WO2016051829A1 - Feuille adhésive électroconductrice sensible à la pression - Google Patents

Feuille adhésive électroconductrice sensible à la pression Download PDF

Info

Publication number
WO2016051829A1
WO2016051829A1 PCT/JP2015/059735 JP2015059735W WO2016051829A1 WO 2016051829 A1 WO2016051829 A1 WO 2016051829A1 JP 2015059735 W JP2015059735 W JP 2015059735W WO 2016051829 A1 WO2016051829 A1 WO 2016051829A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
pressure
sensitive adhesive
based filler
adhesive layer
Prior art date
Application number
PCT/JP2015/059735
Other languages
English (en)
Japanese (ja)
Inventor
翔 大高
貴洋 植田
大雅 松下
智史 川田
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2016551566A priority Critical patent/JPWO2016051829A1/ja
Publication of WO2016051829A1 publication Critical patent/WO2016051829A1/fr

Links

Images

Classifications

    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives

Definitions

  • the present invention relates to a conductive adhesive sheet.
  • Conductive substances such as copper powder, silver powder, nickel powder, aluminum powder, and other metal powders are used for the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet. Are widely used in which they are dispersed in an adhesive resin.
  • Patent Document 1 discloses a conductive pressure-sensitive adhesive in which at least one of carbon nanotubes and carbon microcoils, which are conductive materials, is dispersed in an acrylic or rubber-based pressure-sensitive adhesive using a roll kneader or the like, And the electroconductive adhesive sheet using the said electroconductive adhesive is disclosed.
  • a large amount of a conductive material is blended in the pressure-sensitive adhesive composition that is the material for forming the pressure-sensitive adhesive layer, It is necessary to have close contact between the particles.
  • the adhesive strength to the adherend and the adhesiveness to the substrate tend to be lowered.
  • a general conductive material has a higher specific gravity than an adhesive composition, if it is added in a large amount, it will hinder weight reduction of an electronic device.
  • the content of the conductive material is reduced in order to increase the adhesive strength, there is a trade-off problem that the conductivity is lowered.
  • An object of the present invention is to provide a conductive pressure-sensitive adhesive sheet having good adhesive strength and excellent antistatic properties and conductivity.
  • the present inventors pay attention to the dispersion state of the carbon-based filler in the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet, and adjust the occupation area ratio of the carbon-based filler on the sticking surface of the pressure-sensitive adhesive layer to a predetermined range.
  • the inventors have found that the above problems can be solved, and have completed the present invention. That is, the present invention provides the following [1] to [11].
  • a conductive adhesive sheet having an adhesive layer containing an adhesive resin (A) and a carbon-based filler (B), The content of the carbon-based filler (B) in the pressure-sensitive adhesive layer is 0.01 to 20% by mass with respect to the total mass of the pressure-sensitive adhesive layer;
  • a conductive pressure-sensitive adhesive sheet wherein when the adhesive surface of the pressure-sensitive adhesive layer is viewed in plan, the occupation area ratio of the carbon-based filler (B) in an arbitrarily selected region on the adhesive surface is 17% or more.
  • the adhesive layer is prepared by stirring using a stirrer
  • the carbon-based filler (B) is dispersed in a string shape,
  • the average thickness of the carbon-based filler (B) dispersed in a string in the pressure-sensitive adhesive layer is 0.5 to 5.0 ⁇ m, and the average aspect ratio is 3.0 or more, [1 ] Or the conductive adhesive sheet according to [2].
  • the carbon-based filler (B) aggregates with respect to the total occupied area occupied by the carbon-based filler (B) in an arbitrarily selected region on the adhesive surface.
  • the adhesive resin (A) according to any one of [1] to [5] above, wherein the adhesive resin (A) includes one or more adhesive resins selected from the group consisting of acrylic resins and urethane resins.
  • Conductive adhesive sheet [7]
  • the content of the carbon filler (B) in the pressure-sensitive adhesive layer is 0.1 to 7% by mass with respect to the total mass of the pressure-sensitive adhesive layer, according to the above [1] to [6]
  • the conductive pressure-sensitive adhesive sheet of the present invention has a good adhesive force and is excellent in antistatic properties and conductivity.
  • 4B is a digital image of Comparative Example 6;
  • an arbitrarily selected region of 10,000 ⁇ m 2 (a square with a side length of 100 ⁇ m) was selected.
  • an arbitrarily selected region of 10,000 ⁇ m 2 (a square with a side length of 100 ⁇ m) is selected.
  • a binarized image obtained by binarizing a digital image obtained by photographing at a magnification of 2000 times (a) is Comparative Example 1, (b) is Comparative Example 2, and (c) is Comparative Example 3.
  • (D) is a comparative example 4, (e) is a comparative example 5, (f) is a comparative example 6, (g) is a comparative example 7, and (h) is a binary image.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • (meth) acrylate is used as a term indicating both “acrylate” and “methacrylate”, and the same applies to other similar terms.
  • unsubstituted in the term “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted by a substituent.
  • surface resistivity of the conductive adhesive sheet means that the adhesive layer of the conductive adhesive sheet is exposed, unless otherwise specified. The surface resistivity measured from the surface side is meant, and a specific measuring method is as described in the examples.
  • FIG. 1 is a cross-sectional view of the conductive pressure-sensitive adhesive sheet showing an example of the configuration of the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention.
  • the conductive pressure-sensitive adhesive sheet according to one embodiment of the present invention include a conductive pressure-sensitive adhesive sheet 1a having a configuration in which a pressure-sensitive adhesive layer 11 is laminated on a substrate 12 as shown in FIG.
  • the electroconductive adhesive sheet 1b which has the structure which laminated
  • pressure-sensitive adhesive layers 11 and 11 ′ are respectively laminated on both surfaces of a base material as shown in FIG.
  • the electroconductive adhesive sheet 1c which has the structure which the peeling sheets 13 and 13 'laminated
  • the pressure-sensitive adhesive layer 11 and the pressure-sensitive adhesive layer 11 ′ of the conductive pressure-sensitive adhesive sheet 1c may be layers formed from the same type of pressure-sensitive adhesive composition, and are formed from different types of pressure-sensitive adhesive compositions. It may be a layer.
  • the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention may be a substrate-less conductive pressure-sensitive adhesive sheet.
  • a baseless conductive adhesive sheet for example, as shown in FIG. 1 (d), a conductive adhesive sheet 1d having a configuration in which an adhesive layer 11 is sandwiched between two release sheets 13, 13 ′.
  • mode of this invention the electroconductivity which has the structure which wound what provided the adhesive layer on the single side
  • FIG.2 (a) is an example of the perspective view of the adhesive layer which showed typically the mode of dispersion
  • FIG. 2B is an example of a plan view of the pasting surface 11a when the pasting surface 11a of the pressure-sensitive adhesive layer 11 in FIG.
  • the area occupied by the carbon-based filler (B) in an arbitrarily selected region on the sticking surface when the sticking surface of the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet is viewed in plan view The rate (hereinafter also referred to as “occupied area ratio of the carbon-based filler (B) on the pasting surface”) is 17% or more.
  • the above-mentioned “when the adhesive surface of the adhesive layer is viewed in plan” means that the adhesive surface 11a of the adhesive layer in FIGS. 1A and 2A is observed from the direction ⁇ . .
  • the occupation area ratio of the carbon-based filler (B) in an arbitrarily selected region on the pasting surface may be 17% or more.
  • there are two sticking surfaces of the adhesive layer to be exposed when the release sheet is removed such as the conductive adhesive sheet 1c in FIG. 1 (c) and the conductive adhesive sheet 1d in FIG. 1 (d).
  • the occupation area rate of the carbon-type filler (B) on each sticking surface should just be 17% or more.
  • the present inventors paid attention to the dispersion state of the carbon-based filler (B) in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • the area occupied by the carbon-based filler (B) on the adhesive surface of the pressure-sensitive adhesive layer About the relationship between the rate and the surface resistivity of the conductive adhesive sheet, it was found that there is a certain relationship.
  • the inventors of the present invention increase the occupation area ratio of the carbon-based filler (B) on the pasting surface, and become conductive. It was discovered that the surface resistivity of the pressure-sensitive adhesive sheet was remarkably improved, and the present invention was completed based on the discovery.
  • the dispersion state of the carbon-based filler (B) in the pressure-sensitive adhesive layer is as shown in FIG. It is considered that not only the vicinity of the pasting surface 11a but also the inside of the pressure-sensitive adhesive layer 11 is uniformly dispersed, and a plurality of carbon-based fillers (B) 15 are in contact with each other to form a network network.
  • the carbon-based filler (B) forms a network-like network inside the pressure-sensitive adhesive layer 11, so that the surface resistivity of the conductive pressure-sensitive adhesive sheet can be effectively reduced, and antistatic properties can be obtained. And it is estimated that it can become an electroconductive adhesive sheet excellent in electroconductivity.
  • the carbon-based filler (B) 15 that can be visually recognized from the pasting surface 11a is not necessarily dispersed on the pasting surface 11a or the surface layer portion of the pasting surface 11a, but may be dispersed inside the adhesive layer. included. That is, the carbon-based filler (B) dispersed inside the pressure-sensitive adhesive layer is only in a state that can be visually recognized on the pasting surface 11a when the pasting surface 11a is viewed in plan.
  • FIG. 5A is a photograph of an arbitrarily selected region on the sticking surface at a predetermined magnification when the sticking surface of the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet produced in Example 1 is viewed in plan view. It is the acquired digital image. According to the digital image of FIG. 5A, the outline of the carbon-based filler (B) in the vicinity of the application surface of the adhesive layer is dark, but the outline of the carbon-based filler (B) becomes thinner as the distance from the application surface increases. It can be confirmed. In the present application, the digital image is binarized with a predetermined threshold value, and the occupied area of the carbon-based filler (B) in the region is specified (see FIGS. 6 and 7). It is considered that the ratio of occupied portions (occupied area ratio) of the carbon-based filler (B) affects the surface resistivity and adhesive strength of the conductive adhesive sheet.
  • the area occupied by the carbon-based filler (B) in an arbitrarily selected region on the pasting surface is 17% or more, preferably 20 to 99.999%, more preferably It is 25 to 98%, more preferably 35 to 90%, still more preferably 45 to 85%, still more preferably 50 to 80%, and still more preferably 55 to 75%. If the occupied area ratio is less than 17%, it is difficult to reduce the surface resistivity of the conductive adhesive sheet, which is not preferable. On the other hand, the adhesive force of a conductive adhesive sheet can be maintained moderately by the said occupied area rate being 99.999% or less.
  • the value of the occupation area rate of the carbon-type filler (B) on the sticking surface means the value measured by the method as described in an Example. An example of a method for adjusting the value of the occupied area ratio is as described later.
  • the carbon-based filler (B) is preferably dispersed in a string shape in the pressure-sensitive adhesive layer.
  • a carbon-based filler dispersed in a string (hereinafter, also referred to as a “string-like carbon-based filler”) is a long like carbon-based filler (B) 15 shown in FIG.
  • the “cross section” is a cross section obtained by cutting perpendicularly to a tangential direction at an arbitrary point of the carbon-based filler dispersed in a string (for example, a radial cross section in the case of a cylinder).
  • a string for example, a radial cross section in the case of a cylinder.
  • the type, shape, and content of a carbon-based filler blended as a raw material in the preparation of the pressure-sensitive adhesive composition
  • adhesive The pressure-sensitive adhesive layer in which the carbon-based filler (B) is dispersed in a string shape can be formed by appropriately selecting the preparation method (stirring method) of the adhesive composition; a more specific adjustment method will be described later. It is as follows.
  • the average thickness (d) of the carbon-based filler (B) dispersed in a string in the pressure-sensitive adhesive layer is preferably 0.3 to 5.0 ⁇ m, more preferably 0.00.
  • the thickness is 4 to 4.0 ⁇ m, more preferably 0.5 to 3.0 ⁇ m, and still more preferably 0.6 to 2.0 ⁇ m. If the average of thickness (d) is 0.3 micrometer or more, the effect of reducing the surface resistivity of a conductive adhesive sheet can fully be expressed. On the other hand, if the average thickness (d) is 5.0 ⁇ m or less, a plurality of carbon-based fillers (B) dispersed in a string form can easily come into contact with each other, and a network network can be easily formed. As a result, the surface resistivity of the conductive adhesive sheet can be effectively reduced.
  • the thickness (d) of the carbon-based filler (B) dispersed in a string is perpendicular to the tangential direction at an arbitrary point of the string-like carbon-based filler (B).
  • the side of the polygon This means the length of the longest side, specifically the length d in FIG.
  • the value of the above "average of the thickness (d) of a string-like carbon-type filler (B)” means the value measured by the method as described in an Example.
  • the carbon-based fillers (B) blended as raw materials come into contact with each other and aggregate to form a thick carbon-based filler (B) dispersed in a string in the pressure-sensitive adhesive layer.
  • This is considered to be within the above range. Therefore, the average value of the thickness (d) of the carbon-based filler (B) dispersed in a string is usually the average of the short diameter (L) of the carbon-based filler that is a raw material used for preparing the adhesive composition. The value is larger than the value.
  • the average aspect ratio of the carbon-based filler (B) dispersed in a string in the pressure-sensitive adhesive layer is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 7 0.0 or more, more preferably 15.0 or more. If the average aspect ratio of the carbon-based fillers (B) dispersed in a string is 3.0 or more, the carbon-based fillers (B) dispersed in a string are easily in contact with each other, and a network network Of the carbon-based filler (B) on the pasting surface increases. As a result, the surface resistivity of the conductive adhesive sheet can be effectively reduced.
  • the upper limit of the average aspect ratio of the string-like carbon-based filler (B) is not particularly limited, but is usually 10,000 or less, preferably 5000 or less.
  • the aspect ratio of the carbon-based filler (B) dispersed in a string means the thickness (d) of the string-shaped carbon-based filler (B) (the length of d in FIG. 3). Is a value calculated by the ratio of the length (x) of the string-like carbon-based filler (B) (the length of x in FIG. 3), that is, “length (x) / thickness (d)”. .
  • the value of the “average aspect ratio of the carbon-based filler (B) dispersed in a string” means a value measured by the method described in Examples.
  • Length (x) of string-like carbon-based filler (B) refers to the distance between the two most distant points in the portion having the thickness (d) of the target carbon-based filler, In the string-like carbon fillers (B) 15, 151, 152 shown in FIGS. 3A, 3B, 3C, the length indicated by x is indicated.
  • the length (x ′) of the string-shaped portion is measured in the same manner as the “length (x) of the string-like carbon-based filler (B)”, and the aspect ratio [(x ′ ) / (D)] is 3.0 or more (preferably 5.0 or more, more preferably 7.0 or more, and still more preferably 15.0 or more), the target carbon-based filler (B) can be judged as a carbon-based filler (B) dispersed in a string shape.
  • the carbon-based filler (B) having such a string-shaped portion also contributes to the formation of a network-like network, and can be a factor that increases the value of the occupied area ratio of the carbon-based filler (B) on the pasting surface.
  • the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet A short diameter formed by agglomeration of the carbon-based filler (B) with respect to the total occupied area (100%) occupied by the carbon-based filler (B) in an arbitrarily selected region on the pasting surface when the pasting surface is viewed in plan.
  • the content of non-string aggregates of 4 ⁇ m or more is preferably 50% or less, more preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, and still more preferably 2% or less.
  • non-string-like aggregate is an aggregate having a short diameter of 4 ⁇ m or more formed by agglomeration of the carbon filler (B), and the above-mentioned string-like carbon as shown in FIG. Meaning the aggregate 21 that exists independently without contacting with the system filler (B), more specifically, the thickness (d) can be measured by the method described in the Examples, The aggregate which does not have a string-shaped part whose above-mentioned aspect ratio is 3.0 or more is pointed out.
  • a non-string-like aggregate such as the aggregate 21 in FIG. 4A does not form a network network by the carbon-based filler (B).
  • non-string aggregate is also considered to be a factor that hinders the formation of a network network of the carbon-based filler (B) dispersed in a string. Therefore, it is preferable to reduce the content of the non-string aggregates as much as possible.
  • the aspect ratio [(x ′) / (d)] of at least one of the four string-shaped portions 15a, 15b, 15c, and 15d in contact with the aggregate 22 is 3.0 or more (preferably Is not less than 5.0, more preferably not less than 7.0, and still more preferably not less than 15.0, the aggregate 22 does not fall under the above-mentioned “non-string-like aggregate”. .
  • the string-shaped portion contributes to the formation of a network network, and the occupied area ratio of the carbon-based filler (B) on the pasting surface This can be said to be a factor that increases the value of.
  • the “thickness of the string-shaped portion (d)” is a length measured by the same method as the above-described “thickness (d) of the carbon-based filler (B) dispersed in a string”.
  • the “string-shaped portion length (x ′)” refers to the distance between the two most distant points in the portion having the measurable string-shaped portion thickness (d). For example, FIG. The string-shaped portion 15a shown in b) indicates the length indicated by x ′.
  • the thickness of the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately adjusted according to the use of the conductive pressure-sensitive adhesive sheet, but is preferably 1 to 1200 ⁇ m, more preferably 2 to 600 ⁇ m, and more preferably It is 3 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, still more preferably 10 to 200 ⁇ m, and still more preferably 15 to 150 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is 1 ⁇ m or more, good adhesive force can be expressed regardless of the type of adherend.
  • the thickness of the pressure-sensitive adhesive layer is 1200 ⁇ m or less, the resulting conductive pressure-sensitive adhesive sheet has good conductivity.
  • the said electroconductive adhesive sheet is used as a wound body, the winding shift by the adhesive layer deform
  • the content of the carbon-based filler (B) in the pressure-sensitive adhesive layer is 0.01 to 20% by mass with respect to the total mass (100% by mass) of the pressure-sensitive adhesive layer. It is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass, still more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 3.5% by mass.
  • the content of the carbon-based filler (B) is less than 0.01% by mass, it is difficult to increase the occupied area ratio of the carbon-based filler (B) on the pasting surface, and the surface resistance of the obtained conductive adhesive sheet It becomes difficult to lower the rate.
  • the content of the carbon-based filler (B) exceeds 20% by mass, it is difficult to obtain a conductive adhesive sheet having sufficient adhesive force. Moreover, even if content is made high, the surface resistivity of the electroconductive adhesive sheet obtained does not fall so much.
  • the content of the conductive carbon-based filler (B) is usually increased. However, if the content is simply increased, a large amount of the above-mentioned non-string aggregates are formed and hinder the formation of a network network of the carbon-based filler (B). It becomes difficult to lower the surface resistivity as a result.
  • the content of the adhesive resin (A) in the adhesive layer is preferably from 30 to the total mass (100% by mass) of the adhesive layer. It is 99.9% by mass, more preferably 35 to 99% by mass, still more preferably 40 to 98% by mass, and still more preferably 45 to 97% by mass.
  • the content of the adhesive resin (A) or the carbon-based filler (B) with respect to the total mass of the adhesive layer is “effective in the adhesive composition that is a material for forming the adhesive layer. It can also be regarded as “the blending amount of the adhesive resin (A) or the carbon-based filler (B) relative to the total amount (100% by mass) of the component (solid content)”.
  • active ingredient in the adhesive composition means an ingredient excluding a solvent such as water or an organic solvent contained in the adhesive composition.
  • the adhesive layer which the electroconductive adhesive sheet of 1 aspect of this invention has is formed from the adhesive composition containing adhesive resin (A) and a carbonaceous filler (b).
  • a "carbon-type filler (b)" points out the carbon-type filler currently disperse
  • the said adhesive composition may contain general purpose additives, such as a tackifier, a crosslinking agent, a catalyst, a crosslinking accelerator, according to the kind of adhesive resin (A).
  • each component contained in the said adhesive composition which is a forming material of an adhesive layer is demonstrated.
  • the adhesive resin (A) means a resin having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the pressure-sensitive adhesive resin (A) is preferably from the viewpoint of forming a pressure-sensitive adhesive composition that easily forms a pressure-sensitive adhesive layer having a high occupation area ratio of the carbon-based filler (B) on the pasting surface. It is 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 30,000 to 1,000,000.
  • the content of the adhesive resin (A) in the adhesive composition is preferably 30 to 99.9% by mass with respect to the total amount (100% by mass) of the active ingredient (solid content) in the adhesive composition. More preferably, it is 35 to 99% by mass, still more preferably 40 to 98% by mass, and still more preferably 45 to 97% by mass.
  • the adhesive resin (A) used in one embodiment of the present invention may be an adhesive resin that can form an adhesive composition that easily forms an adhesive layer having a high occupied area ratio of the carbon-based filler (B) on the pasting surface.
  • an adhesive resin that can form an adhesive composition that easily forms an adhesive layer having a high occupied area ratio of the carbon-based filler (B) on the pasting surface.
  • acrylic resins urethane resins, polyisobutylene resins, polyester resins, and polyolefin resins. These adhesive resins may be used alone or in combination of two or more.
  • a pressure-sensitive adhesive composition (A) used in one embodiment of the present invention from the viewpoint of easily forming a pressure-sensitive adhesive layer having a high occupation area ratio of the carbon-based filler (B) on the pasting surface.
  • Preferably contains at least one adhesive resin selected from acrylic resins and urethane resins, and more preferably contains at least one adhesive resin selected from acrylic resins and silyl group-containing urethane resins.
  • it contains a silyl group-containing urethane resin.
  • an acrylic resin used in one embodiment of the present invention for example, a polymer including a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, or derived from a (meth) acrylate having a cyclic structure And a polymer containing the structural unit.
  • the form of copolymerization is not particularly limited, and examples of the acrylic copolymer include block copolymers, random copolymers, and graft copolymers. Either may be sufficient.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 100,000 to from the viewpoint of easily forming an adhesive layer having a high occupied area ratio of the carbon-based filler (B) on the pasting surface. It is 1.5 million, more preferably 200,000 to 1.3 million, still more preferably 350,000 to 1.1 million, and still more preferably 500,000 to 900,000.
  • the acrylic resin used in one embodiment of the present invention includes an alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “monomer (a1 ′)”).
  • An acrylic copolymer containing the structural unit (a2) derived from the structural unit (a1) derived from and the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) is preferable.
  • the said acrylic copolymer may contain the structural unit (a3) derived from other monomers (a3 ') other than a monomer (a1') (a2 ').
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 12, more preferably 4 to 8, and further preferably 4 to 6, from the viewpoint of improving the adhesive property.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate.
  • butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, and still more preferably based on all the structural units (100% by mass) of the acrylic copolymer. Is 70 to 97% by mass, more preferably 80 to 95% by mass.
  • Examples of the monomer (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. .
  • a carboxy group-containing monomer is preferable.
  • Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and (meth) acrylic acid is preferred.
  • the content of the structural unit (a2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably based on all the structural units (100% by weight) of the acrylic copolymer. Is 5 to 30% by mass, more preferably 7 to 20% by mass.
  • Examples of the monomer (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl.
  • Examples include (meth) acrylates having a cyclic structure such as (meth) acrylates and imide (meth) acrylates, vinyl acetate, acrylonitrile, and styrene.
  • the content of the structural unit (a3) is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and still more preferably 0 to 0% with respect to all the structural units (100% by weight) of the acrylic copolymer.
  • the amount is 10% by mass, more preferably 0 to 5% by mass.
  • the monomers (a1 ′) to (a3 ′) described above may be used alone or in combination of two or more.
  • the urethane resin used in one embodiment of the present invention is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of a main chain and a side chain.
  • a chain extender is further added to the urethane-based prepolymer (U1) obtained by reacting a polyol and a polyvalent isocyanate compound, or the urethane-based prepolymer (U1).
  • Examples thereof include a urethane polymer (U2) obtained by performing the chain extension reaction used.
  • the mass average molecular weight (Mw) of the urethane-based resin is preferably 10,000 to 10,000 from the viewpoint of easily forming a pressure-sensitive adhesive layer having a high occupation area ratio of the carbon-based filler (B) on the pasting surface. It is 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, and still more preferably 20,000 to 70,000.
  • Examples of the polyol used as a raw material for the urethane-based prepolymer (U1) include polyol compounds such as alkylene diol, polyether-type polyol, polyester-type polyol, and polycarbonate-type polyol. It may be a bifunctional diol or a trifunctional triol. Among these polyols, diols are preferable from the viewpoints of availability, reactivity, and the like.
  • diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, and ethylene.
  • alkylene glycols such as glycol, propylene glycol, diethylene glycol and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol, and polyoxyalkylene glycols such as polytetramethylene glycol.
  • a glycol having a mass average molecular weight of 1000 to 3000 is preferable from the viewpoint of suppressing gelation in the reaction.
  • Examples of the polyvalent isocyanate compound used as a raw material for the urethane prepolymer (U1) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxyly
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca.
  • HMDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodeca examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.
  • IPDI 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • these polyisocyanate compounds may be a trimethylolpropane adduct modified product of the above polyisocyanate, a burette modified product reacted with water, or an isocyanurate modified product containing an isocyanurate ring.
  • polyvalent isocyanate compounds 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesive properties.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is more preferable.
  • the isocyanate group content (NCO%) in the urethane-based prepolymer (U1) is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass, as measured according to JIS K 1603. is there.
  • chain extender a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.
  • the compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
  • aliphatic diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
  • alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
  • Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
  • Examples of bisphenol include bisphenol A and the like.
  • Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
  • Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino-2,3-propanediol, and 1-methyl.
  • Examples include amino alcohols such as amino-2,3-propanediol and N- (2-hydroxypropylethanolamine), and ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine.
  • silyl A group-containing urethane resin is preferred.
  • the silyl group-containing urethane resin is preferably a polymer having a hydrolyzable silyl group represented by the following general formula (1) at least one of the main chain and side chain of the above urethane resin. More preferably, the polymer has a hydrolyzable silyl group represented by the following general formula (1) at both ends of the main chain of the urethane resin.
  • X 1 and X 2 each independently represent a hydroxy group or a substituted or unsubstituted alkoxy group, and R 1 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
  • R 1 represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
  • X 1 and X 2 in the general formula (1) are alkoxy groups, the number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 1, from the viewpoint of hydrolytic dehydration condensation reactivity. 6, more preferably 1 to 3, and still more preferably 1 to 2.
  • the number of carbon atoms of the alkyl group represented by R 1 is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 1, from the viewpoint of the hydrolytic dehydration condensation reactivity. 3, more preferably 1 to 2.
  • substituents when X 1 , X 2 , and R 1 have a substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, a cyano group, a nitro group, and an amino group. Is mentioned.
  • terminal part of the main chain or side chain of the silyl group-containing urethane resin used in one embodiment of the present invention is represented by the following general formulas (2) to (8) (terminal parts -A to G). It is preferable that it has a structure represented by the following general formula (2).
  • X 1 , X 2 and R 1 are the same as those in the general formula (1).
  • R 2 and R 3 each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, Preferably it is 1-6, and more preferably 1-3.
  • A represents an alkylene group, and the alkylene group preferably has 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6.
  • B represents an organic group having 1 to 20 carbon atoms.
  • Examples of the organic group include a substituted or substituted alkyl group having 1 to 20 carbon atoms, a substituted or substituted alkyl group having 1 to 20 carbon atoms, and a substituted or substituted aryl group having 6 to 20 carbon atoms.
  • substituted or substituted alkoxy group having 1 to 20 carbon atoms substituted or substituted aryloxy group having 6 to 20 carbon atoms, substituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, substituted or substituted Substituent heterocyclic group having 2 to 20 carbon atoms, substituted or substituted alkenyl group having 2 to 20 carbon atoms, substituted or substituted alkynyl group having 2 to 20 carbon atoms, substituted or substituted carbon atom having 3 to 3 carbon atoms 20 cycloalkyl groups and the like.
  • R 2 , R 3 , A, and B in the general formulas (2) to (8) have a substituent
  • substituents include a halogen atom (a fluorine atom, a chlorine atom, Bromine atom, iodine atom), cyano group, nitro group and the like.
  • the skeleton of the main chain and side chain of the silyl group-containing urethane resin is the same as that of the above-mentioned urethane resin, but gives an appropriate flexibility to the obtained adhesive composition, and is formed From the viewpoint of facilitating uniform dispersion of the carbon-based filler (B) in the agent layer, a silyl group-containing urethane polymer having a polyoxyalkylene skeleton as the main chain is preferable.
  • the polyoxyalkylene polyoxypropylene and polyoxyethylene are preferable from the above viewpoint, and polyoxypropylene is more preferable.
  • the suitable range of the mass average molecular weight (Mw) of silyl group containing urethane type resin is the same as the suitable range of the above-mentioned mass average molecular weight (Mw) of urethane type resin.
  • the polyisobutylene resin (hereinafter also referred to as “PIB resin”) used in one embodiment of the present invention is not particularly limited as long as it has a polyisobutylene skeleton in at least one of the main chain and the side chain.
  • the mass average molecular weight (Mw) of the PIB-based resin is preferably 20,000 or more from the viewpoint of easily forming a pressure-sensitive adhesive layer having a high occupied area ratio of the carbon-based filler (B) on the pasting surface. More preferably, it is 30,000 to 1,000,000, more preferably 50,000 to 800,000, and still more preferably 70,000 to 600,000.
  • PIB resin examples include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers.
  • examples thereof include halogenated butyl rubber that has been brominated or chlorinated.
  • the structural unit which consists of isobutylene shall be contained most in all the structural units.
  • the content of the structural unit composed of isobutylene is preferably 80 to 100% by weight, more preferably 90 to 100% by weight, and still more preferably 95 to 100% by weight with respect to all the structural units (100% by weight) of the PIB resin. %.
  • These PIB resins may be used alone or in combination of two or more.
  • PIB resin When using a PIB resin, it is preferable to use a PIB resin having a high mass average molecular weight in combination with a PIB resin having a low mass average molecular weight. More specifically, the mass average molecular weight is 270,000 to 600,000.
  • PIB resin (p1) hereinafter also referred to as “PIB resin (p1)”
  • PIB resin (p2) PIB resin having a mass average molecular weight of 50,000 to 250,000
  • the PIB resin (p1) having a high mass average molecular weight it is possible to improve the durability and weather resistance of the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition, and also improve the pressure-sensitive adhesive force. Further, by using the PIB resin (p2) having a low mass average molecular weight, it can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately plasticized. The wettability of the layer to the adherend can be increased, and the adhesive properties, flexibility, and the like can be improved.
  • the mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. It is.
  • the mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 210,000. It is.
  • the content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and even more.
  • the amount is preferably 8 to 20 parts by mass.
  • the polyester resin used in one embodiment of the present invention is a copolymer obtained by a polycondensation reaction of an acid component and a diol component or a polyol component, and includes a modified product of the copolymer.
  • the polycondensation reaction is performed by a general polyesterification reaction such as a direct esterification method or a transesterification method.
  • the form of copolymerization of the polyester resin is not particularly limited, and the polyester resin may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the said polyester-type resin may use individually or in combination of 2 or more types.
  • the acid component examples include terephthalic acid, isophthalic acid, phthalic anhydride, ⁇ -naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or esters thereof, pimelic acid, suberic acid, and azelain.
  • examples thereof include aliphatic dicarboxylic acids such as acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid or esters thereof; and alicyclic dicarboxylic acids such as 1,4-cyclohexahydrophthalic anhydride.
  • diol component or polyol component examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc.
  • Alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic glycols such as bisphenol A.
  • the polyolefin resin used in one embodiment of the present invention is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
  • the polyolefin resin is a copolymer
  • the form of copolymerization is not particularly limited, and the polyolefin resin may be any of a block copolymer, a random copolymer, and a graft copolymer. May be.
  • the polyolefin resin may be used alone or in combination of two or more.
  • polyolefin resins include, for example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other ⁇ - Copolymers of olefins, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers Examples thereof include ethylene (vinyl-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and the like.
  • Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • Examples of the ethylenically unsaturated monomer include vinyl acetate, (meth) acrylic acid, alkyl (meth) acrylate, vinyl alcohol, and the like.
  • polypropylene resins containing a structural unit derived from propylene such as polypropylene, a copolymer of ethylene and propylene, and a copolymer of propylene and other ⁇ -olefin are preferable.
  • the carbon-based filler (b) contained in the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer is a carbon-based filler dispersed in the pressure-sensitive adhesive composition before forming the pressure-sensitive adhesive layer, In the formation process of the layer, the carbon fillers (b) can be aggregated to form the carbon filler (B).
  • the content of the carbon-based filler (b) in the adhesive composition is such that the adhesive resin (A ) Preferably from 100 to 20 parts by weight, preferably from 0.01 to 20 parts by weight, more preferably from 0.05 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight, still more preferably from 0.3 to 7 parts by weight. More preferably, it is 0.5 to 4.5 parts by mass, and still more preferably 0.7 to 3.8 parts by mass.
  • the content of the carbon-based filler (b) with respect to the total amount (100% by mass) of the pressure-sensitive adhesive composition is preferably 0.01 to 20% by mass, more preferably 0.05 to It is 10% by mass, more preferably 0.1-7% by mass, still more preferably 0.2-5% by mass, and still more preferably 0.3-3.5% by mass.
  • the average aspect ratio of the carbon-based filler (b) is a string-like carbon-based filler (in the pressure-sensitive adhesive layer formed so that the occupied area ratio of the carbon-based filler (B) on the pasting surface is increased. From the viewpoint of facilitating dispersion as B), it is preferably 100 to 1200, more preferably 120 to 1000, still more preferably 135 to 500, and still more preferably 140 to 400.
  • the “aspect ratio of the carbon-based filler (b)” is the ratio of the length (H) of the long side to the length (L) of the short side of the target carbon-based filler (b). That is, it is a value calculated from “long side length (H) / short side length (L)”. Further, the “average aspect ratio” is an average value of the “aspect ratio” calculated for 10 carbon fillers (b) as targets. Further, the length (H) of the long side of the carbon-based filler (b) means the length in the height direction (long direction) of the target carbon-based filler (b). In actual measurement, the distance between the two most distant points of the carbon filler (b) as a target may be defined as “long side length (H)”.
  • the short side length (L) of the carbon-based filler (b) is the maximum area of the cut surface when cut perpendicular to the tangential direction at an arbitrary point of the target carbon-based filler.
  • the cross section is a circle or an ellipse, it is a diameter or a long diameter, and if the cross section is a polygon, it means the length of the longest side among the sides of the polygon.
  • the average length (H) of the long side of the carbon-based filler (b) is preferably 0.01 to 2000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, still more preferably 0.3 to 500 ⁇ m, and still more preferably. 0.5 to 100 ⁇ m.
  • the average short side length (L) of the carbon-based filler (b) is preferably 1 to 1000 nm, more preferably 2 to 750 nm, more preferably 3 to 500 nm, still more preferably 5 to 100 nm, and still more preferably. Is 7 to 50 nm.
  • the carbon-based filler (B) can be uniformly dispersed in the pressure-sensitive adhesive layer so that the occupied area ratio of the carbon-based filler (B) on the pasting surface is increased.
  • the shape is not particularly limited as long as it is a simple shape, but a columnar shape, a cylindrical shape, a weight shape, a fiber shape, and a combination thereof are preferable, and a columnar shape, a cylinder shape, a fiber shape, and a combination thereof are more preferable.
  • the carbon-based filler (b) is preferably a carbon-based filler having a shape formed by a fibrous material in which a plurality of single yarns are intertwined, such as wool, and the plurality of single yarns are intertwined.
  • a cylindrical carbon-based filler formed of a fibrous material is more preferable.
  • Examples of the carbon-based filler (b) include conductive fillers containing carbon atoms, and specific examples include carbon nanomaterials, carbon black, milled carbon fiber, and graphite.
  • carbon nanomaterials are preferable from the viewpoints of reducing the surface resistivity of the formed pressure-sensitive adhesive layer and improving the adhesive strength.
  • the carbon nanomaterial is composed of a substance including a graphite sheet having a six-membered ring arrangement as a main structure, but the graphite structure may contain atoms other than carbon atoms such as boron atoms and nitrogen atoms.
  • the carbon nanomaterial may be in a form containing another substance, and the carbon nanomaterial may be in a form modified with another conductive substance.
  • Examples of the carbon nanomaterial include carbon nanotube (CNT), carbon nanofiber, carbon nanohorn, carbon nanocone, fullerene, and the like, and carbon nanotube is preferable.
  • the carbon nanotube is a cylindrical carbon polyhedron having a structure in which a graphite (graphite) sheet mainly having a carbon 6-membered ring structure is closed in a cylindrical shape.
  • the carbon nanotube includes a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape, a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape, and a three-layered graphite sheet
  • a single-walled carbon nanotube having a structure in which a single-layer graphite sheet is closed in a cylindrical shape a double-walled carbon nanotube having a structure in which a two-layer graphite sheet is closed in a cylindrical shape
  • a three-layered graphite sheet There are multi-walled carbon nanotubes having a multi-layered structure concentrically closed as described above, and any two or more of these can be used in combination.
  • the pressure-sensitive adhesive composition that is a material for forming the pressure-sensitive adhesive layer may further contain a tackifier.
  • a tackifier when the above-mentioned urethane-based resin and PIB-based resin are used as the adhesive resin (A), it is preferable to contain a tackifier from the viewpoint of improving the adhesive strength of the formed adhesive layer.
  • the mass average molecular weight (Mw) of this tackifier is usually less than 10,000, and is distinguished from the above-mentioned adhesive resin (A).
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to 4000, more preferably 800 to 1500, from the viewpoint of improving the adhesive strength of the formed pressure-sensitive adhesive layer.
  • the softening point of the tackifier is preferably 110 ° C. or higher, more preferably 110 to 180 ° C., still more preferably 115 to 175 ° C., and still more preferably 120 to 170 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • the tackifier examples include rosin resins such as rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, terpene phenols Terpene resins such as pentene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerization of C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 petroleum resin obtained and hydrogenated petroleum resin of this C5 petroleum resin; obtained by copolymerization of C9 fraction such as indene, vinyltoluene, ⁇ - or ⁇ -methylstyrene generated by thermal decomposition of petroleum naphtha C9 petroleum resin and hydrogenated petroleum resin of this C9 petroleum resin.
  • the tackifiers may be used alone or in combination of
  • the content of the tackifier in the adhesive composition is preferably 1 to 200 parts by weight, more preferably 5 to 160 parts by weight, and still more preferably 10 to 120 parts by weight with respect to 100 parts by weight of the adhesive resin (A). Part by mass.
  • the adhesive resin (A) contains an acrylic resin
  • the content of the tackifier is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the acrylic resin. Part, more preferably 10 to 40 parts by weight.
  • the adhesive resin (A) contains a urethane resin
  • the content of the tackifier is preferably 5 to 200 parts by mass, more preferably 40 to 160 parts by mass with respect to 100 parts by mass of the urethane resin.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, with respect to 100 parts by mass of the PIB resin. More preferably, it is 15 to 40 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the polyester resin. More preferably, it is 25 to 60 parts by mass.
  • the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 25 to 60 parts by mass.
  • the pressure-sensitive adhesive composition that is a material for forming the pressure-sensitive adhesive layer may further contain a crosslinking agent.
  • a crosslinking agent In particular, when the above-mentioned acrylic resin (particularly, the acrylic resin having the above-mentioned functional group) is used as the adhesive resin (A), crosslinking is performed from the viewpoint of improving the adhesive strength of the formed adhesive layer. It is preferable to contain an agent.
  • the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These crosslinking agents may be used alone or in combination of two or more. Among these, from the viewpoint of improving the adhesive strength of the conductive adhesive sheet, an isocyanate-based crosslinking agent is preferable.
  • isocyanate-based crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanate compounds such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate Is mentioned.
  • the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the content of the crosslinking agent in the adhesive composition is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 100 parts by mass of the adhesive resin (A). 0.1 to 5 parts by mass.
  • the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer may further contain a curing accelerator.
  • a curing accelerator when the above-mentioned silyl group-containing urethane resin is contained as the adhesive resin (A), the crosslinking reaction between the silyl groups of the silyl group-containing urethane resin is promoted, and the pressure-sensitive adhesive composition is crosslinked. From the viewpoint of further improving the physical properties, it is preferable to contain a curing accelerator.
  • this hardening accelerator (E) functions as a catalyst.
  • the curing accelerator is preferably one or more selected from the group consisting of an aluminum catalyst, a titanium catalyst, a zirconium catalyst, and a boron trifluoride catalyst.
  • aluminum catalyst aluminum alkoxide, aluminum chelate, and aluminum chloride (III) are preferable.
  • titanium-based catalyst titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable.
  • zirconium-based catalyst zirconium alkoxide, zirconium chelate, and zirconium (IV) chloride are preferable.
  • boron trifluoride-based catalyst an amine complex of boron trifluoride such as boron trifluoride monoethylamine complex or an alcohol complex is preferable.
  • the content of the curing accelerator is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.03 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin (A). 5 parts by mass.
  • the pressure-sensitive adhesive composition that is a material for forming the pressure-sensitive adhesive layer may further contain a crosslinking aid.
  • a crosslinking aid in particular, when the above-mentioned silyl group-containing urethane resin is contained as the adhesive resin (A), it is preferable to contain a crosslinking aid in combination with the above-described curing accelerator.
  • the crosslinking aid amino group-containing alkoxysilanes are preferred.
  • amino group-containing alkoxysilane examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl). ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like.
  • the content of the crosslinking aid is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 6 parts by weight, still more preferably 0.1 to 3 parts by weight based on 100 parts by weight of the adhesive resin (A). Part by mass.
  • the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer, may contain general-purpose additives used for general pressure-sensitive adhesives as long as the effects of the present invention are not impaired.
  • general-purpose additives include ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, and dyes.
  • the amount of each general-purpose additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin (A). 2 parts by mass.
  • the occupation area ratio of the carbon-based filler (B) on the adhesive surface of the pressure-sensitive adhesive layer is within the above range, and the carbon-based filler (B) Can be easily adjusted by appropriately combining the following items [1] to [5].
  • the items [1] to [5] below are merely examples, and it is naturally possible to make adjustments based on general technical common sense other than the items.
  • the pressure-sensitive adhesive layer is prepared by mixing the adhesive resin (A) with the dispersion of the carbon-based filler (b) prepared by applying ultrasonic vibration, and then stirring with a stirrer. It is a layer formed from the adhesive composition.
  • the mixture of the carbon filler (b) dispersion and the adhesive resin (A) is manually stirred, the presence of the adhesive resin (A) causes the carbon filler (b) to be uniformly dispersed.
  • the carbon-based fillers (b) are too close to each other and tend to form aggregates.
  • process (1) and "process (2)” regarding the manufacturing method of the electroconductive adhesive sheet mentioned later. The matter is as follows.
  • a carbon filler having an average aspect ratio in the above range is used as the carbon filler (b) before dispersion.
  • the adhesive resin (A) an adhesive resin having a mass average molecular weight belonging to the above range is used.
  • the adhesive resin (A) one or more adhesive resins selected from the group consisting of acrylic resins and urethane resins are used. More detailed aspects of the acrylic resin and the urethane resin are as described above.
  • the carbon-based filler (b) it is preferable to use a carbon-based filler having a shape formed by a fibrous material in which a plurality of single yarns are entangled, such as wool, and the plurality of single yarns are entangled. It is more preferable to use a cylindrical carbon-based filler formed of a fibrous material. By using such a carbon-based filler, it is easy to form a network network in the process of forming the pressure-sensitive adhesive layer, and it is easy to adjust the occupation area ratio of the carbon-based filler (B) on the pasting surface to the above range. .
  • the base material used for the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention is appropriately selected according to the purpose of use of the conductive pressure-sensitive adhesive sheet.
  • the electroconductive base material containing the electroconductive material of this may be sufficient.
  • an insulating substrate refers to a substrate having a surface resistivity of 1.0 ⁇ 10 14 ⁇ / ⁇ or more (preferably 1.0 ⁇ 10 16 ⁇ / ⁇ or more).
  • the insulating base material include various types of paper such as fine paper, art paper, coated paper, glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials; Material: Polyolefin resin such as polyethylene resin and polypropylene resin, Polybutylene terephthalate resin, Polyester resin such as polyethylene terephthalate resin, Plastic film or sheet made of acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc .; Mixture of these resins A plastic film or sheet comprising: a plastic film or sheet comprising a laminate of these plastic films or sheets.
  • the base material such as a plastic film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral.
  • These insulating base materials may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant, and the like.
  • the conductive substrate examples include a metal foil, a film or sheet obtained by laminating the metal foil with a resin or the like that forms the above-described insulating substrate, and a film obtained by performing a metal deposition process on the surface of the above-described insulating substrate.
  • seat which knitted the metal wire in mesh shape, etc. are mentioned.
  • a metal used for an electroconductive base material aluminum, copper, silver, gold
  • the thickness of the substrate is not particularly limited, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoint of ease of handling.
  • the surface of the base material is subjected to a surface treatment such as an oxidation method or an unevenness method as necessary.
  • the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • a corona discharge treatment method for example, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
  • corrugated method For example, a sandblasting method, a solvent processing method, etc. are mentioned.
  • These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the pressure-sensitive adhesive layer and operability.
  • primer treatment can also be performed.
  • peeling sheet used for the electroconductive adhesive sheet of 1 aspect of this invention, the peeling sheet by which the double-sided peeling process was carried out, the peeling sheet by which the single-sided peeling process was carried out, etc. are used, and it peels on the base material for peeling sheets. The thing etc. which apply
  • Examples of the base material for the release sheet include paper base materials such as glassine paper, coated paper, and high-quality paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, or polyethylene terephthalate resin, polybutylene. Examples thereof include polyester resin films such as terephthalate resin and polyethylene naphthalate resin, and plastic films such as polyolefin resin films such as polypropylene resin and polyethylene resin.
  • Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release sheet is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
  • a pressure-sensitive adhesive composition is prepared by blending the above-described components, and further diluted by adding an organic solvent to form a pressure-sensitive adhesive composition solution. And a method of producing the adhesive layer by forming the solution on the above-mentioned substrate or release sheet by known coating and drying.
  • the method for producing the conductive pressure-sensitive adhesive sheet of the present invention includes the following steps (1) to A production method having (3) is preferred.
  • Step (1) A step of preparing a dispersion of the carbon-based filler (b) by applying vibration by ultrasonic waves.
  • -Process (2) The process which mixes adhesive resin (A) with the dispersion liquid obtained at the process (1), and prepares an adhesive composition by stirring using the stirrer which has a stirring blade.
  • -Process (3) The process of forming an adhesive layer using the adhesive composition obtained at the process (2).
  • Step (1) is a step of preparing a dispersion liquid of carbon-based filler (b) by applying vibration by ultrasonic waves.
  • the carbon-based filler (b) is preferably mixed with a component such as an adhesive resin (A) after being in the form of a dispersion liquid dispersed in a solvent.
  • a component such as an adhesive resin (A) after being in the form of a dispersion liquid dispersed in a solvent.
  • Examples of the solvent used for the preparation of the carbon filler (b) dispersion include water and organic solvents, with organic solvents being preferred.
  • Examples of the organic solvent used for the preparation of the carbon filler (b) dispersion include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, 1-propanol, isopropyl alcohol, and dimethylformamide. N-methylpyrrolidone, dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.
  • At least one selected from methyl ethyl ketone, ethyl acetate, toluene, and isopropyl alcohol is preferable, and at least one selected from ethyl acetate and isopropyl alcohol is more preferable.
  • the carbon-based filler (b) is added to the solvent, and the vibration of the ultrasonic wave (the amplitude is preferably 1 to 50 ⁇ m, more preferably 5 to 40 ⁇ m) is given for a certain period of time.
  • a dispersion of (b) is prepared.
  • the carbon-based fillers (b) are close to each other in the dispersion and moderately (non-string aggregates are not formed. To a degree). As a result, it becomes easy to form a pressure-sensitive adhesive layer in which the occupied area ratio of the carbon-based filler (B) is dispersed.
  • the solid content concentration of the carbon filler (b) dispersion is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 3% by mass.
  • step (2) an adhesive resin (A) or the above-mentioned other additive was blended into the carbon-based filler (b) dispersion obtained in step (1), and a stirrer having a stirring blade was used.
  • a stirrer having a stirring blade was used.
  • This is a step of preparing an adhesive composition by stirring. In this step, when the adhesive resin (A) and other additives are added to the dispersion of the carbon-based filler (b), an organic solvent is further added and diluted to form a solution of the adhesive composition It is good.
  • organic solvent used for preparing the adhesive composition examples include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, 1-propanol, isopropyl alcohol, dimethylformamide, N-methylpyrrolidone. And dimethyl sulfoxide. These organic solvents may be used alone or in combination of two or more.
  • the organic solvent used in the synthesis of the adhesive resin (A) or the organic solvent used when the carbon-based filler (b) is prepared in the form of a dispersion may be used as it is. More than one organic solvent other than the organic solvent used in the dispersion of the carbon-based filler (b) or during the synthesis of the adhesive resin (A) component so that the resulting adhesive composition solution can be uniformly applied An organic solvent may be added.
  • the solid content concentration of the adhesive composition solution is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, still more preferably 5 to 70% by mass, and even more preferably 7 to 60% by mass. .
  • the adhesive resin (A) is blended with the dispersion liquid of the carbon-based filler (b) and mixed by stirring using a stirrer having a stirring blade to prepare an adhesive composition.
  • the carbon fillers (b) are uniformly close to each other in the pressure-sensitive adhesive composition, and moderately (to the extent that non-string aggregates are not formed). Aggregates easily. As a result, it becomes easy to form a pressure-sensitive adhesive layer in which the occupied area ratio of the carbon-based filler (B) is dispersed.
  • the rotation speed of the stirring blade of the stirrer when stirring by the stirrer is preferably 500 to 10,000 rpm, more preferably 1000 to 5000 rpm, still more preferably 1200 to 3500 rpm, and still more preferably 1500 to 3000 rpm.
  • the average aspect ratio is relatively large as the carbon-based filler (b) before dispersion.
  • the rotational speed of the stirring blade is preferably relatively high, and specifically, 3000 rpm or more is preferable.
  • the rotation speed of the stirring blade is preferably relatively slow. Is preferably 1500 rpm or less.
  • Step (3) is a step of forming a pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition obtained in step (2).
  • the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition on a substrate or a release material to form a coating film, and then drying the coating film.
  • Examples of the method for applying the adhesive composition onto the substrate or release sheet include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, and die coating. Method, gravure coating method and the like.
  • drying the drying treatment it is preferable to dry at a drying temperature of 25 to 150 ° C. (preferably 50 to 120 ° C.) for 10 seconds to 50 minutes (preferably 30 seconds to 30 minutes). Further, in order to increase the cohesive strength of the pressure-sensitive adhesive layer, after the drying treatment, for example, it is allowed to stand in an environment of 23 ° C. and 50% RH (relative humidity) for about 7 days to 30 days. It is preferable to sufficiently crosslink the pressure-sensitive adhesive layer (coating film).
  • the conductive pressure-sensitive adhesive sheet of one embodiment of the present invention is produced by appropriately bonding the base material or release sheet onto the pressure-sensitive adhesive layer as necessary. be able to.
  • the adhesive strength of the conductive adhesive sheet of one embodiment of the present invention is preferably 5.0 N / 25 mm or more, more preferably 7.0 N / 25 mm or more, still more preferably 10.0 N / 25 mm or more, and still more preferably 15 0.0 N / 25 mm or more.
  • the value of said adhesive force is an adhesive force when a to-be-adhered body is a stainless steel board, Comprising: The value measured by the method as described in an Example is meant.
  • the surface resistivity of the conductive adhesive sheet of one embodiment of the present invention is preferably 1.0 ⁇ 10 12 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 10 ⁇ / ⁇ or less, more preferably 1.0 ⁇ . 10 9 ⁇ / ⁇ or less, more preferably 3.0 ⁇ 10 8 ⁇ / ⁇ or less, more preferably 1.0 ⁇ 10 7 ⁇ / ⁇ or less, and still more preferably 1.0 ⁇ 10 5 ⁇ / ⁇ or less. is there.
  • urethane resin (1) a resin (hereinafter also referred to as “urethane resin (1)”).
  • the “urethane resin (1)” was synthesized by using N-aminoethyl- ⁇ -aminopropylmethyldimethoxysilane as a raw material for the silylating agent. As shown, a bifunctional silyl group has been introduced.
  • CNT (1) trade name "NC7000", manufactured by Nanosil, cylindrical multi-walled carbon nanotubes formed by a fibrous material in which a plurality of single yarns are intertwined, average aspect ratio before dispersion (H / L ): 200 (long side length (H): 2 ⁇ m, short side length (L): 10 nm).
  • CNT (2) trade name “PLT-CN22”, manufactured by BRANET, Inc., cylindrical multi-walled carbon nanotube, average aspect ratio before dispersion (H / L): 100 (long side length (H ): 15 ⁇ m, short side length (L): 15 nm).
  • CNT (3) trade name “CVD-MWNT CM-95”, manufactured by Nanotechnology, cylindrical multi-walled carbon nanotube, average aspect ratio before dispersion (H / L): 1250 (length of long side) (H): 15 ⁇ m, short side length (L): 12 nm).
  • CNT (4) trade name “VGCF-H”, manufactured by Showa Denko KK, cylindrical multi-walled carbon nanotube, average aspect ratio before dispersion (H / L): 5.54 (long side length) (H): 6 ⁇ m, short side length (L): 150 nm).
  • CNT (5) trade name "C-150P”, manufactured by Bayer, cylindrical multi-walled carbon nanotube, average aspect ratio before dispersion (H / L): 133 (long side length (H): 2 ⁇ m, short side length (L): 15 nm).
  • CNT (6) trade name "K-nanos 100P”, manufactured by Korea Kumho Petrochemical, cylindrical multi-walled carbon nanotubes formed by a fibrous material in which a plurality of single yarns are intertwined, average aspect before dispersion Ratio (H / L): 200 (long side length (H): 2 ⁇ m, short side length (L): 10 nm).
  • Crosslinking agent trade name “Coronate L”, manufactured by Tosoh Corporation, isocyanate crosslinking agent, solid content concentration: 75 mass%.
  • “Curing accelerator” Boron trifluoride monoethylamine complex.
  • Crosslinking aid 3-aminopropyltrimethoxysilane.
  • Examples 1 to 4 and Comparative Examples 1 to 6 (1) Preparation of dispersion liquid of carbon-based filler A carbon-based filler of the type and solid content (solid content ratio with respect to 100 parts by mass of adhesive resin (solid content)) shown in Table 1 is added to ethyl acetate, and ultrasonic dispersion is performed. Of a carbon-based filler having a solid content concentration of 0.3 mass% by applying vibration with ultrasonic waves having an amplitude of 30 ⁇ m for 15 minutes using a machine (trade name “Ultrasonic Disperser for Testing GSD600AT” manufactured by Sonic Technology Co., Ltd.). A dispersion was prepared.
  • Comparative Examples 7-8 (1) Preparation of carbon-based filler dispersion A carbon-based filler of the type and solid content (solid content ratio with respect to 100 parts by mass (adhesive content) of the adhesive resin) shown in Table 1 is added to ethyl acetate, and 15 manually. The mixture was stirred for a minute to prepare a carbon-based filler dispersion having a solid concentration of 0.3% by mass.
  • Adhesive Composition Solution With respect to 100 parts by mass (solid content) of the “acrylic resin (2)”, 2.86 parts by mass of the carbon-based filler dispersion prepared in (1) above ( (Solid content ratio) and 2.1 parts by mass (solid content ratio) of the above-mentioned “crosslinking agent” were added and stirred manually for 10 minutes to prepare a solution of an adhesive composition having a solid content concentration of 10 mass%.
  • FIG. 5A is the digital image of Example 1
  • FIG. 5B is the digital image of Comparative Example 6.
  • the dispersion shape of the carbon-based filler in the pressure-sensitive adhesive layer is “string” if the string-like material can be confirmed from the digital image, and “aggregate” if the string-like material cannot be confirmed and only the aggregate. It was judged.
  • ⁇ Adhesive strength of conductive adhesive sheet The produced conductive adhesive sheet was cut into a size of 5 mm ⁇ 300 mm as a test piece, and the release sheet of the test piece was removed and exposed in an environment of 23 ° C. and 50% RH (relative humidity).
  • the pressure-sensitive adhesive layer was attached to a stainless steel plate (SUS304, No. 360 polishing) and allowed to stand for 24 hours in the same environment. After standing, in accordance with JIS Z0237: 2000, the adhesive strength when the test piece was peeled from the stainless steel plate at a pulling speed of 300 mm / min was measured by a 180 ° peeling method.
  • ⁇ Surface resistivity of conductive adhesive sheet> The measurement was performed according to JIS K 7194. Specifically, the produced conductive adhesive sheet was cut into a size of 20 mm ⁇ 40 mm and allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity). The surface resistivity was measured using a low resistivity meter (product name: “Loresta GP MCP-T610”, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) did. The surface resistivity was measured three times, and Table 1 shows the average value of the three times.
  • the area ratio of the carbon-based filler in a specific region in plan view is within a predetermined range when the adhesive surface of the adhesive layer is viewed in plan view. It can be seen that the surface resistivity is lower than that of the conductive adhesive sheets of Comparative Examples 1 to 8.
  • the carbon-based filler is dispersed in a string shape in the pressure-sensitive adhesive layer.
  • the carbon-based filler was dispersed in the form of a string, as in the digital image shown in FIG. 5 (a). .
  • the carbon-based filler aggregates in the pressure-sensitive adhesive layer to form a non-string-like aggregate having no string-like material and dispersed. Yes.
  • the value of the occupied area ratio of the carbon-based filler when the adhesive surface of the pressure-sensitive adhesive layer is viewed in plan is small.
  • the conductive pressure-sensitive adhesive sheet of the present invention is excellent in antistatic property and conductivity because of having good adhesive force and low surface resistivity. Therefore, the conductive pressure-sensitive adhesive sheet of the present invention prevents, for example, ignition due to sparks generated from static electricity such as electromagnetic shielding materials for containers for storing electronic devices such as computers and communication devices, grounding wires for electrical components, and even triboelectricity. It is suitable as a joining member used for members such as materials.

Landscapes

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

Abstract

L'invention concerne une feuille adhésive sensible à la pression et électriquement conductrice qui comprend une couche adhésive sensible à la pression qui comprend une résine adhésive sensible à la pression (A) et une charge à base de carbone (B), la couche adhésive sensible à la pression ayant une teneur en charge à base de carbone (B) de 0,01 à 20% en masse par rapport à la masse totale de la couche adhésive sensible à la pression. Lorsque la surface adhésive de la couche adhésive sensible à la pression est observée depuis le sens d'une vue en plan, la proportion de la zone occupée par la charge à base de carbone (B) dans l'une quelconque des régions sélectionnée à partir de la surface adhésive est de 17% ou plus. La feuille adhésive sensible à la pression et électriquement conductrice présente une force d'adhérence satisfaisante et est excellente en termes de propriété antistatique et de conductivité électrique.
PCT/JP2015/059735 2014-09-30 2015-03-27 Feuille adhésive électroconductrice sensible à la pression WO2016051829A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016551566A JPWO2016051829A1 (ja) 2014-09-30 2015-03-27 導電性粘着シート

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-200395 2014-09-30
JP2014200395 2014-09-30

Publications (1)

Publication Number Publication Date
WO2016051829A1 true WO2016051829A1 (fr) 2016-04-07

Family

ID=55629888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/059735 WO2016051829A1 (fr) 2014-09-30 2015-03-27 Feuille adhésive électroconductrice sensible à la pression

Country Status (2)

Country Link
JP (1) JPWO2016051829A1 (fr)
WO (1) WO2016051829A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021859A (zh) * 2018-06-22 2018-12-18 北京无线电计量测试研究所 一种导电胶的搅拌方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308158A (ja) * 2006-05-17 2007-11-29 Sumitomo Bakelite Co Ltd 電子部品包装用カバーテープ
JP2008288189A (ja) * 2007-05-18 2008-11-27 Korea Electrotechnology Research Inst 炭素ナノチューブとバインダーを含有する透明伝導性フィルムの製造方法、およびこれにより製造された透明伝導性フィルム
JP2010163586A (ja) * 2008-03-04 2010-07-29 Lintec Corp 粘着剤組成物及び粘着シート
JP2010163587A (ja) * 2008-03-04 2010-07-29 Lintec Corp 粘着剤組成物及び粘着シート
JP2011236327A (ja) * 2010-05-10 2011-11-24 Shinshu Univ 複合粘着剤の製造方法、複合粘着剤及び粘着シート
JP2012087041A (ja) * 2010-09-22 2012-05-10 Yamagata Prefecture 多層カーボンナノチューブ分散配合水性ゲル及びその製造方法並びにその用途
JP2012144624A (ja) * 2011-01-11 2012-08-02 Shinshu Univ 複合粘着剤の製造方法、複合粘着剤及び粘着シート
WO2014007353A1 (fr) * 2012-07-05 2014-01-09 リンテック株式会社 Feuillet adhésif sensible à la pression

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308158A (ja) * 2006-05-17 2007-11-29 Sumitomo Bakelite Co Ltd 電子部品包装用カバーテープ
JP2008288189A (ja) * 2007-05-18 2008-11-27 Korea Electrotechnology Research Inst 炭素ナノチューブとバインダーを含有する透明伝導性フィルムの製造方法、およびこれにより製造された透明伝導性フィルム
JP2010163586A (ja) * 2008-03-04 2010-07-29 Lintec Corp 粘着剤組成物及び粘着シート
JP2010163587A (ja) * 2008-03-04 2010-07-29 Lintec Corp 粘着剤組成物及び粘着シート
JP2011236327A (ja) * 2010-05-10 2011-11-24 Shinshu Univ 複合粘着剤の製造方法、複合粘着剤及び粘着シート
JP2012087041A (ja) * 2010-09-22 2012-05-10 Yamagata Prefecture 多層カーボンナノチューブ分散配合水性ゲル及びその製造方法並びにその用途
JP2012144624A (ja) * 2011-01-11 2012-08-02 Shinshu Univ 複合粘着剤の製造方法、複合粘着剤及び粘着シート
WO2014007353A1 (fr) * 2012-07-05 2014-01-09 リンテック株式会社 Feuillet adhésif sensible à la pression

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHO OTAKA ET AL.: "Dodensei Carbon o Donyu shita Nenchakusei Jushi no Dodensei to Bunsansei", THE ADHESION SOCIETY OF JAPAN NENJI TAIKAI KOEN YOSHISHU, vol. 51, 2013, pages 37 - 38 *
SHO OTAKA ET AL.: "Influence of Surface Free Energy of Polymer on Dispersibility of Multi- walled Carbon Nanotube and Conductivity of Carbon/Polymer Composites", JOURNAL OF THE ADHESION SOCIETY OF JAPAN, vol. 50, no. 4, 2014, pages 115 - 122, [retrieved on 20140401] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021859A (zh) * 2018-06-22 2018-12-18 北京无线电计量测试研究所 一种导电胶的搅拌方法
CN109021859B (zh) * 2018-06-22 2021-04-02 北京无线电计量测试研究所 一种导电胶的搅拌方法

Also Published As

Publication number Publication date
JPWO2016051829A1 (ja) 2017-07-13

Similar Documents

Publication Publication Date Title
KR102388869B1 (ko) 도전성 점착 시트
JP6270721B2 (ja) 粘着性シート
WO2009041674A1 (fr) Ruban adhésif électroconducteur sensible à la pression
JP7059873B2 (ja) 導電性組成物、および導電膜
TWI740935B (zh) 黏著薄片
JP2017132874A (ja) 電子部品貼付用アースラベル
WO2016051829A1 (fr) Feuille adhésive électroconductrice sensible à la pression
KR102390524B1 (ko) 도전성 점착 시트
KR102389424B1 (ko) 도전성 점착 시트
CN108300371A (zh) 导电性压敏粘合带
TWI673337B (zh) 導電性黏著薄片
JP6204189B2 (ja) 粘着剤組成物、及び導電性粘着シート
WO2015098965A1 (fr) Composition adhésive, feuille adhésive et procédé de traitement d'une feuille adhésive
JP6470944B2 (ja) 導電性粘着剤組成物及び導電性粘着シート

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15845679

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016551566

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15845679

Country of ref document: EP

Kind code of ref document: A1