用者為佳。 More specifically, the PIB resin used in one aspect of the present invention is a PIB resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter, also referred to as "PIB resin (p1)" ), preferably combined with a PIB resin (p2) with a mass average molecular weight of 50,000 to 250,000 (hereinafter, also referred to as "PIB resin (p2)").

質量平均分子量較高之PIB系樹脂(p1)，於提高所得黏著性組成物所形成之黏著性導電層(X)之耐久性及耐候性的同時，亦可期待黏著力之提升。 The PIB-based resin (p1) with a higher mass average molecular weight can also be expected to improve the adhesion while improving the durability and weather resistance of the adhesive conductive layer (X) formed by the obtained adhesive composition.

又，質量平均分子量較低之PIB系樹脂(p2)，可與PIB系樹脂(p1)良好地相溶，適度地使PIB系樹脂(p1)形 成可塑化，對於黏著性導電層(X)之被附著體，可期待其濕潤性之提高、黏著物性、柔軟性等之提升等。 In addition, the PIB resin (p2) with a low mass average molecular weight can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately shaped. It can be plasticized. For the adherend of the adhesive conductive layer (X), we can expect improvement in wettability, adhesive properties, and flexibility.

PIB系樹脂(p1)之質量平均分子量(Mw)，就上述之觀點而言，較佳為27萬~60萬、更佳為29萬~48萬、特佳為31萬~45萬、最佳為32萬~40萬。 The mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, and particularly preferably 310,000 to 450,000, most preferably from the above viewpoint From 320,000 to 400,000.

PIB系樹脂(p2)之質量平均分子量(Mw)，就上述之觀點而言，較佳為5萬~25萬、更佳為8萬~23萬、特佳為14萬~22萬、最佳為18萬~21萬。 The mass average molecular weight (Mw) of the PIB-based resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, and particularly preferably 140,000 to 220,000. It is 180,000 to 210,000.

相對於PIB系樹脂(p1)100質量份，PIB系樹脂(p2)之含有比例，較佳為5~55質量份、更佳為6~40質量份、特佳為7~30質量份、最佳為8~20質量份。 The content ratio of the PIB resin (p2) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, and particularly preferably 7 to 30 parts by mass, most preferably 100 parts by mass of the PIB resin (p1). Preferably it is 8-20 parts by mass.

PIB系樹脂(p2)之含有比例為5質量份以上時，PIB系樹脂(p1)可充分進行塑化，使所形成之黏著性導電層(X)對被附著體具有良好濕潤性的同時，也可以提高黏著力。 When the content ratio of the PIB-based resin (p2) is 5 parts by mass or more, the PIB-based resin (p1) can be sufficiently plasticized so that the formed adhesive conductive layer (X) has good wettability to the adherend, It can also improve adhesion.

另一方面，PIB系樹脂(p2)之含有比例為55質量份以下時，可提高所形成之黏著性導電層(X)之黏著力、保持力，及耐久性。 On the other hand, when the content ratio of the PIB-based resin (p2) is 55 parts by mass or less, the adhesion, retention, and durability of the formed adhesive conductive layer (X) can be improved.

(苯乙烯系樹脂) (Styrene resin)

作為黏著性樹脂(x1)使用的苯乙烯系樹脂，為具有由苯乙烯所產生之結構單位的聚合物。 The styrene resin used as the adhesive resin (x1) is a polymer having structural units derived from styrene.

本發明之一態樣所使用的苯乙烯系樹脂中，由苯乙烯所產生之結構單位之含量，相對於該苯乙烯系樹脂之全結構單位(100質量%)，較佳為5~50質量%、更佳為10~40 質量%、特佳為15~35質量%。 In the styrene-based resin used in one aspect of the present invention, the content of structural units derived from styrene is preferably 5-50 masses relative to the total structural unit (100% by mass) of the styrene-based resin %, more preferably 10~40 The mass%, especially good is 15~35 mass%.

苯乙烯系樹脂之質量平均分子量(Mw)，就提高導電性黏著薄片之黏著力之觀點，較佳為1萬~40萬、更佳為2萬~30萬、特佳為2.5萬~20萬。 The mass average molecular weight (Mw) of the styrenic resin is preferably 10,000 to 400,000, more preferably 20,000 to 300,000, and particularly preferably 25,000 to 200,000 from the viewpoint of improving the adhesion of the conductive adhesive sheet .

苯乙烯系樹脂之軟化點，就提高導電性黏著薄片之黏著力之觀點，較佳為80~200℃、更佳為90~160℃、特佳為100~140℃、最佳為105~135℃。 The softening point of the styrene resin is from the viewpoint of improving the adhesion of the conductive adhesive sheet, preferably 80 to 200°C, more preferably 90 to 160°C, particularly preferably 100 to 140°C, and most preferably 105 to 135 ℃.

又，本發明中，苯乙烯系樹脂之軟化點，係指依JIS K 2531為基準所測定之值之意。 In addition, in the present invention, the softening point of the styrene-based resin means the value measured in accordance with JIS K 2531.

苯乙烯系樹脂，例如，苯乙烯-丁二烯-苯乙烯三嵌段共聚物(以下，亦稱為「SBS」)、苯乙烯-block-(伸乙基-co-伸丁基)-block-苯乙烯三嵌段共聚物(以下，亦稱為「SEBS」)、苯乙烯-block-(伸乙基-co-伸丁基)-block二嵌段共聚物(以下，亦稱為「SEB」)、苯乙烯-丁二烯二嵌段共聚物、苯乙烯-異戊二烯二嵌段共聚物、苯乙烯-異戊二烯-苯乙烯三嵌段共聚物、苯乙烯-block-(丁二烯-co-異戊二烯)-block二嵌段共聚物、苯乙烯-block-(丁二烯-co-異戊二烯)-block-苯乙烯三嵌段共聚物等，或該些共聚物之羧基變性物，或苯乙烯與α-甲基苯乙烯等芳香族系乙烯化合物之共聚物等。 Styrene-based resins, for example, styrene-butadiene-styrene triblock copolymer (hereinafter, also referred to as "SBS"), styrene-block-(ethyl-co-butyl)-block -Styrene triblock copolymer (hereinafter also referred to as "SEBS"), styrene-block-(ethylidene-co-butylene)-block diblock copolymer (hereinafter also referred to as "SEB" ''), styrene-butadiene diblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene-block-( Butadiene-co-isoprene)-block diblock copolymer, styrene-block-(butadiene-co-isoprene)-block-styrene triblock copolymer, etc., or the Modified carboxyl groups of these copolymers, or copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene, etc.

上述苯乙烯系樹脂，可單獨使用亦可、將2種以上組合使用亦可。 The styrene-based resin may be used alone or in combination of two or more.

該些苯乙烯系樹脂之中，又以SBS、SEBS，及SEB為佳、以SBS及SEBS為較佳。 Among these styrene-based resins, SBS, SEBS, and SEB are preferred, and SBS and SEBS are preferred.

又，該苯乙烯系樹脂為共聚物之情形，共聚形態並未有特別之限定。即，該苯乙烯系樹脂，可為嵌段共聚物、無規共聚物、接枝共聚物之任一者。 In addition, when the styrene-based resin is a copolymer, the copolymerization form is not particularly limited. That is, the styrene-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

(聚酯系樹脂) (Polyester resin)

作為黏著性樹脂(x1)使用的聚酯系樹脂為，酸成份與二醇成份或聚醇成份經聚縮合反應而得之共聚物，亦包含該共聚物之變性物。 The polyester resin used as the adhesive resin (x1) is a copolymer obtained by polycondensation reaction of an acid component and a diol component or a polyalcohol component, and also includes a modified product of the copolymer.

上述聚縮合反應，可以直接酯化法、酯交換法等一般性聚酯化反應進行。 The above-mentioned polycondensation reaction can be carried out by a general polyesterification reaction such as direct esterification method and transesterification method.

又，該聚酯系樹脂之共聚形態並未有特別之限定。即，該聚酯系樹脂，可為嵌段共聚物、無規共聚物、接枝共聚物之任一者。 In addition, the copolymerization form of the polyester resin is not particularly limited. That is, the polyester-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

上述酸成份，例如，對苯二甲酸、異苯二甲酸、苯二甲酸酐、α-萘二羧酸、5-鈉磺醯異苯二甲酸、5-鉀磺醯異苯二甲酸或該些之酯類、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二羧酸或該些之酯類等脂肪族二羧酸；1,4-環六氫苯二甲酸酐等脂環式二羧酸等。 The above acid component, for example, terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or these Aliphatic dicarboxylic acids such as esters, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedicarboxylic acid or esters of these; 1,4-cyclo Alicyclic dicarboxylic acids such as hexahydrophthalic anhydride.

上述二醇成份或聚醇成份，例如，乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、新戊二醇、3-甲基戊二醇、2,2,3-三甲基戊二醇、二乙二醇、三乙二醇、二丙二醇等脂肪族二醇、1,4-環己二醇、1,4-環 己烷二甲醇等脂環式二醇、雙酚A等芳香族二醇等。 The aforementioned diol component or polyalcohol component, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol , Diethylene glycol, triethylene glycol, dipropylene glycol and other aliphatic diols, 1,4-cyclohexanediol, 1,4-cyclo Alicyclic diols such as hexanedimethanol, aromatic diols such as bisphenol A, etc.

又，上述聚酯系樹脂，可單獨使用亦可、將2種以上組合使用亦可。 In addition, the polyester resin may be used alone or in combination of two or more kinds.

(聚烯烴系樹脂) (Polyolefin resin)

作為黏著性樹脂(x1)使用的聚烯烴系樹脂為具有由乙烯基、丙烯基等烯烴化合物產生之結構單位的聚合物。 The polyolefin resin used as the adhesive resin (x1) is a polymer having a structural unit derived from an olefin compound such as a vinyl group and a propylene group.

聚烯烴系樹脂，例如，低密度聚乙烯、中密度聚乙烯、高密度聚乙烯，及線狀低密度聚乙烯等聚乙烯、聚丙烯、乙烯基與丙烯基之共聚物、乙烯基與其他α-烯烴之共聚物、丙烯基與其他α-烯烴之共聚物、乙烯基與丙烯基與其他α-烯烴之共聚物、乙烯基與其他乙烯基性不飽和單體之共聚物(乙烯基-乙酸乙烯酯共聚物、乙烯基-烷基(甲基)丙烯酸酯共聚物等)等。 Polyolefin-based resins, such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, copolymers of vinyl and propylene, vinyl and other α -Copolymers of olefins, copolymers of propylene and other α-olefins, copolymers of vinyl and propylene and other α-olefins, copolymers of vinyl and other ethylenically unsaturated monomers (vinyl-acetic acid Vinyl ester copolymer, vinyl-alkyl (meth) acrylate copolymer, etc.).

又，該聚烯烴系樹脂為共聚物之情形，共聚形態並未有特別之限定。即，該聚烯烴系樹脂，可為嵌段共聚物、無規共聚物、接枝共聚物之任一者。 In addition, when the polyolefin resin is a copolymer, the copolymerization form is not particularly limited. That is, the polyolefin-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

上述α-烯烴，例如，1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、4-甲基-1-己烯等。 The aforementioned α-olefin, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene Ene etc.

上述乙烯性不飽和單體，例如，乙酸乙烯酯、(甲基)丙烯酸、烷基(甲基)丙烯酸酯、乙烯醇等。 Examples of the ethylenically unsaturated monomer include vinyl acetate, (meth)acrylic acid, alkyl (meth)acrylate, and vinyl alcohol.

該些聚烯烴系樹脂之中，又以聚丙烯、乙烯基與丙烯基之共聚物、丙烯基與其他α-烯烴之共聚物等含有由伸丙基所產生之結構單位之聚丙烯系樹脂為佳。 Among these polyolefin resins, polypropylene resins containing structural units derived from propylene groups such as polypropylene, copolymers of vinyl groups and propylene groups, and copolymers of propylene groups and other α-olefins are preferred .

又，上述聚烯烴系樹脂，可單獨使用亦可、將2種以上組合使用亦可。 In addition, the polyolefin resin may be used alone or in combination of two or more.

<碳系填料(x2)> <Carbon filler (x2)>

作為黏著性導電層(X)之形成材料的黏著性組成物中，與黏著性樹脂(x1)同時含有的碳系填料(x2)，以平均長徑比為1.5以上之碳系填料為佳。 In the adhesive composition as the forming material of the adhesive conductive layer (X), the carbon-based filler (x2) contained together with the adhesive resin (x1) is preferably a carbon-based filler having an average aspect ratio of 1.5 or more.

含有平均長徑比為1.5以上之碳系填料時，可降低所形成之黏著性導電層(X)之表面電阻率，且經由再設有非黏著性導電層(Y)方式，而可充分產生降低導電性黏著薄片之表面電阻率之效果。又，也可使黏著性導電層(X)之黏著力良好。 When the carbon-based filler with an average aspect ratio of 1.5 or more is used, the surface resistivity of the adhesive conductive layer (X) formed can be reduced, and it can be fully produced by the non-adhesive conductive layer (Y) method. The effect of reducing the surface resistivity of the conductive adhesive sheet. In addition, the adhesion of the adhesive conductive layer (X) can also be improved.

碳系填料(x2)之平均長徑比，就上述之觀點而言，較佳為1.5以上、更佳為2~10000、更佳為3~5000、更較佳為4~1000、特佳為5~500、特較佳為6~400、最佳為10~300。 From the above viewpoint, the average aspect ratio of the carbon-based filler (x2) is preferably 1.5 or more, more preferably 2 to 10,000, more preferably 3 to 5000, more preferably 4 to 1000, and particularly preferably 5 to 500, particularly preferably 6 to 400, and most preferably 10 to 300.

本發明中，「長徑比」係指，作為對象之碳系填料中的相對於短邊長度(L)之長邊的長度(H)之比例，即由「長邊之長度(H)/短邊之長度(L)」所算出之值。又，「平均長徑比」係指，由10個作為對象之碳系填料所算出的該「長徑比」之平均值。 In the present invention, "aspect ratio" refers to the ratio of the length (H) of the long side to the short side length (L) in the target carbon-based filler, that is, the "length of the long side (H)/ The value calculated by the length of the short side (L)". In addition, the "average aspect ratio" refers to the average value of the "aspect ratio" calculated from ten target carbon-based fillers.

又，碳系填料(x2)之長邊之長度(H)，係指作為對象之碳系填料中之高度方向(長度方向)之長度之意。 In addition, the length (H) of the long side of the carbon-based filler (x2) means the length in the height direction (longitudinal direction) of the carbon-based filler to be targeted.

另一方面，碳系填料(x2)之短邊之長度(L)，係指與作 為對象之碳系填料的高度方向(長度方向)形成垂直交叉之切斷面中，該斷面為圓形或橢圓形時，係指直徑或長徑，該斷面為多角形時，則指該多角形的外接圓之直徑之意。 On the other hand, the length (L) of the short side of the carbon-based filler (x2) refers to the The height direction (longitudinal direction) of the target carbon-based filler forms a cross section perpendicular to the cross section. When the cross section is circular or elliptical, it refers to the diameter or long diameter. When the cross section is polygonal, it refers to The diameter of the circumscribed circle of the polygon.

碳系填料(x2)之長邊之長度(H)，較佳為0.01~2000μm、更佳為0.05~1000μm、特佳為0.07~500μm、最佳為0.10~100μm。 The length (H) of the long side of the carbon-based filler (x2) is preferably 0.01 to 2000 μm, more preferably 0.05 to 1000 μm, particularly preferably 0.07 to 500 μm, and most preferably 0.10 to 100 μm.

又，本發明中，任意選擇10個碳系填料之長邊之長度的平均值，可視為上述「碳系填料(x2)之長邊之長度(H)」之值。 In addition, in the present invention, the average value of the lengths of the long sides of 10 carbon-based fillers can be arbitrarily selected as the value of the "length (H) of the long side of the carbon-based filler (x2)".

碳系填料(x2)之短邊之長度(L)，較佳為1~1000nm、更佳為2~750nm、更較佳為3~500nm、特佳為5~100nm、最佳為7~50nm。 The length (L) of the short side of the carbon-based filler (x2) is preferably 1 to 1000 nm, more preferably 2 to 750 nm, more preferably 3 to 500 nm, particularly preferably 5 to 100 nm, and most preferably 7 to 50 nm .

又，本發明中，任意選擇10個碳系填料之短邊之長度的平均值，可視為上述「碳系填料(x2)之短邊之長度(L)」之值。 In addition, in the present invention, the average value of the lengths of the short sides of 10 carbon-based fillers can be arbitrarily selected as the value of the "length (L) of the short sides of the carbon-based filler (x2)".

碳系填料(x2)之形狀，例如，柱狀、筒狀、錘狀、纖維狀、扁球狀(正球度為通常0.7以下)，及該些所組合之形狀等。 The shape of the carbon-based filler (x2) is, for example, a columnar shape, a cylindrical shape, a hammer shape, a fibrous shape, a spheroid shape (positive sphericity is usually 0.7 or less), and a combination of these shapes.

該些形狀之中，就形成具有良好導電性之黏著性導電層(X)之觀點，又以由柱狀之碳系填料、筒狀之碳系填料，及纖維狀之碳系填料所選出之1種以上為佳。 Among these shapes, from the viewpoint of forming an adhesive conductive layer (X) with good conductivity, it is selected from columnar carbon fillers, cylindrical carbon fillers, and fibrous carbon fillers One or more is better.

黏著性組成物中之碳系填料(x2)之含量，相對於黏著性樹脂(x1)100質量份，較佳為0.01~15質量份，更佳為0.02~10質量份、更較佳為0.30~7.0質量份、特佳 為0.40~5.0質量份、特較佳為0.50~4.5質量份、最佳為0.70~3.8質量份。 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 by mass, and more preferably 0.30 relative to 100 parts by mass of the adhesive resin (x1). ~7.0 parts by mass, excellent It is 0.40 to 5.0 parts by mass, particularly preferably 0.50 to 4.5 parts by mass, and most preferably 0.70 to 3.8 parts by mass.

碳系填料(x2)之含量為0.01質量份以上時，於可降低所形成之黏著性導電層(X)單獨之表面電阻率的同時，且經由再設有非黏著性導電層(Y)方式，而可充分產生降低導電性黏著薄片之表面電阻率之效果。 When the content of the carbon-based filler (x2) is 0.01 parts by mass or more, the surface resistivity of the adhesive conductive layer (X) formed alone can be reduced, and the non-adhesive conductive layer (Y) method is provided. , And can fully produce the effect of reducing the surface resistivity of the conductive adhesive sheet.

另一方面，碳系填料(x2)之含量為15質量份以下時，可使所形成之黏著性導電層(X)之黏著力良好。 On the other hand, when the content of the carbon-based filler (x2) is 15 parts by mass or less, the adhesion of the formed adhesive conductive layer (X) can be made good.

又，本發明之導電性黏著薄片中，黏著性導電層(X)中之碳系填料(x2)之含量於少量時，即可產生優良之抗靜電性及導電性，故無需大量添加碳系填料(x2)。 In addition, in the conductive adhesive sheet of the present invention, when the content of the carbon-based filler (x2) in the adhesive conductive layer (X) is small, excellent antistatic properties and conductivity can be produced, so there is no need to add a large amount of carbon-based Filler (x2).

又，有關相對於黏著性組成物之全量(100質量%)的碳系填料(x2)之含量，就上述之觀點而言，通常0.01~10質量%、較佳為0.30~7.0質量%、更佳為0.40~5.0質量%、特佳為0.50~4.5質量%、最佳為0.70~3.8質量%。 The content of the carbon-based filler (x2) relative to the total amount (100% by mass) of the adhesive composition is generally 0.01 to 10% by mass, preferably 0.30 to 7.0% by mass, and more The best is 0.40 to 5.0% by mass, the particularly good is 0.50 to 4.5% by mass, and the best is 0.70 to 3.8% by mass.

碳系填料(x2)，例如，碳奈米材料、碳黑、礦碳纖維、石墨等，就可降低所形成之黏著性導電層(X)之表面電阻率，且具有良好黏著力之觀點，又以碳奈米材料為佳。 Carbon-based fillers (x2), for example, carbon nanomaterials, carbon black, mineral carbon fiber, graphite, etc., can reduce the surface resistivity of the adhesive conductive layer (X) formed, and have a good adhesion point of view, and Carbon nanomaterials are preferred.

碳奈米材料為，以六員環配列構造為主構造之含有石墨薄片的物質所形成者，石墨構造中可含有硼或氮等碳以外的元素，亦可為於碳奈米材料中內含其他物質之形態，此外，亦可為碳奈米材料被其他導電性物質所修飾之形 態。 Carbon nanomaterials are made of graphite flakes with a six-membered ring arrangement as the main structure. The graphite structure may contain elements other than carbon such as boron or nitrogen, or may be contained in carbon nanomaterials. The form of other substances, in addition, it can also be a form of carbon nanomaterials modified by other conductive substances state.

碳奈米材料，例如，碳奈米管(CNT)、碳奈米纖維、碳奈米角、碳奈米錐、富勒烯等，又以碳奈米管為佳。 Carbon nanomaterials, for example, carbon nanotubes (CNT), carbon nanofibers, carbon nanohorns, carbon nanocones, fullerenes, etc., are more preferably carbon nanotubes.

碳奈米管為，具有以碳6員環構造為主構造之石墨(石墨)薄片形成圓筒狀封閉構造的筒狀的碳多面體。 The carbon nanotube is a cylindrical carbon polyhedron having a graphite (graphite) sheet with a carbon 6-member ring structure as the main structure and a cylindrical closed structure.

碳奈米管中，具有由1層之石墨薄片封閉為圓筒狀之構造的單層碳奈米管，與具有由2層之石墨薄片封閉為圓筒狀之構造的二層碳奈米管，與具有石墨薄片以3層以上同心筒狀封閉而得之多層構造的多層碳奈米管等，可於該些之中，任意併用2個以上。 Among the carbon nanotubes, there is a single-layer carbon nanotube closed by a single layer of graphite flakes and a two-layer carbon nanotube closed by a two-layer graphite flakes. It can be used in combination with two or more carbon multilayer nanotubes with a multilayer structure in which graphite flakes are sealed in a concentric cylindrical shape with three or more layers.

<交聯劑> <crosslinking agent>

作為黏著性導電層(X)之形成材料的黏著性組成物中，可再含有交聯劑。 The adhesive composition as a material for forming the adhesive conductive layer (X) may further contain a crosslinking agent.

特別是，使用上述丙烯酸系樹脂(特別是具有上述結構單位(a2)之丙烯酸系共聚物)作為黏著性樹脂(x1)使用之情形，就提高所形成之黏著性導電層(X)之黏著力之觀點，以含有交聯劑者為佳。 In particular, when the above acrylic resin (especially the acrylic copolymer having the above structural unit (a2)) is used as the adhesive resin (x1), the adhesion of the formed adhesive conductive layer (X) is improved In view of this, those containing a crosslinking agent are preferred.

交聯劑，例如，異氰酸酯系交聯劑、環氧系交聯劑、吖環丙烷(aziridine)系交聯劑、金屬螯合物系交聯劑、胺系交聯劑、胺基樹脂系交聯劑等。該些之交聯劑，可單獨或將2種以上組合使用亦可。 Cross-linking agent, for example, isocyanate-based cross-linking agent, epoxy-based cross-linking agent, aziridine-based cross-linking agent, metal chelate-based cross-linking agent, amine-based cross-linking agent, amine-based resin-based cross-linking agent Joint agent, etc. These crosslinking agents may be used alone or in combination of two or more.

該些之中，就提高導電性黏著薄片之黏著力之觀點， 又以異氰酸酯系交聯劑為佳。 Among these, from the viewpoint of improving the adhesion of the conductive adhesive sheet, Isocyanate-based crosslinking agents are also preferred.

異氰酸酯系交聯劑，例如，2,4-伸甲苯基二異氰酸酯、2,6-伸甲苯基二異氰酸酯、1,3-二甲苯二異氰酸酯、1,4-二甲苯二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、二苯基甲烷-2,4’-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、伸六甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、二環己基甲烷-2,4’-二異氰酸酯、離胺酸異氰酸酯等聚異氰酸酯化合物等。 Isocyanate-based crosslinking agent, for example, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 1,3-xylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane -4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl Polyisocyanate compounds such as methane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and amine acid isocyanate.

又，聚異氰酸酯化合物可為，上述化合物之三羥甲基丙烷加成物型變性物、與水反應而得之滴定管(burette)型變性物、含有異三聚氰酸酯環之異三聚氰酸酯型變性物。 In addition, the polyisocyanate compound may be a trimethylolpropane adduct-type denaturant of the above compound, a burette-type denaturant obtained by reacting with water, or isocyanurate containing an isocyanurate ring Ester type denatured.

交聯劑之含量，相對於黏著性樹脂(x1)100質量份，較佳為0.01~15質量份、更佳為0.05~10質量份、特佳為0.1~5質量份。 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 particularly preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the adhesive resin (x1).

<黏著賦予劑> <adhesion imparting agent>

作為黏著性導電層(X)之形成材料的黏著性組成物，可再含有黏著賦予劑。 The adhesive composition as a material for forming the adhesive conductive layer (X) may further contain an adhesion-imparting agent.

特別是，使用上述胺基甲酸酯系樹脂、PIB系樹脂，及苯乙烯系樹脂作為黏著性樹脂(x1)之情形，就提高所形成之黏著性導電層(X)之黏著力之觀點，以具有黏著賦予劑者為佳。 In particular, when the above-mentioned urethane-based resin, PIB-based resin, and styrene-based resin are used as the adhesive resin (x1), from the viewpoint of improving the adhesion of the formed adhesive conductive layer (X), It is better to have an adhesion-imparting agent.

又，該黏著賦予劑之質量平均分子量(Mw)，通常為未達1萬，而與上述黏著性樹脂(x1)作區別者。 In addition, the mass average molecular weight (Mw) of the adhesion-imparting agent is usually less than 10,000, and is distinguished from the above-mentioned adhesive resin (x1).

黏著賦予劑之質量平均分子量(Mw)，就提高所形成之黏著性導電層(X)之黏著力之觀點，較佳為400~4000、更佳為800~1500。 The mass average molecular weight (Mw) of the adhesion-imparting agent is preferably 400 to 4000, and more preferably 800 to 1500, from the viewpoint of improving the adhesion of the formed adhesive conductive layer (X).

黏著賦予劑之軟化點，較佳為110℃以上、更佳為110~180℃、特佳為115~175℃、最佳為120~170℃。 The softening point of the adhesion-imparting agent is preferably 110°C or higher, more preferably 110 to 180°C, particularly preferably 115 to 175°C, and most preferably 120 to 170°C.

又，本發明中，黏著賦予劑之「軟化點」，係指依JIS K 2531為基準所測定之值之意。 In the present invention, the "softening point" of the adhesion-imparting agent means a value measured in accordance with JIS K 2531.

黏著賦予劑，例如，松脂樹脂、松脂酚樹脂，及其酯化合物等松脂系樹脂；該些松脂系樹脂經氫化而得之氫化松脂系樹脂；萜烯樹脂、芳香族變性萜烯樹脂、萜烯酚系樹脂等萜烯系樹脂；該些萜烯系樹脂經氫化而得之氫化萜烯樹脂；石油腦經熱分解而生成之戊烯、異戊二烯、胡椒鹼、1.3-戊二烯等C5餾份經共聚而得之C5系石油樹脂及該C5系石油樹脂經氫化之石油樹脂；石油腦經熱分解而生成之茚、乙烯基甲苯、α-或β-甲基苯乙烯等C9餾份經共聚而得之C9系石油樹脂及該C9系石油樹脂經氫化之石油樹脂；等。 Adhesion-imparting agents, such as rosin resins, rosin phenol resins, and ester compounds thereof; rosin-based resins obtained by hydrogenation of these rosin-based resins; terpene resins, aromatic modified terpene resins, terpenes Terpene resins such as phenol resins; hydrogenated terpene resins obtained by hydrogenation of these terpene resins; pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 fraction obtained by copolymerization of C5 series petroleum resin and the C5 series petroleum resin hydrogenated petroleum resin; C9 distillation of indene, vinyl toluene, α- or β-methylstyrene etc. produced by thermal decomposition of petroleum naphtha The C9 petroleum resin obtained by copolymerization and the hydrogenated petroleum resin of the C9 petroleum resin; etc.

又，本發明中，黏著賦予劑，可單獨或將或2種以上軟化點或構造相異者組合使用。 In addition, in the present invention, the adhesion-imparting agent may be used alone or in combination of two or more kinds of softening points or structures.

黏著賦予劑之含量，相對於黏著性樹脂(x1)100質量份，較佳為1~200質量份、更佳為5~160質量份、特佳為10~120質量份。 The content of the adhesion-imparting agent is preferably 1 to 200 parts by mass, more preferably 5 to 160 parts by mass, and particularly preferably 10 to 120 parts by mass relative to 100 parts by mass of the adhesive resin (x1).

又，黏著性樹脂(x1)含有丙烯酸系樹脂之情形，該黏 著賦予劑之含量，相對於丙烯酸系樹脂100質量份，較佳為1~100質量份、更佳為5~50質量份、特佳為10~40質量份。 In addition, when the adhesive resin (x1) contains acrylic resin, the adhesive The content of the imparting agent is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass relative to 100 parts by mass of the acrylic resin.

黏著性樹脂(x1)含有胺基甲酸酯系樹脂之情形，該黏著賦予劑之含量，相對於胺基甲酸酯系樹脂100質量份，較佳為5~200質量份、更佳為40~160質量份、特佳為80~120質量份。 When the adhesive resin (x1) contains a urethane-based resin, the content of the adhesion-imparting agent is preferably 5 to 200 parts by mass, and more preferably 40 parts by mass relative to 100 parts by mass of the urethane-based resin. ~160 parts by mass, 80-120 parts by mass is especially good.

黏著性樹脂(x1)含有PIB系樹脂之情形，該黏著賦予劑之含量，相對於PIB系樹脂100質量份，較佳為5~100質量份、更佳為10~80質量份、特佳為15~40質量份。 When the adhesive resin (x1) contains a PIB-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 100 parts by mass of the PIB-based resin. 15~40 parts by mass.

黏著性樹脂(x1)含有苯乙烯系樹脂之情形，該黏著賦予劑之含量，相對於苯乙烯系樹脂100質量份，較佳為5~100質量份、更佳為15~80質量份、特佳為25~60質量份。 When the adhesive resin (x1) contains a styrene-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the styrene-based resin. It is preferably 25 to 60 parts by mass.

黏著性樹脂(x1)含有聚酯系樹脂之情形，該黏著賦予劑之含量，相對於聚酯系樹脂100質量份，較佳為5~100質量份、更佳為15~80質量份、特佳為25~60質量份。 When the adhesive resin (x1) contains a polyester-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the polyester resin. It is preferably 25 to 60 parts by mass.

黏著性樹脂(x1)含有聚烯烴系樹脂之情形，該黏著賦予劑之含量，相對於聚烯烴系樹脂100質量份，較佳為5~100質量份、更佳為15~80質量份、特佳為25~60質量份。 When the adhesive resin (x1) contains a polyolefin-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the polyolefin-based resin. It is preferably 25 to 60 parts by mass.

<其他之添加劑> <Other additives>

作為黏著性導電層(X)之形成材料的黏著性組成物 中，於無損本發明效果之範圍，一般而言，可含有與黏著性樹脂共同使用之常用添加劑。 Adhesive composition as a forming material for adhesive conductive layer (X) In general, as long as the effect of the present invention is not impaired, in general, it may contain common additives used together with the adhesive resin.

該些常用添加劑，例如，紫外線吸收劑、抗氧化劑、軟化劑(可塑劑)、填充劑、防鏽劑、顏料、染料、硬化劑、硬化助劑、觸媒等。 These common additives, for example, ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, hardeners, hardening aids, catalysts, etc.

添加該些常用添加劑之情形，常用添加劑之各個之添加量，相對於黏著性樹脂(x1)100質量份，較佳為0.01~6質量份、更佳為0.01~2質量份。 When adding these common additives, the amount of each of the common additives is preferably 0.01 to 6 parts by mass, and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the adhesive resin (x1).

作為黏著性導電層(X)之形成材料的黏著性組成物之全量(100質量%)中的黏著性樹脂(x1)與碳系填料(x2)之合計含量，較佳為20質量%以上、更佳為30質量%以上。 The total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition as the forming material of the adhesive conductive layer (X) is preferably 20 mass% or more. It is more preferably 30% by mass or more.

又，使用黏著性樹脂(x1)作為丙烯酸系樹脂之主成份使用之情形，黏著性組成物之全量(100質量%)中的黏著性樹脂(x1)與碳系填料(x2)之合計含量，較佳為60質量%以上、更佳為70質量%以上、特佳為80質量%以上、最佳為90質量%以上。 In addition, when the adhesive resin (x1) is used as the main component of the acrylic resin, 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, It is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

使用黏著性樹脂(x1)作為胺基甲酸酯系樹脂之主成份使用之情形，黏著性組成物之全量(100質量%)中的黏著性樹脂(x1)與碳系填料(x2)之合計含量，較佳為35質量%以上、更佳為40質量%以上、特佳為45質量%以上，黏著性樹脂(x1)與碳系填料(x2)與黏著賦予劑之合計含量，較佳為70質量%以上、更佳為80質量%以上、特佳為90質量%以上。 When the adhesive resin (x1) is used as the main component of the urethane resin, the total of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition The content is preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. The total content of the adhesive resin (x1) and the carbon-based filler (x2) and the adhesion-imparting agent is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

使用黏著性樹脂(x1)作為PIB系樹脂之主成份使用之情形，黏著性組成物之全量(100質量%)中的黏著性樹脂(x1)與碳系填料(x2)之合計含量，較佳為50質量%以上、更佳為60質量%以上、特佳為70質量%以上，黏著性樹脂(x1)與碳系填料(x2)與黏著賦予劑之合計含量，較佳為70質量%以上、更佳為80質量%以上、特佳為90質量%以上。 When the adhesive resin (x1) is used as the main component of the PIB resin, 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 preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, the total content of the adhesive resin (x1) and the carbon-based filler (x2) and the adhesion-imparting agent is preferably 70% by mass or more , More preferably 80% by mass or more, and particularly preferably 90% by mass or more.

使用黏著性樹脂(x1)作為苯乙烯系樹脂之主成份使用之情形，黏著性組成物之全量(100質量%)中的黏著性樹脂(x1)與碳系填料(x2)之合計含量，較佳為20質量%以上、更佳為25質量%以上、特佳為30質量%以上。 When the adhesive resin (x1) is used as the main component of the styrene resin, 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 It is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more.

又，「使用ZZ系樹脂作為主成份之黏著性樹脂(x1)」之標記，係指「黏著性樹脂(x1)所含之樹脂中，ZZ系樹脂的含量為最多」之意。 In addition, the mark "adhesive resin (x1) using ZZ resin as the main component" means "the content of ZZ resin is the largest in the resin contained in the adhesive resin (x1)".

該記載中，具體的ZZ系樹脂之含量，相對於黏著性樹脂(x1)之全量(100質量%)，通常50質量%以上、較佳為65~100質量%、更佳為75~100質量%、特佳為85~100質量%。 In this description, the specific content of the ZZ-based resin is usually 50% by mass or more, preferably 65-100% by mass, and more preferably 75-100% with respect to the total amount (100% by mass) of the adhesive resin (x1). % And Tejia are 85~100% by mass.

<黏著性導電層(X)之形成方法> <Method of forming adhesive conductive layer (X)>

黏著性導電層(X)之形成方法，並未有特別之限制，其可依公知之方法予以製造，例如，下述方法(X-1)及(X-2)等。 The method for forming the adhesive conductive layer (X) is not particularly limited, and it can be manufactured according to a known method, for example, the following methods (X-1) and (X-2).

．方法(X-1)：製作黏著性組成物之有機溶劑之溶液， 將該溶液依公知之塗佈方法塗佈於後述之剝離薄片上，形成塗佈膜，再使塗佈膜乾燥形成黏著性導電層(X)之方法。 . Method (X-1): Make a solution of the organic solvent of the adhesive composition, This solution is applied to a peeling sheet described later according to a known coating method to form a coating film, and then the coating film is dried to form an adhesive conductive layer (X).

．方法(X-2)：黏著性樹脂(x1)及碳系填料(x2)等經加熱混練，製得複合物之後，將該複合物依公知之成形法形成為薄片狀，再形成黏著性導電層(X)之方法。 . Method (X-2): After the adhesive resin (x1) and the carbon-based filler (x2) are kneaded to obtain a composite, the composite is formed into a thin sheet according to a well-known molding method, and then the adhesive conductive is formed Layer (X) method.

(方法(X-1)) (Method (X-1))

方法(X-1)中，黏著性樹脂(x1)，以使用丙烯酸系樹脂、胺基甲酸酯系樹脂，及PIB系樹脂等之情形為較佳之形成方法。 In method (X-1), the adhesive resin (x1) is preferably formed using acrylic resin, urethane resin, PIB resin, or the like.

方法(X-1)中，所使用之有機溶劑，例如，甲基乙基酮、丙酮、乙酸乙酯、四氫呋喃、二噁烷、環己烷、n-己烷、甲苯、二甲苯、n-丙醇、異丙醇、二甲基甲醯胺、N-甲基吡咯啶酮、二甲基亞碸等。 In method (X-1), the organic solvents used are, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n- Propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.

又，該些有機溶劑，可以合成黏著性樹脂(x1)時所使用之有機溶劑之狀態下使用。 Moreover, these organic solvents can be used in the state of synthesizing the organic solvent used when the adhesive resin (x1) is synthesized.

方法(X-1)中，碳系填料(x2)，以分散於溶劑中形成分散液之形態，對黏著性樹脂(x1)進行添加者為佳。 In the method (X-1), the carbon-based filler (x2) is preferably dispersed in a solvent to form a dispersion liquid, and the adhesive resin (x1) is preferably added.

碳系填料(x2)以分散液之形態進行添加時，因於低黏度之狀態下可與黏著性樹脂(x1)產生混合，故碳系填料(x2)相互間容易互相接近，經由形成填料之網絡，而容易降低所形成之黏著性導電層(X)之表面電阻率及體積電阻 率。 When the carbon-based filler (x2) is added in the form of a dispersion, it can be mixed with the adhesive resin (x1) in the state of low viscosity, so the carbon-based filler (x2) is easily close to each other. Network, and it is easy to reduce the surface resistivity and volume resistance of the formed adhesive conductive layer (X) rate.

製作碳系填料(x2)之分散液所使用的溶劑，可列舉如，水或上述有機溶劑等，又以有機溶劑為佳。 The solvent used for preparing the dispersion liquid of the carbon-based filler (x2) includes, for example, water or the above-mentioned organic solvents, and organic solvents are more preferred.

碳系填料(x2)之分散液的製作方法，例如，於溶劑中添加碳系填料(x2)，使用超音波等振動一定時間之方式予以製作之方法等。 The method for preparing the dispersion liquid of the carbon-based filler (x2) is, for example, a method of adding the carbon-based filler (x2) to a solvent and using ultrasonic waves or the like to vibrate for a certain time.

碳系填料(x2)之分散液的固體成份濃度，較佳為0.01~60質量%、更佳為0.05~10質量%、特佳為0.1~3質量%。 The solid content concentration of the dispersion liquid of the carbon-based filler (x2) is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 3% by mass.

方法(X-1)中，將黏著性組成物之溶液塗佈於剝離薄片上之方法，例如，旋轉塗佈法、噴灑塗佈法、條狀塗佈法、刮刀塗佈法、滾筒刮刀塗佈法、滾筒塗佈法、平板塗佈法、鑄模塗佈法、凹版塗佈法等。 In method (X-1), a method of applying a solution of an adhesive composition on a release sheet, for example, a spin coating method, a spray coating method, a strip coating method, a blade coating method, a roller blade coating method Cloth method, roller coating method, plate coating method, mold coating method, gravure coating method, etc.

又，將黏著性組成物之溶液塗佈於剝離薄片上形成塗佈膜之後，進行乾燥處理，以去除塗佈膜中所含溶劑者為佳。 In addition, after applying the solution of the adhesive composition on the release sheet to form a coating film, it is preferably dried to remove the solvent contained in the coating film.

此外，方法(X-1)中，就提高黏著力之目的，以將該乾燥處理後之塗佈層，例如，靜置於23℃、50%RH(相對濕度)之環境下7日~30日左右，使塗佈層內部充分進行交聯者為佳。 In addition, in the method (X-1), for the purpose of improving adhesion, the coating layer after the drying treatment, for example, is allowed to stand in an environment of 23°C and 50% RH (relative humidity) for 7 days to 30 days It is preferable that the inside of the coating layer is sufficiently cross-linked in about days.

(方法(X-2)) (Method (X-2))

方法(X-2)中，黏著性樹脂(x1)，以使用將苯乙烯系樹脂等加熱混練而得之耐久性樹脂之情形為較佳之形成方 法。 In the method (X-2), the adhesive resin (x1) is preferably formed by using a durable resin obtained by heating and kneading styrene resin or the like. law.

加熱混練裝置，例如，單軸擠壓機、二軸擠壓機、滾筒研磨機、複合研磨機、班伯里混練機、混合器(intermixture)、加壓捏合機等。 The heating and kneading device is, for example, a uniaxial extruder, a biaxial extruder, a barrel mill, a compound mill, a Banbury kneader, an intermixture, and a pressure kneader.

將使用該加熱混練裝置而得之複合物成形之方法，例如，溶融擠壓法、簾幕法、壓縮成形法等，又以壓縮成形法為佳。 The method of molding the compound obtained by using the heating and kneading device, for example, the melt extrusion method, the curtain method, the compression molding method, etc., is also preferably a compression molding method.

壓縮成形法之具體方法，例如將所製得之複合物，以2片剝離薄片挾夾，再使用熱擠壓機等進行加熱壓縮，而形成薄片狀之黏著性導電層(X)。又，2片剝離薄片以外，亦可以挾夾基材與剝離薄片所製得之複合物，而形成薄片狀之黏著性導電層(X)亦可。 A specific method of the compression molding method is, for example, sandwiching the prepared composite with two peeling sheets, and then heating and compressing with a hot extruder to form a sheet-shaped adhesive conductive layer (X). In addition to the two peeling sheets, it is also possible to sandwich the composite of the substrate and the peeling sheet to form a sheet-shaped adhesive conductive layer (X).

〔非黏著性導電層(Y)之形成材料〕 [Forming material of non-adhesive conductive layer (Y)]

非黏著性導電層(Y)，就可充分發揮降低導電性黏著薄片之表面電阻率之效果的觀點，以含有由導電性高分子、碳系填料，及金屬氧化物所成之群所選出之1種以上的導電材料之層為佳，以含有由聚噻吩、PEDOT-PSS、碳奈米材料，及ITO(氧化銦錫)所成之群所選出之1種以上的導電材料者為較佳，以含有由聚噻吩、PEDOT-PSS，及碳奈米材料所成之群所選出之1種以上的導電材料為更佳。 The non-adhesive conductive layer (Y) can fully exert the effect of reducing the surface resistivity of the conductive adhesive sheet. It is selected from the group consisting of conductive polymers, carbon-based fillers, and metal oxides. A layer of more than one conductive material is preferred, and one containing more than one conductive material selected from the group consisting of polythiophene, PEDOT-PSS, carbon nanomaterials, and ITO (indium tin oxide) is preferred It is better to contain more than one kind of conductive material selected from the group consisting of polythiophene, PEDOT-PSS, and carbon nanomaterials.

非黏著性導電層(Y)中所含之導電材料之密度，就導電性黏著薄片之輕量化的觀點，較佳為 0.8~2.5g/cm3、更佳為0.8~2.0g/cm3、特佳為0.8~1.7g/cm3。 The density of the conductive material contained in the non-adhesive conductive layer (Y) is preferably 0.8 to 2.5 g/cm 3 and more preferably 0.8 to 2.0 g/cm 3 from the viewpoint of the lightweight of the conductive adhesive sheet. Especially good is 0.8~1.7g/cm 3 .

以下，將對構成非黏著性導電層(Y)的導電材料進行說明。 Hereinafter, the conductive material constituting the non-adhesive conductive layer (Y) will be described.

<導電性高分子> <conductive polymer>

導電性高分子，例如，聚噻吩、PEDOT-PSS(聚(3,4-伸乙基二氧基噻吩)-聚(苯乙烯磺酸))、聚苯胺、聚吡咯、聚喹噁啉(quinoxaline)等。 Conductive polymers, for example, polythiophene, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)), polyaniline, polypyrrole, polyquinoxaline (quinoxaline )Wait.

該些之中，又以聚噻吩，及PEDOT-PSS為佳。 Among these, polythiophene and PEDOT-PSS are preferred.

含有導電性高分子之非黏著性導電層(Y)，與導電性高分子同時，又含有非黏著性樹脂者為佳，非黏著性樹脂，又以由丙烯酸系樹脂、胺基甲酸酯系樹脂、PIB系樹脂，及苯乙烯系樹脂所選出之1種以上之非黏著性樹脂為佳。 Non-adhesive conductive layer (Y) containing conductive polymer is preferred to contain non-adhesive resin at the same time as conductive polymer. Non-adhesive resin is composed of acrylic resin and urethane resin. One or more non-adhesive resins selected from resins, PIB resins, and styrene resins are preferred.

導電性高分子作為導電材料使用之情形，導電性高分子之含量，相對於非黏著性導電層(Y)之全量(100質量%)，較佳為4~100質量%、更佳為8~100質量%。 When the conductive polymer is used as a conductive material, the content of the conductive polymer is preferably 4 to 100% by mass, more preferably 8 to the total amount (100% by mass) of the non-adhesive conductive layer (Y). 100% by mass.

含有導電性高分子之非黏著性導電層(Y)之形成方法，並未有特別之限制，例如，製作含有導電性高分子之有機溶劑之溶液，使用公知之塗佈方法將該溶液塗佈於基材或剝離薄片上，形成塗佈膜，再使塗佈膜乾燥而成形之方法等。 The method for forming the non-adhesive conductive layer (Y) containing a conductive polymer is not particularly limited. For example, a solution of an organic solvent containing a conductive polymer is prepared, and the solution is coated using a known coating method A method of forming a coating film on a substrate or a peeling sheet, and then drying and forming the coating film.

該方法所使用之有機溶劑之種類，及溶液之塗佈方 法，與有關上述黏著性導電層(X)之形成方法之「方法(X-1)」之記載為相同內容。 The type of organic solvent used in this method and the application method of the solution The method is the same as the description of the "method (X-1)" regarding the method for forming the adhesive conductive layer (X).

<碳系填料> <Carbon filler>

碳系填料，例如與上述碳系填料(x2)為相同之內容，又以碳奈米材料為佳。 The carbon-based filler, for example, has the same content as the above-mentioned carbon-based filler (x2), and is preferably a carbon nanomaterial.

含有碳系填料之非黏著性導電層(Y)，與碳系填料同時，又含有非黏著性樹脂者為佳，非黏著性樹脂，以由丙烯酸系樹脂、胺基甲酸酯系樹脂、PIB系樹脂，及苯乙烯系樹脂所選出之1種以上之非黏著性樹脂為佳。 The non-adhesive conductive layer (Y) containing carbon-based filler is preferred to contain non-adhesive resin at the same time as the carbon-based filler. The non-adhesive resin is composed of acrylic resin, urethane resin, PIB It is better to choose one or more non-adhesive resins based on resins and styrene resins.

使用碳系填料作為導電材料之情形，該碳系填料之含量，相對於非黏著性導電層(Y)之全量(100質量%)，較佳為0.1~20質量%、更佳為0.5~15質量%、特佳為1.0~10質量%、最佳為2.0~7質量%。 When a carbon-based filler is used as a conductive material, the content of the carbon-based filler is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15 relative to the total amount (100% by mass) of the non-adhesive conductive layer (Y). The mass%, especially good, is 1.0-10 mass%, and the best is 2.0-7 mass%.

含有碳系填料之非黏著性導電層(Y)之形成方法，並未有特別之限制，例如，將碳系填料之分散液，與非黏著性樹脂之有機溶劑之溶液混合，製得樹脂組成物之溶液後，使用公知之塗佈方法將該溶液塗佈於基材或剝離薄片上，形成塗佈膜，再使塗佈膜乾燥而成形之方法等。 The method for forming the non-adhesive conductive layer (Y) containing the carbon-based filler is not particularly limited. For example, the dispersion of the carbon-based filler is mixed with the organic solvent solution of the non-adhesive resin to prepare the resin composition After the solution of the substance, a method of applying the solution to a substrate or a release sheet using a known coating method to form a coating film, and then drying and shaping the coating film, etc.

該方法所使用之有機溶劑之種類、碳系填料之分散液的製作方法，及溶液之塗佈方法，與有關上述黏著性導電層(X)之形成方法之「方法(X-1)」之記載為相同內容。 The type of organic solvent used in this method, the method of making the dispersion of carbon-based filler, and the method of coating the solution, and the "method (X-1)" related to the method of forming the above-mentioned adhesive conductive layer (X) Recorded as the same content.

又，含有碳系填料之非黏著性導電層(Y)之形成方法，亦可為將碳系填料與非黏著性樹脂經加熱混練， 製得複合物之後，依公知之成形法將該複合物形成薄片狀而製得之方法。 In addition, the method of forming the non-adhesive conductive layer (Y) containing the carbon-based filler may also be heating and mixing the carbon-based filler and the non-adhesive resin, After the composite is prepared, the composite is formed into a thin sheet according to a known molding method.

該方法所使用之加熱混練機、複合物之成形法，與有關上述黏著性導電層(X)之形成方法之「方法(X-2)」所記載之內容為相同。 The heating kneading machine and the composite forming method used in this method are the same as those described in "Method (X-2)" concerning the method for forming the above-mentioned adhesive conductive layer (X).

<金屬氧化物> <metal oxide>

金屬氧化物，例如，ITO(氧化銦錫)、ZnO(氧化鋅)、IZO(氧化鋅銦)、AZO(氧化鋅鋁)、GZO(氧化鋅鎵)、IGZO(酸化銦鎵鋅)、ATO(氧化錫銻)等。 Metal oxides, for example, ITO (indium tin oxide), ZnO (zinc oxide), IZO (zinc indium oxide), AZO (zinc aluminum oxide), GZO (zinc gallium oxide), IGZO (indium gallium zinc oxide), ATO ( Tin oxide antimony) etc.

該些之中，又以ITO(氧化銦錫)為佳。 Among these, ITO (indium tin oxide) is preferred.

又，使用金屬氧化物作為導電材料使用之情形，非黏著性導電層(Y)，以僅由該金屬氧化物所形成之層為佳。 In addition, when a metal oxide is used as the conductive material, the non-adhesive conductive layer (Y) is preferably a layer formed only of the metal oxide.

又，含有金屬氧化物之非黏著性導電層(Y)之形成方法，以對基材進行蒸鍍而形成之方法為佳。 In addition, the method of forming the non-adhesive conductive layer (Y) containing metal oxide is preferably a method of forming a substrate by vapor deposition.

〔基材〕 〔Substrate〕

本發明之一態樣之導電性黏著薄片所使用之基材，可配合導電性黏著薄片之用途作適當之選擇，其可為含有絕緣性材料之絕緣性基材、含有金屬等導電性材料之導電性基材等。 The substrate used in the conductive adhesive sheet according to one aspect of the present invention can be appropriately selected in accordance with the use of the conductive adhesive sheet. It can be an insulating substrate containing an insulating material, or a conductive material containing metal, etc. Conductive substrates, etc.

本發明中，絕緣性基材係指，表面電阻率為1.0×1014Ω/□以上(較佳為1.0×1016Ω/□以上)之基材。 In the present invention, the insulating substrate means a substrate having a surface resistivity of 1.0×10 14 Ω/□ or more (preferably 1.0×10 16 Ω/□ or more).

絕緣性基材，例如，優質紙、表面加工紙、印刷用 紙、蠟紙等或該些之紙基材層合聚乙烯等熱可塑性樹脂而得之層合紙等各種紙類；不織布等多孔質材料；聚乙烯樹脂、聚丙烯樹脂等聚烯烴樹脂、聚苯二甲酸丁二醇酯樹脂、聚苯二甲酸乙二醇酯樹脂等聚酯樹脂、乙酸酯樹脂、ABS樹脂、聚苯乙烯樹脂、二氯乙烯樹脂等所形成之塑膠薄膜或薄片；該些樹脂之混合物所形成之塑膠薄膜或薄片；該些之塑膠薄膜或薄片的層合物所形成之塑膠薄膜或薄片等。 Insulating substrates, such as high-quality paper, surface-processed paper, printing Paper, wax paper, etc. or these paper substrates laminated with thermoplastic resins such as polyethylene and other papers; porous materials such as non-woven fabrics; polyolefin resins such as polyethylene resins and polypropylene resins, polyphenylene Plastic films or sheets formed from polyester resins such as butanediol dicarboxylate resin, polyethylene terephthalate resin, acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc.; A plastic film or sheet formed by a mixture of resins; a plastic film or sheet formed by a laminate of these plastic films or sheets, etc.

又，塑膠薄膜或薄片等基材，可為未延伸者，或以縱或橫等一軸方向或二軸方向延伸者皆可。 In addition, the base material such as plastic film or sheet may be unextended, or may be extended in one or two axis directions such as longitudinal or horizontal.

又，該些之絕緣性基材(特別是塑膠薄膜或薄片)，可再含有紫外線吸收劑、光安定劑、抗氧化劑、抗靜電劑、滑劑、抗斷裂劑、著色劑等。 Furthermore, these insulating substrates (especially plastic films or sheets) may further contain ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-breaking agents, colorants, and the like.

導電性基材，例如，金屬箔、金屬箔層合於形成上述絕緣性基材之樹脂等而得之薄膜或薄片、於上述之絕緣性基材的表面上進行金屬蒸鍍處理之薄膜或薄片、於上述之絕緣性基材的表面上進行抗靜電處理之薄膜或薄片、將金屬線編織為網狀之薄片等。 Conductive substrate, for example, a film or sheet obtained by laminating a metal foil or a metal foil to the resin that forms the above-mentioned insulating substrate, or a film or sheet that is subjected to metal vapor deposition on the surface of the above-mentioned insulating substrate 1. A film or sheet that is subjected to antistatic treatment on the surface of the above-mentioned insulating base material, a sheet in which a metal wire is woven into a mesh, etc.

又，導電性基材所使用之金屬，例如，鋁、銅、銀、金等。 In addition, metals used for the conductive base material are, for example, aluminum, copper, silver, gold, and the like.

基材之厚度，並未有特別之限制，就容易處理之觀點，較佳為10~250μm、更佳為15~200μm、特佳為20~150μm。 The thickness of the substrate is not particularly limited. From the viewpoint of ease of handling, it is preferably 10 to 250 μm, more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

基材為塑膠薄膜或薄片之情形，就提高基材 與非黏著性導電層(Y)之密著性之觀點，必要時，以對基材表面施以氧化法或凹凸化法等表面處理為佳。 If the substrate is a plastic film or sheet, increase the substrate From the viewpoint of adhesion to the non-adhesive conductive layer (Y), if necessary, it is preferable to apply surface treatment such as an oxidation method or a bumping method to the surface of the substrate.

氧化法，並未有特別之限制，例如，電暈放電處理法、電漿處理法、鉻酸氧化(濕式)、火焰處理、熱風處理、臭氧．紫外線照射處理等。又，凹凸化法，並未有特別之限制，例如，噴沙處理法、溶劑處理法等。該些表面處理，可配合基材種類作適當之選擇，就提高與非黏著性導電層(Y)之密著性之效果或操作性的觀點，以電暈放電處理法為佳。又，亦可施以電漿處理。 The oxidation method is not particularly limited, for example, corona discharge treatment method, plasma treatment method, chromic acid oxidation (wet type), flame treatment, hot air treatment, ozone. Ultraviolet irradiation treatment, etc. In addition, the bumping method is not particularly limited, for example, a sandblasting method, a solvent treatment method and the like. These surface treatments can be appropriately selected in accordance with the type of substrate. From the viewpoint of the effect of improving the adhesion with the non-adhesive conductive layer (Y) or operability, the corona discharge treatment method is preferred. In addition, plasma treatment can also be applied.

〔剝離薄片〕 〔Peeling sheet〕

又，本發明之一態樣之導電性黏著薄片所使用之剝離薄片，可使用經兩面剝離處理後之剝離薄片，或使用經單面剝離處理後之剝離薄片等、剝離薄片用基材上塗佈剝離劑者等。 In addition, the release sheet used for the conductive adhesive sheet of one aspect of the present invention may be a release sheet after being peeled on both sides, or a release sheet after being peeled on one side, etc. Cloth stripper etc.

剝離薄片用基材，例如，蠟紙、印刷用紙、優質紙等紙基材、該些之紙基材上層合聚乙烯等熱塑性樹脂而得之層合紙、或聚苯二甲酸乙二醇酯樹脂、聚苯二甲酸丁二醇酯樹脂、聚萘二甲酸乙二酯樹脂等聚酯樹脂薄膜、聚丙烯樹脂、聚乙烯樹脂等聚烯烴樹脂薄膜等塑膠薄膜等。 Substrates for peeling sheets, for example, paper substrates such as wax paper, printing paper, high-quality paper, laminated paper obtained by laminating thermoplastic resins such as polyethylene, or polyethylene terephthalate resin on these paper substrates , Polybutylene terephthalate resin, polyethylene naphthalate resin and other polyester resin films, polypropylene resin, polyethylene resin and other polyolefin resin films and other plastic films.

剝離劑，例如，聚矽氧系樹脂、烯烴系樹脂、異戊二烯系樹脂、丁二烯系樹脂等橡膠系彈性體、長鏈烷基系樹脂、醇酸系樹脂、氟系樹脂等。 The release agent includes, for example, rubber-based elastomers such as polysiloxane-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

剝離薄片之厚度，並未有特別之限制，較佳為10~200μm、更佳為25~150μm。 The thickness of the peeling sheet is not particularly limited, but it is preferably 10 to 200 μm, and more preferably 25 to 150 μm.

〔導電性黏著薄片之製造方法、物性〕 [Manufacturing method and physical properties of conductive adhesive sheet]

本發明之一態樣的導電性黏著薄片，可將依上述形成方法所形成之黏著性導電層(X)及非黏著性導電層(Y)，及基材或剝離薄片經適當之貼合方式予以製造。 According to one aspect of the present invention, the conductive adhesive sheet can be formed by the appropriate bonding method between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) formed by the above-mentioned forming method, and the substrate or release sheet Be manufactured.

對本發明之一態樣的導電性黏著薄片所具有之黏著性導電層(X)之表面的探針測試之峰頂之值，較佳為0.1N以上、更佳為0.1~49N、特佳為0.5~49N、最佳為1.0~49N。 The peak value of the probe test on the surface of the adhesive conductive layer (X) of the conductive adhesive sheet according to one aspect of the present invention is preferably 0.1 N or more, more preferably 0.1 to 49 N, and particularly preferably 0.5~49N, the best is 1.0~49N.

又，該探針測試之峰頂值，係指依實施例記載之方法所測定之值之意。又，該探針測試之峰頂值，為作為導電性黏著薄片之黏著力的指標之物性值，該數值越大時，並是其具有高度之黏著力。 In addition, the peak top value measured by the probe refers to the value measured according to the method described in the examples. In addition, the peak top value measured by the probe is a physical property value that is an indicator of the adhesive force of the conductive adhesive sheet. The larger the value, the higher the adhesive force.

由表面側測定本發明之一態樣導電性黏著薄片所具有之黏著性導電層(X)的表面電阻率(ρS)、較佳為9.0×104Ω/□以下，更佳為1.0×104Ω/□以下，特佳為5.0×103Ω/□以下，最佳為2.0×103Ω/□以下。 The surface resistivity (ρ S ) of the adhesive conductive layer (X) included in the conductive adhesive sheet according to one aspect of the present invention is measured from the surface side, preferably 9.0×10 4 Ω/□ or less, more preferably 1.0× 10 4 Ω/□ or less, particularly preferably 5.0×10 3 Ω/□ or less, and most preferably 2.0×10 3 Ω/□ or less.

又，上述「由表面側測定導電性黏著薄片所具有之黏著性導電層(X)的表面電阻率」之值為，至少由黏著性導電層(X)及非黏著性導電層(Y)層合之本發明之導電性黏著薄片所露出之黏著性導電層(X)之表面側所測定之表面電阻率之值，其與上述「黏著性導電層(X)單獨之表面電阻 率(ρSX)」之值並不相同。 In addition, the value of "measure the surface resistivity of the adhesive conductive layer (X) of the conductive adhesive sheet from the surface side" is at least composed of the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) layer The surface resistivity value measured on the surface side of the adhesive conductive layer (X) exposed by the conductive adhesive sheet of the present invention is the same as the surface resistivity (ρ SX ) of the above "adhesive conductive layer (X) alone )" values are not the same.

[實施例] [Example]

以下之實施例及比較例所使用的各成份之物性，及，導電性黏著薄片、黏著性導電層(X)，及非黏著性導電層之各物性，為依以下記載之方法所測定者。 The physical properties of each component used in the following examples and comparative examples, and the physical properties of the conductive adhesive sheet, the adhesive conductive layer (X), and the non-adhesive conductive layer were measured according to the methods described below.

<質量平均分子量(Mw)> <Mass average molecular weight (Mw)>

使用凝膠浸透層析裝置(東曹股份有限公司製、製品名「HLC-8020」)，依下述條件下進行測定，使用依標準聚苯乙烯換算而得之測定值。 Using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020"), the measurement was performed under the following conditions, and the measured value converted from standard polystyrene was used.

(測定條件) (Measurement conditions)

．管柱：「TSK guard column HXL-H」、「TSK gel GMHXL(×2)」及「TSK gel G2000HXL」(皆為東曹股份有限公司製)依序連結者。 . Tubular column: "TSK guard column HXL-H", "TSK gel GMHXL (×2)" and "TSK gel G2000HXL" (both manufactured by Tosoh Corporation) in sequence.

．管柱溫度：40℃ . Column temperature: 40℃

．展開溶劑：四氫呋喃 . Expand solvent: Tetrahydrofuran

．流速：1.0mL/min . Flow rate: 1.0mL/min

<碳系填料之長徑比、長邊及短邊之長度> <Length-to-diameter ratio of carbon-based filler, length of long side and short side>

使用掃瞄型電子顯微鏡(日立高科技股份有限公司製、製品名「S-4700」)，觀察10個隨機萃取之碳系填料之粒子，分別測定各個長邊之長度及短邊之長度，將10個碳系填料之粒子的平均值，作為該填料之「長邊之長度 (H)」及「短邊之長度(L)」。又，長徑比(H/L)則依「長邊之長度(H)/短邊之長度(L)」算出。 Using a scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., product name "S-4700"), observe 10 randomly extracted particles of carbon-based filler, and measure the length of each long side and the length of the short side respectively. The average value of the particles of 10 carbon-based fillers is used as the "length of the long side" (H)" and "Length of Short Side (L)". In addition, the aspect ratio (H/L) is calculated according to "length of long side (H)/length of short side (L)".

<軟化點> <softening point>

依JIS K 2531為基準測定者。 Measured according to JIS K 2531.

<密度> <density>

依JIS Z 8807：2012為基準測定者。 Measured according to JIS Z 8807:2012.

<探針測試(probe tack)> <probe tack>

依JIS Z0237(1991)為基準測定者。 Measured according to JIS Z0237 (1991).

具體而言，可為，將10mm×10mm大小之試驗片，靜置於23℃、50%RH(相對濕度)之環境下24小時之後，使該試驗片之測定對象之層的表面露出，使用黏度試驗機(理學工業股份有限公司製、製品名「PROBE TACK TESTER」)，對該層之表面測定其探針測試(probe tack)值。 Specifically, a test piece of 10 mm×10 mm size is allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity) to expose the surface of the layer to be measured of the test piece for use. A viscosity tester (manufactured by Rigaku Corporation, product name "PROBE TACK TESTER") measures the probe tack value of the surface of the layer.

又，該探針測試值為，使用直徑5mm之不銹鋼製探針以1秒鐘、接觸荷重0.98N/cm2之條件，接觸測定對象之層的表面之後，使探針以600mm/秒之速度，由該表面離開所使用之必要力量，作為該層之表面的探針測試值。 In addition, the test value of this probe is to use a stainless steel probe with a diameter of 5 mm for 1 second and a contact load of 0.98 N/cm 2. After contacting the surface of the layer to be measured, the probe is made at a speed of 600 mm/sec. , The necessary force used to leave the surface is used as the probe test value of the surface of the layer.

又，對該非黏著性導電層之表面，測定探針測試值之峰頂值。又，對於導電性黏著薄片所具有之黏著性導電層(X)之表面，測定探針測試值之峰頂值及積分值。 In addition, the peak top value of the probe test value is measured on the surface of the non-adhesive conductive layer. In addition, for the surface of the adhesive conductive layer (X) of the conductive adhesive sheet, the peak top value and the integrated value of the probe test value are measured.

此外，測定對象之層的表面不具有黏著性，而無法測定探針測試值之峰頂值之情形，則該峰頂之值為「0(N)」。 In addition, when the surface of the layer to be measured does not have adhesiveness and the peak top value of the probe test value cannot be measured, the peak top value is "0(N)".

<表面電阻率、體積電阻率> <surface resistivity, volume resistivity>

依JIS K 7194為基準之測定者。 Measured according to JIS K 7194.

具體而言，可為，將20mm×40mm大小之試驗片，靜置於23℃、50%RH(相對濕度)之環境下24小時之後，使該試驗片之測定對象之層的表面露出，使用低電阻率計(三菱化學Analytech股份有限公司製、製品名「Loresta GP MCP-T610型」)，測定表面電阻率及體積電阻率。 Specifically, a test piece of 20 mm×40 mm size is allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity) to expose the surface of the layer to be measured of the test piece and used Low resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name "Loresta GP MCP-T610 type") to measure surface resistivity and volume resistivity.

表面電阻率為進行3次上述之測定，體積電阻率為進行5次上述之測定，表1及2中，為分別記載所測定之測定值的平均值。 The surface resistivity was measured three times as described above, and the volume resistivity was measured five times as described above. In Tables 1 and 2, the average values of the measured values are described.

又，測定黏著性導電層(X)單獨之表面電阻率及體積電阻率為，將由2片剝離薄片僅挾夾黏著性導電層(X)而得之層合體作為試驗片，去除該試驗片之一側的剝離薄片，對露出之黏著性導電層(X)之表面，測定該些之數值。 Furthermore, the surface resistivity and volume resistivity of the adhesive conductive layer (X) alone were measured, and the laminate obtained by sandwiching only the adhesive conductive layer (X) from two peeling sheets was used as a test piece, and the test piece was removed. On one side of the peeling sheet, the values of the exposed adhesive conductive layer (X) were measured.

又，測定非黏著性導電層單獨之表面電阻率及體積電阻率為，使用附有非黏著性導電層之基材作為試驗片，對該試驗片之非黏著性導電層之表面，測定該些之數值。 In addition, the surface resistivity and volume resistivity of the non-adhesive conductive layer alone were measured. Using the substrate with the non-adhesive conductive layer as the test piece, the surface of the non-adhesive conductive layer of the test piece was measured. Of the value.

此外，導電性黏著薄片之表面電阻率之測定為，將依實施例及比較例所製作之基材、非黏著性導電層、黏著性 導電層(X)，及剝離薄片，依此順序層合而得之導電性黏著薄片作為試驗片，將該試驗片之剝離薄片去除，對於露出之黏著性導電層(X)之表面，僅測定表面電阻率之值。 In addition, the measurement of the surface resistivity of the conductive adhesive sheet is based on the substrate, the non-adhesive conductive layer, and the adhesion prepared according to the examples and comparative examples. The conductive layer (X) and the peeling sheet, the conductive adhesive sheet laminated in this order is used as a test piece, the peeling sheet of the test piece is removed, and only the surface of the exposed adhesive conductive layer (X) is measured The value of surface resistivity.

製造例1 Manufacturing Example 1 (附有非黏著性導電層(Y-1)之基材的製作) (Fabrication of substrate with non-adhesive conductive layer (Y-1))

於作為基材使用之厚度50μm之聚苯二甲酸乙二醇酯(PET)薄膜(東麗股份有限公司製、商品名「Lumirror」、表面電阻率：1.18×1018Ω/□)上，塗佈聚噻吩之溶液(總研化學股份有限公司製、商品名「Verazol IW-103」)，形成乾燥後之厚度為2.4μm之塗佈膜，將該塗佈膜乾燥，製得附有含聚噻吩之非黏著性導電層(Y-1)之基材。 Coated with a 50 μm thick polyethylene terephthalate (PET) film (made by Toray Industries, Ltd., trade name "Lumirror", surface resistivity: 1.18×10 18 Ω/□) used as a substrate A solution of polythiophene (manufactured by Soken Chemical Co., Ltd. under the trade name "Verazol IW-103") was formed to form a coating film with a thickness of 2.4 μm after drying, and the coating film was dried to prepare Substrate for non-adhesive conductive layer (Y-1) of thiophene.

製造例2 Manufacturing Example 2 (附有非黏著性導電層(Y-2)之基材的製作) (Fabrication of substrate with non-adhesive conductive layer (Y-2))

調製含有相對於丙烯酸系水溶性聚合物(荒川化學工業股份有限公司製、商品名「Tamanori G-37」、聚丙烯酸)100質量份(固體成份)，聚(3,4-伸乙基二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT-PSS)之分散液(Agfa公司製、商品名「Orgacon S305」)10質量份(固體成份比)，及乙二醇10質量份之溶液。 It contains 100 parts by mass (solid content) of poly(3,4-ethylidene dioxygen) relative to 100 parts by mass (solid content) of acrylic water-soluble polymer (Arakawa Chemical Industry Co., Ltd., trade name "Tamanori G-37", polyacrylic acid) A solution of 10 parts by mass (solid component ratio) of a dispersion liquid of thiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) (manufactured by Agfa, trade name "Orgacon S305") and 10 parts by mass of ethylene glycol.

隨後，將與製造例1所使用之相同物品，塗佈於PET薄膜上，形成上述溶液乾燥後之厚度為1.0μm之塗佈膜，使該塗佈膜乾燥，得附有含PEDOT-PSS之非黏著性導電 層(Y-2)之基材。 Subsequently, the same article as used in Manufacturing Example 1 was coated on a PET film to form a coating film with a thickness of 1.0 μm after the above solution was dried, and the coating film was dried to obtain a PEDOT-PSS-containing coating. Non-adhesive conductive The substrate of layer (Y-2).

製造例3 Manufacturing Example 3 (附有非黏著性導電層(Y-3)之基材的製作) (Fabrication of substrate with non-adhesive conductive layer (Y-3))

相對於苯乙烯系樹脂(Kraton公司製、商品名「1726M」、SEBS)100質量份(固體成份)，添加多層碳奈米管(CNT)(Nanocyl公司製、商品名「NC7000」，詳細內容如後所述)10質量份(固體成份比)，使用加熱混練機(東洋精機製作所股份有限公司製，製品名「30C150」)，於100℃、50rpm之條件進行混練，製得複合物。 Multi-layer carbon nanotubes (CNT) (manufactured by Nanocyl, trade name "NC7000") are added to 100 parts by mass (solid content) of styrene resin (manufactured by Kraton, trade name "1726M", SEBS). Details are as follows: (Described later) 10 parts by mass (solid content ratio), using a heating kneading machine (manufactured by Toyo Seiki Co., Ltd., product name "30C150"), and kneading at 100°C and 50 rpm to obtain a composite.

隨後，使用與製造例1所使用之物為相同之PET薄膜，與厚度75μm之剝離薄片(琳德股份有限公司製、商品名「SP-PET751031」)挾夾上述複合物，使用熱押機(Tester產業股份有限公司製、製品名「SA-302」)，於130℃、10MPa之條件下進行10分鐘之熱擠押。熱擠押後，去除剝離薄片，製得附有含厚度100.0μm之SEBS及CNT(10質量份)之非黏著性導電層(Y-3)之基材。 Then, using the same PET film as that used in Production Example 1, the above-mentioned composite was sandwiched between a 75 μm-thick release sheet (manufactured by Linde Co., Ltd., trade name “SP-PET751031”), and a hot pressing machine ( Tester Industries Co., Ltd., product name "SA-302"), under the conditions of 130 ℃, 10MPa hot extrusion for 10 minutes. After hot extrusion, the peeling sheet was removed to prepare a substrate with a non-adhesive conductive layer (Y-3) containing SEBS and CNT (10 parts by mass) with a thickness of 100.0 μm.

製造例4 Manufacturing Example 4 (附有非黏著性導電層(Y-4)之基材之製作) (Fabrication of substrate with non-adhesive conductive layer (Y-4))

除將多層碳奈米管之添加量設定為「4質量份」以外，其他皆依製造例3相同方法般，製得含有厚度100.0μm之SEBS及CNT(4質量份)之附有非黏著性導電層(Y-4)之基材。 With the exception of setting the amount of multi-layer carbon nanotubes to "4 parts by mass", the same method as in Manufacturing Example 3 was used to prepare non-adhesive materials containing SEBS and CNT (4 parts by mass) with a thickness of 100.0 μm. Base material of conductive layer (Y-4).

本實施例及比較例中，除上述製造例1~4所製作之附有非黏著性導電層之基材以外，也使用以下的附有非黏著性導電層之基材。 In the present examples and comparative examples, in addition to the non-adhesive conductive layer-attached substrates produced in the above Production Examples 1 to 4, the following non-adhesive conductive layer-attached substrates were also used.

．「附有由ITO所形成之非黏著性導電層(Y-A)之基材」：商品名「ITO-聚苯二甲酸乙二醇酯」(尾池工業股份有限公司製)。為於厚度50μm之PET薄膜(表面電阻率：1.18×1018Ω/□)之單側面上，蒸鍍厚度1.6μm之ITO膜者。 . "Substrate with non-adhesive conductive layer (YA) formed of ITO": Trade name "ITO-polyethylene terephthalate" (made by Oike Industries Co., Ltd.). It is an ITO film with a thickness of 1.6 μm deposited on one side of a PET film (surface resistivity: 1.18×10 18 Ω/□) with a thickness of 50 μm.

．「附有由銅所形成之非黏著性導電層(Y-B)之基材」：商品名「NIKAFLEX」(Nikkan工業股份有限公司製)。為於厚度50μm之PET薄膜(表面電阻率：1.18×1018Ω/□)之單側面上，使用接著劑貼合厚度35.0μm之銅膜者。 . "Substrate with non-adhesive conductive layer (YB) formed of copper": Trade name "NIKAFLEX" (manufactured by Nikkan Industries Co., Ltd.). It is used to bond a copper film with a thickness of 35.0 μm on one side of a PET film (surface resistivity: 1.18×10 18 Ω/□) with a thickness of 50 μm using an adhesive.

．附有由鋁所形成之非黏著性導電層(Y-C)之基材：商品名「Metalumy#50」(東麗薄膜加工股份有限公司製。為於厚度50μm之PET薄膜(表面電阻率：1.18×1018Ω/□)之單側面上，蒸鍍厚度10.0μm之鋁膜者。 . Substrate with a non-adhesive conductive layer (YC) formed of aluminum: trade name "Metalumy#50" (manufactured by Toray Film Processing Co., Ltd.. PET film with a thickness of 50 μm (surface resistivity: 1.18× 10 18 Ω/□) On one side, an aluminum film with a thickness of 10.0 μm is deposited.

本實施例及比較例所使用之附有非黏著性導電層之基材的非黏著性導電層的各種物性，係如表1所示者。 Various physical properties of the non-adhesive conductive layer of the substrate with a non-adhesive conductive layer used in the examples and comparative examples are shown in Table 1.

Figure 104128147-A0202-12-0050-1
Figure 104128147-A0202-12-0050-1

實施例1~15、比較例1~8 Examples 1 to 15, Comparative Examples 1 to 8 (1)黏著性導電層(X)之形成 (1) Formation of adhesive conductive layer (X)

依表2所示種類及添加量(相對於黏著性樹脂100質量份(固體成份)之固體成份比)，將碳系填料(x2)添加於乙酸乙酯中，使用超音波洗淨機，以超音波(42kHz、125W)賦予振動1小時，預先製得固體成份濃度0.5質量%之碳系填料(x2)之分散液。 Add the carbon-based filler (x2) to ethyl acetate according to the types and addition amounts (solid content ratio relative to 100 parts by mass (solid content) of the adhesive resin) shown in Table 2 and use an ultrasonic cleaner to Ultrasonic wave (42kHz, 125W) was given vibration for 1 hour, and a dispersion of carbon-based filler (x2) with a solid content concentration of 0.5% by mass was prepared in advance.

其次、於表2所示種類之黏著性樹脂(x1)100質量份(固體成份)中，加入該碳系填料(x2)之分散液，配合必要時，再添加依表2所示種類及添加量(固體成份比)之交聯劑或黏著賦予劑。隨後，使用乙酸乙酯適度地稀釋，攪拌至均勻為止，製得黏著性組成物之溶液。 Next, add the dispersion of the carbon-based filler (x2) to 100 parts by mass (solid content) of the adhesive resin (x1) shown in Table 2 and add the types and additions shown in Table 2 if necessary. Amount (solid content ratio) of crosslinking agent or adhesion-imparting agent. Subsequently, dilute moderately with ethyl acetate and stir until uniform to prepare a solution of the adhesive composition.

隨後，將依上述方法所製得之黏著性組成物之溶液，塗佈於剝離薄片(琳德股份有限公司製、商品名「SP- PET381031」、厚度：38μm、表面經聚矽氧剝離處理之聚苯二甲酸乙二醇酯薄膜)之剝離處理面上，而形成塗佈膜，使其乾燥後形成塗佈層。 Then, apply the solution of the adhesive composition prepared by the above method to the peeling sheet (made by Linde Co., Ltd., trade name "SP- PET381031", thickness: 38 μm, polyethylene terephthalate film (polyethylene terephthalate film) whose surface has been subjected to silicone peeling treatment, to form a coating film, which was dried to form a coating layer.

其次，於該塗佈層上，在另外層合與上述為相同種類之剝離薄片，於23℃、50%RH(相對濕度)之環境下靜置14小時後，使塗佈層處交聯，而製得表2所示厚度之由2片剝離薄片僅挾夾黏著性導電層(X)而得之層合體。 Next, on this coating layer, a release sheet of the same type as above was laminated separately, and after allowing it to stand for 14 hours in an environment of 23°C and 50% RH (relative humidity), the coating layer was crosslinked. A laminate obtained by sandwiching the adhesive conductive layer (X) from the two peeling sheets with the thickness shown in Table 2 was prepared.

(2)導電性黏著薄片之製作 (2) Fabrication of conductive adhesive sheet

實施例1~15及比較例7~8中，為將上述層合體之一側的剝離薄片去除而露出之黏著性導電層(X)，與表2所示種類之附有非黏著性導電層的非黏著性導電層貼合，以製作導電性黏著薄片。 In Examples 1 to 15 and Comparative Examples 7 to 8, the adhesive conductive layer (X) exposed by removing the peeling sheet on one side of the above-mentioned laminate is the same as the type shown in Table 2 with a non-adhesive conductive layer The non-adhesive conductive layer is bonded to make a conductive adhesive sheet.

比較例1~6中，為將上述層合體之一側的剝離薄片去除而露出之黏著性導電層(X)，與厚度50μm之PET薄膜(東麗股份有限公司製、商品名「Lumirror」)貼合，以製作導電性黏著薄片。 In Comparative Examples 1 to 6, the adhesive conductive layer (X) exposed by removing the release sheet on one side of the above-mentioned laminate, and a PET film with a thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror”) Laminate to make conductive adhesive sheet.

實施例16 Example 16 (1)黏著性導電層(X)之形成 (1) Formation of adhesive conductive layer (X)

對於苯乙烯系樹脂(東洋ADL股份有限公司製、商品名「P-907Y」，詳細內容如後所述)100質量份(固體成份)，依表2所示添加量(固體成份比)添加多層碳奈米管(CNT)(Nanocyl公司製、商品名「NC7000」，詳細內容如 後所述)，使用加熱混練機(東洋精機製作所股份有限公司製，製品名「30C150」)，於100℃、50rpm之條件進行混練，製得複合物。 For styrene-based resin (manufactured by Toyo ADL Co., Ltd., trade name "P-907Y", details will be described later) 100 parts by mass (solid content), multi-layers are added according to the addition amount (solid content ratio) shown in Table 2 Carbon Nanotube (CNT) (manufactured by Nanocyl Corporation, trade name "NC7000", details are as follows (Described later), using a heating and kneading machine (manufactured by Toyo Seiki Co., Ltd., product name "30C150"), kneading was performed under the conditions of 100°C and 50 rpm to obtain a composite.

隨後，使用2片剝離薄片(琳德股份有限公司製、商品名「SP-PET751031」、厚度：75μm)挾夾上述複合物，使用熱押機(Tester產業股份有限公司製、製品名「SA-302」)，於130℃、10MPa之條件下進行10分鐘之熱擠押，製得由2片剝離薄片僅挾夾黏著性導電層(X)而得之層合體。 Subsequently, the above compound was sandwiched between two peeling sheets (manufactured by Linde Co., Ltd., trade name "SP-PET751031, thickness: 75 μm), and a hot pressing machine (manufactured by Tester Industries Co., Ltd., product name "SA-" 302"), under the conditions of 130°C and 10MPa for 10 minutes of hot extrusion, a laminate obtained by sandwiching only the adhesive conductive layer (X) from two peeling sheets.

(2)導電性黏著薄片之製作 (2) Fabrication of conductive adhesive sheet

將含有去除上述層合體之一側的剝離薄片後所露出之苯乙烯系樹脂的黏著性導電層(X)，與附有非黏著性導電層(Y-2)之基材的非黏著性導電層貼合，以製作導電性黏著薄片。 The non-adhesive conductive material containing the adhesive conductive layer (X) of the styrene resin exposed after removing the peeling sheet on one side of the laminate and the substrate with the non-adhesive conductive layer (Y-2) The layers are laminated to make a conductive adhesive sheet.

表2所示實施例及比較例所使用之黏著性組成物中之各成份的詳細內容，係如以下所示。 The details of each component in the adhesive composition used in the examples and comparative examples shown in Table 2 are shown below.

(黏著性樹脂(x1)) (Adhesive resin (x1))

．「丙烯酸系樹脂」：n-丁基丙烯酸酯(BA)及丙烯酸(AA)所形成之丙烯酸系聚合物之乙酸甲酯溶液、BA/AA=90.0/10.0(質量份)、Mw：70萬、固體成份濃度：33.6質量%。 . "Acrylic resin": methyl acetate solution of acrylic polymer formed by n-butyl acrylate (BA) and acrylic acid (AA), BA/AA=90.0/10.0 (parts by mass), Mw: 700,000, Solid component concentration: 33.6% by mass.

．「胺基甲酸酯系樹脂」：LION SPECIALTY CHEMICALS股份有限公司製、商品名「US-902A」、胺 基甲酸酯系樹脂、Mw=56,000。 . "Carbamate Resin": LION SPECIALTY CHEMICALS Co., Ltd., trade name "US-902A", amine Carbamate resin, Mw=56,000.

．「PIB系樹脂」：Mw34萬之PIB系樹脂(BASF公司製、商品名「Oppanol B50」)90.9質量份(固體成份比)，及、Mw20萬之PIB系樹脂(BASF公司製、商品名「Oppanol B30」)9.1質量份(固體成份比)之混合樹脂。 . "PIB-based resin": 90.9 parts by mass (solid component ratio) of PIB-based resin (manufactured by BASF Corporation, trade name "Oppanol B50") of Mw340,000, and PIB-based resin (manufactured by BASF Corporation, trade name "Oppanol" of Mw200,000 B30") 9.1 parts by mass (solid content ratio) of mixed resin.

．「苯乙烯系樹脂」：含有東洋ADL股份有限公司製、商品名「P-907Y」、SEBS及SEB之混合樹脂、SEBS及SEB之合計含量=30質量%、軟化點=112℃。 . "Styrene-based resin": a mixed resin containing Toyo ADL Co., Ltd., trade name "P-907Y", SEBS and SEB, total content of SEBS and SEB = 30% by mass, softening point = 112°C.

(碳系填料(x2)) (Carbon filler (x2))

．「NC7000」：商品名、Nanocyl公司製、圓筒狀之多層碳奈米管、平均長徑比(H/L)：150、長邊之長度(H)：1.5μm、短邊之長度(L)：10nm。 . "NC7000": trade name, manufactured by Nanocyl Corporation, cylindrical multilayer carbon nanotube, average aspect ratio (H/L): 150, length of long side (H): 1.5 μm, length of short side (L ): 10 nm.

．「AMC」：商品名、宇部興產股份有限公司製、圓筒狀之多層碳奈米管、平均長徑比(H/L)：100、長邊之長度(H)：1.1μm、短邊之長度(L)：11nm。 . "AMC": trade name, manufactured by Ube Kosei Co., Ltd., cylindrical multilayer carbon nanotube, average aspect ratio (H/L): 100, length of long side (H): 1.1 μm, short side Length (L): 11nm.

(交聯劑) (Crosslinking agent)

．「Coronate L」：商品名、東曹股份有限公司製、異氰酸酯系交聯劑、固體成份濃度：75質量%。 . "Coronate L": trade name, manufactured by Tosoh Corporation, isocyanate-based crosslinking agent, solid content concentration: 75% by mass.

(黏著賦予劑) (Adhesion-imparting agent)

．「Alcone P-125」：商品名、荒川化學工業股份有限公司製、氫化石油樹脂、軟化點：125℃。 . "Alcone P-125": trade name, manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point: 125°C.

．「YS Polystar K125」：商品名、Yasuhara化學股份 有限公司製、萜烯酚系樹脂、軟化點：125℃。 . "YS Polystar K125": trade name, Yasuhara Chemical Co., Ltd. Co., Ltd., terpene phenol resin, softening point: 125℃.

(其他成份) (Other ingredients)

．作為苯乙烯系樹脂使用之「P-907Y」中，所含的(x1)成份以外的其他成份(黏著賦予劑、可塑劑等)之混合物。 . A mixture of other components (adhesion-imparting agent, plasticizer, etc.) other than the (x1) component contained in "P-907Y" used as a styrene resin.

實施例17~23 Examples 17~23

將市售品之導電性雙面膠帶(日新EM股份有限公司製、商品名「導電性碳雙面膠帶7311」、具有含丙烯酸系樹脂及碳粉的黏著劑層被2片剝離薄片所挾夾之構成的導電性黏著薄片)的黏著劑層，作為黏著性導電層(X)使用。 A commercially available double-sided adhesive tape (manufactured by Nissin EM Co., Ltd. under the trade name "conductive carbon double-sided tape 7311") and an adhesive layer containing an acrylic resin and carbon powder are held by two release sheets The adhesive layer of the conductive adhesive sheet composed of the clip is used as the adhesive conductive layer (X).

將由上述市售品之導電性雙面膠帶的一側之剝離薄片去除所露出之黏著劑層(黏著性導電層(X))，與表3所示種類之附有非黏著性導電層(Y-1)之基材或附有非黏著性導電層(Y-4)之基材的非黏著性導電層貼合，以製作導電性黏著薄片。 Remove the exposed adhesive layer (adhesive conductive layer (X)) from the release sheet on the side of the conductive double-sided tape of the above-mentioned commercially available product, and the non-adhesive conductive layer (Y -1) The substrate or the non-adhesive conductive layer of the substrate with a non-adhesive conductive layer (Y-4) is bonded to make a conductive adhesive sheet.

比較例9 Comparative Example 9

將上述市售品之導電性雙面膠帶的一側之露出剝離薄片的黏著劑層(黏著性導電層(X))，與厚度50μm之PET薄膜(東麗股份有限公司製、商品名「Lumirror」)貼合，以製作導電性黏著薄片。 The adhesive layer (adhesive conductive layer (X)) on the side of the conductive double-sided adhesive tape of the above-mentioned commercially available product exposed to a peeling sheet, and a PET film (manufactured by Toray Co., Ltd. under the trade name "Lumirror" with a thickness of 50 μm) ") Lamination to make a conductive adhesive sheet.

以上方式所製得之導電性黏著薄片，依上述方法為基準所測定之各種物性值係如表2及表3所示。 The various physical property values of the conductive adhesive sheet prepared in the above manner based on the above method are shown in Table 2 and Table 3.

Figure 104128147-A0202-12-0056-2
Figure 104128147-A0202-12-0056-2

Figure 104128147-A0202-12-0057-3
Figure 104128147-A0202-12-0057-3

由表2及表3得知，實施例1~23之導電性黏著薄片，於具有良好黏著力的同時，與比較例1~9之導電性黏著薄片相比較時，確認其表面電阻率較低，且具有優良之抗靜電性及導電性。 It is known from Tables 2 and 3 that the conductive adhesive sheets of Examples 1 to 23, while having good adhesion, were compared with the conductive adhesive sheets of Comparative Examples 1 to 9 to confirm that the surface resistivity was lower , And has excellent antistatic properties and conductivity.

[產業上之利用性] [Industrial utility]

本發明之導電性黏著薄片，於具有良好黏著力的同時，因具有低表面電阻率，故具有優良之抗靜電性及導電性。 The conductive adhesive sheet of the present invention has good adhesion and low surface resistivity, so it has excellent antistatic properties and conductivity.

因此，本發明之導電性黏著薄片，適合作為例如，放置電腦、通信機器等電子機器的容器之電磁遮蔽材料、電氣零件等接地線，甚至因摩擦靜電等靜電所產生之火花的抗發火材料等的構件所使用的接合構件。 Therefore, the conductive adhesive sheet of the present invention is suitable as, for example, an electromagnetic shielding material for a container for placing electronic equipment such as computers and communication equipment, a grounding wire for electrical parts, and even an anti-ignition material for sparks generated by static electricity such as friction and static electricity. The joint member used by the member.

1A、1B、2A、2B‧‧‧導電性黏著薄片 1A, 1B, 2A, 2B ‧‧‧ conductive adhesive sheet

11‧‧‧黏著性導電層(X) 11‧‧‧Adhesive conductive layer (X)

11a‧‧‧第一黏著性導電層(X-I) 11a‧‧‧The first adhesive conductive layer (X-I)

11b‧‧‧第二黏著性導電層(X-II) 11b‧‧‧Second adhesive conductive layer (X-II)

12‧‧‧非黏著性導電層(Y) 12‧‧‧non-adhesive conductive layer (Y)

12a‧‧‧第一非黏著性導電層(Y-I) 12a‧‧‧The first non-adhesive conductive layer (Y-I)

12b‧‧‧第二非黏著性導電層(Y-II) 12b‧‧‧Second non-adhesive conductive layer (Y-II)

13‧‧‧基材 13‧‧‧ Base material

14‧‧‧剝離薄片 14‧‧‧Peeling flakes

14a、14b‧‧‧剝離薄片 14a, 14b ‧‧‧ peel sheet

21‧‧‧二層體 21‧‧‧two-layer body

21a‧‧‧第一之二層體 21a‧‧‧The first two-layer body

21b‧‧‧第二之二層體 21b‧‧‧Second layer

Claims (16)

一種導電性黏著薄片，其為至少具有黏著性導電層(X)及非黏著性導電層(Y)之導電性黏著薄片，其特徵為，黏著性導電層(X)單獨之表面電阻率(ρSX)之值為1.0×102~1.0×1010Ω/□，非黏著性導電層(Y)單獨之表面電阻率(ρSY)之值為1.0×10-2~1.0×105Ω/□，且，滿足式(1)：0<log10(ρSX/ρSY)≦6.0。 A conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), characterized in that the surface conductivity of the adhesive conductive layer (X) alone (ρ SX ) is 1.0×10 2 ~1.0×10 10 Ω/□, and the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 -2 ~1.0×10 5 Ω/ □, and satisfy the formula (1): 0<log 10 (ρ SX /ρ SY )≦6.0. 如請求項1記載之導電性黏著薄片，其中，黏著性導電層(X)之厚度(tX)為1~1200μm。 The conductive adhesive sheet as described in claim 1, wherein the thickness (t X ) of the adhesive conductive layer ( X ) is 1 to 1200 μm. 如請求項1或2記載之導電性黏著薄片，其中，非黏著性導電層(Y)之厚度(tY)為0.01~200μm。 The conductive adhesive sheet according to claim 1 or 2, wherein the thickness (t Y ) of the non-adhesive conductive layer ( Y ) is 0.01 to 200 μm. 如請求項1記載之導電性黏著薄片，其中，黏著性導電層(X)為，由含有黏著性樹脂(x1)及碳系填料(x2)之黏著性組成物所形成之層。 The conductive adhesive sheet according to claim 1, wherein the adhesive conductive layer (X) is a layer formed of an adhesive composition containing an adhesive resin (x1) and a carbon-based filler (x2). 如請求項4記載之導電性黏著薄片，其中，前述黏著性組成物中所含之黏著性樹脂(x1)為，含有由丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、苯乙烯系樹脂、聚酯系樹脂，及聚烯烴系樹脂所成之群所選出之1種以上的黏著性樹脂。 The conductive adhesive sheet according to claim 4, wherein the adhesive resin (x1) contained in the adhesive composition contains acrylic resin, urethane resin, rubber resin, styrene More than one type of adhesive resin selected from the group consisting of resins, polyester resins, and polyolefin resins. 如請求項4或5記載之導電性黏著薄片，其中，前述黏著性組成物中所含有之碳系填料(x2)的平均長徑比為1.5以上。 The conductive adhesive sheet according to claim 4 or 5, wherein the average aspect ratio of the carbon-based filler (x2) contained in the adhesive composition is 1.5 or more. 如請求項4或5記載之導電性黏著薄片，其中，前述黏著性組成物中所含之碳系填料(x2)之含量，相對於黏著性樹脂(x1)100質量份，為0.01~15質量份。 The conductive adhesive sheet according to claim 4 or 5, wherein the content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass relative to 100 parts by mass of the adhesive resin (x1) Copies. 如請求項4或5記載之導電性黏著薄片，其中，前述黏著性組成物中所含之碳系填料(x2)為碳奈米材料。 The conductive adhesive sheet according to claim 4 or 5, wherein the carbon-based filler (x2) contained in the adhesive composition is a carbon nanomaterial. 如請求項1或2記載之導電性黏著薄片，其中，非黏著性導電層(Y)為，含有由導電性高分子、碳系填料，及金屬氧化物所成之群所選出之1種以上的導電材料之層。 The conductive adhesive sheet as described in claim 1 or 2, wherein the non-adhesive conductive layer (Y) is one or more selected from the group consisting of a conductive polymer, a carbon-based filler, and a metal oxide Of conductive material. 如請求項1或2記載之導電性黏著薄片，其中，非黏著性導電層(Y)為，含有由聚噻吩、PEDOT-PSS、碳奈米材料，及ITO(氧化銦錫)所成之群所選出之1種以上的導電材料之層。 The conductive adhesive sheet as described in claim 1 or 2, wherein the non-adhesive conductive layer (Y) is composed of polythiophene, PEDOT-PSS, carbon nanomaterials, and ITO (indium tin oxide) A layer of more than one selected conductive material. 如請求項9記載之導電性黏著薄片，其中，非黏著性導電層(Y)中所含之導電材料的密度為0.8~2.5g/cm3。 The conductive adhesive sheet according to claim 9, wherein the density of the conductive material contained in the non-adhesive conductive layer (Y) is 0.8 to 2.5 g/cm 3 . 如請求項1或2記載之導電性黏著薄片，其為具有依基材、非黏著性導電層(Y)，及黏著性導電層(X)之順序層合之構成內容。 The conductive adhesive sheet as described in claim 1 or 2, which has a constitution in which a substrate, a non-adhesive conductive layer (Y), and an adhesive conductive layer (X) are laminated in this order. 如請求項12記載之導電性黏著薄片，其於基材之兩面上，分別具有由非黏著性導電層(Y)及黏著性導電層(X)所構成之二層體。 The conductive adhesive sheet according to claim 12 has two layers composed of a non-adhesive conductive layer (Y) and an adhesive conductive layer (X) on both sides of the substrate. 如請求項12記載之導電性黏著薄片，其中，前述基材為表面電阻率為1.0×1014Ω/□以上之絕緣性基材。 The conductive adhesive sheet according to claim 12, wherein the substrate is an insulating substrate having a surface resistivity of 1.0×10 14 Ω/□ or more. 如請求項1或2記載之導電性黏著薄片，其為具 有，黏著性導電層(X)及非黏著性導電層(Y)所構成之二層體被2枚剝離薄片所挾夾之構成內容。 The conductive adhesive sheet as described in claim 1 or 2 is Yes, the two-layer body composed of the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) is sandwiched by two peeling sheets. 如請求項1或2記載之導電性黏著薄片，其為具有，依第一黏著性導電層(X-I)、非黏著性導電層(Y)，及第二黏著性導電層(X-II)之順序層合而得之三層體被2枚剝離薄片所挾夾之構成內容。 The conductive adhesive sheet as described in claim 1 or 2, which is composed of a first adhesive conductive layer (XI), a non-adhesive conductive layer (Y), and a second adhesive conductive layer (X-II) The three-layered body laminated in sequence is sandwiched by two peeling sheets.
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