TWI677555B - Conductive adhesive sheet - Google Patents

Conductive adhesive sheet Download PDF

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Publication number
TWI677555B
TWI677555B TW104128148A TW104128148A TWI677555B TW I677555 B TWI677555 B TW I677555B TW 104128148 A TW104128148 A TW 104128148A TW 104128148 A TW104128148 A TW 104128148A TW I677555 B TWI677555 B TW I677555B
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Taiwan
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adhesive
conductive layer
conductive
resin
mass
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TW104128148A
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Chinese (zh)
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TW201621012A (en
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植田貴洋
Takahiro Ueda
大高翔
Syo OTAKA
松下大雅
Taiga Matsushita
松下香織
Kaori Matsushita
宮田壮
Sou Miyata
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日商琳得科股份有限公司
Lintec Corporation
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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，其中，黏著性導電層(X)單獨之體積電阻率(ρVX)之值為1.0×100~1.0×108Ω‧cm，非黏著性導電層(Y)單獨之體積電阻率(ρVY)之值為1.0×10-4~1.0×106Ω‧cm，且，黏著性導電層(X)之厚度(tX)與非黏著性導電層(Y)之厚度(tY)之厚度比〔tx/tY〕為20000以下。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 present 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), wherein the volume resistivity of the adhesive conductive layer (X) alone ( The value of ρ VX ) is 1.0 × 10 0 ~ 1.0 × 10 8 Ω‧cm, and the value of the volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone is 1.0 × 10 -4 ~ 1.0 × 10 6 Ω ‧Cm, and the thickness ratio [t x / t Y ] of the thickness (t X ) of the adhesive conductive layer (X) to the thickness (t Y ) of the non-adhesive conductive layer (Y) is 20,000 or less. The conductive adhesive sheet, while having good adhesion, 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, various types of bonding such as electromagnetic shielding materials for containers containing electronic equipment such as computers and communication equipment, grounding wires for electrical parts, and even fire-resistant materials such as sparks generated by static electricity such as frictional static electricity have been used. 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 conductive properties of metal powders such as copper powder, silver powder, nickel powder, and aluminum powder are often used. The substance is dispersed in an 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 using at least one of a carbon nanotube and a carbon microcoil dispersed as a conductive substance in the adhesive, and a conductive adhesive using the conductive adhesive. Flakes and more.

[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 brought into 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 substance 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, if the content of the conductive substance in the adhesive layer is reduced for the purpose of improving the adhesive force, the electrical conductivity of the adhesive layer will be reduced, and a problem that cannot be taken into account will occur.

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 insufficient problems in terms of simultaneously improving adhesion and conductivity.

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 having excellent adhesive force and excellent antistatic property and electrical 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，再將黏著性導電層及非黏著性導電層的各個單獨體積電阻率設定於特定之範圍，且，將該2層之厚度比調整至特定範圍而得之導電性黏著 薄片時，即可解決上問題，因而完成本發明。 The inventors have found that they have at least an adhesive conductive layer and a non-adhesive conductive layer as the constituent content, and then set the individual volume resistivity of each of the adhesive conductive layer and the non-adhesive conductive layer to a specific range. Conductive adhesion obtained by adjusting the thickness ratio of two layers to a specific range The above problem can be solved when the sheet is thinned, thus completing the present invention.

即，本發明為，提供下述〔1〕~〔16〕者。 That is, this invention provides the following [1]-[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)單獨之體積電阻率(ρVX)之值為1.0×100~1.0×108Ω‧cm，非黏著性導電層(Y)單獨之體積電阻率(ρVY)之值為1.0×10-4~1.0×106Ω‧cm，且，黏著性導電層(X)之厚度(tX)與非黏著性導電層(Y)之厚度(tY)之厚度比〔tx/tY〕為20000以下。 [1] A conductive adhesive sheet is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), wherein the volume resistivity of the adhesive conductive layer (X) alone ( The value of ρ VX ) is 1.0 × 10 0 to 1.0 × 10 8 Ω‧cm, and the value of the volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone is 1.0 × 10 -4 to 1.0 × 10 6 Ω ‧Cm, and the thickness ratio [t x / t Y ] of the thickness (t X ) of the adhesive conductive layer (X) to the thickness (t Y ) of the non-adhesive conductive layer (Y) is 20,000 or less.

〔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 according to the above [1], 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 according to the above [1] or [2], 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 the above [1] to [3], wherein the adhesive conductive layer (X) is composed of an adhesive resin (x1) and a carbon-based filler (x2). A layer formed by an 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 according to the above [4], wherein the adhesive resin (x1) contained in the adhesive composition is composed of an acrylic resin, a urethane resin, and a rubber-based resin. One or more adhesive resins selected from the group consisting of resin, styrene resin, polyester resin, and polyolefin resin.

〔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 according to the above [4] or [5], 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 the above [4] to [6], 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 the above [4] to [7], 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 according to any one of the above [1] to [8], wherein the non-adhesive conductive layer (Y) contains a conductive polymer, a carbon-based filler, and a metal oxide A layer of one or more conductive materials selected from the formed 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 according to any one of the above [1] to [9], wherein the non-adhesive conductive layer (Y) contains polythiophene, PEDOT-PSS, a carbon nano material, and A layer of one or more conductive materials selected from the group consisting 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 according to the above [9] or [10], 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 is an ordered layer having a substrate, a non-adhesive conductive layer (Y), and an adhesive conductive layer (X). The combined 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 according to the above [12], which has a two-layer body 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1.0×1014Ω/□以上之絕緣性基材。 [14] The conductive adhesive sheet according to the above [12] or [13], 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 according to any one of the above [1] to [11], which is a two-layer body composed of an adhesive conductive layer (X) and a non-adhesive conductive layer (Y). The structure of 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 sequentially laminating the adhesive conductive layer (X-II) is constituted 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, while having good adhesion, also has excellent antistatic properties and electrical 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‧‧‧ substrate

14‧‧‧剝離薄片 14‧‧‧ peeling sheet

21‧‧‧二層體 21‧‧‧Layer

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

21b‧‧‧第二之二層體 21b‧‧‧Second Layer

22‧‧‧三層體 22‧‧‧Trilayer

[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] The constitutional content of one of the preferable 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。 [Figure 2] Structure of one of the preferred aspects of the conductive adhesive sheet of the present invention The content is a cross-sectional view of a conductive adhesive sheet without a substrate.

[實施發明之形態] [Form of Implementing Invention]

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, the "mass average molecular weight (Mw)" is a value converted into a standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, a 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" means a user who uses 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 a conductive adhesive sheet" means the surface resistivity measured from the surface side of the adhesive conductive layer (X) which a conductive adhesive sheet has, without being specifically limited.

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 the present invention, the values of surface resistivity and volume resistivity of each layer are values measured using JIS K 7194 as a reference, and specifically, they are values measured according to the method 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 electrical conductivity can be improved. As a result, the adhesive conductive layer (X) does not need to contain a large amount of carbon-based filler, so 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 the "adhesive conductive layer (X)" and the "non-adhesive conductive layer (Y)" is to distinguish the presence or absence of adhesion, and the presence or absence of adhesion, as a probe using the surface of each conductive layer. The peak top value of the probe tack is used for judgment.

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 test value of the probe test on the surface of the target conductive layer is 0.1N or more, the conductive layer is judged to have adhesiveness, 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 conductive layer as the object does not reach 0.1 N, the conductive layer is judged as 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。 In addition, the peak value of the probe test on the surface of the target conductive layer is a value set in accordance with JIS Z 0237 (1991) as a reference, and specifically, a value measured in accordance with a method described in the examples 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。 The conductive adhesive sheet of the present invention is not particularly limited when it includes at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), and it may have layers other 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 have a structure in which another layer is provided between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), but the conductive adhesion is reduced. From the viewpoints of surface resistivity of the sheet, improvement of antistatic property, and electrical conductivity, it is preferable that the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) are 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 shows a preferred state of the conductive adhesive sheet of the present invention. One of the constituents is a cross-sectional view of 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。 In one aspect of the present invention, the conductive adhesive sheet includes, as shown in FIG. 1 (a), a substrate 13, a non-adhesive conductive layer (Y) 12, and an adhesive conductive layer (X). The conductive adhesive sheet 1A and the like obtained in the constitution of 11 were obtained. The conductive adhesive sheet 1A has a two-layer body 21 composed of a non-adhesive conductive layer (Y) 12 and an adhesive conductive layer (X) 11 on one side of a substrate.

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。 For the configuration of the conductive adhesive sheet 1A, the release 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。 In addition, the conductive adhesive sheet according to one aspect of the present invention may have non-adhesive conductive layers (Y) on both sides of the substrate, as shown in FIGS. 1 (c) and (d), for example. 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) has a first non-adhesive conductive layer (YI) 12a and a first adhesive conductive layer (XI) on a surface of 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. ) 11b is a second two-layer body 21b.

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 in which the conductive adhesive sheet 2A is provided on the first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (X). -II) 11b, respectively The structure of the laminated release sheet 14a, 14b.

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。 In addition, FIG. 2 is a cross-sectional view of the constitution of one of the preferable aspects of the conductive adhesive sheet of the present invention, which is a conductive adhesive sheet without a base material.

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 conductive adhesive sheet without a substrate. Specifically, as shown in FIG. 2 (a), it has an adhesive conductive layer (X) 11 and a non-adhesive layer. The two-layered body 21 made of the conductive layer (Y) 12 is a conductive adhesive sheet 3 made of two sandwiched release sheets 14a and 14b 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。 In addition, 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 obtained by laminating the second adhesive conductive layer (X-II) 11b in this order may be a conductive adhesive sheet 4 formed by sandwiching two release sheets 14a and 14b.

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 one aspect of the present invention having a structure other than the above, for example, one side of which is a release sheet having both sides subjected to a release treatment, has an adhesive conductive layer (X) and a non-adhesive conductive layer (Y). The formed two-layer body is a conductive adhesive sheet having a configuration obtained by rolling in a roll shape with the adhesive conductive layer (X) as an appearance.

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 formed of the same adhesive composition or different adhesive compositions. Layers are also available.

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 (Y-I) 12a and the second non-adhesive conductive layer (Y-II) 12b may also be made of the same material. The formed layer may be a layer formed of a different forming material.

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。 In addition, in the present invention, the structures of the first adhesive conductive layer (XI) and the second adhesive conductive layer (X-II) are the same as those of the adhesive conductive layer (X), and the first non-adhesive conductive layer (YI) ) And the second non-adhesive conductive layer (Y-II) have the same configuration 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) has adhesiveness (the value of the peak top of the above probe test is 0.1N or more) and has electrical conductivity (the individual volume resistivity (ρ VX ) of the layer is 1.0 × 10 8 Ω ‧Cm or less).

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 non-adhesive layer (the peak value of the above-mentioned probe test is less than 0.1N) and has conductivity (the 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)單獨之體積電阻率(ρVX)為，1.0×100~1.0×108Ω‧cm，較佳為1.0×100~1.0×106Ω‧cm、更佳為1.0×100~1.0×105Ω‧cm、特佳為1.0×100~1.0×104Ω‧cm。 In the present invention, the volume resistivity (ρ VX ) of the adhesive conductive layer (X) alone is 1.0 × 10 0 to 1.0 × 10 8 Ω‧cm, preferably 1.0 × 10 0 to 1.0 × 10 6 Ω‧cm , More preferably 1.0 × 10 0 to 1.0 × 10 5 Ω‧cm, and particularly preferably 1.0 × 10 0 to 1.0 × 10 4 Ω‧cm.

為使體積電阻率(ρVX)未達1.0×100Ω‧cm，因必須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。 In order to make the volume resistivity (ρ VX ) less than 1.0 × 10 0 Ω · cm, it is necessary to contain a large amount of conductive material, so it is easy to cause the adhesive force of the adhesive conductive layer (X) to decrease, and it is also not economical. good.

另一方面，體積電阻率(ρVX)超過1.0×108Ω‧cm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 volume resistivity (ρ VX ) exceeds 1.0 × 10 8 Ω · cm, even if a non-adhesive conductive layer (Y) is provided, it is extremely difficult to find the effect of reducing the surface resistivity of the conductive adhesive sheet.

又，非黏著性導電層(Y)單獨之體積電阻率(ρVY)為，1.0×10-4~1.0×106Ω‧cm，較佳為1.0×10-4~ 1.0×104Ω‧cm、更佳為1.0×10-4~1.0×103Ω‧cm、特佳為1.0×10-4~1.0×102Ω‧cm、特較佳為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 1.0 × 10 -4 to 1.0 × 10 6 Ω‧cm, preferably 1.0 × 10 -4 to 1.0 × 10 4 Ω‧ cm, more preferably 1.0 × 10 -4 to 1.0 × 10 3 Ω‧cm, particularly preferably 1.0 × 10 -4 to 1.0 × 10 2 Ω‧cm, particularly preferably 1.0 × 10 -4 to 1.0 × 10 1 Ω‧cm, preferably 1.0 × 10 -4 ~ 1.0 × 10 0 Ω‧cm.

即使設有體積電阻率(ρVY)未達1.0×10-4Ω‧cm，或超過1.0×106Ω‧cm之非黏著性導電層(Y)時，所得之導電性黏著薄片之表面電阻率也不容易發現降低之效果。 Even when a non-adhesive conductive layer (Y) having a volume resistivity (ρ VY ) of less than 1.0 × 10 -4 Ω‧cm or exceeding 1.0 × 10 6 Ω‧cm is provided, the surface resistance of the obtained conductive adhesive sheet is It is not easy to find the effect of reduction.

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 of efficiently reducing the surface resistivity of the conductive adhesive sheet, the volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone can be used to conduct electricity more adhesively. The volume resistivity (ρ VX ) of the layer (X) alone is preferably a smaller value.

黏著性導電層(X)單獨之表面電阻率(ρSX)，就具有良好黏著力、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1.0×102~1.0×1010Ω/□、更佳為1.0×102~1.0×108Ω/□、特佳為1.0×102~1.0×107Ω/□、最佳為1.0×102~1.0×106Ω/□。 The surface resistivity (ρ SX ) of the adhesive conductive layer (X) alone is preferably 1.0 × 10 2 to 1.0 × 10 10 from the viewpoint of a conductive adhesive sheet having good adhesion and effectively reducing the surface resistivity. Ω / □, more preferably 1.0 × 10 2 to 1.0 × 10 8 Ω / □, particularly preferred is 1.0 × 10 2 to 1.0 × 10 7 Ω / □, and most preferably 1.0 × 10 2 to 1.0 × 10 6 Ω / □.

另一方面，非黏著性導電層(Y)單獨之表面電阻率(ρSY)，就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1.0×10-2~1.0×108Ω/□、更佳為1.0×10-2~1.0×107Ω/□、特佳為1.0×10-2~1.0×106Ω/□、特較佳為1.0×10-2~1.0×105Ω/□、最佳為1.0×10-2~1.0×104Ω/□、最特佳為1.0×10-2~1.0×103Ω/□。 On the other hand, the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone can effectively reduce the surface resistivity of the conductive adhesive sheet, and is preferably 1.0 × 10 -2 to 1.0 × 10 8 Ω / □, more preferably 1.0 × 10 -2 to 1.0 × 10 7 Ω / □, particularly preferred is 1.0 × 10 -2 to 1.0 × 10 6 Ω / □, particularly preferred is 1.0 × 10 -2 ~ 1.0 × 10 5 Ω / □, preferably 1.0 × 10 -2 to 1.0 × 10 4 Ω / □, and most preferably 1.0 × 10 -2 to 1.0 × 10 3 Ω / □.

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)單獨之表面電阻率(ρSY)，以較黏著性導電層(X)單獨之表 面電阻率(ρSX)為更小之值為佳。 In addition, in one aspect of the present invention, the surface resistivity of the conductive adhesive sheet can be effectively reduced, and the surface resistivity (ρ SY ) of the non-adhesive conductive layer (Y) alone can be used to conduct electricity more adhesively. The surface resistivity (ρ SX ) of the layer (X) alone is preferably a smaller value.

又，本發明中，黏著性導電層(X)之厚度(tX)與非黏著性導電層(Y)之厚度(tY)之厚度比〔tX/tY〕，為20000以下，較佳為10000以下，更佳為5000以下，更較佳為1000以下，特佳為500以下，特較佳為400以下，最佳為250以下。 In addition, in the present invention, the thickness ratio [t X / t Y ] of the thickness (t X ) of the adhesive conductive layer (X) to the thickness (t Y ) of the non-adhesive conductive layer (Y) is 20,000 or less. It is preferably 10,000 or less, more preferably 5,000 or less, more preferably 1,000 or less, particularly preferably 500 or less, particularly preferably 400 or less, and most preferably 250 or less.

該厚度比超過20000時，因相對於黏著性導電層(X)，非黏著性導電層(Y)之厚度並不充分，故即使設有非黏著性導電層(Y)，以不容易充分地降低導電性黏著薄片之表面電阻率。 When the thickness ratio exceeds 20,000, the thickness of the non-adhesive conductive layer (Y) is insufficient with respect to the adhesive conductive layer (X). Therefore, even if the non-adhesive conductive layer (Y) is provided, it is not easy to sufficiently Reduce the surface resistivity of the conductive adhesive sheet.

又，該厚度比之下限值，並未有特別之限制，就可產生良好的黏著力之觀點，該厚度比〔tX/tY〕，較佳為0.01以上、更佳為0.1以上、特佳為0.2以上。 In addition, the lower limit value of the thickness ratio is not particularly limited, and from the viewpoint that good adhesion can be produced, the thickness ratio [t X / t Y ] is preferably 0.01 or more, more preferably 0.1 or more, Particularly preferred is 0.2 or more.

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 appropriately adjusted according to the application, etc., preferably 1 to 1200 μm, more preferably 2 to 600 μm, more preferably 3 to 300 μm, and particularly preferably 5 to 250 μm, more preferably 10 to 200 μm, and most preferably 15 to 150 μm.

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 the adherend. 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 the conductive adhesive sheet is used as a wound body, it is possible to suppress the curl shift caused by deformation of the adhesive conductive layer (X), or to squeeze the adhesive conductive layer (X) from the end of the wound body ) And so on.

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 appropriately adjusted according to the application, etc., 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 100 μm.

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 a rolled body, the curl deviation caused by deformation of the non-adhesive conductive layer (Y) or the rolled body can be suppressed The disadvantage is that the non-adhesive conductive layer (Y) is extruded at the end. Furthermore, 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 a small electronic device.

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

黏著性導電層(X)，以含有黏著性樹脂(x1)及碳系填料(x2)之黏著性組成物所形成的層為佳。 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 may be mixed with the type of the adhesive resin (x1), and further contains a cross-linking agent or an adhesion-imparting agent, and other commonly used additives.

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 this adhesive composition is demonstrated.

<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 which is a material for forming the adhesive conductive layer (X) refers to 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) From the viewpoint of the adhesion of the highly conductive adhesive sheet, it is preferably 10,000 to 2 million, and more preferably 20,000 to 1.5 million.

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 relative to the total amount (100% by mass) of the adhesive composition. It is 80.0 to 99.5 mass%, and most preferably 90.0 to 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), from the viewpoint of improving the adhesive force of the conductive adhesive sheet and improving the antistatic property and electrical conductivity, it contains acrylic resin, urethane resin, polyisobutylene resin, and styrene. One or more adhesive resins selected from the group consisting of resins, polyester resins, and polyolefin resins, containing acrylic resins, urethane resins, polyisobutylene resins, and One or more adhesive resins selected from the group consisting of styrene resins are preferable, and one or more adhesive resins selected from the group consisting of acrylic resins and urethane resins are included. For the better.

(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) is, 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. (Meth) acrylic acid esters and other structural units of polymers.

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 ') (hereinafter, also referred to as "monomer (a1')") having an alkyl group having 1 to 20 carbon atoms The unit (a1) and the acrylic copolymer having a structural unit (a2) derived from a functional group-containing monomer (a2 ') (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)。 The acrylic copolymer may have a structural unit (a3) derived from a monomer (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。 The form of copolymerization of the acrylic copolymer is not particularly limited. That is, the acrylic copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer.

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 number of carbon atoms of the alkyl group in 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 the 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, and the like.

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 preferable, and butyl (meth) acrylate is more preferable.

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 relative to the total structural unit (100% by mass) of the acrylic copolymer. Mass%, more preferably 60 to 99% by mass, particularly good 70 to 97% by mass, and most preferably 80 to 95% by 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, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an epoxy group, a monomer containing an amine group, a monomer containing a cyano group, a monomer containing a 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 '), a carboxyl group-containing monomer is more preferable.

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。 Monomers containing a carboxyl group, for example, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like, and (meth) acrylic acid is preferred.

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% by mass, more preferably 1 to 40% by mass, and particularly preferably 5 to 30% relative to the total structural unit (100% by mass) of the acrylic copolymer described above. %, Preferably 7 to 20% by 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, isofluorenyl (meth) acrylate, dicyclopentyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, ammonium (meth) acrylate, etc., (meth) acrylate, acetic acid having 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。 The monomers (a1 ') to (a3') may be individually separated. Use it, or use 2 or more types together.

(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。 When the urethane resin used as the adhesive resin (x1) has a polymer having at least one of a urethane bond and a urea bond on the main chain and / or side chain, and There is no particular limitation, for example, a urethane-based prepolymer (α) obtained by reacting a polyol with a polyisocyanate compound, or the urethane-based prepolymer (α), and then a chain is used. The urethane-based polymer (β) and the like obtained by an elongation 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, particularly preferably 15,000 to 100,000, and most preferably 20,000 to 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 of the urethane-based prepolymer (α) include, for example, polyalcohol compounds such as butanediol, polyether-based polyols, polyester-based polyols, and polycarbonate-based polyols. When it is a polyalcohol, there is no particular limitation, 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 from the viewpoints of easiness 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. two Alkyl glycols such as alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutanediol, and polyoxyalkyl didiols such as polytetramethyl glycol Alcohol and so on. These diols can be used alone or in combination of two or more kinds.

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, diols having a mass average molecular weight of 1,000 to 3,000 are preferred from the viewpoint that gelation during the reaction can be suppressed when they are reacted with a chain extender.

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, such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolyl diisocyanate Isocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), 4,4'-tolylamine diisocyanate, 2,4,6-triisocyanate toluene, 1, 3,5-triisocyanate benzene, diaminoanisole diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethane Methylxylene diisocyanate, 1,3-tetramethylxylene diisocyanate, and the like.

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, trimethyldiisocyanate, tetramethyldiisocyanate, hexamethyldiisocyanate (HMDI), pentamethylenediisocyanate, 1,2-propylenediisocyanate, 2,3- Butyl diisocyanate, 1,3-Butyl diisocyanate, Dodecyl methyl diisocyanate, 2,4,4-Trimethyl methyl 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-tri Methylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate , Methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate Methyl) cyclohexane and the like.

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。 The polyisocyanate compound may be a modified product of a compound (polyisocyanate) selected from the aforementioned aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specifically, the compound may be a trimethylolpropane adduct-type denaturant of the compound, a burette-type denaturant obtained by reacting the compound with water, and the compound may include an isotricyanate ring. The obtained isotricyanate-type denatured product 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)及乾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 that an urethane polymer having excellent adhesion can be obtained, 4,4'-diphenylmethane diisocyanate (MDI), Tolyl diisocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5 -Trimethylcyclohexyl isocyanate (IPDI) and more than one selected from dry denatures are preferred. From the viewpoint of weather resistance, from HMDI, IPDI and more than one selected from these denatures are: Better.

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 value measured in accordance with 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。 Chain extender, a compound having at least one of two hydroxyl groups and amine groups, or a compound having three or more hydroxyl groups and amine groups A compound of at least one of them is preferred.

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。 Compounds having at least one of two hydroxyl groups and amine groups, at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines 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 diols, such as 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, dipropylene glycol, and the like.

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, ethylenediamine, 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 are, for example, monoethanolamine, monopropanolamine, isopropanolamine, and the like.

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, diphenylmethanediamine, xylylenediamine, xylenediamine, and the like.

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付加物等。 Compounds having at least one of three or more hydroxyl groups and amine groups, for example, polyhydric alcohols such as trimethylolpropane, di-trimethylolpropane, pentaerythritol, and dipentaerythritol, and 1-amino-2,3- Amino alcohols such as propylene glycol, 1-methylamino-2,3-propanediol, N- (2-hydroxypropylethanolamine), ethylene oxide or propylene oxide adducts of tetramethylxylene diamine, and the like.

(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 the 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，及防止被付著物汚染等觀點，較佳為2萬以上，再就對被付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 PIB resin can be The viewpoints of making the obtained adhesive composition have sufficient cohesive force, improving the adhesive force of the conductive adhesive sheet, and the viewpoint of preventing contamination by the adherend are preferably 20,000 or more, and then the wettability of the adherend or From the viewpoint of 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, such as polyisobutylene, homopolymer of isobutylene, copolymer of isobutylene and isoprene, copolymer of isobutylene and n-butene, isobutylene and butyl Diene copolymers, and halogenated butyl rubbers of these copolymers after bromination or chlorination.

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 the case where the PIB-based resin is a copolymer, the structural unit derived from isobutylene is the most abundant among the total 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%。 The content of the structural unit produced by isobutylene in the PIB-based resin used in one aspect of the present invention is preferably 80 to 100 mass relative to the total structural unit (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 weatherability of the formed adhesive conductive layer (X), during the polymerization, it contains a large number of dense molecular structures, and the main chain and side chains are not polymerized. It is preferred that the structural double bond is a structural unit derived from isobutylene.

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, there is no polymerizable double bond in these main chains and side chains, and structural units derived from isobutylene The content 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 the total structural unit (100% by mass) of the PIB-based resin. 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 the case of using a PIB-based resin, it is preferable to combine a user with a PIB-based resin having a higher mass average molecular weight and a PIB-based 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-based resin used in one aspect of the present invention is a PIB-based resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter, also referred to as "PIB-based resin (p1)" ), Preferably combined with a PIB-based resin (p2) (hereinafter, also referred to as "PIB-based resin (p2)") having a mass average molecular weight of 50,000 to 250,000.

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 improve the durability and weather resistance of the adhesive conductive layer (X) formed from the obtained adhesive composition, and can also expect an increase in adhesive force.

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)之被付著體，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-based resin (p2) having a low mass average molecular weight can be well compatible with the PIB-based resin (p1), and the PIB-based resin (p1) can be plasticized to a moderate degree. For the adhesive conductive layer (X), The adhered body can be expected to improve its wettability, adhesion 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。 From the viewpoints described above, the mass average molecular weight (Mw) of the PIB-based resin (p1) is preferably from 270,000 to 600,000, more preferably from 290,000 to 480,000, and particularly preferably from 310,000 to 450,000. It is 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 PIB-based resin (p2) From the viewpoints mentioned above, it is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, particularly preferably 140,000 to 220,000, and most preferably 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-based 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 based on 100 parts by mass of the PIB-based resin (p1). It is preferably 8 to 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)對被付著體具有良好濕潤性的同時，也可以提高黏著力。 When the content 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, and , 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-based resin used as the adhesive resin (x1) is a polymer having a structural unit 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 resin used in one aspect of the present invention, the content of the structural unit generated from styrene is preferably 5 to 50 mass relative to the total structural unit (100% by mass) of the styrene resin. %, More preferably 10 to 40% by mass, and particularly good 15 to 35% by 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 styrene 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 adhesive force 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 preferably 80 to 200 ° C, more preferably 90 to 160 ° C, particularly preferably 100 to 140 ° C, and most preferably 105 to 135 from the viewpoint of improving the adhesive force of the conductive adhesive sheet. ℃.

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 the present invention, the softening point of the styrene resin means a 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- (ethylene-co-butylene) -block -Styrene triblock copolymer (hereinafter, also referred to as "SEBS"), styrene-block- (ethylene-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.

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。 These styrene resins may be used alone or in combination of two or more kinds.

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 resins, SBS, SEBS, and SEB are preferred, and SBS and SEBS are more 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。 When the styrene resin is a copolymer, the copolymerization form is not particularly limited. That is, the styrene 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 a polycondensation reaction between an acid component and a diol component or a polyalcohol component, and also includes a denatured 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 polycondensation reaction can be carried out by a general polyesterification reaction such as a direct esterification method and a 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。 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 is, for example, terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalenedicarboxylic acid, 5-sodium sulfonium isophthalic acid, 5-potassium sulfonium isophthalic acid, or these Aliphatic dicarboxylic acids such as esters, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanediocarboxylic acid, or some of these esters; 1,4-cyclic 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 above diol component or polyol component, for example, ethylene glycol, 1,2-propylene glycol, 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 Aliphatic diols such as diethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and aromatics such as bisphenol A Diols, 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。 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-based 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, for example, 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 groups with other α-olefins, copolymers of vinyl groups with propylene groups and other α-olefins, copolymers of vinyl groups with 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。 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-olefins are, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene Olefin and so on.

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, such as polypropylene, copolymers of vinyl and propylene groups, copolymers of propylene groups and other α-olefins, and polypropylene resins containing structural units derived from propylene 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。 Moreover, the said polyolefin resin can be used individually or in combination of 2 or more types.

<碳系填料(x2)> <Carbon-based 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)，以長徑比為1.5以上之碳系填料為佳。 The carbon-based filler (x2) contained together with the adhesive resin (x1) in the adhesive composition as a material for forming the adhesive conductive layer (X) is preferably a carbon-based filler having an 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 a carbon-based filler having 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 a non-adhesive conductive layer (Y) method can be further provided to sufficiently generate the The effect of reducing the surface resistivity of the conductive adhesive sheet. Moreover, the adhesive force of the adhesive conductive layer (X) can also be made good.

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 viewpoints described above, 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 1,000, 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, the "length-to-diameter 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 "long side length (H) / Short side length (L) ". The "average aspect ratio" refers to an 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。 The length (H) of the long side of the carbon-based filler (x2) means the length in the height direction (longitudinal direction) of the target carbon-based filler.

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 a cut surface that perpendicularly intersects with the height direction (length direction) of the target carbon-based filler, and the cross-section is circular. When it is elliptical, it means diameter or long diameter. When the section is polygonal, it means 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, an 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 sides 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 the present invention, the average value of the lengths of the short sides of 10 carbon-based fillers is 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) includes, for example, a columnar shape, a cylindrical shape, a hammer shape, a fibrous shape, and an oblate shape (normally, the sphericity is generally 0.7 or less), and the shape of the combination thereof.

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) having good conductivity, it is selected from columnar carbon-based fillers, cylindrical carbon-based fillers, and fibrous carbon-based fillers. More than one kind is preferable.

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、更佳為0.30~7.0質量份、特佳為0.40~5.0質量份、特佳為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 even more preferably 0.30 to 100 parts by mass of the adhesive resin (x1). 7.0 parts by mass, particularly preferably 0.40 to 5.0 parts by mass, particularly preferred 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, While reducing the surface resistivity of the formed adhesive conductive layer (X) alone, and by providing a non-adhesive conductive layer (Y) method, the effect of reducing the surface resistivity of the conductive adhesive sheet can be fully produced.

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 adhesive force 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 electrical conductivity can be generated, so it is not necessary to add a large amount of carbon-based fillers. 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%。 In addition, regarding the content of the carbon-based filler (x2) with respect to the total amount (100% by mass) of the adhesive composition, from the viewpoint described above, usually 0.01 to 10% by mass, preferably 0.30 to 7.0% by mass, more It is preferably 0.40 to 5.0% by mass, particularly preferably 0.50 to 4.5% by mass, and most preferably 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 formed adhesive conductive layer (X) and have a good adhesion. Carbon nano materials 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 formed by a graphite flake-containing substance whose main structure is a six-membered ring array 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 may also be a form in which carbon nanomaterials are modified by other conductive substances.

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, such as carbon nanotubes (CNTs), carbon Nano-fiber, carbon nano-horn, carbon nano-cone, fullerene, etc., and carbon nano-tube is preferred.

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。 A carbon nanotube is a cylindrical carbon polyhedron having a graphite (graphite) sheet having a carbon 6-membered ring structure as a main structure to form 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 carbon nanotubes, a single-layer carbon nanotube having a structure enclosed in a cylindrical shape by one layer of graphite flakes and a two-layer carbon nanotube having a structure enclosed in a cylindrical shape by two layers of graphite flakes A multilayer carbon nanotube having a multilayer structure obtained by closing a graphite sheet in a concentric cylindrical shape with three or more layers may be used arbitrarily in combination of two or more of them.

<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-mentioned acrylic resin (especially an acrylic copolymer having the above-mentioned structural unit (a2)) is used as the adhesive resin (x1), the adhesive force of the formed adhesive conductive layer (X) is increased. From the standpoint, 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 agents, for example, isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, amine-based cross-linking agents, and amine resin-based cross-linking agents联 剂 Such as. 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, an isocyanate-based crosslinking agent is preferred from the viewpoint of improving the adhesive force of the conductive adhesive sheet.

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 diiso Cyanate, 2,6-tolyl diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane- 2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethyldiisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane -2,4'-diisocyanate, polyisocyanate compounds such as lysine isocyanate, etc.

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。 The polyisocyanate compound may be a trimethylolpropane adduct-type modified product of the above compound, a burette-type modified product obtained by reacting with water, or an isocyanurate containing an isocyanurate ring. Ester type denaturants.

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 with respect 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 preferable to have a tackifier.

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。 The mass average molecular weight (Mw) of the adhesion-imparting agent is usually less than 10,000, and is different 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 increases the From the viewpoint of the adhesion of the formed adhesive conductive layer (X), it is preferably from 400 to 4000, more preferably from 800 to 1500.

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 110-180 ° C, particularly preferably 115-175 ° C, and most preferably 120-170 ° 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, for example, turpentine resins such as turpentine resin, turpentol resin, and ester compounds thereof; hydrogenated turpentine resins obtained by hydrogenating these turpentine resins; terpene resins, aromatic denatured terpene resins, and terpenes Terpene-based resins such as phenol-based resins; hydrogenated terpene resins obtained by hydrogenation of these terpene-based resins; pentene, isoprene, piperine, 1.3-pentadiene, etc. produced by thermal decomposition of petroleum brain C5 distillate obtained by copolymerization of C5 fraction and hydrogenated petroleum resin of the C5 distillate; C9 distillate such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum brain Copolymerized C9 petroleum resin and 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 the present invention, the adhesion-imparting agent can be used alone or in combination of two or more different softening points or different 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 based on 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。 When the tackifying resin (x1) contains an acrylic resin, the content of the tackifier is more than 100 parts by mass of the acrylic resin. It 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.

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, more preferably 40 to 100 parts by mass of the urethane-based resin. ~ 160 parts by mass, particularly preferably 80 ~ 120 parts by mass.

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 from 5 to 100 parts by mass, more preferably from 10 to 80 parts by mass, and particularly preferably from 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 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, based on 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, based on 100 parts by mass of the polyolefin 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。 The adhesive composition, which is a material for forming the adhesive conductive layer (X), may generally contain additives commonly used with adhesive resins, as long as the effects of the present invention are not impaired.

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 commonly used additives are, for example, ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, hardeners, hardening aids, catalysts, and the like.

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 these common additives are added, 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, relative 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% by mass) of the adhesive composition as the forming material of the adhesive conductive layer (X) is preferably 20% by 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。 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-based 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), the carbon-based filler (x2), and the adhesion-imparting agent is more preferably 70% by mass or better It is 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 using the adhesive resin (x1) as the main component of the PIB-based 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 is preferred. It is 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), the carbon-based filler (x2), and the adhesion-imparting agent is preferably 70% by mass or more. It is 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-based filler (x2) in the total amount (100% by mass) of the adhesive composition is smaller than 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 of "adhesive resin (x1) using ZZ resin as a main component" means that "the content of the 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 record, the content of the specific ZZ-based resin is usually 50% by mass or more, preferably 65 to 100% by mass, and more preferably 75 to 100% by mass relative to the total amount (100% by mass) of the adhesive resin (x1). %, Especially good for 85 ~ 100 mass%.

<黏著性導電層(X)之形成方法> <Method for 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 method (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): A solution of an organic solvent of an adhesive composition is prepared, and the solution is coated on a release sheet described later according to a known coating method to form a coating film, and the coating film is dried to form an adhesive Method of the 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): Adhesive resin (x1) and carbon-based filler (x2) are heated and kneaded to prepare a composite, and then the composite is formed into a sheet shape according to a known molding method, and then adhesiveness is formed. Method of conductive layer (X).

(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 the method (X-1), the adhesive resin (x1) is preferably formed using an acrylic resin, a urethane resin, or a PIB resin.

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 solvent used is, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n- Propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfinium and the like.

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 the organic solvent used when synthesizing the adhesive resin (x1).

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), it is preferable that the carbon-based filler (x2) is dispersed in a solvent to form a dispersion, and the adhesive resin (x1) is 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 liquid, it can be mixed with the adhesive resin (x1) in a state of low viscosity. The materials (x2) are easily accessible to each other. By forming a network of fillers, it is easy to reduce the surface resistivity and volume resistivity of the formed adhesive conductive layer (X).

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。 Examples of the solvent used for preparing the dispersion liquid of the carbon-based filler (x2) include water and the above-mentioned organic solvent, and an organic solvent is more preferable.

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

Figure TWI677555B_D0001
振動一定時間之方式予以製作之方法等。 A method for producing a dispersion liquid of a carbon-based filler (x2), for example, adding a carbon-based filler (x2) to a solvent, using an ultrasonic wave, etc.
Figure TWI677555B_D0001
How to make it by shaking 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 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 the method (X-1), a method of applying a solution of an adhesive composition to a release sheet, for example, a spin coating method, a spray coating method, a strip coating method, a blade coating method, or a roller blade coating method. Cloth method, roll coating method, flat plate coating method, mold coating method, gravure coating method, and the like.

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 the solution of the adhesive composition is applied on the release sheet to form a coating film, a drying treatment is performed to remove a 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 the adhesion, the coating layer after the drying treatment is, for example, left in an environment of 23 ° C and 50% RH (relative humidity) for 7 to 30 days. It is preferable that the inside of the coating layer be sufficiently crosslinked within a few 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 a styrene resin or the like.

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 kneading device is, for example, a uniaxial extruder, a biaxial extruder, a roller mill, a compound mill, a Banbury mixer, an intermixture, a pressure kneader, and the like.

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 for forming a composite obtained by using the heating and kneading device, for example, melt extrusion method, curtain method, compression molding method, and the like, is preferably 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, compressing the obtained composite with two sheets of a peeling sheet, and then heating and compressing it using a hot extruder to form a sheet-like adhesive conductive layer (X). Further, in addition to the two release sheets, a composite made of the substrate and the release sheet may be sandwiched to form a sheet-like adhesive conductive layer (X).

〔非黏著性導電層(Y)之形成材料〕 [Material for forming 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) is selected from the group consisting of conductive polymers, carbon-based fillers, and metal oxides from the viewpoint that the effect of reducing the surface resistivity of the conductive adhesive sheet can be fully exerted. The layer of one or more conductive materials 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 more preferable to include one or more conductive materials 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 weight reduction of the conductive adhesive sheet. Particularly preferred is 0.8 to 1.7 g / 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 such as polythiophene, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)), polyaniline, polypyrrole, polyquinoxaline )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。 The non-adhesive conductive layer (Y) containing a conductive polymer is preferably a conductive polymer containing a non-adhesive resin. The non-adhesive resin is composed of an acrylic resin and a urethane system. 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 a conductive polymer is used as a conductive material, the content of the conductive polymer is preferably 4 to 100% by mass, and 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 by a known coating method. A method of forming a coating film on a substrate or a release 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 the organic solvent used in this method and the method for applying the solution are the same as those described in "Method (X-1)" regarding the method for forming the above-mentioned adhesive conductive layer (X).

<碳系填料> <Carbon-based 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 is, for example, the same as the carbon-based filler (x2) described above, and a carbon nanomaterial is more preferable.

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 a carbon-based filler is preferred to contain a non-adhesive resin at the same time as the carbon-based filler. The non-adhesive resin consists of an acrylic resin, a urethane resin, and PIB. Non-adhesive resins based on resins and styrene resins are preferred.

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 the conductive material, the content of the carbon-based filler is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15 with respect to the total amount (100% by mass) of the non-adhesive conductive layer (Y). Mass%, particularly good is 1.0 to 10 mass%, and best is 2.0 to 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 a carbon-based filler is not particularly limited. For example, a dispersion of a carbon-based filler and a solution of an organic solvent of a non-adhesive resin are mixed to obtain a resin composition. 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 the coating film to form the solution.

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 for preparing the dispersion of carbon-based fillers, the method for coating the solution, and the "Method (X-1)" for the method for forming the above-mentioned adhesive conductive layer (X) Documented as within 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 for forming the non-adhesive conductive layer (Y) containing a carbon-based filler may be heating and kneading the carbon-based filler and a non-adhesive resin to obtain a composite, and then the composite is prepared by a known molding method. A method for forming a thin sheet.

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 kneader and the method for forming the composite used in this method are the same as those described in "Method (X-2)" regarding 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 such as ITO (indium tin oxide), ZnO (zinc oxide), IZO (indium zinc oxide), AZO (zinc aluminum oxide), GZO (zinc gallium oxide), IGZO (acid indium gallium zinc oxide), ATO ( Tin antimony oxide) and the like.

該些之中，又以ITO(氧化銦錫)為佳。 Among these, ITO (Indium Tin Oxide) is more preferable.

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。 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。 The method for forming the non-adhesive conductive layer (Y) containing a metal oxide is preferably a method in which a substrate is formed 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 for the conductive adhesive sheet according to one aspect of the present invention can be appropriately selected according to the application of the conductive adhesive sheet, and it may contain Insulating base material of edge material, conductive base material containing conductive material such as metal, 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 refers to 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, for example, various papers such as high-quality paper, surface-treated paper, printing paper, wax paper, etc., or laminated papers obtained by laminating thermoplastic resins such as polyethylene; porous materials such as non-woven fabrics Polyolefin resins such as polyethylene resins and polypropylene resins, polyester resins such as polybutylene terephthalate resins, polyethylene terephthalate resins, acetate resins, ABS resins, polystyrene resins, Plastic films or sheets formed from vinyl chloride resin, etc .; plastic films or sheets formed from mixtures of these resins; plastic films or sheets formed from laminates of these plastic films or sheets.

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 substrate such as a plastic film or sheet may be unstretched, or may be stretched in one or two axial 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。 These insulating substrates (especially plastic films or sheets) may further contain ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-fracture 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。 A conductive substrate, for example, a film or sheet obtained by laminating a metal foil or a metal foil on a resin forming the above-mentioned insulating substrate, or a film or sheet subjected to metal vapor deposition on the surface of the above-mentioned insulating substrate. Films or sheets that have been subjected to antistatic treatment on the surface of the above-mentioned insulating base material, sheets that are braided with metal wires into a net shape, and the like.

又，導電性基材所使用之金屬，例如，鋁、銅、銀、 金等。 The metal used for the conductive substrate is, for example, aluminum, copper, silver, Kim et al.

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, and from the viewpoint of easy 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。 When the base material is a plastic film or sheet, from the viewpoint of improving the adhesion between the base material and the non-adhesive conductive layer (Y), if necessary, the surface of the base material is subjected to a surface treatment such as an oxidation method or a bumping method. good.

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, and examples thereof include a corona discharge treatment method, a plasma treatment method, a chromic acid oxidation (wet type), a flame treatment, a hot air treatment, and an ozone and ultraviolet irradiation treatment. There is no particular limitation on the unevenness method, and examples thereof include a sandblasting method and a solvent method. These surface treatments can be appropriately selected depending on the type of the substrate, and a corona discharge treatment method is preferred from the viewpoint of improving the effect of adhesion with the non-adhesive conductive layer (Y) or operability. Alternatively, a plasma treatment may 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。 The release sheet used for the conductive adhesive sheet according to one aspect of the present invention may be a release sheet after a double-sided release treatment, or a release sheet after a single-sided release treatment, etc. Those who apply a release agent.

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 release sheets, for example, paper substrates such as wax paper, printing paper, and high-quality paper, laminated papers obtained by laminating thermoplastic resins such as polyethylene on these paper substrates, or polyethylene terephthalate resins Polyester resins such as polybutylene terephthalate resin and polyethylene naphthalate resin Film, 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。 Examples of the release agent include rubber-based elastomers such as silicone resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl resins, alkyd 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 release sheet is not particularly limited, but 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〕 [Production 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 applying the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), and the base material or the release sheet by an appropriate bonding method. Make it.

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 of one aspect of the present invention is preferably 0.1N or more, more preferably 0.1 to 49N, 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，丙是其具有高度之黏著力。 In addition, the peak value of the probe test means the value measured according to the method described in the examples. In addition, the peak value of the probe test is a physical property value that is an index 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) of the conductive adhesive sheet of one aspect of the present invention measured from the surface side is preferably 9.0 × 10 4 Ω / □ or less, and 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 "the surface resistivity of the adhesive conductive layer (X) of the conductive adhesive sheet measured from the surface side" is at least the adhesive conductive layer (X) and the non-adhesive conductive layer (Y). The value of the surface resistivity measured on the surface side of the adhesive conductive layer (X) exposed by the conductive adhesive sheet of the present invention is the surface resistivity of the adhesive conductive layer (X) alone (ρ SX ) "Have different values.

[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 by 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。 A gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020") was used to perform the measurement under the following conditions, and a measurement value obtained in terms of standard polystyrene conversion 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。 ‧Column: "TSK guard column HXL-H", "TSK gel GMHXL (× 2)" and "TSK gel G2000HXL" (all manufactured by Tosoh Corporation) are connected in order.

‧管柱溫度：40℃ ‧Column temperature: 40 ℃

‧展開溶劑：四氫呋喃 ‧Developing 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-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日立高科技製、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 (Hitachi High-Tech Co., Ltd., Hitachi High-Tech, product name "S-4700"), observe 10 randomly extracted carbon-based filler particles, and measure the length of each long side and the length of each short side. For the length, the average value of 10 carbon-based filler particles is taken as the "length of the long side (H)" and "length of the short side (L)" of the filler. The aspect ratio (H / L) is calculated based on the "length of the long side (H) / length of the short side (L)".

<軟化點> <Softening point>

依JIS K 2531為基準測定者。 Measured in accordance with JIS K 2531.

<密度> <Density>

依JIS Z 8807：2012為基準測定者。 Measured in accordance with JIS Z 8807: 2012.

<探針測試(probe tack)> <Probe tack>

依JIS Z0237(1991)為基準測定者。 Measured in accordance with 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, after a test piece having a size of 10 mm × 10 mm is left in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, the surface of the layer to be measured of the test piece is exposed and used. The viscosity tester (manufactured by Rigaku Industries, Ltd., product name "PROBE TACK TESTER") measures the probe tack value of the surface of the layer.

又，該探針測試(probe tack)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。 The probe tack value is that a probe made of stainless steel with a diameter of 5 mm was used to contact the surface of the layer to be measured under the conditions of a contact load of 0.98 N / cm 2 for 1 second, and the probe was set to 600 mm. The speed per second, 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。 The surface of the non-adhesive conductive layer was measured for the peak top value of the probe test value. In addition, for the surface of the adhesive conductive layer (X) of the conductive adhesive sheet, the peak-to-peak value and integrated value of the probe test value were 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, if 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 value of the peak top is "0 (N)".

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

依JIS K 7194為基準之測定值。 Measured value based on 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, after a test piece having a size of 20 mm × 40 mm is left in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, the surface of the layer to be measured of the test piece may be exposed and used. Low-resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name "Loresta GP MCP-T610"), and measured 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. Tables 1 and 2 are the average values of the measured values.

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。 In addition, the surface resistivity and volume resistivity of the adhesive conductive layer (X) alone were measured, and the adhesive conductive layer was sandwiched only by the two peeling sheets. The laminate obtained in (X) was used as a test piece, and the release sheet on one side of the test piece was removed, and the values of the exposed surface of the 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，使用付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, and the substrate with the non-adhesive conductive layer was used as a test piece. The surface of the non-adhesive conductive layer of the test piece was measured. 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 surface resistivity of the conductive adhesive sheet was measured by laminating the substrate prepared in accordance with the examples and comparative examples, the non-adhesive conductive layer, the adhesive conductive layer (X), and the release sheet in this order. The obtained conductive adhesive sheet was used as a test piece, and the release sheet of the test piece was removed. Only the surface resistivity value was measured for the exposed surface of the adhesive conductive layer (X).

製造例1 Manufacturing example 1 (付有非黏著性導電層(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，製得付有含聚噻吩之非黏著性導電層(Y-1)之基材。 Apply 50 μm-thick polyethylene terephthalate (PET) film (made by Toray Co., Ltd. under the trade name "Lumirror", surface resistivity: 1.18 × 10 18 Ω / □) to a substrate. A solution of polythiophene (manufactured by Soken Chemical Co., Ltd. under the trade name "Verazol IW-103") was formed into a coated film having a thickness of 2.4 μm after drying, and the coated film was dried to obtain a polymer-containing film Substrate of thiophene non-adhesive conductive layer (Y-1).

製造例2 Manufacturing example 2 (付有非黏著性導電層(Y-2)之基材的製作) (Fabrication of base material 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-ethylenedioxy) based on 100 parts by mass (solid content) of acrylic water-soluble polymer (made by Arakawa Chemical Industries, Ltd., trade name "Tamanori G-37", polyacrylic acid). Thiophene) -poly (styrenesulfonic acid) (PEDOT-PSS) dispersion (manufactured by Agfa, trade name "Orgacon S305") 10 parts by mass (solid content ratio), and a solution of 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，得付有含PEDOT-PSS之非黏著性導電層(Y-2)之基材。 Subsequently, the same article as that used in Manufacturing Example 1 was coated on a PET film to form a coating film having a thickness of 1.0 μm after the solution was dried, and the coating film was dried to obtain a coating containing PEDOT-PSS. Substrate for non-adhesive conductive layer (Y-2).

製造例3 Manufacturing example 3 (付有非黏著性導電層(Y-3)之基材的製作) (Fabrication of base material 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。 Multilayer carbon nanotubes (CNT) (manufactured by Nanocyl, trade name "NC7000") are added to 100 parts by mass (solid content) of styrene-based resin (manufactured by Kraton, trade name "1726M", SEBS). 10 parts by mass (solid content ratio), using a heating kneader (manufactured by Toyo Seiki Seisakusho 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，製得付有含厚度100.0μm之SEBS及CNT(10質量份)之非黏著性導電層(Y-3)之基材。 Subsequently, the above-mentioned composite was sandwiched between a PET film having the same material as that used in Production Example 1 and a peeling sheet (made by Linde Co., Ltd., trade name "SP-PET751031") having a thickness of 75 μm, and a heat press machine ( Tester Industry Co., Ltd., product name "SA-302"), in Hot extrusion at 130 ° C and 10 MPa for 10 minutes. After heat extrusion, the release sheet was removed to obtain a substrate coated 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 (付有非黏著性導電層(Y-4)之基材之製作) (Fabrication of base material 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)之付有非黏著性導電層(Y-4)之基材。 Except that the addition amount of the multilayer carbon nanotube was set to "4 parts by mass", the same method as in Production Example 3 was used to prepare non-adhesive materials containing SEBS and CNT (4 parts by mass) with a thickness of 100.0 μm. Substrate of conductive layer (Y-4).

本實施例及比較例中，除上述製造例1~4所製作之付有非黏著性導電層之基材以外，也使用以下的付有非黏著性導電層之基材。 In this example and the comparative example, in addition to the substrate with a non-adhesive conductive layer produced in the above-mentioned Production Examples 1 to 4, the following substrate with a non-adhesive conductive layer was also used.

‧「付有由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 Phthalate" (made by Oike Industry Co., Ltd.). It is a film with a thickness of 1.6 μm on one side of a PET film (surface resistivity: 1.18 × 10 18 Ω / □) with a thickness of 50 μm.

‧「付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) made of copper": trade name "NIKAFLEX" (manufactured by Nikkan Industries, Ltd.). For a 50 μm thick PET film (surface resistivity: 1.18 × 10 18 Ω / □) on one side, a copper film with a thickness of 35.0 μm was bonded using an adhesive.

‧付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 non-adhesive conductive layer (YC) made of aluminum: Trade name "Metalumy # 50" (manufactured by Toray Film Processing Co., Ltd.). A 50 μm-thick PET film (surface resistivity: 1.18 × 10 18 Ω / □) was used to vapor-deposit an aluminum film having a thickness of 10.0 μm.

本實施例及比較例所使用之付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。 The various physical properties of the non-adhesive conductive layer of the base material used in this example and the comparative example with a non-adhesive conductive layer are shown in Table 1.

實施例1~15、比較例1~8 Examples 1 to 15 and 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。 Carbon type filler (x2) was added to ethyl acetate in accordance with the type and addition amount (solid content ratio with respect to 100 parts by mass (solid content) of the adhesive resin) shown in Table 2, using an ultrasonic washing machine, and Ultrasonic waves (42 kHz, 125 W) were applied to the vibration for 1 hour, and a carbon-based filler (x2) dispersion liquid having 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, to 100 parts by mass (solid content) of the adhesive resin (x1) of the kind shown in Table 2, add the dispersion of the carbon-based filler (x2), and if necessary, add the kind shown in Table 2 and add The amount (solid content ratio) of the crosslinking agent or adhesion-imparting agent. Subsequently, it was moderately diluted with ethyl acetate, and it stirred until it became uniform, and the solution of the adhesive composition was prepared.

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。 Subsequently, the solution of the adhesive composition prepared according to the above method was applied to a release sheet (manufactured by Linde Co., Ltd. under the trade name "SP-PET381031", thickness: 38 μm, and the surface was subjected to a polysiloxane removal treatment A polyethylene terephthalate film) is formed on the peeling treatment surface to form a coating film, which is 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 the coating layer, another release sheet of the same kind as the above is laminated, and after standing for 14 hours in an environment of 23 ° C. and 50% RH (relative humidity), the coating layer is crosslinked. A laminated body having two thicknesses of the peeling sheet shown in Table 2 was obtained by sandwiching only the adhesive conductive layer (X).

(2)導電性黏著薄片之製作 (2) Production 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所示種類之付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 in order to remove the release sheet on one side of the laminated body is provided with a non-adhesive conductive layer of the type shown in Table 2 The non-adhesive conductive layer is laminated 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 to remove the release sheet on one side of the laminate, and a PET film (made by Toray Co., Ltd., under the trade name "Lumirror") having a thickness of 50 μm. paste Together to make a 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。 100 parts by mass (solid content) of a styrene resin (manufactured by Toyo ADL Co., Ltd. under the brand name "P-907Y", as described later), and multiple layers were added according to the amount (solid content ratio) shown in Table 2 Carbon nano tube (CNT) (manufactured by Nanocyl, trade name "NC7000", details will be described later), using a heating kneading machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "30C150"), at 100 ° C, Kneading was performed at 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 composite was clamped using two release sheets (made by Linde Co., Ltd., trade name "SP-PET751031", thickness: 75 µm), and a heat press machine (made by Tester Industry Co., Ltd., product name "SA- 302 ″), and heat-extruded under conditions of 130 ° C. and 10 MPa for 10 minutes to obtain a laminated body obtained by only sandwiching the adhesive conductive layer (X) with two release sheets.

(2)導電性黏著薄片之製作 (2) Production 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)，與付有非黏著性導電層(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 layer (X) containing the styrene-based resin exposed after removing the release sheet on one side of the laminated body and the base material provided 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。 Adhesive groups used in the examples and comparative examples shown in Table 2 The details of each component in the finished product 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 (mass parts), 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。 ‧ "Urethane-based resin": manufactured by LION SPECIALTY CHEMICALS Co., Ltd., trade name "US-902A", urethane-based 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 content ratio) of PIW-based resin (manufactured by BASF, trade name "Oppanol B50") of Mw 340,000, and PIW-based resin (manufactured by BASF, trade name " Oppanol 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℃。 ‧ "Styrenic resin": It contains a mixed resin made by Toyo ADL Co., Ltd. under the trade name "P-907Y", SEBS and SEB, total content of SEBS and SEB = 30% by mass, and softening point = 112 ° C.

(碳系填料(x2)) (Carbon-based 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, cylindrical multilayer carbon nanotube made by Nanocyl Corporation, 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, made by Ube Kosan Co., Ltd., cylindrical The multilayer carbon nanotube, the average aspect ratio (H / L): 100, the length of the long side (H): 1.1 μm, and the length of the short side (L): 11 nm.

(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 Industries, Ltd., hydrogenated petroleum resin, softening point: 125 ° C.

‧「YS Polystar K125」：商品名、Y asuhara化學股份有限公司製、萜烯酚系樹脂、軟化點：125℃。 ‧ "YS Polystar K125": Trade name, manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point: 125 ° C.

(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。 ‧P-907Y, which is used as a styrenic resin, is a mixture of components (adhesion imparting agent, plasticizer, etc.) other than the component (x1).

實施例17~23 Examples 17 to 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 conductive double-sided tape (manufactured by Nisshin EM Co., Ltd. under the trade name "conductive carbon double-sided tape 7311") and an adhesive layer containing an acrylic resin and carbon powder were placed on two release sheets. The adhesive layer of the conductive adhesive sheet (a sandwiched structure) is used as an 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所示種類之付有非黏著性導電層(Y-1)之基材或付有非黏著性導電層(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。 The exposed adhesive layer (adhesive conductive layer (X)) was removed from the release sheet on one side of the above-mentioned commercially available conductive double-sided tape, and a non-adhesive conductive layer (Y The base material of -1) or the non-adhesive conductive layer of the base material with the non-adhesive conductive layer (Y-4) is laminated 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)) of the release sheet on one side of the conductive double-sided tape of the commercial product described above, and a PET film (manufactured by Toray Co., Ltd. under the trade name "Lumirror" ”) To form 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 conductive adhesive sheets prepared in the above manner are shown in Tables 2 and 3 in terms of various physical property values measured according to the methods described above.

[表2] [Table 2]

[表3] [table 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。 As can be seen from Tables 2 and 3, when the conductive adhesive sheets of Examples 1 to 23 have good adhesion, when compared with the conductive adhesive sheets of Comparative Examples 1 to 9, the surface resistivity was confirmed to be low. , And has excellent antistatic and electrical conductivity.

[產業上之利用性] [Industrial availability]

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, while having good adhesion, has low surface resistivity, and therefore has excellent antistatic properties and electrical 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, for example, as an electromagnetic shielding material for containers for placing electronic equipment such as computers and communication equipment, as a ground wire for electrical parts, and even as a fire-resistant material for sparks generated by static electricity such as frictional static electricity. The components used are the joining components.

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，黏著性導電層(X)單獨之體積電阻率(ρVX)之值為1.0×100~1.0×108Ω‧cm，非黏著性導電層(Y)單獨之體積電阻率(ρVY)之值為1.0×10-4~1.0×106Ω‧cm，且，黏著性導電層(X)之厚度(tX)與非黏著性導電層(Y)之厚度(tY)之厚度比〔tx/tY〕為20000以下。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 the volume resistivity (ρ VX ) of the adhesive conductive layer (X) alone 1.0 × 10 0 ~ 1.0 × 10 8 Ω‧cm, the value of the volume resistivity (ρ VY ) of the non-adhesive conductive layer (Y) alone is 1.0 × 10 -4 ~ 1.0 × 10 6 Ω‧cm, and, The thickness ratio [t x / t Y ] of the thickness (t X ) of the adhesive conductive layer (X) to the thickness (t Y ) of the non-adhesive conductive layer (Y) is 20,000 or less. 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 according to 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 is composed of an acrylic resin, a urethane resin, a rubber resin, and styrene. One or more adhesive resins 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 aforementioned adhesive composition is 0.01 to 15 parts by mass relative to 100 parts by mass of the adhesive resin (x1). Serving. 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 according to claim 1 or 2, wherein the non-adhesive conductive layer (Y) contains 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 according to claim 1 or 2, wherein the non-adhesive conductive layer (Y) is a group consisting of polythiophene, PEDOT-PSS, a carbon nanomaterial, 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 according to 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, which has a two-layer body 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, which has a constitution in which a two-layer body composed of an adhesive conductive layer (X) and a non-adhesive conductive layer (Y) is sandwiched by two release 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 according to claim 1 or 2, which has the following characteristics: the first adhesive conductive layer (XI), the non-adhesive conductive layer (Y), and the second adhesive conductive layer (X-II). The constituents of the three-layer body obtained by sequential lamination are sandwiched by two release sheets.
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