CN106661398A - Conductive adhesive sheet - Google Patents

Conductive adhesive sheet Download PDF

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Publication number
CN106661398A
CN106661398A CN201580045647.9A CN201580045647A CN106661398A CN 106661398 A CN106661398 A CN 106661398A CN 201580045647 A CN201580045647 A CN 201580045647A CN 106661398 A CN106661398 A CN 106661398A
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CN
China
Prior art keywords
conductive layer
adhesive
resin
cohesive
electroconductive
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CN201580045647.9A
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Chinese (zh)
Inventor
植田贵洋
大高翔
松下大雅
松下香织
宫田壮
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Lintec Corp
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Lintec Corp
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Publication of CN106661398A publication Critical patent/CN106661398A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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

A conductive adhesive sheet which comprises at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), and wherein: the volume resistivity (Ruo VX) of the adhesive conductive layer (X) alone is from 1.0 X 100 omega cm to 1.0 X 108 omega cm; the volume resistivity (RHO VY) of the non-adhesive conductive layer (Y) alone is from 1.0 x 10-4 omega cm to 1.0 x 106 omega cm; and the ratio of the thickness (tX) of the adhesive conductive layer (X) to the thickness (tY) of the non-adhesive conductive layer (Y), namely tX/tY is 20,000 or less. This conductive adhesive sheet exhibits excellent antistatic properties and electrical conductivity, while having good adhesive power.

Description

Electroconductive adhesive sheet
Technical field
The present invention relates to electroconductive adhesive sheet.
Background technology
In the past, connecing in electromagnetic shielding material, the electric components of container of electronic equipment such as storage computer, communication apparatus etc. In the various engagements of ground wire and the material on fire that causes of spark that prevents from being produced by electrostatic such as friction electricity etc., tool has been used There is the electroconductive adhesive sheet of simple cementability.
For the adhesive composition of the adhesive phase having for electroconductive adhesive sheet, in order to give antistatic Property and electric conductivity, being used mostly makes the conductive materials such as the metal dusts such as copper powder, silver powder, nickel powder, aluminium powder be scattered in cohesive tree Composition in fat.
For example, Patent Document 1 discloses in the CNT and carbon micro-coil for making as conductive material at least Conductive adhesive that one is scattered in adhesive and the electroconductive adhesive sheet for having used the conductive adhesive.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-172582 publications
The content of the invention
Problems to be solved by the invention
However, the electric conductivity in order to improve the adhesive phase that above-mentioned electroconductive adhesive sheet has, needs as bonding It is a large amount of in the adhesive composition of the formation material of oxidant layer to coordinate conductive material, so as to conductive material particle is mutual connect Thixotroping is close.
However, when coordinating a large amount of conductive materials in adhesive composition, existing causes by the adhesive composition shape Into adhesive phase bonding force decline tendency.On the other hand, if reducing being led in adhesive phase to improve bonding force The content of conductive substances, then there is a problem of causing the electric conductivity of adhesive phase to reduce such compromise selection.
Electroconductive adhesive sheet disclosed in patent document 1 improves at the same time bonding force and electric conductivity aspect is still insufficient.
It is an object of the invention to provide with good bonding force, while the electric conductivity of static electricity resistance and excellent electric conductivity Bonding sheet.
The method of solve problem
The present inventor etc. has found, the structure for being formed as at least there is cohesive conductive layer and non-adhesive conductive layer and Make each specific insulation of single cohesive conductive layer and non-adhesive conductive layer in specific scope and by this 2 layers of thickness Degree can solve the above problems than adjusting to the electroconductive adhesive sheet of given range, and then complete the present invention.
That is, the present invention provides following [1]～[16].
[1] a kind of electroconductive adhesive sheet, it at least has cohesive conductive layer (X) and non-adhesive conductive layer (Y), its In,
Specific insulation (the ρ of single cohesive conductive layer (X)VX) value be 1.0 × 100～1.0 × 108Ω cm,
Specific insulation (the ρ of single non-adhesive conductive layer (Y)VY) value be 1.0 × 10-4～1.0 × 106Ω· Cm,
Also, thickness (the t of cohesive conductive layer (X)X) with the thickness (t of non-adhesive conductive layer (Y)Y) thickness ratio [tx/tY] it is less than 20000.
[2] electroconductive adhesive sheet described in above-mentioned [1], wherein, the thickness (t of cohesive conductive layer (X)X) it is 1～1200 μ m。
[3] electroconductive adhesive sheet described in above-mentioned [1] or [2], wherein, the thickness (t of non-adhesive conductive layer (Y)Y) be 0.01～200 μm.
[4] electroconductive adhesive sheet any one of above-mentioned [1]～[3], wherein, cohesive conductive layer (X) is by gluing The layer that conjunction property composition is formed, the adhesive composition includes resin of binding property (x1) and carbon system filler (x2).
[5] electroconductive adhesive sheet described in above-mentioned [4], wherein, the resin of binding property included in the adhesive composition (x1) include selected from acrylic resin, polyurethane based resin, rubber resin, styrene resin, polyester resin and gather More than a kind resin of binding property in olefine kind resin.
[6] electroconductive adhesive sheet described in above-mentioned [4] or [5], wherein, the carbon system included in the adhesive composition fills out The average aspect ratio of material (x2) is more than 1.5.
[7] electroconductive adhesive sheet any one of above-mentioned [4]～[6], wherein, include in the adhesive composition Carbon system filler (x2) content relative to the mass parts of resin of binding property (x1) 100 be 0.01～15 mass parts.
[8] electroconductive adhesive sheet any one of above-mentioned [4]～[7], wherein, include in the adhesive composition Carbon system filler (x2) be carbon nanomaterial.
[9] electroconductive adhesive sheet any one of above-mentioned [1]～[8], wherein, non-adhesive conductive layer (Y) is bag Layer containing more than a kind conductive material in electroconductive polymer, carbon system filler and metal oxide.
[10] electroconductive adhesive sheet any one of above-mentioned [1]～[9], wherein, non-adhesive conductive layer (Y) is bag Layer containing more than a kind conductive material in polythiophene, PEDOT-PSS, carbon nanomaterial and ITO (tin indium oxide).
[11] electroconductive adhesive sheet described in above-mentioned [9] or [10], wherein, what is included in non-adhesive conductive layer (Y) leads The density of electric material is 0.8～2.5g/cm3。
[12] electroconductive adhesive sheet any one of above-mentioned [1]～[11], it has laminated substrate, non-adhering successively The structure of property conductive layer (Y) and cohesive conductive layer (X).
[13] electroconductive adhesive sheet described in above-mentioned [12], it has respectively conductive by non-adhesive on the two sides of base material Two layers of body that layer (Y) and cohesive conductive layer (X) are constituted.
[14] electroconductive adhesive sheet described in above-mentioned [12] or [13], wherein, above-mentioned base material be surface resistivity 1.0 × 1014The insulating properties base material of Ω/more than.
[15] electroconductive adhesive sheet any one of above-mentioned [1]～[11], its have using the clamping of 2 stripping films by The structure of two layers of body that cohesive conductive layer (X) and non-adhesive conductive layer (Y) are constituted.
[16] electroconductive adhesive sheet any one of above-mentioned [1]～[11], its have using the clamping of 2 stripping films according to Three layers of the cohesive conductive layer (X-I) of secondary lamination the 1st, non-adhesive conductive layer (Y) and the 2nd cohesive conductive layer (X-II) The structure of body.
The effect of invention
The electroconductive adhesive sheet of the present invention has good bonding force, and static electricity resistance and excellent electric conductivity.
Description of the drawings
Fig. 1 is the electric conductivity with base material of the structure of one of the preferred embodiment of electroconductive adhesive sheet as the present invention The profile of bonding sheet.
Fig. 2 is the conduction without base material of the structure of one of the preferred embodiment of electroconductive adhesive sheet as the present invention The profile of property bonding sheet.
Symbol description
1A, 1B, 2A, the electroconductive adhesive sheet of 2B, 3,4
11 cohesive conductive layers (X)
The cohesive conductive layers (X-I) of 11a the 1st
The cohesive conductive layers (X-II) of 11b the 2nd
12 non-adhesive conductive layers (Y)
The non-adhesive conductive layers (Y-I) of 12a the 1st
The non-adhesive conductive layers (Y-II) of 12b the 2nd
13 base materials
14 stripping films
21 2 layers of body
The 1st two layer of body of 21a
The 2nd two layer of body of 21b
22 3 layers of body
Specific embodiment
In this specification, " weight average molecular weight (Mw) " is that standard is determined and be converted into gel permeation chromatography (GPC) to gather Cinnamic value, is the value determined based on the method described in embodiment specifically.
In addition, when for example using the term of " (methyl) acrylate ", expression is " acrylate " and " methacrylic acid Both esters ", other similar terms are similarly.
Additionally, in the case of without specified otherwise, " surface resistivity of electroconductive adhesive sheet " is represented from conduction Property the surface resistivity that determines of the face side of cohesive conductive layer (X) that has of bonding sheet.
It should be noted that in the present invention, the surface resistivity of each layer and the value of specific insulation are based on JIS K 7194 and the value that determines, the value that the concrete method using described in embodiment is determined.
[electroconductive adhesive sheet]
The electroconductive adhesive sheet of the present invention at least has cohesive conductive layer (X) and non-adhesive conductive layer (Y).
The electroconductive adhesive sheet of the present invention can make cohesive conductive layer (X) by arranging non-adhesive conductive layer (Y) Surface resistivity is greatly reduced, improves static electricity resistance and electric conductivity.As a result, need not be containing big in cohesive conductive layer (X) The carbon system filler of amount, therefore the electroconductive adhesive sheet of the present invention has good bonding force.
In the present invention, " cohesive conductive layer (X) " and " non-adhesive conductive layer (Y) " is according to the presence or absence of cohesive come area Not, the presence or absence of cohesive judges according to the peak value of the probe adhesion (probe tack) on the surface relative to each conductive layer.
That is, in the present invention, if the peak of the probe adhesion relative to the surface of the conductive layer as object It is worth for more than 0.1N, then judges that the conductive layer has cohesive, is classified as " cohesive conductive layer (X) ".
If conversely, being less than 0.1N relative to the peak value of the probe adhesion on the surface of the conductive layer as object, sentenced The conductive layer break for non-adhesive, is classified as " non-adhesive conductive layer (Y) ".
It should be noted that being based on JIS relative to the peak value of the probe adhesion on the surface of the conductive layer as object The value of Z 0237 (1991) and measure, specifically refers to, the value determined using the method described in hereafter described embodiments.
As long as the electroconductive adhesive sheet of the present invention at least has cohesive conductive layer (X) and non-adhesive conductive layer (Y) Structure be just not particularly limited, it is possible to have other layers in addition.
In addition, the electroconductive adhesive sheet of one of embodiments of the present invention can also be cohesive conductive layer (X) with it is non- The structure of other layers is set between cohesive conductive layer (Y), but prevents quiet from the surface resistivity of electroconductive adhesive sheet, raising is reduced Electrically and from the viewpoint of electric conductivity, preferably cohesive conductive layer (X) and the direct lamination of non-adhesive conductive layer (Y) Structure.
Fig. 1 is the electric conductivity with base material of the structure of one of the preferred embodiment of electroconductive adhesive sheet as the present invention The profile of bonding sheet.
As the electroconductive adhesive sheet of one of embodiments of the present invention, having as shown in such as Fig. 1 (a) can be enumerated The electroconductive adhesive sheet of the structure of laminated substrate 13, non-adhesive conductive layer (Y) 12 and cohesive conductive layer (X) 11 successively 1A.Electroconductive adhesive sheet 1A has by non-adhesive conductive layer (Y) 12 and cohesive conductive layer on the face of the side of base material (X) the 11 two layers of body 21 for constituting.
Alternatively, it is also possible to form the structure relative to electroconductive adhesive sheet 1A further on cohesive conductive layer (X) 11 Electroconductive adhesive sheet 1B as shown in Fig. 1 (b) of lamination stripping film 14.
In addition, the electroconductive adhesive sheet, or such as Fig. 1 (c), (d) institute as one of embodiments of the present invention Respectively with two layers be made up of non-adhesive conductive layer (Y) and cohesive conductive layer (X) on the two sides of base material as showing The electroconductive adhesive sheet of body 21a, 21b.
That is, the electroconductive adhesive sheet 2A shown in Fig. 1 (c) has by the 1st non-stick on the face of the side of base material 13 The 1st two layer of body 21a that conjunction property conductive layer (Y-I) 12a and the 1st cohesive conductive layer (X-I) 11a is constituted, in the another of base material 13 There is the 2nd two be made up of the 2nd non-adhesive conductive layer (Y-II) 12b and the 2nd cohesive conductive layer (X-II) 11b on the face of side Layer body 21b.
In addition, there is the electroconductive adhesive sheet 2B shown in Fig. 1 (d) structure relative to electroconductive adhesive sheet 2A further to exist 1st cohesive conductive layer (X-I) 11a is upper and the 2nd cohesive conductive layer (X-II) 11b on respectively lamination have stripping film 14a, 14b Structure.
In addition, Fig. 2 is the composition of one of the preferred embodiment of electroconductive adhesive sheet as the present invention without base material Electroconductive adhesive sheet profile.
Electroconductive adhesive sheet, or the conductive adhesive without base material as one of embodiments of the present invention Piece, specifically can enumerate as shown in Fig. 2 (a) with being clamped by cohesive conductive layer (X) using 2 stripping films 14a, 14b 11 and non-adhesive conductive layer (Y) 12 constitute two layers of body 21 structure electroconductive adhesive sheet 3.
In addition, as the electroconductive adhesive sheet of one of embodiments of the present invention, can also be as shown in Fig. 2 (b) With using 2 stripping films 14a, 14b clamping successively cohesive conductive layer (X-I) 11a of lamination the 1st, non-adhesive conductive layer (Y) electroconductive adhesive sheet 4 of the structure of three layers of body 22 of the 12 and the 2nd cohesive conductive layer (X-II) 11b.
As the electroconductive adhesive sheet of one of the embodiments of the present invention with structure other than the above, tool can be also enumerated There is the one side of the stripping film by have passed through lift-off processing on two sides so that the mode that cohesive conductive layer (X) exposes is arranged by bonding Property conductive layer (X) and the electric conductivity of structure that is rolled into a roll of the material of two layers of body that constitutes of non-adhesive conductive layer (Y) glue Close piece etc..
Above-mentioned the 1st cohesive conductive layer (X-I) 11a and the 2nd cohesive conductive layer (X-II) 11b can be by identical The layer of adhesive composition formation, or the layer formed by different adhesive compositions.
In addition, with regard to the 1st non-adhesive conductive layer (Y-I) 12a and the 2nd non-adhesive conductive layer (Y-II) 12b, similarly Ground, both can be to form layer that material formed, or by the different layers that material is formed that formed by identical.
It should be noted that in the present invention, the 1st cohesive conductive layer (X-I) and the 2nd cohesive conductive layer (X-II) Constitute, the structure of 1st non-adhesive conductive layer (Y-I) and 2nd non-adhesive conductive layer (Y-II) identical with cohesive conductive layer (X) Into identical with non-adhesive conductive layer (Y).
Cohesive conductive layer (X) is with cohesive (peak value of above-mentioned probe adhesion is more than 0.1N) and has Electric conductivity (specific insulation (the ρ of single layerVX) it is 1.0 × 108Below Ω cm) layer.
On the other hand, non-adhesive conductive layer (Y) is non-adhesive (peak value of above-mentioned probe adhesion is less than 0.1N) Layer, also, be with the electric conductivity (specific insulation (ρ of single layerVY) it is 1.0 × 108Below Ω cm) layer.
In the present invention, the specific insulation (ρ of single cohesive conductive layer (X)VX) it is 1.0 × 100～1.0 × 108 Ω cm, be preferably 1.0 × 100～1.0 × 106Ω cm, more preferably 1.0 × 100～1.0 × 105Ω cm, further Preferably 1.0 × 100～1.0 × 104Ω·cm。
Due in order that specific insulation (ρVX) it is less than 1.0 × 100Ω/ would have to contain conductive material in a large number, Therefore, being easily caused the bonding force of cohesive conductive layer (X) reduces, and also not preferred from the economic viewpoint.
On the other hand, specific insulation (ρVX) more than 1.0 × 108During Ω/, even if arranging non-adhesive conductive layer (Y) Also it is difficult to show the effect that the surface resistivity of electroconductive adhesive sheet of sening as an envoy to is reduced.
In addition, specific insulation (the ρ of single non-adhesive conductive layer (Y)VY) it is 1.0 × 10-4～1.0 × 106Ω· Cm, be preferably 1.0 × 10-4～1.0 × 104Ω cm, more preferably 1.0 × 10-4～1.0 × 103Ω cm, further preferably For 1.0 × 10-4～1.0 × 102Ω cm, still more preferably be 1.0 × 10-4～1.0 × 101It is Ω cm, further excellent Elect 1.0 × 10 as-4～1.0 × 100Ω·cm。
Even if arranging specific insulation (ρVY) it is less than 1.0 × 10-4Ω/ or more than 1.0 × 106The non-adhesive of Ω/ Conductive layer (Y), it is also difficult to show the effect that the surface resistivity of gained electroconductive adhesive sheet of sening as an envoy to is reduced.
It should be noted that in an embodiment of the invention, have from the surface resistivity of electroconductive adhesive sheet is made From the viewpoint of effect is reduced, the specific insulation (ρ of preferably single non-adhesive conductive layer (Y)VY) it is than single cohesive Specific insulation (the ρ of conductive layer (X)VX) little value.
It is single from obtaining bonding force well and can make from the viewpoint of the electroconductive adhesive sheet that surface resistivity is effectively reduced Surface resistivity (the ρ of only cohesive conductive layer (X)SX) it is preferably 1.0 × 102～1.0 × 1010Ω/, more preferably 1.0 ×102～1.0 × 108Ω/, more preferably 1.0 × 102～1.0 × 107Ω/, still more preferably be 1.0 × 102 ～1.0 × 106Ω/□。
On the other hand, from obtain surface resistivity is effectively reduced electroconductive adhesive sheet from the viewpoint of, individually Surface resistivity (the ρ of non-adhesive conductive layer (Y)SY) it is preferably 1.0 × 10-2～1.0 × 108Ω/, more preferably 1.0 × 10-2～1.0 × 107Ω/, more preferably 1.0 × 10-2～1.0 × 106Ω/, still more preferably be 1.0 × 10-2 ～1.0 × 105Ω/, much further preferably from 1.0 × 10-2～1.0 × 104Ω/, particularly preferably 1.0 × 10-2～1.0 ×103Ω/□。
It should be noted that in an embodiment of the invention, have from the surface resistivity of electroconductive adhesive sheet is made From the viewpoint of effect is reduced, the surface resistivity (ρ of preferably single non-adhesive conductive layer (Y)SY) it is than single cohesive Surface resistivity (the ρ of conductive layer (X)SX) little value.
In addition, in the present invention, the thickness (t of cohesive conductive layer (X)X) with the thickness (t of non-adhesive conductive layer (Y)Y) Thickness ratio [tX/tY] for less than 20000, be preferably less than 10000, more preferably less than 5000, more preferably 1000 with Under, still more preferably for less than 500, much further preferably from less than 400, particularly preferably less than 250.
When the thickness ratio is more than 20000, for cohesive conductive layer (X), the thickness of non-adhesive conductive layer (Y) It is insufficient, therefore, even if arrange non-adhesive conductive layer (Y) to be also difficult to make the surface resistivity of electroconductive adhesive sheet fully drop It is low.
It should be noted that with regard to the lower limit of the thickness ratio, be not particularly limited, from showing good bonding force Viewpoint is set out, used as thickness ratio [tX/tY], preferably more than 0.01, more preferably more than 0.1, more preferably 0.2 with On.
Thickness (the t of cohesive conductive layer (X)X) can suitably be adjusted according to purposes etc., but preferably 1～1200 μm, more Preferably 2～600 μm, more preferably 3～300 μm, be still more preferably 5～250 μm, much further preferably from 10～ 200 μm, particularly preferably 15～150 μm.
Thickness (tX) for more than 1 μm when, can show that the good bonding force of the species for not relying on adherend.Separately On the one hand, thickness (tX) for less than 1200 μm when, the electric conductivity of gained electroconductive adhesive sheet becomes good.In addition, this is being led When electrically bonding sheet makes coiling body, the winding for deforming and causing because of cohesive conductive layer (X) can be suppressed to misplace, bond The drawbacks of property conductive layer (X) exposes such relative to the end of coiling body.
Thickness (the t of non-adhesive conductive layer (Y)Y) can suitably be adjusted according to purposes etc., but preferably 0.01～200 μ M, more preferably 0.1～160 μm, more preferably 0.5～130 μm, be still more preferably 1.0～100 μm.
Thickness (tY) for more than 0.01 μm when, the surface resistivity of non-adhesive conductive layer (Y) can be effectively reduced.
On the other hand, thickness (tY) for less than 200 μm when, when electroconductive adhesive sheet is made into coiling body, can suppress The winding for deforming and causing because of non-adhesive conductive layer (Y) misplaces, non-adhesive conductive layer (Y) relative to coiling body end The drawbacks of portion exposes such.In addition, the gross thickness by reducing electroconductive adhesive sheet, can obtain being readily adapted for use in miniature electric The electroconductive adhesive sheet of equipment.
[the formation material of cohesive conductive layer (X)]
Cohesive conductive layer (X) is preferably by the adhesive composition comprising resin of binding property (x1) and carbon system filler (x2) The layer of formation.
It should be noted that the adhesive composition can also contain friendship according to the species of resin of binding property (x1) difference Connection agent, thickener, the universal additive beyond these.
Hereinafter, each composition for including in the adhesive composition is illustrated.
<Resin of binding property (x1)>
The resin of binding property (x1) included in adhesive composition as the formation material of cohesive conductive layer (X) is referred to Weight average molecular weight is more than 10,000 resin with cohesive.
As the weight average molecular weight (Mw) of resin of binding property (x1), go out from the viewpoint of the bonding force for improving electroconductive adhesive sheet Send out, preferably 10,000～2,000,000, more preferably 20,000～1,500,000.
Total amount (100 matter of the content of the resin of binding property (x1) in adhesive composition relative to the adhesive composition Amount %) it is preferably 60.0～99.99 mass %, more preferably 70.0～99.9 mass %, is more preferably 80.0～99.5 Quality %, still more preferably be 90.0～99.0 mass %.
As resin of binding property (x1), improve from the bonding force for making electroconductive adhesive sheet, make static electricity resistance and electric conductivity good From the viewpoint of good, preferably comprise selected from acrylic resin, polyurethane based resin, polyisobutene resinoid, phenylethylene tree More than a kind resin of binding property in fat, polyester resin and polyolefin resin, more preferably comprising selected from acrylic resin, More than a kind resin of binding property in polyurethane based resin, polyisobutene resinoid and styrene resin, further preferably includes More than a kind resin of binding property in acrylic resin and polyurethane based resin.
(acrylic resin)
As the acrylic resin that can serve as resin of binding property (x1), can enumerate for example：Containing from straight chain Or the construction unit of (methyl) alkyl acrylate of the alkyl of side chain polymer, containing from circulus (first Base) acrylate the polymer of construction unit etc..
As the weight average molecular weight (Mw) of acrylic resin, preferably 50,000～1,500,000, more preferably 150,000～130 Ten thousandth, it is more preferably 250,000～1,100,000, is still more preferably 350,000～900,000.
In acrylic resin, (methyl) alkyl acrylate from the alkyl with carbon number 1～20 is preferably comprised The construction unit (a1) of base ester (a1 ') (hereinafter also referred to as " monomer (a1 ') ") and from containing monomer (a2 ') (below, The acrylic copolymer of construction unit (a2) also referred to as " monomer (a2 ') ").
It should be noted that the acrylic copolymer can also be with its beyond being derived from demonomerization (a1 ') and (a2 ') The construction unit (a3) of its monomer (a3 ').
In addition, the copolymerization form of the acrylic copolymer is not particularly limited.That is, common as the acrylic compounds Polymers, can be any copolymer in block copolymer, random copolymer, graft copolymer.
The carbon number of the alkyl having as monomer (a1 '), from from the viewpoint of raising adhesion characteristic, preferably 1 ～12, more preferably 4～8, more preferably 4～6.
As monomer (a1 '), can enumerate for example：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Propyl propionate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) propylene Sour tridecane base ester, (methyl) stearyl acrylate ester etc..
In these monomers (a1 '), preferably (methyl) butyl acrylate and (methyl) 2-EHA, more preferably (methyl) butyl acrylate.
Relative to the entire infrastructure unit (100 mass %) of aforesaid propylene acid copolymer, the content of construction unit (a1) It is preferably 50～99.5 mass %, more preferably 60～99 mass %, more preferably 70～97 mass %, further excellent Elect 80～95 mass % as.
As monomer (a2 '), can enumerate for example：Hydroxyl monomer, carboxyl group-containing monomer, containing epoxy based monomers, list containing amino Body, cyano-containing monomer, ketone group containing monomer, monomer containing alkoxysilyl etc..
In these monomers (a2 '), preferred carboxyl group-containing monomer.
As carboxyl group-containing monomer, can enumerate：(methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid etc., preferably (methyl) Acrylic acid.
The content of construction unit (a2) is excellent relative to the entire infrastructure unit (100 mass %) of aforesaid propylene acid copolymer Elect 0.5～50 mass %, more preferably 1～40 mass % as, more preferably 5～30 mass %, be still more preferably 7 ～20 mass %.
As monomer (a3 '), can enumerate for example：(methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) third Olefin(e) acid isobornyl thiocyanoacetate, the ring pentyl ester of (methyl) acrylic acid two, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl (methyl) acrylate, vinyl acetate, the propylene with circulus such as epoxide ethyl ester, acid imide (methyl) acrylate Nitrile, styrene etc..
The content of construction unit (a3) is preferably relative to the entire infrastructure unit (100 mass %) of acrylic copolymer 0～30 mass %, more preferably 0～20 mass %, more preferably 0～10 mass %, still more preferably it is 0～5 matter Amount %.
It should be noted that above-mentioned monomer (a1 ')～(a3 ') can be used alone respectively or make two or more combination With.
(polyurethane based resin)
As the polyurethane based resin that can serve as resin of binding property (x1), as long as main chain and/or side chain have amino The polymer of at least one of formic acid ester bond and urea bond is just not particularly limited, and can enumerate for example：Make polyalcohol and polynary different Cyanate esters reaction obtained from carbamates prepolymer (α), enter relative to the carbamates prepolymer (α) Carbamates polymer (β) etc. obtained from the chain extending reaction for having used chain extender is exercised in one stepping.
In the middle of these, as the polyurethane based resin that one of embodiments of the present invention are used, preferably comprise with poly- The carbamates polymer of oxyalkylene skeleton.
As the weight average molecular weight (Mw) of polyurethane based resin, preferably 10,000～200,000, more preferably 1.2 ten thousand～150,000, More preferably 1.5 ten thousand～100,000, still more preferably it is 20,000～70,000.
As the polyalcohol of the raw material for becoming carbamates prepolymer (α), can enumerate for example：It is aklylene glycol, poly- The polyol compounds such as ether type polyalcohol, polyester polyol, polycarbonate polyol, as long as polyalcohol is not just special Limit, can be glycol, the triol of 3 senses of 2 senses.
In these polyalcohols, from the viewpoints such as easiness, the reactivity for obtaining, preferred diol.
As glycol, can enumerate for example：1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, neopentyl glycol, 1,6- oneself The aklylene glycols such as alkanediol, ethylene glycol, propane diols, diethylene glycol, the DPGs such as glycol, 1,7- heptandiols, poly- second two Polyether polyols such as the PAGs such as alcohol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol etc..Need explanation , these glycol may be used singly or in combination of two or more.
In these glycol, from the case where the reaction with chain extender is further carried out, gelation is suppressed in the reaction From the viewpoint of, the glycol of preferable weight-average molecular weight 1000～3000.
As the polyhydric isocyanate compound of the raw material for becoming carbamates prepolymer (α), can enumerate：Aromatic series Polyisocyanates, aliphatic polyisocyante, ester ring type polyisocyanates etc..
As aromatic polyisocyanate, can enumerate for example：1,3- phenylene vulcabonds, the isocyanide of 1,4- phenylenes two Acid esters, 4,4 '-methyl diphenylene diisocyanate (MDI), 2,4 toluene diisocyanate (2,4-TDI), 2,6- toluene two are different Cyanate (2,6-TDI), 4,4 '-toluidine diisocyanate, 2,4,6- triisocyanate toluene, 1,3,5- triisocyanates Benzene, dianisidine diisocyanate, 4,4 '-diphenyl ether diisocyanate, 4,4 ', 4 " isocyanic acid of-triphenyl methane three Ester, 1,4- tetramethylxylylene diisocyanates, 1,3- tetramethylxylylene diisocyanates etc..
As aliphatic polyisocyante, can enumerate for example：Trimethylene diisocyanate, the isocyanic acid of tetramethylene two Ester, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2- trimethylene diisocyanates, 2,3- Aden Group diisocyanate, 1,3- tetramethylene diisocyanates, ten dimethylene diisocyanates, 2,4,4- tri-methyl hexamethylenes two Isocyanates etc..
As ester ring type polyisocyanates, can enumerate for example：3- isocyanates methylene -3,5,5- trimethylcyclohexyls Isocyanates (IPDI), 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanates, the isocyanic acid of 1,4- hexamethylenes two Ester, methyl -2,4- cyclohexane diisocyanates, methyl -2,6- cyclohexane diisocyanates, (cyclohexyl is different for 4,4 '-di-2-ethylhexylphosphine oxide Cyanate), double (isocyanatomethyl) hexamethylenes of 1,4-, double (isocyanatomethyl) hexamethylenes of 1,4- etc..
It should be noted that polyhydric isocyanate compound can also be selected from above-mentioned aromatic polyisocyanate, fat The modified body of the compound (polyisocyanates) in race's polyisocyanates and ester ring type polyisocyanates.Specifically, it is also possible to It is the biuret form modified body of the trimethylolpropane adduct type modified body of the compound, the compound and water reaction, makes this Compound contains the isocyanurate type modified body of isocyanurate ring.
In these polyhydric isocyanate compounds, from the viewpoint for obtaining the excellent carbamates polymer of cohesive Set out, be preferably selected from 4,4 '-methyl diphenylene diisocyanate (MDI), 2,4- toluene di-isocyanate(TDI)s (2,4-TDI), 2, 6- toluene di-isocyanate(TDI)s (2,6-TDI), hexamethylene diisocyanate (HMDI), 3- isocyanates methylene -3,5,5- More than a kind in trimethylcyclohexylisocyanate (IPDI) and their modified body, from from the viewpoint of weatherability, more preferably It is more than a kind in HMDI, IPDI and their modified body.
Isocyanate group content (NCO%) in carbamates prepolymer (α) is determined with being based on JIS K 1603 Value meter, preferably 0.5～12 mass %, more preferably 1～4 mass %.
As chain extender, preferably with least one of hydroxyl and amino in 2 groups compound or with hydroxyl The compound of more than 3 groups at least one of base and amino.
As the compound of 2 groups in at least one of hydroxyl and amino, aliphatic two is preferably selected from At least a kind compound in alcohol, aliphatic diamine, alkanolamine, bis-phenol, aromatic diamine.
As aliphatic diol, can enumerate for example：1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, neopentyl glycol, The aklylene glycols such as alkanediol, ethylene glycol, propane diols, diethylene glycol, the DPGs such as 1,6-HD, 1,7- heptandiols.
As aliphatic diamine, can enumerate for example：Ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, 1,5- pentanediamines, 1, 6- hexamethylene diamines etc..
As alkanolamine, can enumerate for example：MEA, single Propanolamine, isopropanolamine etc..
As bis-phenol, such as bisphenol-A etc. can be enumerated.
As aromatic diamine, can enumerate for example：Diphenylmethanediamiand, toluenediamine, benzene dimethylamine etc..
As the compound of more than 3 groups in at least one of hydroxyl and amino, can enumerate for example：Three hydroxyls The polyalcohols such as methylpropane, double trimethylolpropane, pentaerythrite, dipentaerythritol, 1- amino -2,3- propane diols, 1- methyl The amino alcohols such as amino -2,3- propane diols, N- (2- hydroxypropyl monoethanolamines), the ethylene oxide of durol dimethylamine or oxidation third Alkene addition product etc..
(polyisobutene resinoid)
Can be as the polyisobutene resinoid (hereinafter also referred to as " PIB resinoids ") that resin of binding property (x1) is used Main chain or side chain have the resin of polyisobutene skeleton.
As the resinoid weight average molecular weight of PIB (Mw), from the cohesiveness, the raising that fully obtain gained adhesive composition The viewpoint of the bonding force of electroconductive adhesive sheet and from the viewpoint of preventing the pollution of adherend, preferably more than 20,000, enter One step, from from the viewpoint of the wetability for adherend, dissolubility in a solvent, preferably 30,000～1,000,000, more excellent Elect 50,000～800,000, more preferably 70,000～600,000 as.
As PIB resinoids, can enumerate for example：Polyisobutene, isobutene and isoamyl two as the homopolymers of isobutene The copolymer and these copolymers Jing brominations of the copolymer of alkene, the copolymer of isobutene and n-butene, isobutene and butadiene Or the halogenated butyl rubber of chlorination etc. etc..
It should be noted that being whole knots from the construction unit of isobutene in the case where PIB resinoids are copolymer Content is most in structure unit.
In the PIB resinoids that one of embodiments of the present invention are used, from the content of the construction unit of isobutene 80～100 mass %, more preferably 90～100 are preferably relative to the resinoid entire infrastructure units of PIB (100 mass %) Quality %, more preferably 95～100 mass %, still more preferably it is 98～100 mass %.
These PIB resinoids may be used alone, or two or more kinds may be used in combination.
In the middle of these, from from the viewpoint of the durability and weatherability for improving formed cohesive conductive layer (X), preferably In polymerization with fine and close molecular structure, more comprising main chain and side chain do not exist polymerism double bond from isobutene The PIB resinoids of construction unit.
In the PIB resinoids that one of embodiments of the present invention are used, relative to the resinoid entire infrastructures of the PIB There is no the content of the construction unit from isobutene of polymerism double bond in unit (100 mass %), such main chain and side chain Preferably 80～100 mass %, more preferably 90～100 mass %, more preferably 95～100 mass %, further Preferably 98～100 mass %.
In addition, using PIB it is resinoid in the case of, preferably by the high PIB resinoids of weight average molecular weight and weight average molecular weight Low PIB resinoids are applied in combination.
More specifically, the PIB resinoids for being used as one of embodiments of the present invention, preferably by weight average molecular weight PIB resinoids (p1) (hereinafter also referred to " PIB resinoids (p1) ") and weight average molecular weight for 270,000～600,000 is 50,000～250,000 PIB resinoids (p2) (hereinafter also referred to " PIB resinoids (p2) ") be applied in combination.
The high PIB resinoids (p1) of weight average molecular weight are favorably improved the cohesive formed by gained adhesive composition and lead The durability and weatherability of electric layer (X), while improving bonding force.
In addition, the low PIB resinoids (p2) of weight average molecular weight are compatible well with PIB resinoids (p1), can be moderately Plasticising is carried out to PIB resinoids (p1), so as to be favorably improved wetability of the cohesive conductive layer (X) relative to adherend, Improve bonding physical property, flexibility etc..
From the above point of view, the weight average molecular weight (Mw) of PIB resinoids (p1) is preferably 270,000～600,000, is more preferably 290000～480,000, it is more preferably 310,000～450,000, is still more preferably 320,000～400,000.
From from the viewpoint of above-mentioned, the weight average molecular weight (Mw) of PIB resinoids (p2) is preferably 50,000～250,000, more preferably For 80,000～230,000, more preferably 140,000～220,000, be still more preferably 180,000～210,000.
Relative to the mass parts of PIB resinoids (p1) 100, the content ratio of PIB resinoids (p2) is preferably 5～55 mass Part, more preferably 6～40 mass parts, more preferably 7～30 mass parts, be still more preferably 8～20 mass parts.
The content ratio of PIB resinoids (p2) be 5 mass parts more than when, can fully by PIB resinoids (p1) plasticising, So as to make formed cohesive conductive layer (X) relative to adherend wetability it is good while, it is also possible to make bonding Power is improved.
On the other hand, when the content ratio of PIB resinoids (p2) is below 55 mass parts, formed cohesive can be made The bonding force of conductive layer (X), confining force and durability are improved.
(styrene resin)
The styrene resin that can be used as resin of binding property (x1) is with from cinnamic construction unit Polymer.
In the styrene resin that one of embodiments of the present invention are used, relative to the complete of the styrene resin Portion's construction unit (100 mass %), from the content of cinnamic construction unit 5～50 mass %, more preferably 10 are preferably ～40 mass %, more preferably 15～35 mass %.
From from the viewpoint of the bonding force for improving electroconductive adhesive sheet, the weight average molecular weight (Mw) of styrene resin is preferably For 10,000～400,000, more preferably 20,000～300,000, more preferably 2.5 ten thousand～200,000.
As the softening point of styrene resin, from from the viewpoint of the bonding force for improving electroconductive adhesive sheet, preferably 80～200 DEG C, more preferably 90～160 DEG C, more preferably 100～140 DEG C, be still more preferably 105～135 DEG C.
It should be noted that in the present invention, the softening point of styrene resin represents what is determined based on JIS K 2531 Value.
As styrene resin, can enumerate for example：SBS (is also referred to as below For " SBS "), styrene-embedding-(ethylene-co-butylene)-embedding-styrene triblock copolymer (hereinafter also referred to " SEBS "), benzene Ethene-embedding-(ethylene-co-butylene) diblock copolymer (hereinafter also referred to " SEB "), styrene-butadiene di-block copolymer Thing, styrene-isoprene diblock copolymer, SIS, styrene-embedding- (butadiene -co- isoprene) diblock copolymer, styrene-embedding-(butadiene -co- isoprene)-embedding-styrene three is embedding The carboxy-modified body or styrene of section copolymer etc. or these copolymers is vinylated with the fragrant same clan such as AMS Copolymer of compound etc..
Above-mentioned styrene resin may be used alone, or two or more kinds may be used in combination.
In these styrene resins, preferred SBS, SEBS and SEB, more preferably SBS and SEBS.
It should be noted that in the case that the styrene resin is copolymer, for the form of copolymerization does not have special limit It is fixed.That is, can be any in block copolymer, random copolymer, graft copolymer as the styrene resin Type.
(polyester resin)
Can be sour composition and diol component or polyol component as the polyester resin that resin of binding property (x1) is used Copolymer obtained from Jing polycondensation reactions, also including the modifier of the copolymer.
Above-mentioned polycondensation reaction can be carried out by the conventional polyesterification reaction such as direct esterification, ester-interchange method.
It should be noted that the copolymerization form of the polyester resin is not particularly limited.That is, as the polyesters Resin, can be any type in block copolymer, random copolymer, graft copolymer.
As above-mentioned sour composition, can enumerate for example：Terephthalic acid (TPA), M-phthalic acid, phthalic anhydride, α-naphthalene dicarboxyl Acid, 5-sodium sulfo isophthalate, M-phthalic acid -5- potassium sulfonates or their esters, pimelic acid, suberic acid, azelaic acid, The aliphatic dicarboxylic acids such as decanedioic acid, undecenoic acid, dodecanedicarboxylic acid or their esters；1,4- ring hexahydrophthalic acids Ester ring type dicarboxylic acids such as acid anhydride etc..
As above-mentioned diol component or polyol component, can enumerate for example：Ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 1,9- nonanediols, neopentyl glycol, 3- The aliphatic diols such as methyl pentanediol, 2,2,3- TMPDs, diethylene glycol, triethylene glycol, DPG, 1,4- hexamethylenes Aromatic diols such as the ester ring type glycol such as glycol, 1,4 cyclohexane dimethanol, bisphenol-A etc..
It should be noted that above-mentioned polyester resin may be used alone, or two or more kinds may be used in combination.
(polyolefin resin)
Can be have to be derived from the olefin(e) compounds such as ethene, propylene as the polyolefin resin that resin of binding property (x1) is used Construction unit polymer.
As polyolefin resin, can enumerate for example：Low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE) and The copolymer of the polyethylene such as LLDPE, polypropylene, ethene and propylene, the copolymer of ethene and other alpha-olefins, Propylene is unsaturated with the copolymer of other alpha-olefins, the copolymer of ethene and propylene and other alpha-olefins, ethene and other olefinics Copolymer (vinyl-vinyl acetate copolymer, ethene-(methyl) alkyl acrylate copolymer etc.) of monomer etc..
It should be noted that in the case that the polyolefin resin is copolymer, the form of copolymerization is not particularly limited. That is, can be any type in block copolymer, random copolymer, graft copolymer as the polyolefin resin.
As above-mentioned alpha-olefin, can enumerate for example：1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 4- methyl- 1- amylenes, 4- methyl isophthalic acids-hexene etc..
As above-mentioned ethylenically unsaturated monomer, can enumerate for example：Vinyl acetate, (methyl) acrylic acid, (methyl) propylene Acid alkyl ester, vinyl alcohol etc..
In these polyolefin resins, the copolymer of preferred polypropylene, ethene and propylene, propylene and other alpha-olefins are total to The polypropylene-based resin comprising the construction unit from propylene such as polymers.
It should be noted that said polyolefins resinoid may be used alone, or two or more kinds may be used in combination.
<Carbon system filler (x2)>
As the cohesive group that the formation material as cohesive conductive layer (X) is commonly included in resin of binding property (x1) Carbon system filler (x2) in compound, preferred draw ratio is more than 1.5 carbon system filler.
By the way that containing the carbon system filler that average aspect ratio is more than 1.5, can fully show reduces formed bonding Property conductive layer (X) surface resistivity so that reduce electroconductive adhesive sheet obtained from by arranging non-adhesive conductive layer (Y) Surface resistivity effect.In addition it is possible to make the bonding force of cohesive conductive layer (X) also good.
As the average aspect ratio of carbon system filler (x2), from the above point of view, preferably more than 1.5, more preferably 2～ 10000th, more preferably 3～5000 be still more preferably, 4～1000, much further preferably from 5～500, further Preferably 6～400, particularly preferably 10～300.
In the present invention, " draw ratio " is relative to minor face according to the long edge lengths (H) of the carbon system filler as object The ratio of length (L), i.e. " long edge lengths (H)/bond length (L) " and the value that calculates.In addition, " average aspect ratio " is right The mean value for being somebody's turn to do " draw ratio " that 10 carbon system fillers as object are calculated.
In addition, the long edge lengths (H) of carbon system filler (x2) refer to short transverse (the length side of the carbon system filler as object To) length.
On the other hand, for the bond length (L) of carbon system filler (x2), in the carbon system filler as object and height On the orthogonal cutting plane in direction (length direction), if the section is circle or oval, the bond length (L) of carbon system filler (x2) Diameter or major diameter are referred to, if the section is polygon, the bond length (L) of carbon system filler (x2) refers to that this is polygonal outer Cut diameter of a circle.
As the long edge lengths (H) of carbon system filler (x2), preferably 0.01～2000 μm, more preferably 0.05～1000 μ M, more preferably 0.07～500 μm, it still more preferably it is 0.10～100 μm.
It should be noted that in the present invention, it is also possible to by the average of the long edge lengths of optional 10 carbon systems filler Value is considered as the value of above-mentioned " the long edge lengths (H) of carbon system filler (x2) ".
As the bond length (L) of carbon system filler (x2), preferably 1～1000nm, more preferably 2～750nm, further Preferably 3～500nm, still more preferably for 5～100nm, much further preferably from 7～50nm.
It should be noted that in the present invention, it is also possible to by the average of the bond length of optional 10 carbon systems filler Value is considered as the value of above-mentioned " bond length (L) of carbon system filler (x2) ".
As the shape of carbon system filler (x2), can enumerate for example：Column, tubular, fusiform, threadiness, oblate spheroid shape (positive ball Degree is usually less than 0.7) and by these shapes for combining etc..
In these shapes, from being formed from the viewpoint of the cohesive conductive layer (X) with satisfactory electrical conductivity, it is preferably selected from More than a kind in the carbon system filler of column, the carbon system filler of tubular and fibrous carbon system filler.
The content of carbon system filler (x2) in adhesive composition is preferably relative to the mass parts of resin of binding property (x1) 100 0.01～15 mass parts, more preferably 0.02～10 mass parts, more preferably 0.30～7.0 mass parts, more preferably 0.40～5.0 mass parts, more preferably 0.50～4.5 mass parts, still more preferably it is 0.70～3.8 mass parts.
When the content of carbon system filler (x2) is more than 0.01 mass parts, can fully show that reduction is formed single The surface resistivity of cohesive conductive layer (X) and reduce leading obtained from non-adhesive conductive layer (Y) by further arranging The effect of the surface resistivity of electrical bonding sheet.
On the other hand, when the content of carbon system filler (x2) is below 15 mass parts, the cohesive conductive layer (X) for being formed Bonding force becomes good.
It should be noted that for the electroconductive adhesive sheet of the present invention, even if due to the carbon in cohesive conductive layer (X) It is that the content of filler (x2) also can be shown that less excellent static electricity resistance and electric conductivity, therefore need not in a large number coordinates carbon system filler (x2)。
In addition, the content of carbon system filler (x2) as the total amount (100 mass %) relative to adhesive composition, from upper From the viewpoint of stating, usually 0.01～10 mass %, be preferably 0.30～7.0 mass %, more preferably 0.40～5.0 matter Measure %, more preferably 0.50～4.5 mass %, be still more preferably 0.70～3.8 mass %.
As carbon system filler (x2), can enumerate for example：Carbon nanomaterial, carbon black, ground carbon fiber, graphite etc., but from making From the viewpoint of the surface resistivity of the cohesive conductive layer (X) for being formed is reduced and makes bonding force good, preferred carbon nanometer material Material.
Carbon nanomaterial is made up of the material comprising the graphite flake with hexatomic ring arrangement architecture as main structure, can be in graphite Element, or carbon nanomaterial in structure containing boron, nitrogen etc. in addition to carbon encapsulates the form of other materials, additionally, also It can be form that carbon nanomaterial is modified by other conductive materials.
As carbon nanomaterial, can enumerate for example：CNT (CNT), carbon nano-fiber, carbon nanohorn, carbon nanocone, Fullerene etc., preferred CNT.
There is CNT graphite (graphite) piece with carbon six-membered ring structure as main structure to be closed into the knot of cylindrical shape The carbon polyhedron of the tubular of structure.
CNT includes：With one layer of graphite flake be closed into cylindrical shape structure SWCN, with two-layer Graphite flake is closed into the double-walled carbon nano-tube of the structure of cylindrical shape and is closed into more than 3 layers concentric tubulars with graphite flake The multi-walled carbon nano-tubes of sandwich construction, it is also possible to by these it is any two or more be applied in combination.
<Crosslinking agent>
Can also further contain crosslinking agent in adhesive composition as the formation material of cohesive conductive layer (X).
Particularly, using above-mentioned acrylic resin (the particularly above-mentioned acrylic acid with construction unit (a2) Analog copolymer) as resin of binding property (x1) in the case of, from the sight of the bonding force for improving formed cohesive conductive layer (X) Point sets out, and preferably comprises crosslinking agent.
As crosslinking agent, can enumerate for example：Isocyanates crosslinking agent, epoxies crosslinking agent, the crosslinking of aziridine class Agent, metal-chelating species crosslinking agent, amine cross-linking agent, amino resins class crosslinking agent etc..These crosslinking agents can be used alone or Two or more is applied in combination.
In the middle of these, from from the viewpoint of the bonding force for improving electroconductive adhesive sheet, preferred isocyanate class crosslinking agent.
As isocyanates crosslinking agent, can enumerate for example：2,4 toluene diisocyanate, 2,6- toluene diisocynates Ester, 1,3- XDIs, 1,4- XDIs, the isocyanic acid of '-two of diphenyl methane -4,4 Ester, diphenyl methane -2,4 '-diisocyanate, 3- MDPM diisocyanate, hexamethylene diisocyanate, IPDI, dicyclohexyl methyl hydride -4,4 '-diisocyanate, dicyclohexyl methyl hydride -2,4 '-diisocyanate, The polyhydric isocyanate compounds such as LDI.
In addition, the trimethylolpropane adduct type that polyhydric isocyanate compound can also be above-claimed cpd is modified Body and biuret form modified body, the isocyanurate type modified body comprising isocyanurate ring of water reaction.
The content of crosslinking agent relative to the mass parts of resin of binding property (x1) 100, preferably 0.01～15 mass parts, more preferably For 0.05～10 mass parts, more preferably 0.1～5 mass parts.
<Thickener>
Can also further contain thickener as the adhesive composition of the formation material of cohesive conductive layer (X).
Particularly, using above-mentioned polyurethane based resin, PIB resinoids and styrene resin as resin of binding property (x1) in the case of, from from the viewpoint of the bonding force for improving formed cohesive conductive layer (X), thickener is preferably comprised.
It should be noted that the weight average molecular weight (Mw) of the thickener is usually less than 10,000, it is to be different from above-mentioned cohesive The composition of resin (x1).
From from the viewpoint of the bonding force for improving formed cohesive conductive layer (X), the weight average molecular weight of thickener (Mw) 400～4000, more preferably 800～1500 are preferably.
As the softening point of thickener, preferably more than 110 DEG C, more preferably 110～180 DEG C, more preferably 115 ～175 DEG C, still more preferably be 120～170 DEG C.
It should be noted that in the present invention, " softening point " of thickener refers to the value determined based on JIS K 2531.
As thickener, can enumerate for example：The rosin resinoid such as rosin resin, rosin phenolic resin and its ester compounds； By these hydrogenated rosin resinoids obtained from rosin hydrogenate resins；Terpene resin, aromatic modified terpene resin, terpene phenolic The terpenoid resins such as resinoid；By these hydrogenated terpene resins obtained from terpenoid resin hydrogenation；Make by naphtha Jing hot tearings The C5 through-stones obtained from C 5 fraction copolymerization such as amylene, isoprene, pipering (piperine), the 1,3- pentadienes for solving and generating The hydrogenated petroleum resin of oleoresin and the C5 through-stone oleoresins；Make indenes, vinyl first hot cracked by naphtha and generate The hydrogenation stone of C9 through-stones oleoresin and the C9 through-stone oleoresins obtained from the C9 cut copolymerization such as benzene, α-or Beta-methyl styrene Oleoresin；Etc..
It should be noted that in the present invention, thickener can be used alone, or by different two or more of softening point, structure It is applied in combination.
The content of thickener is preferably 1～200 mass parts, more preferably 5 relative to the mass parts of resin of binding property (x1) 100 ～160 mass parts, more preferably 10～120 mass parts.
It should be noted that in the case that resin of binding property (x1) includes acrylic resin, the content phase of the thickener For the mass parts of acrylic resin 100 are preferably 1～100 mass parts, more preferably 5～50 mass parts, are more preferably 10～40 mass parts.
, comprising in the case of polyurethane based resin, the content of the thickener is relative to polyurethanes tree for resin of binding property (x1) The mass parts of fat 100 are preferably 5～200 mass parts, more preferably more preferably 40～160 mass parts, 80～120 mass Part.
Resin of binding property (x1) comprising PIB it is resinoid in the case of, the content of the thickener is relative to PIB resinoids 100 Mass parts are preferably 5～100 mass parts, more preferably more preferably 10～80 mass parts, 15～40 mass parts.
, comprising in the case of styrene resin, the content of the thickener is relative to phenylethylene tree for resin of binding property (x1) The mass parts of fat 100 are preferably 5～100 mass parts, more preferably more preferably 15～80 mass parts, 25～60 mass parts.
, comprising in the case of polyester resin, the content of the thickener is relative to polyester resin for resin of binding property (x1) 100 mass parts are preferably 5～100 mass parts, more preferably more preferably 15～80 mass parts, 25～60 mass parts.
, comprising in the case of polyolefin resin, the content of the thickener is relative to TPO tree for resin of binding property (x1) The mass parts of fat 100 are preferably 5～100 mass parts, more preferably more preferably 15～80 mass parts, 25～60 mass parts.
<Other additives>
Do not destroying in the range of effect of the present invention, as the cohesive combination of the formation material of cohesive conductive layer (X) The universal additive being used in conjunction with resin of binding property can generally also be contained in thing.
As such universal additive, can enumerate for example：Ultra-violet absorber, antioxidant, softening agent (plasticizer), fill out Fill agent, antirust agent, pigment, dyestuff, curing agent, auxiliary curing agent, catalyst etc..
In the case of coordinating these universal additives, relative to the mass parts of resin of binding property (x1) 100, universal additive Respective use level is respectively preferably 0.01～6 mass parts, more preferably 0.01～2 mass parts.
As the bonding in the total amount (100 mass %) of the adhesive composition of the formation material of cohesive conductive layer (X) Property resin (x1) and carbon system filler (x2) total content be preferably more than 20 mass %, it is more than more preferably 30 mass %.
In addition, in the case of using the resin of binding property (x1) with acrylic resin as principal component, adhesive composition Total amount (100 mass %) in resin of binding property (x1) and carbon system filler (x2) total content be preferably more than 60 mass %, More than more preferably 70 mass %, more than more preferably 80 mass %, still more preferably for more than 90 mass %.
In the case of the resin of binding property (x1) with polyurethane based resin as principal component, the total amount of adhesive composition The total content of resin of binding property (x1) and carbon system filler (x2) in (100 mass %) is preferably more than 35 mass %, more preferably For more than 40 mass %, more than more preferably 45 mass %, resin of binding property (x1), carbon system filler (x2) and thickener Total content is preferably more than 70 mass %, is more preferably more than 80 mass %, is more preferably more than 90 mass %.
In the case of the resin of binding property (x1) with PIB resinoids as principal component, the total amount of adhesive composition The total content of resin of binding property (x1) and carbon system filler (x2) in (100 mass %) is preferably more than 50 mass %, more preferably For more than 60 mass %, more than more preferably 70 mass %, resin of binding property (x1), carbon system filler (x2) and thickener Total content is preferably more than 70 mass %, is more preferably more than 80 mass %, is more preferably more than 90 mass %.
In the case of the resin of binding property (x1) with styrene resin as principal component, the total amount of adhesive composition The total content of resin of binding property (x1) and carbon system filler (x2) in (100 mass %) is preferably more than 20 mass %, more preferably For more than 25 mass %, more than more preferably 30 mass %.
It should be noted that the implication of the statement of " resin of binding property (x1) with ZZ resinoids as principal component " is：" viscous In resin contained by conjunction property resin (x1), the resinoid contents of ZZ are most ".
The resinoid contents of specific ZZ in as the record, relative to total amount (100 matter of resin of binding property (x1) Amount %), usually more than 50 mass %, it is preferably 65～100 mass %, more preferably 75～100 mass %, further preferably For 85～100 mass %.
<The forming method of cohesive conductive layer (X)>
As the forming method of cohesive conductive layer (X), it is not particularly limited, can be manufactured using known method, example Following methods (X-1) and (X-2) can such as be enumerated.
Method (X-1)：The solution of the organic solvent of adhesive composition is prepared, it is using known coating process that this is molten Liquid is coated on stripping film described below and forms coated film, is dried coated film and forms the side of cohesive conductive layer (X) Method.
Method (X-2)：To resin of binding property (x1) and carbon system filler (x2) etc. carry out plus hot milling and prepare compound It is using known forming process that this is composite formed for sheet after material, so as to form the side of cohesive conductive layer (X) Method.
(method (X-1))
Method (X-1) be using acrylic resin, polyurethane based resin and PIB resinoids etc. as resin of binding property (x1) method is preferably formed in the case of.
In method (X-1), as the organic solvent for being used, can enumerate for example：MEK, acetone, ethyl acetate, four Hydrogen furans, dioxane, hexamethylene, n-hexane, toluene, dimethylbenzene, normal propyl alcohol, isopropanol, dimethylformamide, N- first Base pyrrolidones, dimethyl sulfoxide etc..
It should be noted that these organic solvents can also be directly used in having of using during synthetic adhesive resin (x1) Machine solvent.
In method (X-1), carbon system filler (x2) is preferably coordinated in bonding with the form for disperseing dispersion liquid in a solvent In property resin (x1).
Due to coordinating carbon system's filler (x2) by the form with dispersion liquid, can be with low viscous state and resin of binding property (x1) mix, therefore easily make carbon system filler (x2) closer to each other, the network of filler can be formed, be thus easily reduced what is formed The surface resistivity and specific insulation of cohesive conductive layer (X).
As the solvent of the dispersion liquid for being used to prepare carbon system filler (x2), water or above-mentioned organic solvent can be enumerated, preferably be had Machine solvent.
As the preparation method of the dispersion liquid of carbon system filler (x2), can enumerate for example：Add carbon system filler in a solvent (x2) and using ultrasonic wave etc. method for vibrating to be prepared of certain hour etc. is applied.
As the solid component concentration of the dispersion liquid of carbon system filler (x2), preferably 0.01～60 mass %, more preferably 0.05～10 mass %, more preferably 0.1～3 mass %.
In method (X-1), as the coating process of the solution that adhesive composition is coated with stripping film, example can be enumerated Such as：Spin-coating method, spraying process, stick coating method, scraper for coating method, roller knife rubbing method, rolling method, scraper plate rubbing method, die coating method, gravure are applied Cloth method etc..
It should be noted that it is preferred that be coated with the solution of adhesive composition on the stripping film and formed after coated film, entering Row dried process, so as to solvent contained in coated film be removed.
Additionally, in method (X-1), in order that bonding force is improved, preferably by the coating layer after the dried process for example 23 DEG C, stand 7 days～30 days or so in the environment of 50%RH (relative humidity) so that coating layer inside is full cross-linked.
(method (X-2))
Method (X-2) is to be resistant to the resin for adding hot milling as resin of binding property using styrene resin etc. (x1) method is preferably formed in the case of.
As heating kneading device, can enumerate for example：Single screw extrusion machine, double screw extruder, roller mill, plasticator (plastomill), Banbury, banbury (intermix), pressure kneader etc..
Method as forming to the composite obtained from the heating kneading device, can enumerate for example：It is molten Melt extrusion molding, rolling process, compression forming method etc., preferred compressed forming process.
As the concrete grammar of compression forming method, prepared composite can be sandwiched with 2 stripping films, and using heat Press etc. is carried out plus hot compression, thus carrys out the cohesive conductive layer (X) of formed sheet.It should be noted that 2 can also be replaced Stripping film and prepared composite is sandwiched the cohesive conductive layer (X) come formed sheet using base material and stripping film.
[the formation material of non-adhesive conductive layer (Y)]
From from the viewpoint of the effect for fully showing the surface resistivity for reducing electroconductive adhesive sheet, non-adhesive is conductive Layer (Y) preferably includes the layer of more than a kind conductive material in electroconductive polymer, carbon system filler and metal oxide, More preferably comprising more than a kind conductive material in polythiophene, PEDOT-PSS, carbon nanomaterial and ITO (tin indium oxide), Further preferably comprising more than a kind conductive material in polythiophene, PEDOT-PSS and carbon nanomaterial.
As the density of the conductive material included in non-adhesive conductive layer (Y), from the lighting of electroconductive adhesive sheet Viewpoint is set out, preferably 0.8～2.5g/cm3, more preferably 0.8～2.0g/cm3, more preferably 0.8～1.7g/cm3。
Hereinafter, the conductive material for constituting non-adhesive conductive layer (Y) is illustrated.
<Electroconductive polymer>
As electroconductive polymer, can enumerate for example：Polythiophene, PEDOT-PSS (poly- (3,4- ethyldioxythiophenes)- Poly- (styrene sulfonic acid)), polyaniline, polypyrrole, polyquinoxaline etc..
In the middle of these, preferred polythiophene and PEDOT-PSS.
Non-adhesive conductive layer (Y) comprising electroconductive polymer is preferably comprising non-while comprising electroconductive polymer Resin of binding property, as non-adhesive resin, is preferably selected from acrylic resin, polyurethane based resin, PIB resinoids and benzene More than a kind non-adhesive resin in vinyl resins.
Using electroconductive polymer as conductive material in the case of, relative to the total amount of non-adhesive conductive layer (Y) (100 mass %), the content of electroconductive polymer is preferably 4～100 mass %, more preferably 8～100 mass %.
As the forming method of the non-adhesive conductive layer (Y) comprising electroconductive polymer, it is not particularly limited, can enumerates Such as following methods：The solution of the organic solvent comprising electroconductive polymer is prepared, and the solution is utilized into known coating side Method is coated on base material or stripping film and forms coated film, coated film is dried and is formed as non-comprising electroconductive polymer Cohesive conductive layer (Y).
The coating process of species and solution with regard to the organic solvent used in the method, with above-mentioned with regard to as bonding The record of " method (X-1) " of the forming method of property conductive layer (X) is identical.
<Carbon system filler>
As carbon system filler, can enumerate and above-mentioned carbon system filler (x2) identical material, preferred carbon nanomaterial.
Non-adhesive conductive layer (Y) comprising carbon system filler is preferably comprising non-adhesive tree while comprising carbon system filler Fat, as non-adhesive resin, is preferably selected from acrylic resin, polyurethane based resin, PIB resinoids and phenylethylene tree More than a kind non-adhesive resin in fat.
Using carbon system filler as conductive material in the case of, relative to total amount (100 matter of non-adhesive conductive layer (Y) Amount %), the content of the carbon system filler is preferably 0.1～20 mass %, more preferably 0.5～15 mass %, is more preferably 1.0～10 mass %, still more preferably be 2.0～7 mass %.
As the forming method of the non-adhesive conductive layer (Y) comprising carbon system filler, it is not particularly limited, can enumerates for example Following methods：The solution mixing of the dispersion liquid of carbon system filler and the organic solvent of non-adhesive resin is prepared into resin combination Solution after, using known coating process by the solution coating on base material or stripping film and formed coated film, make coating Film is dried and forms the non-adhesive conductive layer (Y) comprising carbon system filler.
Species, the preparation method of the dispersion liquid of carbon system filler and solution with regard to the organic solvent used in the method Coating process is identical with the record of " method (X-1) " of the above-mentioned forming method with regard to as cohesive conductive layer (X).
In addition, as comprising carbon system filler non-adhesive conductive layer (Y) forming method, or carbon system is being filled out Material and non-adhesive resin carry out plus hot milling and prepare after composite, using known forming process make the composite into The method that the non-adhesive conductive layer (Y) comprising carbon system filler is obtained for sheet.
With regard to the heating kneading machine used in the method, the forming process of composite, with above-mentioned with regard to leading as cohesive The record of " method (X-2) " of the forming method of electric layer (X) is identical.
<Metal oxide>
As metal oxide, can enumerate：ITO (tin indium oxide), ZnO (zinc oxide), IZO (indium zinc oxide), AZO (oxygen Change zinc-aluminium), GZO (zinc-gallium oxide), IGZO (indium gallium zinc), ATO (tin-antiomony oxide) etc..
In the middle of these, preferred ITO (tin indium oxide).
In addition, in the case of using metal oxide as conductive material, preferred non-adhesive conductive layer (Y) for only by The layer that the metal oxide is formed.
It should be noted that as comprising metal oxide non-adhesive conductive layer (Y) forming method, preferably relatively In the method that base material is formed by evaporation.
[base material]
As the base material that electroconductive adhesive sheet in one of embodiments of the present invention is used, can be according to electroconductive adhesive sheet Purposes and suitably select, can be comprising Ins. ulative material insulating properties base material, or comprising the electric conductivity material such as metal The conductive substrate of material.
In the present invention, the insulating properties base material refers to that surface resistivity is 1.0 × 1014Ω/more than (preferably 1.0 × 1016Ω/more than) base material.
As insulating properties base material, can enumerate for example：Full slurrying paper, art paper, art paper, glassine paper etc. and in these paper The various stationeries such as laminated paper of the thermoplastic resin such as laminated polyethylene on base material；The porous materials such as non-woven fabrics；By polyethylene The vistanexes such as resin, acrylic resin, polybutylene terephthalate (PBT) resin, pet resin Deng the plastic foil or piece of the formation such as polyester resin, acetate resins, ABS resin, polystyrene resin, vinyl chloride resin；By this Plastic foil or piece that the mixture of a little resins is formed；The plastic foil formed by the laminated body of these plastic foils or piece or piece etc..
It should be noted that the base material such as plastic foil or piece can be with unstretched, it is also possible to the single shaft for waiting longitudinally or transversely Direction or biaxially oriented have passed through extension.
In addition, can also further contain in these insulating properties base materials (particularly plastic foil or piece) ultra-violet absorber, Light stabilizer, antioxidant, antistatic agent, slipping agent, antiblocking agent, colouring agent etc..
As conductive substrate, can enumerate for example：Metal forming, utilization form resin of above-mentioned insulating properties base material etc. by metal The film or piece of layers of foil pressure, the surface to above-mentioned insulating properties base material carry out metal evaporation process film or piece, to above-mentioned The surface of insulating properties base material carries out the film or piece of antistatic process, metal wire is woven into piece of mesh etc..
It should be noted that as the metal for conductive substrate, can enumerate for example：Aluminium, copper, silver, gold etc..
The thickness of base material is not particularly limited, but from from the viewpoint of processing ease degree, preferably 10～250 μm, more Preferably 15～200 μm, more preferably 20～150 μm.
In the case that base material is plastic foil or piece, from the viewpoint for improving base material and the adaptation of non-adhesive conductive layer (Y) Set out, preferably as needed the surface treatment of oxidizing process, further provided for contouring method etc. is implemented to the surface of base material.
As oxidizing process, it is not particularly limited, can enumerates for example：Corona discharge Treatment method, plasma processing, chromic acid oxygen Change (wet type), flame treatment, hot blast process, ozone/ultraviolet treatment with irradiation etc..In addition, as further provided for contouring method, without special limit It is fixed, can enumerate for example：Sand-blast, solvent treatment method etc..These surface treatments can suitably be selected according to the species of base material, but from From the viewpoint of the improvement and operability of the adaptation of non-adhesive conductive layer (Y), preferred Corona discharge Treatment method.Separately Outward, it is also possible to implement plasma treatment.
[stripping film]
In addition, the stripping film used as the electroconductive adhesive sheet in one of embodiments of the present invention, can use Jing The stripping film of two-sided lift-off processing crossed, have passed through stripping film of one side lift-off processing etc., can be set forth on stripping film base material Stripping film of coating remover etc..
As stripping film base material, can enumerate for example：The paper base materials such as glassine paper, art paper, full slurrying paper, in these paper substrates Laminated paper or pet resin, the poly- terephthaldehyde of the thermoplastic resin such as laminated polyethylene on material The polyenes such as polyester resin film, acrylic resin, the polyvinyl resins such as sour butanediol ester resin, PEN resin Plastic foils such as hydrocarbon resin film etc..
As remover, can enumerate for example：Silicone resin, olefine kind resin, isoprene resinoid, butadiene type The heat-resistant powder fillers such as resin, chain alkyl resinoid, alkyd based resin, fluorine-type resin etc..
The thickness of stripping film is not particularly limited, but preferably 10～200 μm, more preferably 25～150 μm.
[manufacture method of electroconductive adhesive sheet, physical property]
Electroconductive adhesive sheet in one of embodiments of the present invention can be by will be formed using above-mentioned forming method Cohesive conductive layer (X) and non-adhesive conductive layer (Y) and base material, stripping film carry out suitably fitting and manufacturing.
As the cohesive conductive layer (X) having relative to the electroconductive adhesive sheet in one of embodiments of the present invention Surface probe adhesion peak value, preferably more than 0.1N, more preferably 0.1～49N, more preferably 0.5～ 49N, still more preferably be 1.0～49N.
It should be noted that the peak value of the probe adhesion represents the value determined by the method described in embodiment. In addition, the peak value of the probe adhesion is the physics value of the index of the bonding force as electroconductive adhesive sheet, the value is more big, has There is higher bonding force.
The face side of the cohesive conductive layer (X) that the electroconductive adhesive sheet from one of embodiments of the present invention has Surface resistivity (the ρ of measureS) it is preferably 9.0 × 104Ω/below, more preferably 1.0 × 104It is Ω/below, further excellent Elect 5.0 × 10 as3Ω/below, still more preferably be 2.0 × 103Ω/below.
It should be noted that above-mentioned, " face side of the cohesive conductive layer (X) having from electroconductive adhesive sheet is determined The value of surface resistivity " is from least by the of the invention of cohesive conductive layer (X) and non-adhesive conductive layer (Y) lamination The value of the surface resistivity that the face side of the cohesive conductive layer (X) for exposing of electroconductive adhesive sheet is determined, it is different from above-mentioned " surface resistivity (ρ SX) of single cohesive conductive layer (X) " value.
Embodiment
Physical property and electroconductive adhesive sheet, bonding for each composition used in below example and comparative example Each physical property of property conductive layer (X) and non-adhesive conductive layer, is determined using the method for following record.
<Weight average molecular weight (Mw)>
Use using gel permeation chromatography device (TOSOH Co., Ltd's system, product name " HLC-8020 "), at following The value of polystyrene standard is measured and is converted under part.
(condition determination)
Chromatographic column：By " TSK guard column HXL-H ", " TSK gel GMHXL (× 2) " and " TSK gel The chromatographic column that G2000HXL " (being TOSOH Co., Ltd's system) links successively.
Column temperature：40℃
Eluting solvent：Tetrahydrofuran
Flow velocity：1.0mL/min
<The draw ratio of carbon system filler, longer side and a shorter side length>
Using scanning electron microscope (Co., Ltd.'s Hitachi High-Technologies systems, product name " S- 4700 ") 10 carbon system filler grains to randomly selecting are observed, and determine respective long edge lengths and bond length, and Using the mean value of 10 carbon system filler grains as the filler " long edge lengths (H) " and " bond length (L) ".In addition, major diameter Calculated by " long edge lengths (H)/bond length (L) " than (H/L).
<Softening point>
It is determined based on JIS K 2531.
<Density>
Based on JIS Z 8807:2012 are determined.
<Probe adhesion>
It is determined based on J IS Z0237 (1991).
Specifically, the test film of 10mm × 10mm sizes is stood in 23 DEG C, the environment of 50%RH (relative humidity) 24 hours afterwards, and the surface for making the layer of the measure object of the test film is exposed, using (the industry strain formula meeting of science of adhesion test machine Society's system, product name " PROBE TACK TESTER ") determine the probe adhesion values on surface relative to this layer.
It should be noted that the probe adhesion values are as follows：The stainless steel manufacturing probe of diameter 5mm is made with 0.98N/cm2's Contact load contacts 1 second with the surface of the layer of measure object afterwards, makes probe with the speed of 600mm/ seconds and leaves the surface, will Now required masterpiece is the probe adhesion values on the surface of this layer.
In addition, relative to the surface of non-adhesive conductive layer, determining the peak value of probe adhesion values.In addition, relative to The surface of the cohesive conductive layer (X) that electroconductive adhesive sheet has, determines the peak value and integrated value of probe adhesion values.
Additionally, measure object layer surface without cohesive, in the case of the peak value of probe adhesion values cannot be determined, The peak value is set to " 0 (N) ".
<Surface resistivity, specific insulation>
It is determined based on JIS K 7194.
Specifically, the test film of 20mm × 40mm sizes is stood in 23 DEG C, the environment of 50%RH (relative humidity) 24 hours afterwards, and the surface for making the layer of the measure object of the test film is exposed, using low-resistivity instrument (Co., Ltd. Mitsubishi Chemical Analytech systems, product name " Loresta GP MCP-T610 types ") determine sheet resistance Rate and specific insulation.
3 said determinations are carried out for surface resistivity, for specific insulation 5 said determinations are carried out, in table 1 and 2 The middle mean value for having recorded the measured value obtained in each determining.
It should be noted that in the single surface resistivity of cohesive conductive layer (X) and the measure of specific insulation, Using the laminated body that only cohesive conductive layer (X) is clamped by 2 stripping films as test film, by the side of the test film Stripping film is removed, these values for the surface measurements of cohesive conductive layer (X) exposed.
In addition, in the single surface resistivity of non-adhesive conductive layer and the measure of specific insulation, using with non- The base material of cohesive conductive layer as test film, and for the test film non-adhesive conductive layer surface measurements these Value.
Further, in the measure of the surface resistivity of electroconductive adhesive sheet, make using in embodiment and comparative example Lamination successively have the electroconductive adhesive sheet of base material, non-adhesive conductive layer, cohesive conductive layer (X) and stripping film as test Piece, the stripping film of the test film is removed, and the surface of the cohesive conductive layer (X) for exposing only determines surface resistivity Value.
Production Example 1
(making of the base material with non-adhesive conductive layer (Y-1))
In polyethylene terephthalate (PET) film (Toray Co. Ltd. systems, the business of 50 μm of the thickness as base material The name of an article " LUMIRROR ", surface resistivity：1.18×1018Ω/) on applied in the way of making dried thickness reach 2.4 μm The solution (Soken Chemical ＆ Engineering Co., Ltd.'s system, trade name " Berazol IW-103 ") of cloth polythiophene, forms coated film, and makes the painting Cloth film is dried, and has obtained the base material of band non-adhesive conductive layer (Y-1) comprising polythiophene.
Production Example 2
(making of the base material with non-adhesive conductive layer (Y-2))
It is prepared for relative to acrylic compounds water-soluble polymer (Arakawa Chemical Industries, Ltd.'s system, trade name " Tamanori G-37 ", polyacrylic acid) 100 mass parts (solid constituent) include poly- (3,4- ethyldioxythiophenes)-poly- (benzene Vinyl sulfonic acid) dispersion liquid (Agfa company systems, trade name " Orgacon S305 ") 10 mass parts (PEDOT-PSS) (solid into Point ratio) and the mass parts of ethylene glycol 10 solution.
Then, with the identical PET film used in Production Example 1 on, to make dried thickness reach in the way of in the of 1.0 μm Above-mentioned solution is coated with, coated film is formed, and is dried the coated film, obtained the band non-adhesive comprising PEDOT-PSS conductive The base material of layer (Y-2).
Production Example 3
(making of the base material with non-adhesive conductive layer (Y-3))
Relative to styrene resin (Clayton company systems, trade name " 1726M ", SEBS) 100 mass parts (solid into Point) addition multi-walled carbon nano-tubes (CNT) (Nanoshiru company systems, trade name " NC7000 ", details are as hereinafter described) 10 mass Part (solid constituent ratio), using heating kneading machine (Toyo Co., Ltd.'s essence mechanism makees made, product name " 30C150 ") 100 DEG C, kneaded under conditions of 50rpm, obtained composite.
Then, using stripping film (the Lin get Ke strain formula meetings with 75 μm of the identical PET film used in Production Example 1 and thickness Society's system, trade name " SP-PET751031 ") above-mentioned composite is sandwiched, and using hot press (Tester Sangyo strain formula meetings Society's system, product name " SA-302 ") hot pressing in 10 minutes has been carried out under conditions of 130 DEG C, 10MPa.After hot pressing, stripping film is removed, The base material comprising SEBS and band non-adhesive conductive layer (Y-3) of CNT (10 mass parts) of 100.0 μm of thickness is obtained.
Production Example 4
(making of the base material with non-adhesive conductive layer (Y-4))
In addition to the use level for making multi-walled carbon nano-tubes is " 4 mass parts ", in the same manner as Production Example 3 thickness is obtained 100.0 μm of the base material comprising SEBS and band non-adhesive conductive layer (Y-4) of CNT (4 mass parts).
In the present embodiment and comparative example, except the above-mentioned band non-adhesive conductive layer made by Production Example 1～4 Base material beyond, also use the following base material with non-adhesive conductive layer.
" base material of band non-adhesive conductive layer (Y-A) comprising ITO "：Trade name " ITO-POLYETHYLENE TEREPHTHALATE " (tail vat Industrial Co., Ltd system).In 50 μm of PET film (surface resistivity of thickness：1.18×1018Ω/ The material of the ito film of 1.6 μm of evaporation thickness on one side).
" base material of band non-adhesive conductive layer (Y-B) comprising copper "：Trade name " NIKAFLEX " (Nikkan Industries Co. Ltd. systems).In 50 μm of PET film (surface resistivity of thickness：1.18×1018Ω/) one side on profit With the material of 35.0 μm of copper film of adhesive coating thickness.
The base material of band non-adhesive conductive layer (Y-C) comprising aluminium：Trade name " Metarumi#50 " (' TORAY ' Innovation by Chemistry Co. Ltd. systems).In 50 μm of PET film (surface resistivity of thickness：1.18×1018Ω/ The material of the aluminium film of 10.0 μm of evaporation thickness on one side).
The non-adhesive conductive layer of the base material with non-adhesive conductive layer used in the present embodiment and comparative example it is various Physical property is as shown in table 1.
Table 1
Embodiment 1～15, comparative example 1～8
(1) formation of cohesive conductive layer (X)
By the species and use level shown in table 2 (relative to the solid constituent of the mass parts of resin of binding property 100 (solid constituent) Than) carbon system filler (x2) be added on ethyl acetate, using supersonic wave cleaning machine apply 1 hour based on ultrasonic wave (42kHz, Vibration 125W), the previously prepared dispersion liquid of carbon system filler (x2) of mass % of solid component concentration 0.5.
Then, the carbon system is added to fill out in the mass parts (solid constituent) of resin of binding property (x1) 100 of the species shown in table 2 The dispersion liquid of material (x2), and then add crosslinking agent, the increasing of the species shown in table 2 and use level (solid constituent ratio) as desired Thick dose.Then, suitably diluted using ethyl acetate, and stirred uniform to reaching, be prepared for the solution of adhesive composition.
Then, by the solution coating of the adhesive composition for preparing as described above in stripping film (Lindeke Co., Ltd System, trade name " SP-PET381031 ", thickness：38 μm, surface be the poly terephthalic acid second that have passed through organosilicon lift-off processing Diol ester film) lift-off processing face on and formed coated film so as to be dried, so as to define coating layer.
Then, other lamination and the above-mentioned stripping film for identical type on the coating layer, 23 DEG C, 50%RH it is (relative Humidity) environment in stand 14 hours afterwards, make coating layer full cross-linked, the cohesive for having obtained only thickness shown in table 2 is conductive The laminated body that layer (X) is clamped by 2 stripping films.
(2) making of electroconductive adhesive sheet
In embodiment 1～15 and comparative example 7～8, make that the stripping film of the side of above-mentioned laminated body is removed and exposed The non-adhesive conductive layer laminating of the base material with non-adhesive conductive layer of cohesive conductive layer (X) and species shown in table 2, makes Electroconductive adhesive sheet.
In comparative example 1～6, the cohesive conductive layer that the stripping film of the side of above-mentioned laminated body is removed and exposed is made (X) and 50 μm of thickness PET film (Toray Co. Ltd. systems, trade name " LUMIRROR ") laminating, made conductive adhesive Piece.
Embodiment 16
(1) formation of cohesive conductive layer (X)
Relative to styrene resin (TOYO ADL Co. Ltd. systems, trade name " P-907Y ", details are as hereinafter described) 100 mass parts (solid constituent), with the use level (solid constituent ratio) shown in table 2 multi-walled carbon nano-tubes (CNT) is with the addition of (Nanoshiru company systems, trade name " NC7000 ", details are as hereinafter described), and using heating kneading machine (Toyo Co., Ltd. Smart mechanism makees made, product name " 30C150 ") kneaded under conditions of 100 DEG C, 50rpm, obtain composite.
Then, using 2 stripping films (Lindeke Co., Ltd's system, trade name " SP-PET751031 ", thickness：75 μm) will Above-mentioned composite is sandwiched, using hot press (Tester Sangyo Co. Ltd. systems, product name " SA-302 ") 130 DEG C, Hot pressing 10 minutes under conditions of 10MPa, have obtained the laminated body that only cohesive conductive layer (X) is clamped by 2 stripping films.
(2) making of electroconductive adhesive sheet
Make the cohesive comprising styrene resin that the stripping film of the side of above-mentioned laminated body is removed and exposed conductive The non-adhesive conductive layer laminating of layer (X) and the base material with non-adhesive conductive layer (Y-2), has made electroconductive adhesive sheet.
That Details as Follows is described for each composition in the adhesive composition used in embodiment and comparative example shown in table 2.
(resin of binding property (x1))
" acrylic resin "：The acrylic polymer formed by n-butyl acrylate (BA) and acrylic acid (AA) Methyl acetate solution, BA/AA=90.0/10.0 (mass parts), Mw：700000, solid component concentration：33.6 quality %.
" polyurethane based resin "：Lion Specialty Chemicals Co. Ltd. systems, trade name " US-902A ", Polyurethane based resin, Mw=56,000.
" PIB resinoids "：Mw is 340,000 PIB resinoids (BASF AG's system, trade name " Oppanol B50 ") 90.9 Mass parts (solid constituent ratio) and PIB resinoids (BASF AG's system, trade name " Oppanol B30 ") 9.1 matter that Mw is 200,000 The hybrid resin of amount part (solid constituent ratio).
" styrene resin "：TOYO ADL Co. Ltd. systems, trade name " P-907Y ", mixing containing SEBS and SEB Total content=30 mass % of resin, SEBS and SEB, softening point=112 DEG C.
(carbon system filler (x2))
·“NC7000”：Trade name, Nanoshiru company systems, cylindric multi-walled carbon nano-tubes, average aspect ratio (H/ L)：150th, long edge lengths (H)：1.5 μm, bond length (L)：10nm.
·“AMC”：Trade name, Ube Industries, Ltd's system, cylindric multi-walled carbon nano-tubes, average aspect ratio (H/ L)：100th, long edge lengths (H)：1.1 μm, bond length (L)：11nm.
(crosslinking agent)
·“CORONATE L”：Trade name, TOSOH Co., Ltd's system, isocyanates crosslinking agent, solid component concentration：75 Quality %.
(thickener)
·“Alcon P-125”：Trade name, Arakawa Chemical Industries, Ltd.'s system, hydrogenated petroleum resin, softening point：125 ℃。
·“YS Polystar K125”：Trade name, Yasuhara Chemical Co. Ltd. systems, terpenes phenolic resin, Softening point：125℃.
(other compositions)
Other compositions in addition to (x1) composition included in " P-907Y " are used (to increase as styrene resin Thick dose, plasticizer etc.) mixture.
Embodiment 17～23
Using commercially available product electric conductivity two-sided tape (day new EM Co. Ltd. systems, trade name " conductive carbon two-sided tape 7311 ", the electric conductivity containing acrylic resin and the structure of the adhesive phase of carbon dust is clamped with using 2 stripping films Bonding sheet) adhesive phase as cohesive conductive layer (X).
Make the adhesive phase (bonding that the stripping film of the side of the electric conductivity two-sided tape of above-mentioned commercially available product is removed and exposed Property conductive layer (X)) and species shown in table 3 band non-adhesive conductive layer (Y-1) base material or band non-adhesive conductive layer (Y-4) Base material non-adhesive conductive layer laminating, made electroconductive adhesive sheet.
Comparative example 9
Make the adhesive phase (bonding that the stripping film of the side of the electric conductivity two-sided tape of above-mentioned commercially available product is removed and exposed Property conductive layer (X)) and 50 μm of thickness PET film (Toray Co. Ltd. systems, trade name " LUMIRROR ") laminating, made and led Electrical bonding sheet.
To be shown in for the electroconductive adhesive sheet for making as described above, the various physics values determined based on said method Table 2 and table 3.
From table 2 and table 3, the electroconductive adhesive sheet of embodiment 1～23 has good bonding force, and and comparative example 1～9 electroconductive adhesive sheet is compared, and surface resistivity is low, static electricity resistance and excellent electric conductivity.
Industrial applicibility
The electroconductive adhesive sheet of the present invention has good bonding force, and surface resistivity is low, thus static electricity resistance and Excellent electric conductivity.
Therefore, electroconductive adhesive sheet of the invention is suitable as engagement member and is used to for example receive computer, communication apparatus The ground wire of electromagnetic shielding material, electric component Deng the container of electronic equipment etc. and prevent by the electrostatic such as friction electricity produce The component such as the material anti-on fire on fire that causes of spark.

Claims (16)

1. a kind of electroconductive adhesive sheet, it at least has cohesive conductive layer (X) and non-adhesive conductive layer (Y), wherein,
Specific insulation (the ρ of single cohesive conductive layer (X)VX) value be 1.0 × 100～1.0 × 108Ω cm,
Specific insulation (the ρ of single non-adhesive conductive layer (Y)VY) value be 1.0 × 10-4～1.0 × 106Ω cm,
Also, thickness (the t of cohesive conductive layer (X)X) with the thickness (t of non-adhesive conductive layer (Y)Y) thickness ratio [tx/tY] For less than 20000.
2. electroconductive adhesive sheet according to claim 1, wherein, the thickness (t of cohesive conductive layer (X)X) it is 1～1200 μ m。
3. electroconductive adhesive sheet according to claim 1 and 2, wherein, the thickness (t of non-adhesive conductive layer (Y)Y) be 0.01～200 μm.
4. the electroconductive adhesive sheet according to any one of claims 1 to 3, wherein, cohesive conductive layer (X) is by bonding Property the layer that formed of composition, the adhesive composition includes resin of binding property (x1) and carbon system filler (x2).
5. electroconductive adhesive sheet according to claim 4, wherein, the resin of binding property included in the adhesive composition (x1) include selected from acrylic resin, polyurethane based resin, rubber resin, styrene resin, polyester resin and gather More than a kind resin of binding property in olefine kind resin.
6. the electroconductive adhesive sheet according to claim 4 or 5, wherein, the carbon system included in the adhesive composition fills out The average aspect ratio of material (x2) is more than 1.5.
7. the electroconductive adhesive sheet according to any one of claim 4～6, wherein, include in the adhesive composition Carbon system filler (x2) content relative to the mass parts of resin of binding property (x1) 100 be 0.01～15 mass parts.
8. the electroconductive adhesive sheet according to any one of claim 4～7, wherein, include in the adhesive composition Carbon system filler (x2) be carbon nanomaterial.
9. the electroconductive adhesive sheet according to any one of claim 1～8, wherein, non-adhesive conductive layer (Y) is to include The layer of more than a kind conductive material in electroconductive polymer, carbon system filler and metal oxide.
10. the electroconductive adhesive sheet according to any one of claim 1～9, wherein, non-adhesive conductive layer (Y) is bag Layer containing more than a kind conductive material in polythiophene, PEDOT-PSS, carbon nanomaterial and ITO (tin indium oxide).
11. electroconductive adhesive sheets according to claim 9 or 10, wherein, the conduction included in non-adhesive conductive layer (Y) The density of material is 0.8～2.5g/cm3。
12. electroconductive adhesive sheets according to any one of claim 1～11, it has laminated substrate, non-adhering successively The structure of property conductive layer (Y) and cohesive conductive layer (X).
13. electroconductive adhesive sheets according to claim 12, wherein, have by non-adhesive respectively on the two sides of base material Two layers of body that conductive layer (Y) and cohesive conductive layer (X) are constituted.
14. electroconductive adhesive sheets according to claim 12 or 13, wherein, the base material is surface resistivity for 1.0 × 1014The insulating properties base material of Ω/more than.
15. electroconductive adhesive sheets according to any one of claim 1～11, its have using the clamping of 2 stripping films by The structure of two layers of body that cohesive conductive layer (X) and non-adhesive conductive layer (Y) are constituted.
16. electroconductive adhesive sheets according to any one of claim 1～11, its have using the clamping of 2 stripping films according to Three layers of the cohesive conductive layer (X-I) of secondary lamination the 1st, non-adhesive conductive layer (Y) and the 2nd cohesive conductive layer (X-II) The structure of body.
CN201580045647.9A 2014-08-28 2015-08-24 Conductive adhesive sheet Pending CN106661398A (en)

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Application publication date: 20170510