TWI683871B - Conductive adhesive sheet - Google Patents

Abstract

The invention provides a conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), and a surface resistivity (ρ _SX ) of the adhesive conductive layer (X) The value is 1.0×10 ² ~1.0×10 ¹⁰ Ω/□, and the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) is 1.0×10 ^-2 ~1.0×10 ⁸ Ω/□, and , Satisfying formula (1): 0<log ₁₀ (ρ _SX /ρ _SY )≦6.0. The conductive adhesive sheet not only has good adhesion, but also has excellent antistatic properties and electrical conductivity.

Description

Conductive adhesive sheet

The present invention relates to a conductive adhesive sheet.

In the past, in various joints such as electromagnetic shielding materials for containers of electronic devices such as computers and communication equipment, grounding wires for electrical parts, and even anti-ignition materials such as sparks generated by static electricity such as friction and static electricity, many have used simple adhesion Conductive adhesive sheet.

In the adhesive composition used in the adhesive layer of the conductive adhesive sheet, for the purpose of imparting antistatic properties and electrical conductivity, the conductivity of metal powders such as copper powder, silver powder, nickel powder, aluminum powder, etc. is often used. The substance is dispersed in the adhesive resin.

For example, Patent Document 1 discloses a conductive adhesive in which at least one of a carbon nanotube and a carbon microcoil dispersed as a conductive substance is dispersed in the adhesive, and conductive adhesive using the conductive adhesive Contents such as flakes.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2001-172582

However, for the purpose of improving the conductivity of the adhesive layer having a conductive adhesive sheet, a large amount of conductive substance must be added to the adhesive composition as a material for forming the adhesive layer, so that the particles of the conductive substance are in closer contact .

However, when a large amount of conductive material is added to the adhesive composition, the adhesive force of the adhesive layer formed by the adhesive composition tends to decrease. On the other hand, for the purpose of improving the adhesive force, when the content of the conductive material in the adhesive layer is reduced, the conductivity of the adhesive layer will be reduced, and there will be problems that cannot be taken into account.

The conductive adhesive sheet disclosed in Patent Document 1 still has a problem of insufficiency from the viewpoint of improving adhesion and conductivity at the same time.

The present invention aims to provide a conductive adhesive sheet that has good adhesion and excellent antistatic properties and conductivity.

The present inventors found that at least the adhesive conductive layer and the non-adhesive conductive layer are included as constituents, and the surface resistivities of the adhesive conductive layer and the non-adhesive conductive layer alone, and the surface resistivities of the two layers The ratio can be adjusted to a specific range of conductive adhesive sheets to solve the problem This problem was completed, thus completing the present invention.

That is, the present invention provides the following [1] to [16].

[1] A conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), wherein the surface conductivity of the adhesive conductive layer (X) alone ( ρ _SX ) is 1.0×10 ² ~1.0×10 ¹⁰ Ω/□, and the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 ^-2 ~1.0×10 ⁸ Ω /□, and satisfy formula (1): 0<log ₁₀ (ρ _SX /ρ _SY )≦6.0.

[2] The conductive adhesive sheet described in [1] above, wherein the thickness (t _X ) of the adhesive conductive layer ( _X ) is 1 to 1200 μm.

[3] The conductive adhesive sheet described in [1] or [2] above, wherein the thickness (t _Y ) of the non-adhesive conductive layer ( _Y ) is 0.01 to 200 μm.

[4] The conductive adhesive sheet according to any one of [1] to [3] above, wherein the adhesive conductive layer (X) is composed of an adhesive resin (x1) and a carbon-based filler (x2) The layer formed by the adhesive composition.

[5] The conductive adhesive sheet as described in [4] above, wherein the adhesive resin (x1) contained in the adhesive composition contains acrylic resin, urethane resin, rubber One or more adhesive resins selected from the group consisting of resins, styrene resins, polyester resins, and polyolefin resins.

[6] The conductive adhesive sheet described in [4] or [5] above, wherein the average aspect ratio of the carbon-based filler (x2) contained in the adhesive composition is 1.5 or more.

[7] The conductive adhesive sheet according to any one of [4] to [6] above, wherein the content of the carbon-based filler (x2) contained in the adhesive composition is relative to the adhesive resin (x1 ) 100 parts by mass, 0.01 to 15 parts by mass.

[8] The conductive adhesive sheet according to any one of [4] to [7] above, wherein the carbon-based filler (x2) contained in the adhesive composition is a carbon nanomaterial.

[9] The conductive adhesive sheet as described in any one of [1] to [8] above, wherein the non-adhesive conductive layer (Y) contains a conductive polymer, a carbon-based filler, and a metal oxide A layer of more than one conductive material selected by the group.

[10] The conductive adhesive sheet as described in any one of [1] to [9] above, wherein the non-adhesive conductive layer (Y) is made of polythiophene, PEDOT-PSS, carbon nanomaterial, and A layer of more than one conductive material selected from the group of ITO (indium tin oxide).

[11] The conductive adhesive sheet described in [9] or [10] above, wherein the density of the conductive material contained in the non-adhesive conductive layer (Y) is 0.8 to 2.5 g/cm ³ .

[12] The conductive adhesive sheet according to any one of the above [1] to [11], which has a sequential layer according to a substrate, a non-adhesive conductive layer (Y), and an adhesive conductive layer (X) Together constitute the content.

[13] The conductive adhesive sheet as described in [12] above, which has two layers composed of a non-adhesive conductive layer (Y) and an adhesive conductive layer (X) on both sides of the substrate.

[14] The conductive adhesive sheet according to [12] or [13] above, wherein the substrate is an insulating substrate having a surface resistivity of 1.0×10 ¹⁴ Ω/□ or more.

[15] The conductive adhesive sheet as described in any one of [1] to [11] above, which is a two-layer body consisting of an adhesive conductive layer (X) and a non-adhesive conductive layer (Y) The contents of the sandwich between the two peeling sheets.

[16] The conductive adhesive sheet according to any one of the above [1] to [11], which has a first adhesive conductive layer (XI), a non-adhesive conductive layer (Y), and a second The three-layer body obtained by laminating the adhesive conductive layer (X-II) in sequence is sandwiched by two peeling sheets.

The conductive adhesive sheet of the present invention not only has good adhesion, but also has excellent antistatic properties and conductivity.

1A, 1B, 2A, 2B, 3, 4‧‧‧‧ conductive adhesive sheet

11‧‧‧Adhesive conductive layer (X)

11a‧‧‧The first adhesive conductive layer (X-I)

11b‧‧‧Second adhesive conductive layer (X-II)

12‧‧‧non-adhesive conductive layer (Y)

12a‧‧‧The first non-adhesive conductive layer (Y-I)

12b‧‧‧Second non-adhesive conductive layer (Y-II)

13‧‧‧ Base material

14‧‧‧Peeling flakes

21‧‧‧two-layer body

21a‧‧‧The first two-layer body

21b‧‧‧Second layer

22‧‧‧Triple

[FIG. 1] One of the preferred aspects of the conductive adhesive sheet of the present invention is a cross-sectional view of a conductive adhesive sheet with a substrate.

[FIG. 2] The configuration content of one of the preferred aspects of the conductive adhesive sheet of the present invention is a cross-sectional view of the conductive adhesive sheet without a substrate.

In this specification, "mass average molecular weight (Mw)" is, The value converted to the standard polystyrene measured by the gel permeation chromatography (GPC) method is specifically the value measured based on the method described in the Examples.

In addition, for example, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and other similar terms have the same meaning.

In addition, "surface resistivity of the conductive adhesive sheet" means, without particular limitation, the surface resistivity measured from the surface side of the adhesive conductive layer (X) of the conductive adhesive sheet.

In addition, in the present invention, the values of the surface resistivity and volume resistivity of each layer are the values measured using JIS K 7194 as a reference, and specifically, the values measured according to the methods described in the examples.

[Conductive adhesive sheet]

The conductive adhesive sheet of the present invention has at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y).

Since the conductive adhesive sheet of the present invention is provided with a non-adhesive conductive layer (Y), the surface resistivity of the adhesive conductive layer (X) can be greatly reduced, and the antistatic property and conductivity can be improved. As a result, since the adhesive conductive layer (X) does not need to contain a large amount of carbon-based filler, the conductive adhesive sheet of the present invention has good adhesion.

In the present invention, the difference between "adhesive conductive layer (X)" and "non-adhesive conductive layer (Y)" is based on the presence or absence of adhesion, and the presence or absence of adhesion is used to probe the surface of each conductive layer The peak value of the probe tack is judged.

That is, in the present invention, when the peak top value of the probe test on the surface of the target conductive layer is 0.1 N or more, the conductive layer is judged to be adhesive, and is classified as “adhesive conductive layer (X)”.

Conversely, when the peak value of the probe test on the surface of the target conductive layer is less than 0.1N, the conductive layer is judged to be non-adhesive and is classified as "non-adhesive conductive layer (Y)".

Also, the peak top value of the probe test on the surface of the target conductive layer is a value set according to JIS Z 0237 (1991) as a reference, specifically, a value measured according to the method described in the embodiment described later meaning.

When the conductive adhesive sheet of the present invention has at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), it is not particularly limited, and it may have other layers than the above.

In addition, the conductive adhesive sheet according to one aspect of the present invention may be constituted by providing another layer between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), but the conductive adhesion is reduced From the viewpoint of the surface resistivity of the sheet, improvement of antistatic property and conductivity, it is preferable that the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) be directly laminated.

FIG. 1 is a cross-sectional view of the structure of one of the preferred aspects of the conductive adhesive sheet of the present invention, which is a conductive adhesive sheet with a substrate.

The conductive adhesive sheet of one aspect of the present invention, for example, as shown in FIG. 1(a), has a laminated substrate 13, a non-adhesive conductive layer (Y) 12, and an adhesive conductive layer (X) in this order 11. The resulting conductive adhesive sheet 1A and so on. The conductive adhesive sheet 1A has a surface on one side of the substrate A two-layer body 21 composed of a non-adhesive conductive layer (Y) 12 and an adhesive conductive layer (X) 11.

In addition, for the configuration of the conductive adhesive sheet 1A, the peeling sheet 14 may be laminated on the adhesive conductive layer (X) 11 to form the conductive adhesive sheet 1B as shown in FIG. 1(b).

Moreover, the conductive adhesive sheet of one aspect of the present invention, for example, as shown in FIGS. And the conductive adhesive sheet of the two-layer body 21a, 21b composed of the adhesive conductive layer (X).

That is, the conductive adhesive sheet 2A shown in FIG. 1(c) is provided with a first non-adhesive conductive layer (YI) 12a and a first adhesive conductive layer (XI) on one side of the substrate 13 The first two-layer body 21a composed of 11a has a second non-adhesive conductive layer (Y-II) 12b and a second adhesive conductive layer (X-II) on the other side of the substrate 13 ) The second two-layer body 21b composed of 11b.

In addition, the conductive adhesive sheet 2B shown in FIG. 1(d) has a structure that is further formed on the first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (X) with respect to the configuration of the conductive adhesive sheet 2A -II) A structure in which peeling sheets 14a and 14b are laminated on 11b, respectively.

2 is a cross-sectional view of the structure of one of the preferred aspects of the conductive adhesive sheet of the present invention, which is a conductive adhesive sheet without a substrate.

The conductive adhesive sheet of one aspect of the present invention may also be a substrate-free conductive adhesive sheet. Specifically, as shown in FIG. 2(a), it has adhesion The two-layered body 21 composed of the conductive conductive layer (X) 11 and the non-adhesive conductive layer (Y) 12 is sandwiched by two peeling sheets 14a, 14b, a conductive adhesive sheet 3 and the like.

Moreover, the conductive adhesive sheet of one aspect of the present invention may also have a first adhesive conductive layer (XI) 11a and a non-adhesive conductive layer (Y) 12 as shown in FIG. 2(b). The three-layer body 22 formed by sequentially laminating the second adhesive conductive layer (X-II) 11b may be sandwiched by two peeling sheets 14a and 14b, and the conductive adhesive sheet 4 may be sandwiched.

The conductive adhesive sheet according to an aspect of the present invention having a structure other than the above, for example, has a tacky conductive layer (X) and a non-adhesive conductive layer (Y) on one side of the peeled sheet on both sides of which is peeled off The formed two-layer body is a conductive adhesive sheet composed of a roller-shaped curl formed with the adhesive conductive layer (X) as the outer surface.

The first adhesive conductive layer (XI) 11a and the second adhesive conductive layer (X-II) 11b may be layers formed of the same adhesive composition, or may be formed of different adhesive compositions The layer can also be.

In addition, the first non-adhesive conductive layer (YI) 12a and the second non-adhesive conductive layer (Y-II) 12b are also the same, and may be formed of the same forming material or may be formed differently The layer formed by the material may also be used.

Furthermore, in the present invention, the first adhesive conductive layer (XI) and the second adhesive conductive layer (X-II) are the same as the adhesive conductive layer (X), and the first non-adhesive conductive layer (YI ) And the second non-adhesive conductive layer (Y-II) are the same as the non-adhesive conductive layer (Y).

The adhesive conductive layer (X) is adhesive (the value of the peak top measured by the above probe is 0.1 N or more), and is conductive (the individual volume resistivity (ρ _VX ) of the layer is 1.0×10 ⁸ Ω .Cm below) layer.

On the other hand, the non-adhesive conductive layer (Y) is a layer that is non-adhesive (the value of the peak top measured by the above probe is less than 0.1N) and has conductivity (volume resistivity of the layer alone (ρ _VY ) is a layer of 1.0×10 ⁸ Ω·cm or less).

In the present invention, the surface resistivity (ρ _SX ) of the adhesive conductive layer (X) alone is 1.0×10 ² ~1.0×10 ¹⁰ Ω/□, preferably 1.0×10 ² ~1.0×10 ⁸ Ω/□ , More preferably, it is 1.0×10 ² ~1.0×10 ⁷ Ω/□, and particularly preferably 1.0×10 ² ~1.0×10 ⁶ Ω/□.

When the surface resistivity (ρ _SX ) is less than 1.0×10 ² Ω/□, it contains a lot of conductive materials, so it is easy to cause the adhesion of the adhesive conductive layer (X) to decrease, and it is also not good in terms of economy .

On the other hand, when the surface resistivity (ρ _SX ) exceeds 1.0×10 ¹⁰ Ω/□, even if the non-adhesive conductive layer (Y) is provided, the effect of lowering the surface resistivity of the conductive adhesive sheet is not easily found.

Moreover, the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 ^-2 ~1.0×10 ⁸ Ω/□, preferably 1.0×10 ^-2 ~1.0×10 ⁷ Ω/ □, better 1.0×10 ^-2 ~1.0×10 ⁶ Ω/□, especially good 1.0×10 ^-2 ~1.0×10 ⁵ Ω/□, best 1.0×10 ^-2 ~1.0×10 ⁴ Ω /□, most preferably 1.0×10 ^-2 to 1.0×10 ³ Ω/□.

When the surface resistivity (ρ _SY ) is less than 1.0×10 ^-2 Ω/□, or exceeds 1.0×10 ⁸ Ω/□, even if a non-adhesive conductive layer (Y) is provided, it is very difficult to find conductive adhesion The effect of reducing the surface resistivity of the sheet.

In addition, in the present invention, the value of the surface resistivity (ρ _SX ) of the adhesive conductive layer (X) alone and the value of the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) alone must satisfy the following The content of formula (1).

Formula (1): 0<log ₁₀ (ρ _SX /ρ _SY )≦6.0

When the value of log ₁₀ (ρ _SX /ρ _SY ) exceeds 6.0, the surface resistivity of the conductive adhesive sheet cannot be sufficiently reduced, which may cause the tendency of deterioration of antistatic properties and conductivity.

From the above viewpoint, the value of log ₁₀ (ρ _SX /ρ _SY ) is preferably 5.0 or less, more preferably 4.5 or less, particularly preferably 4.0 or less, and most preferably 3.7 or less.

On the other hand, as shown in the above formula (1), the value of log ₁₀ (ρ _SX /ρ _SY ) must be a value greater than 0.

That is, in the present invention, from the viewpoint of efficiently reducing the surface resistivity of the conductive adhesive sheet, the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) alone is the more adhesive conductive layer (X) The individual surface resistivity (ρ _SX ) is a smaller value.

The volume resistivity (ρ _VX ) of the adhesive conductive layer (X) alone is preferably 1.0×10 ⁰ ~1.0×10 from the viewpoint of a conductive adhesive sheet that has good adhesion and can effectively reduce the surface resistivity ⁸ Ω. cm, more preferably 1.0×10 ⁰ ~1.0×10 ⁶ Ω. cm, especially good is 1.0×10 ⁰ ~1.0×10 ⁵ Ω. cm, the best is 1.0×10 ⁰ ~1.0×10 ⁴ Ω. cm.

The volume resistivity (ρ _VY ) of the non-adhesive conductive layer (Y) alone is preferably 1.0×10 ^-4 ~1.0×10 ⁶ Ω from the viewpoint of the conductive adhesive sheet that efficiently reduces the surface resistivity. cm, more preferably 1.0×10 ^-4 ~1.0×10 ⁴ Ω. cm, especially good is 1.0×10 ^-4 ~1.0×10 ³ Ω. cm, particularly preferably 1.0×10 ^-4 ~1.0×10 ² Ω. cm, especially better is 1.0×10 ^-4 ~1.0×10 ¹ Ω. cm, the best is 1.0×10 ^-4 ~1.0×10 ⁰ Ω. cm.

In addition, in one aspect of the present invention, from the viewpoint that the surface resistivity of the conductive adhesive sheet can be efficiently reduced, the volume resistivity (ρ _VY ) of the non-adhesive conductive layer (Y) alone is conductive with a more adhesive The volume resistivity (ρ _VX ) of the layer (X) alone is preferably smaller.

The thickness (t _X ) of the adhesive conductive layer (X) can be adjusted appropriately according to the application, etc. It is preferably 1 to 1200 μm, more preferably 2 to 600 μm, more preferably 3 to 300 μm, and particularly preferably 5 to 250μm, more preferably 10~200μm, most preferably 15~150μm.

When the thickness (t _X ) is 1 μm or more, it has good adhesion regardless of the type of attached body. On the other hand, when the thickness (t _X ) is 1200 μm or less, the obtained conductive adhesive sheet can have good conductivity. In addition, when this conductive adhesive sheet is used as a winding body, it is possible to suppress the curl deviation of the adhesive conductive layer (X) due to deformation, or to extrude the adhesive conductive layer (X) from the end of the winding body ) And other disadvantages.

The thickness (t _Y ) of the non-adhesive conductive layer (Y) can be adjusted appropriately according to the application, etc. It is preferably 0.01 to 200 μm, more preferably 0.1 to 160 μm, particularly preferably 0.5 to 130 μm, and most preferably 1.0 to 100μm.

When the thickness (t _Y ) is 0.01 μm or more, the surface resistivity of the non-adhesive conductive layer (Y) can be effectively reduced.

On the other hand, when the thickness (t _Y ) is 200 μm or less, when the conductive adhesive sheet is used as the winding body, it is possible to suppress the curl deviation of the non-adhesive conductive layer (Y) due to deformation or the winding body Disadvantages of extruding non-adhesive conductive layer (Y) at the end In addition, when the total thickness of the conductive adhesive sheet is reduced, it can be used as a conductive adhesive sheet that can be easily applied to small electronic equipment.

[Forming material of adhesive conductive layer (X)]

The adhesive conductive layer (X) is preferably a layer formed of an adhesive composition containing an adhesive resin (x1) and a carbon-based filler (x2).

In addition, the adhesive composition can be blended with the type of the adhesive resin (x1), and further contains a crosslinking agent, an adhesion-imparting agent, and other common additives other than these.

Hereinafter, each component contained in the adhesive composition will be described.

<Adhesive resin (x1)>

The adhesive resin (x1) contained in the adhesive composition as the forming material of the adhesive conductive layer (X) means an adhesive resin having a mass average molecular weight of 10,000 or more.

The mass average molecular weight (Mw) of the adhesive resin (x1) is preferably 10,000 to 2 million, and more preferably 20,000 to 1.5 million from the viewpoint of improving the adhesion of the conductive adhesive sheet.

The content of the adhesive resin (x1) in the adhesive composition is preferably 60.0 to 99.99% by mass, more preferably 70.0 to 99.9% by mass, and particularly preferably the total amount of the adhesive composition (100% by mass). It is 80.0-99.5 mass%, and the best is 90.0-99.0 mass%.

Adhesive resin (x1) improves the adhesion of the conductive adhesive sheet to improve antistatic properties and conductivity, and contains acrylic acid Resins, urethane resins, polyisobutylene resins, styrene resins, polyester resins, and polyolefin resins, preferably one or more adhesive resins selected from the group consisting of One or more adhesive resins selected from the group consisting of acrylic resins, urethane resins, polyisobutylene resins, and styrene resins are preferred, including acrylic resins, and amino resins One or more adhesive resins selected from the group of ester resins are more preferred.

(Acrylic resin)

The acrylic resin used as the adhesive resin (x1), for example, a polymer having a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, and having a cyclic structure The polymer of structural unit produced by (meth)acrylate.

The mass average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 1.5 million, more preferably 150,000 to 1.3 million, particularly preferably 250,000 to 1.1 million, and most preferably 350,000 to 900,000.

Among acrylic resins, a structure derived from an alkyl (meth)acrylate (a1') having an alkyl group having 1 to 20 carbon atoms (hereinafter, also referred to as "monomer (a1')") The unit (a1) and the acrylic copolymer of the structural unit (a2) produced by the monomer (a2') having a functional group (hereinafter, also referred to as "monomer (a2')") are preferred.

In addition, the acrylic copolymer may have a structural unit (a3) produced by monomers (a3') other than the monomers (a1') and (a2').

Moreover, the form of copolymerization of the acrylic copolymer is not particularly special limited. That is, the acrylic copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer.

The carbon number of the alkyl group of the monomer (a1') is preferably from 1 to 12, more preferably from 4 to 8, and particularly preferably from 4 to 6, from the viewpoint of improving adhesion characteristics.

Monomer (a1'), for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.

Among these monomers (a1'), butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are more preferred, and butyl (meth)acrylate is more preferred.

The content of the structural unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, and particularly preferably 70 to 97% relative to the total structural unit of the acrylic copolymer (100% by mass). %, the best is 80~95 mass%.

Monomer (a2'), for example, monomer containing hydroxyl group, monomer containing carboxyl group, monomer containing epoxy group, monomer containing amine group, monomer containing cyano group, monomer containing ketone group , Monomers containing alkoxysilyl groups, etc.

Among these monomers (a2'), those containing a carboxyl group are preferred.

The carboxyl group-containing monomers, for example, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, etc., are also preferably (meth)acrylic acid.

The content of the structural unit (a2) is preferably 0.5 to 50 mass%, more preferably 1 to 40 mass%, and particularly preferably 5 to 30 mass relative to the total structural unit (100 mass%) of the acrylic copolymer. %, the best is 7~20 mass%.

Monomer (a3'), for example, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentenyloxy ethyl (meth)acrylate, amide imide (meth)acrylate, etc., (meth)acrylate, acetic acid with a cyclic structure Vinyl ester, acrylonitrile, styrene, etc.

The content of the structural unit (a3) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and particularly preferably 0 to 10% by mass relative to the total structural unit (100% by mass) of the acrylic copolymer. , The best is 0 ~ 5 mass%.

In addition, the monomers (a1') to (a3') may be used alone or in combination of two or more.

(Urethane resin)

The urethane resin used as the adhesive resin (x1), as long as the polymer has at least one of urethane linkage and urea linkage in the main chain and/or side chain, and There is no particular limitation, for example, the carbamate-based prepolymer (α) obtained by reacting a polyalcohol with a polyisocyanate compound, or the carbamate-based prepolymer (α), and then the chain A carbamate-based polymer (β) obtained by a chain extender undergoing a chain extension reaction.

Among these, the urethane-based resin used as one aspect of the present invention is preferably a urethane-based polymer having a polyoxyalkylene skeleton.

The mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, and particularly preferably 15,000 ~100,000, the best is 20,000~70,000.

Polyols as raw materials for the urethane-based prepolymer (α) include, for example, polyalcohol compounds such as alkylene glycols, polyether polyols, polyester polyols, and polycarbonate polyols. There is no particular limitation as long as it is a polyalcohol, and it may be a difunctional diol or a trifunctional triol.

Among these polyalcohols, diols are preferred in terms of ease of acquisition and reactivity.

Glycols, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, etc. Alkyl diols such as diol, ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and polyoxyalkylenes such as polytetramethyl glycol Glycol etc. In addition, these diols can be used alone or in combination of two or more.

Among these diols, in the case of reacting with a chain extender again, the viewpoint of suppressing gelation in the reaction is preferable, and a diol having a mass average molecular weight of 1,000 to 3,000 is preferred.

Examples of the polyisocyanate compound as a raw material of the urethane-based prepolymer (α) include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.

Aromatic polyisocyanates, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-phenylene diisocyanate Isocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), 4,4'-tolyl diisocyanate, 2,4,6-triisocyanate toluene, 1, 3,5-triisocyanate benzene, diaminobenzene Dimethyl ether diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethyl Xylene diisocyanate, etc.

Aliphatic polyisocyanates, for example, trimethyl diisocyanate, tetramethyl diisocyanate, hexamethyl diisocyanate (HMDI), pentamethyl diisocyanate, 1,2-propylene diisocyanate, 2,3- Butyl diisocyanate, 1,3-butyl butyl diisocyanate, dodecyl methyl diisocyanate, 2,4,4-trimethyl hexamethyl diisocyanate, etc.

Alicyclic polyisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1 ,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylidene bis(cyclohexyl isocyanate), 1,4-bis(isocyanate methyl) cyclohexane, 1,4-bis(isocyanate methyl) cyclohexane, etc.

In addition, the polyisocyanate compound may be a denatured compound (polyisocyanate) selected from the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specifically, it may be a trimethylolpropane adduct-type denaturant of the compound, a burette-type denaturant obtained by reacting the compound with water, the compound containing an isocyanurate ring, and The obtained isocyanurate denatured substance may also be used.

Among these polyisocyanate compounds, from the viewpoint of producing a carbamate-based polymer with excellent adhesion, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-extruded Tolyl diisocyanate (2,4-TDI), 2,6-tolyl diisocyanate (2,6-TDI), hexamethyl One or more selected from diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and these denatures are preferred. From the viewpoint of weather resistance, to One or more selected from HMDI, IPDI, and these denatures are preferred.

The isocyanate group content (NCO%) in the urethane-based prepolymer (α) is preferably 0.5 to 12% by mass, and more preferably 1 to 4 of the values measured according to JIS K 1603. %.

The chain extender is preferably a compound having at least one of at least two hydroxyl groups and amine groups, or a compound having at least one of three or more hydroxyl groups and amine groups.

A compound having at least one of two hydroxyl groups and amine groups, at least one compound selected from the group consisting of aliphatic diol, aliphatic diamine, alkanolamine, bisphenol, and aromatic diamine Better.

Aliphatic diol, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, etc. Alkanediols such as alkanediol, ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.

Aliphatic diamines, for example, ethylene diamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.

Alkanolamines, for example, monoethanolamine, monopropanolamine, isopropanolamine, etc.

Bisphenol, for example, bisphenol A and the like.

Aromatic diamines, for example, diphenylmethane diamine, tolyl diamine, xylene diamine, etc.

Compounds with at least one of three or more hydroxyl groups and amine groups, for example, trimethylolpropane, di-trimethylolpropane, pentapentane Polyols such as tetraol and dipentaerythritol, 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, N-(2-hydroxypropylethanolamine) and other amino alcohols, tetramethyl Addition of ethylene oxide or propylene oxide based on xylene diamine.

(Polyisobutylene resin)

The polyisobutylene-based resin (hereinafter also referred to as "PIB-based resin") used as the adhesive resin (x1) refers to a resin having a polyisobutylene skeleton in the main chain or side chain.

The mass average molecular weight (Mw) of the PIB-based resin can provide the adhesive composition with sufficient cohesive force, improve the adhesive force of the conductive adhesive sheet, and prevent contamination by attachments. It is preferably at least 20,000. From the viewpoint of the wettability of the attached body or the solubility of the solvent, it is preferably 30,000 to 1 million, more preferably 50,000 to 800,000, and particularly preferably 70,000 to 600,000.

PIB-based resins, for example, polyisobutylene of isobutylene homopolymer, copolymer of isobutylene and isoprene, copolymer of isobutylene and n-butene, isobutylene and butylene Copolymers of diene and halogenated butyl rubber after bromination or chlorination of these copolymers.

In addition, when the PIB-based resin is a copolymer, the structural unit derived from isobutyl group is the one with the largest content among all structural units.

In the PIB-based resin used in one aspect of the present invention, the content of structural units derived from isobutyl groups is preferably 80 to 100 masses relative to the total structural units (100% by mass) of the PIB-based resin %, more preferably 90 to 100% by mass, particularly good 95 to 100% by mass, and most preferably 98 to 100% by mass.

These PIB-based resins may be used alone or in combination of two or more.

Among these, from the viewpoint of improving the durability and weather resistance of the adhesive conductive layer (X) formed, at the time of polymerization, it contains a large number of dense molecular structures, and the main chain and side chains do not have polymerization It is preferably a double bond and the structural unit produced by isobutyl butyl.

In the PIB-based resin used in one aspect of the present invention, the content of structural units derived from isobutyl groups without polymerizable double bonds in these main chains and side chains is relative to the overall structure of the PIB-based resin The unit (100% by mass) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 98 to 100% by mass.

In addition, when using a PIB resin, it is preferable to combine a PIB resin with a higher mass average molecular weight with a PIB resin with a lower mass average molecular weight.

More specifically, the PIB resin used in one aspect of the present invention is a PIB resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter, also referred to as "PIB resin (p1)" ), preferably combined with a PIB resin (p2) with a mass average molecular weight of 50,000 to 250,000 (hereinafter, also referred to as "PIB resin (p2)").

The PIB-based resin (p1) with a higher mass average molecular weight can also be expected to improve the adhesion while improving the durability and weather resistance of the adhesive conductive layer (X) formed by the obtained adhesive composition.

In addition, the PIB resin (p2) with a low mass average molecular weight can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately shaped. It can be plasticized. For the adherend of the adhesive conductive layer (X), we can expect improvement in wettability, adhesive properties, and flexibility.

The mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, and particularly preferably 310,000 to 450,000, most preferably from the above viewpoint From 320,000 to 400,000.

The mass average molecular weight (Mw) of the PIB-based resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, and particularly preferably 140,000 to 220,000. It is 180,000 to 210,000.

The content ratio of the PIB resin (p2) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, and particularly preferably 7 to 30 parts by mass, most preferably 100 parts by mass of the PIB resin (p1). Preferably it is 8-20 parts by mass.

When the content ratio of the PIB-based resin (p2) is 5 parts by mass or more, the PIB-based resin (p1) can be sufficiently plasticized so that the formed adhesive conductive layer (X) has good wettability to the adherend, It can also improve adhesion.

On the other hand, when the content ratio of the PIB-based resin (p2) is 55 parts by mass or less, the adhesion, retention, and durability of the formed adhesive conductive layer (X) can be improved.

(Styrene resin)

The styrene resin used as the adhesive resin (x1) is a polymer having structural units derived from styrene.

In the styrene-based resin used in one aspect of the present invention, the content of structural units derived from styrene is preferably 5-50 masses relative to the total structural unit (100% by mass) of the styrene-based resin %, more preferably 10~40 The mass%, especially good is 15~35 mass%.

The mass average molecular weight (Mw) of the styrenic resin is preferably 10,000 to 400,000, more preferably 20,000 to 300,000, and particularly preferably 25,000 to 200,000 from the viewpoint of improving the adhesion of the conductive adhesive sheet .

The softening point of the styrene resin is from the viewpoint of improving the adhesion of the conductive adhesive sheet, preferably 80 to 200°C, more preferably 90 to 160°C, particularly preferably 100 to 140°C, and most preferably 105 to 135 ℃.

In addition, in the present invention, the softening point of the styrene-based resin means the value measured in accordance with JIS K 2531.

Styrene-based resins, for example, styrene-butadiene-styrene triblock copolymer (hereinafter, also referred to as "SBS"), styrene-block-(ethyl-co-butyl)-block -Styrene triblock copolymer (hereinafter also referred to as "SEBS"), styrene-block-(ethylidene-co-butylene)-block diblock copolymer (hereinafter also referred to as "SEB" ''), styrene-butadiene diblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene-block-( Butadiene-co-isoprene)-block diblock copolymer, styrene-block-(butadiene-co-isoprene)-block-styrene triblock copolymer, etc., or the Modified carboxyl groups of these copolymers, or copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene, etc.

The styrene-based resin may be used alone or in combination of two or more.

Among these styrene-based resins, SBS, SEBS, and SEB are preferred, and SBS and SEBS are preferred.

In addition, when the styrene-based resin is a copolymer, the copolymerization form is not particularly limited. That is, the styrene-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

(Polyester resin)

The polyester resin used as the adhesive resin (x1) is a copolymer obtained by polycondensation reaction of an acid component and a diol component or a polyalcohol component, and also includes a modified product of the copolymer.

The above-mentioned polycondensation reaction can be carried out by a general polyesterification reaction such as direct esterification method and transesterification method.

In addition, the copolymerization form of the polyester resin is not particularly limited. That is, the polyester-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

The above acid component, for example, terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or these Aliphatic dicarboxylic acids such as esters, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedicarboxylic acid or esters of these; 1,4-cyclo Alicyclic dicarboxylic acids such as hexahydrophthalic anhydride.

The aforementioned diol component or polyalcohol component, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol , Diethylene glycol, triethylene glycol, dipropylene glycol and other aliphatic diols, 1,4-cyclohexanediol, 1,4-cyclo Alicyclic diols such as hexanedimethanol, aromatic diols such as bisphenol A, etc.

In addition, the polyester resin may be used alone or in combination of two or more kinds.

(Polyolefin resin)

The polyolefin resin used as the adhesive resin (x1) is a polymer having a structural unit derived from an olefin compound such as a vinyl group and a propylene group.

Polyolefin-based resins, such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, polypropylene, copolymers of vinyl and propylene, vinyl and other α -Copolymers of olefins, copolymers of propylene and other α-olefins, copolymers of vinyl and propylene and other α-olefins, copolymers of vinyl and other ethylenically unsaturated monomers (vinyl-acetic acid Vinyl ester copolymer, vinyl-alkyl (meth) acrylate copolymer, etc.).

In addition, when the polyolefin resin is a copolymer, the copolymerization form is not particularly limited. That is, the polyolefin-based resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

The aforementioned α-olefin, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene Ene etc.

Examples of the ethylenically unsaturated monomer include vinyl acetate, (meth)acrylic acid, alkyl (meth)acrylate, and vinyl alcohol.

Among these polyolefin resins, polypropylene resins containing structural units derived from propylene groups such as polypropylene, copolymers of vinyl groups and propylene groups, and copolymers of propylene groups and other α-olefins are preferred .

In addition, the polyolefin resin may be used alone or in combination of two or more.

<Carbon filler (x2)>

In the adhesive composition as the forming material of the adhesive conductive layer (X), the carbon-based filler (x2) contained together with the adhesive resin (x1) is preferably a carbon-based filler having an average aspect ratio of 1.5 or more.

When the carbon-based filler with an average aspect ratio of 1.5 or more is used, the surface resistivity of the adhesive conductive layer (X) formed can be reduced, and it can be fully produced by the non-adhesive conductive layer (Y) method. The effect of reducing the surface resistivity of the conductive adhesive sheet. In addition, the adhesion of the adhesive conductive layer (X) can also be improved.

From the above viewpoint, the average aspect ratio of the carbon-based filler (x2) is preferably 1.5 or more, more preferably 2 to 10,000, more preferably 3 to 5000, more preferably 4 to 1000, and particularly preferably 5 to 500, particularly preferably 6 to 400, and most preferably 10 to 300.

In the present invention, "aspect ratio" refers to the ratio of the length (H) of the long side to the short side length (L) in the target carbon-based filler, that is, the "length of the long side (H)/ The value calculated by the length of the short side (L)". In addition, the "average aspect ratio" refers to the average value of the "aspect ratio" calculated from ten target carbon-based fillers.

In addition, the length (H) of the long side of the carbon-based filler (x2) means the length in the height direction (longitudinal direction) of the carbon-based filler to be targeted.

On the other hand, the length (L) of the short side of the carbon-based filler (x2) refers to the The height direction (longitudinal direction) of the target carbon-based filler forms a cross section perpendicular to the cross section. When the cross section is circular or elliptical, it refers to the diameter or long diameter. When the cross section is polygonal, it refers to The diameter of the circumscribed circle of the polygon.

The length (H) of the long side of the carbon-based filler (x2) is preferably 0.01 to 2000 μm, more preferably 0.05 to 1000 μm, particularly preferably 0.07 to 500 μm, and most preferably 0.10 to 100 μm.

In addition, in the present invention, the average value of the lengths of the long sides of 10 carbon-based fillers can be arbitrarily selected as the value of the "length (H) of the long side of the carbon-based filler (x2)".

The length (L) of the short side of the carbon-based filler (x2) is preferably 1 to 1000 nm, more preferably 2 to 750 nm, more preferably 3 to 500 nm, particularly preferably 5 to 100 nm, and most preferably 7 to 50 nm .

In addition, in the present invention, the average value of the lengths of the short sides of 10 carbon-based fillers can be arbitrarily selected as the value of the "length (L) of the short sides of the carbon-based filler (x2)".

The shape of the carbon-based filler (x2) is, for example, a columnar shape, a cylindrical shape, a hammer shape, a fibrous shape, a spheroid shape (positive sphericity is usually 0.7 or less), and a combination of these shapes.

Among these shapes, from the viewpoint of forming an adhesive conductive layer (X) with good conductivity, it is selected from columnar carbon fillers, cylindrical carbon fillers, and fibrous carbon fillers One or more is better.

The content of the carbon-based filler (x2) in the adhesive composition is preferably 0.01 to 15 parts by mass, more preferably 0.02 to 10 parts by mass, and more preferably 0.30 relative to 100 parts by mass of the adhesive resin (x1). ~7.0 parts by mass, excellent It is 0.40 to 5.0 parts by mass, particularly preferably 0.50 to 4.5 parts by mass, and most preferably 0.70 to 3.8 parts by mass.

When the content of the carbon-based filler (x2) is 0.01 parts by mass or more, the surface resistivity of the adhesive conductive layer (X) formed alone can be reduced, and the non-adhesive conductive layer (Y) method is provided. , And can fully produce the effect of reducing the surface resistivity of the conductive adhesive sheet.

On the other hand, when the content of the carbon-based filler (x2) is 15 parts by mass or less, the adhesion of the formed adhesive conductive layer (X) can be made good.

In addition, in the conductive adhesive sheet of the present invention, when the content of the carbon-based filler (x2) in the adhesive conductive layer (X) is small, excellent antistatic properties and conductivity can be produced, so there is no need to add a large amount of carbon-based Filler (x2).

The content of the carbon-based filler (x2) relative to the total amount (100% by mass) of the adhesive composition is generally 0.01 to 10% by mass, preferably 0.30 to 7.0% by mass, and more The best is 0.40 to 5.0% by mass, the particularly good is 0.50 to 4.5% by mass, and the best is 0.70 to 3.8% by mass.

Carbon-based fillers (x2), for example, carbon nanomaterials, carbon black, mineral carbon fiber, graphite, etc., can reduce the surface resistivity of the adhesive conductive layer (X) formed, and have a good adhesion point of view, and Carbon nanomaterials are preferred.

Carbon nanomaterials are made of graphite flakes with a six-membered ring arrangement as the main structure. The graphite structure may contain elements other than carbon such as boron or nitrogen, or may be contained in carbon nanomaterials. The form of other substances, in addition, it can also be a form of carbon nanomaterials modified by other conductive substances state.

Carbon nanomaterials, for example, carbon nanotubes (CNT), carbon nanofibers, carbon nanohorns, carbon nanocones, fullerenes, etc., are more preferably carbon nanotubes.

The carbon nanotube is a cylindrical carbon polyhedron having a graphite (graphite) sheet with a carbon 6-member ring structure as the main structure and a cylindrical closed structure.

Among the carbon nanotubes, there is a single-layer carbon nanotube closed by a single layer of graphite flakes and a two-layer carbon nanotube closed by a two-layer graphite flakes. It can be used in combination with two or more carbon multilayer nanotubes with a multilayer structure in which graphite flakes are sealed in a concentric cylindrical shape with three or more layers.

<crosslinking agent>

The adhesive composition as a material for forming the adhesive conductive layer (X) may further contain a crosslinking agent.

In particular, when the above acrylic resin (especially the acrylic copolymer having the above structural unit (a2)) is used as the adhesive resin (x1), the adhesion of the formed adhesive conductive layer (X) is improved In view of this, those containing a crosslinking agent are preferred.

Cross-linking agent, for example, isocyanate-based cross-linking agent, epoxy-based cross-linking agent, aziridine-based cross-linking agent, metal chelate-based cross-linking agent, amine-based cross-linking agent, amine-based resin-based cross-linking agent Joint agent, etc. These crosslinking agents may be used alone or in combination of two or more.

Among these, from the viewpoint of improving the adhesion of the conductive adhesive sheet, Isocyanate-based crosslinking agents are also preferred.

Isocyanate-based crosslinking agent, for example, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 1,3-xylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane -4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl Polyisocyanate compounds such as methane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and amine acid isocyanate.

In addition, the polyisocyanate compound may be a trimethylolpropane adduct-type denaturant of the above compound, a burette-type denaturant obtained by reacting with water, or isocyanurate containing an isocyanurate ring Ester type denatured.

The content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the adhesive resin (x1).

<adhesion imparting agent>

The adhesive composition as a material for forming the adhesive conductive layer (X) may further contain an adhesion-imparting agent.

In particular, when the above-mentioned urethane-based resin, PIB-based resin, and styrene-based resin are used as the adhesive resin (x1), from the viewpoint of improving the adhesion of the formed adhesive conductive layer (X), It is better to have an adhesion-imparting agent.

In addition, the mass average molecular weight (Mw) of the adhesion-imparting agent is usually less than 10,000, and is distinguished from the above-mentioned adhesive resin (x1).

The mass average molecular weight (Mw) of the adhesion-imparting agent is preferably 400 to 4000, and more preferably 800 to 1500, from the viewpoint of improving the adhesion of the formed adhesive conductive layer (X).

The softening point of the adhesion-imparting agent is preferably 110°C or higher, more preferably 110 to 180°C, particularly preferably 115 to 175°C, and most preferably 120 to 170°C.

In the present invention, the "softening point" of the adhesion-imparting agent means a value measured in accordance with JIS K 2531.

Adhesion-imparting agents, such as rosin resins, rosin phenol resins, and ester compounds thereof; rosin-based resins obtained by hydrogenation of these rosin-based resins; terpene resins, aromatic modified terpene resins, terpenes Terpene resins such as phenol resins; hydrogenated terpene resins obtained by hydrogenation of these terpene resins; pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 fraction obtained by copolymerization of C5 series petroleum resin and the C5 series petroleum resin hydrogenated petroleum resin; C9 distillation of indene, vinyl toluene, α- or β-methylstyrene etc. produced by thermal decomposition of petroleum naphtha The C9 petroleum resin obtained by copolymerization and the hydrogenated petroleum resin of the C9 petroleum resin; etc.

In addition, in the present invention, the adhesion-imparting agent may be used alone or in combination of two or more kinds of softening points or structures.

The content of the adhesion-imparting agent is preferably 1 to 200 parts by mass, more preferably 5 to 160 parts by mass, and particularly preferably 10 to 120 parts by mass relative to 100 parts by mass of the adhesive resin (x1).

In addition, when the adhesive resin (x1) contains acrylic resin, the adhesive The content of the imparting agent is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass relative to 100 parts by mass of the acrylic resin.

When the adhesive resin (x1) contains a urethane-based resin, the content of the adhesion-imparting agent is preferably 5 to 200 parts by mass, and more preferably 40 parts by mass relative to 100 parts by mass of the urethane-based resin. ~160 parts by mass, 80-120 parts by mass is especially good.

When the adhesive resin (x1) contains a PIB-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 100 parts by mass of the PIB-based resin. 15~40 parts by mass.

When the adhesive resin (x1) contains a styrene-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the styrene-based resin. It is preferably 25 to 60 parts by mass.

When the adhesive resin (x1) contains a polyester-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the polyester resin. It is preferably 25 to 60 parts by mass.

When the adhesive resin (x1) contains a polyolefin-based resin, the content of the adhesion-imparting agent is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass relative to 100 parts by mass of the polyolefin-based resin. It is preferably 25 to 60 parts by mass.

<Other additives>

Adhesive composition as a forming material for adhesive conductive layer (X) In general, as long as the effect of the present invention is not impaired, in general, it may contain common additives used together with the adhesive resin.

These common additives, for example, ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, hardeners, hardening aids, catalysts, etc.

When adding these common additives, the amount of each of the common additives is preferably 0.01 to 6 parts by mass, and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the adhesive resin (x1).

The total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition as the forming material of the adhesive conductive layer (X) is preferably 20 mass% or more. It is more preferably 30% by mass or more.

In addition, when the adhesive resin (x1) is used as the main component of the acrylic resin, the total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100% by mass) of the adhesive composition, It is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.

When the adhesive resin (x1) is used as the main component of the urethane resin, the total of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition The content is preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. The total content of the adhesive resin (x1) and the carbon-based filler (x2) and the adhesion-imparting agent is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

When the adhesive resin (x1) is used as the main component of the PIB resin, the total content of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, the total content of the adhesive resin (x1) and the carbon-based filler (x2) and the adhesion-imparting agent is preferably 70% by mass or more , More preferably 80% by mass or more, and particularly preferably 90% by mass or more.

When the adhesive resin (x1) is used as the main component of the styrene resin, the total content of the adhesive resin (x1) and the carbon filler (x2) in the total amount (100% by mass) of the adhesive composition is It is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more.

In addition, the mark "adhesive resin (x1) using ZZ resin as the main component" means "the content of ZZ resin is the largest in the resin contained in the adhesive resin (x1)".

In this description, the specific content of the ZZ-based resin is usually 50% by mass or more, preferably 65-100% by mass, and more preferably 75-100% with respect to the total amount (100% by mass) of the adhesive resin (x1). % And Tejia are 85~100% by mass.

<Method of forming adhesive conductive layer (X)>

The method for forming the adhesive conductive layer (X) is not particularly limited, and it can be manufactured according to a known method, for example, the following methods (X-1) and (X-2).

. Method (X-1): Make a solution of the organic solvent of the adhesive composition, This solution is applied to a peeling sheet described later according to a known coating method to form a coating film, and then the coating film is dried to form an adhesive conductive layer (X).

. Method (X-2): After the adhesive resin (x1) and the carbon-based filler (x2) are kneaded to obtain a composite, the composite is formed into a thin sheet according to a well-known molding method, and then the adhesive conductive is formed Layer (X) method.

(Method (X-1))

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

In method (X-1), the organic solvents used are, for example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n- Propanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.

Moreover, these organic solvents can be used in the state of synthesizing the organic solvent used when the adhesive resin (x1) is synthesized.

In the method (X-1), the carbon-based filler (x2) is preferably dispersed in a solvent to form a dispersion liquid, and the adhesive resin (x1) is preferably added.

When the carbon-based filler (x2) is added in the form of a dispersion, it can be mixed with the adhesive resin (x1) in the state of low viscosity, so the carbon-based filler (x2) is easily close to each other. Network, and it is easy to reduce the surface resistivity and volume resistance of the formed adhesive conductive layer (X) rate.

The solvent used for preparing the dispersion liquid of the carbon-based filler (x2) includes, for example, water or the above-mentioned organic solvents, and organic solvents are more preferred.

The method for preparing the dispersion liquid of the carbon-based filler (x2) is, for example, a method of adding the carbon-based filler (x2) to a solvent and using ultrasonic waves or the like to vibrate for a certain time.

The solid content concentration of the dispersion liquid of the carbon-based filler (x2) is preferably 0.01 to 60% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 3% by mass.

In method (X-1), a method of applying a solution of an adhesive composition on a release sheet, for example, a spin coating method, a spray coating method, a strip coating method, a blade coating method, a roller blade coating method Cloth method, roller coating method, plate coating method, mold coating method, gravure coating method, etc.

In addition, after applying the solution of the adhesive composition on the release sheet to form a coating film, it is preferably dried to remove the solvent contained in the coating film.

In addition, in the method (X-1), for the purpose of improving adhesion, the coating layer after the drying treatment, for example, is allowed to stand in an environment of 23°C and 50% RH (relative humidity) for 7 days to 30 days It is preferable that the inside of the coating layer is sufficiently cross-linked in about days.

(Method (X-2))

In the method (X-2), the adhesive resin (x1) is preferably formed by using a durable resin obtained by heating and kneading styrene resin or the like. law.

The heating and kneading device is, for example, a uniaxial extruder, a biaxial extruder, a barrel mill, a compound mill, a Banbury kneader, an intermixture, and a pressure kneader.

The method of molding the compound obtained by using the heating and kneading device, for example, the melt extrusion method, the curtain method, the compression molding method, etc., is also preferably a compression molding method.

A specific method of the compression molding method is, for example, sandwiching the prepared composite with two peeling sheets, and then heating and compressing with a hot extruder to form a sheet-shaped adhesive conductive layer (X). In addition to the two peeling sheets, it is also possible to sandwich the composite of the substrate and the peeling sheet to form a sheet-shaped adhesive conductive layer (X).

[Forming material of non-adhesive conductive layer (Y)]

The non-adhesive conductive layer (Y) can fully exert the effect of reducing the surface resistivity of the conductive adhesive sheet. It is selected from the group consisting of conductive polymers, carbon-based fillers, and metal oxides. A layer of more than one conductive material is preferred, and one containing more than one conductive material selected from the group consisting of polythiophene, PEDOT-PSS, carbon nanomaterials, and ITO (indium tin oxide) is preferred It is better to contain more than one kind of conductive material selected from the group consisting of polythiophene, PEDOT-PSS, and carbon nanomaterials.

The density of the conductive material contained in the non-adhesive conductive layer (Y) is preferably 0.8 to 2.5 g/cm ³ and more preferably 0.8 to 2.0 g/cm ³ from the viewpoint of the lightweight of the conductive adhesive sheet. Especially good is 0.8~1.7g/cm ³ .

Hereinafter, the conductive material constituting the non-adhesive conductive layer (Y) will be described.

<conductive polymer>

Conductive polymers, for example, polythiophene, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)), polyaniline, polypyrrole, polyquinoxaline (quinoxaline )Wait.

Among these, polythiophene and PEDOT-PSS are preferred.

Non-adhesive conductive layer (Y) containing conductive polymer is preferred to contain non-adhesive resin at the same time as conductive polymer. Non-adhesive resin is composed of acrylic resin and urethane resin. One or more non-adhesive resins selected from resins, PIB resins, and styrene resins are preferred.

When the conductive polymer is used as a conductive material, the content of the conductive polymer is preferably 4 to 100% by mass, more preferably 8 to the total amount (100% by mass) of the non-adhesive conductive layer (Y). 100% by mass.

The method for forming the non-adhesive conductive layer (Y) containing a conductive polymer is not particularly limited. For example, a solution of an organic solvent containing a conductive polymer is prepared, and the solution is coated using a known coating method A method of forming a coating film on a substrate or a peeling sheet, and then drying and forming the coating film.

The type of organic solvent used in this method and the application method of the solution The method is the same as the description of the "method (X-1)" regarding the method for forming the adhesive conductive layer (X).

<Carbon filler>

The carbon-based filler, for example, has the same content as the above-mentioned carbon-based filler (x2), and is preferably a carbon nanomaterial.

The non-adhesive conductive layer (Y) containing carbon-based filler is preferred to contain non-adhesive resin at the same time as the carbon-based filler. The non-adhesive resin is composed of acrylic resin, urethane resin, PIB It is better to choose one or more non-adhesive resins based on resins and styrene resins.

When a carbon-based filler is used as a conductive material, the content of the carbon-based filler is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15 relative to the total amount (100% by mass) of the non-adhesive conductive layer (Y). The mass%, especially good, is 1.0-10 mass%, and the best is 2.0-7 mass%.

The method for forming the non-adhesive conductive layer (Y) containing the carbon-based filler is not particularly limited. For example, the dispersion of the carbon-based filler is mixed with the organic solvent solution of the non-adhesive resin to prepare the resin composition After the solution of the substance, a method of applying the solution to a substrate or a release sheet using a known coating method to form a coating film, and then drying and shaping the coating film, etc.

The type of organic solvent used in this method, the method of making the dispersion of carbon-based filler, and the method of coating the solution, and the "method (X-1)" related to the method of forming the above-mentioned adhesive conductive layer (X) Recorded as the same content.

In addition, the method of forming the non-adhesive conductive layer (Y) containing the carbon-based filler may also be heating and mixing the carbon-based filler and the non-adhesive resin, After the composite is prepared, the composite is formed into a thin sheet according to a known molding method.

The heating kneading machine and the composite forming method used in this method are the same as those described in "Method (X-2)" concerning the method for forming the above-mentioned adhesive conductive layer (X).

<metal oxide>

Metal oxides, for example, ITO (indium tin oxide), ZnO (zinc oxide), IZO (zinc indium oxide), AZO (zinc aluminum oxide), GZO (zinc gallium oxide), IGZO (indium gallium zinc oxide), ATO ( Tin oxide antimony) etc.

Among these, ITO (indium tin oxide) is preferred.

In addition, when a metal oxide is used as the conductive material, the non-adhesive conductive layer (Y) is preferably a layer formed only of the metal oxide.

In addition, the method of forming the non-adhesive conductive layer (Y) containing metal oxide is preferably a method of forming a substrate by vapor deposition.

〔Substrate〕

The substrate used in the conductive adhesive sheet according to one aspect of the present invention can be appropriately selected in accordance with the use of the conductive adhesive sheet. It can be an insulating substrate containing an insulating material, or a conductive material containing metal, etc. Conductive substrates, etc.

In the present invention, the insulating substrate means a substrate having a surface resistivity of 1.0×10 ¹⁴ Ω/□ or more (preferably 1.0×10 ¹⁶ Ω/□ or more).

Insulating substrates, such as high-quality paper, surface-processed paper, printing Paper, wax paper, etc. or these paper substrates laminated with thermoplastic resins such as polyethylene and other papers; porous materials such as non-woven fabrics; polyolefin resins such as polyethylene resins and polypropylene resins, polyphenylene Plastic films or sheets formed from polyester resins such as butanediol dicarboxylate resin, polyethylene terephthalate resin, acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc.; A plastic film or sheet formed by a mixture of resins; a plastic film or sheet formed by a laminate of these plastic films or sheets, etc.

In addition, the base material such as plastic film or sheet may be unextended, or may be extended in one or two axis directions such as longitudinal or horizontal.

Furthermore, these insulating substrates (especially plastic films or sheets) may further contain ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-breaking agents, colorants, and the like.

Conductive substrate, for example, a film or sheet obtained by laminating a metal foil or a metal foil to the resin that forms the above-mentioned insulating substrate, or a film or sheet that is subjected to metal vapor deposition on the surface of the above-mentioned insulating substrate 1. A film or sheet that is subjected to antistatic treatment on the surface of the above-mentioned insulating base material, a sheet in which a metal wire is woven into a mesh, etc.

In addition, metals used for the conductive base material are, for example, aluminum, copper, silver, gold, and the like.

The thickness of the substrate is not particularly limited. From the viewpoint of ease of handling, it is preferably 10 to 250 μm, more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

If the substrate is a plastic film or sheet, increase the substrate From the viewpoint of adhesion to the non-adhesive conductive layer (Y), if necessary, it is preferable to apply surface treatment such as an oxidation method or a bumping method to the surface of the substrate.

The oxidation method is not particularly limited, for example, corona discharge treatment method, plasma treatment method, chromic acid oxidation (wet type), flame treatment, hot air treatment, ozone. Ultraviolet irradiation treatment, etc. In addition, the bumping method is not particularly limited, for example, a sandblasting method, a solvent treatment method and the like. These surface treatments can be appropriately selected in accordance with the type of substrate. From the viewpoint of the effect of improving the adhesion with the non-adhesive conductive layer (Y) or operability, the corona discharge treatment method is preferred. In addition, plasma treatment can also be applied.

〔Peeling sheet〕

In addition, the release sheet used for the conductive adhesive sheet of one aspect of the present invention may be a release sheet after being peeled on both sides, or a release sheet after being peeled on one side, etc. Cloth stripper etc.

Substrates for peeling sheets, for example, paper substrates such as wax paper, printing paper, high-quality paper, laminated paper obtained by laminating thermoplastic resins such as polyethylene, or polyethylene terephthalate resin on these paper substrates , Polybutylene terephthalate resin, polyethylene naphthalate resin and other polyester resin films, polypropylene resin, polyethylene resin and other polyolefin resin films and other plastic films.

The release agent includes, for example, rubber-based elastomers such as polysiloxane-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

The thickness of the peeling sheet is not particularly limited, but it is preferably 10 to 200 μm, and more preferably 25 to 150 μm.

[Manufacturing method and physical properties of conductive adhesive sheet]

According to one aspect of the present invention, the conductive adhesive sheet can be formed by the appropriate bonding method between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) formed by the above-mentioned forming method, and the substrate or release sheet Be manufactured.

The peak value of the probe test on the surface of the adhesive conductive layer (X) of the conductive adhesive sheet according to one aspect of the present invention is preferably 0.1 N or more, more preferably 0.1 to 49 N, and particularly preferably 0.5~49N, the best is 1.0~49N.

In addition, the peak top value measured by the probe refers to the value measured according to the method described in the examples. In addition, the peak top value measured by the probe is a physical property value that is an indicator of the adhesive force of the conductive adhesive sheet. The larger the value, the higher the adhesive force.

The surface resistivity (ρ _S ) of the adhesive conductive layer (X) included in the conductive adhesive sheet according to one aspect of the present invention is measured from the surface side, preferably 9.0×10 ⁴ Ω/□ or less, more preferably 1.0× 10 ⁴ Ω/□ or less, particularly preferably 5.0×10 ³ Ω/□ or less, and most preferably 2.0×10 ³ Ω/□ or less.

In addition, the value of "measure the surface resistivity of the adhesive conductive layer (X) of the conductive adhesive sheet from the surface side" is at least composed of the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) layer The surface resistivity value measured on the surface side of the adhesive conductive layer (X) exposed by the conductive adhesive sheet of the present invention is the same as the surface resistivity (ρ _SX ) of the above "adhesive conductive layer (X) alone )" values are not the same.

[Example]

The physical properties of each component used in the following examples and comparative examples, and the physical properties of the conductive adhesive sheet, the adhesive conductive layer (X), and the non-adhesive conductive layer were measured according to the methods described below.

<Mass average molecular weight (Mw)>

Using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020"), the measurement was performed under the following conditions, and the measured value converted from standard polystyrene was used.

(Measurement conditions)

. Tubular column: "TSK guard column HXL-H", "TSK gel GMHXL (×2)" and "TSK gel G2000HXL" (both manufactured by Tosoh Corporation) in sequence.

. Column temperature: 40℃

. Expand solvent: Tetrahydrofuran

. Flow rate: 1.0mL/min

<Length-to-diameter ratio of carbon-based filler, length of long side and short side>

Using a scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., product name "S-4700"), observe 10 randomly extracted particles of carbon-based filler, and measure the length of each long side and the length of the short side respectively. The average value of the particles of 10 carbon-based fillers is used as the "length of the long side" (H)" and "Length of Short Side (L)". In addition, the aspect ratio (H/L) is calculated according to "length of long side (H)/length of short side (L)".

<softening point>

Measured according to JIS K 2531.

<density>

Measured according to JIS Z 8807:2012.

<probe tack>

Measured according to JIS Z0237 (1991).

Specifically, a test piece of 10 mm×10 mm size is allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity) to expose the surface of the layer to be measured of the test piece for use. A viscosity tester (manufactured by Rigaku Corporation, product name "PROBE TACK TESTER") measures the probe tack value of the surface of the layer.

In addition, the test value of this probe is to use a stainless steel probe with a diameter of 5 mm for 1 second and a contact load of 0.98 N/cm ^2. After contacting the surface of the layer to be measured, the probe is made at a speed of 600 mm/sec. , The necessary force used to leave the surface is used as the probe test value of the surface of the layer.

In addition, the peak top value of the probe test value is measured on the surface of the non-adhesive conductive layer. In addition, for the surface of the adhesive conductive layer (X) of the conductive adhesive sheet, the peak top value and the integrated value of the probe test value are measured.

In addition, when the surface of the layer to be measured does not have adhesiveness and the peak top value of the probe test value cannot be measured, the peak top value is "0(N)".

<surface resistivity, volume resistivity>

Measured according to JIS K 7194.

Specifically, a test piece of 20 mm×40 mm size is allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity) to expose the surface of the layer to be measured of the test piece and used Low resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name "Loresta GP MCP-T610 type") to measure surface resistivity and volume resistivity.

The surface resistivity was measured three times as described above, and the volume resistivity was measured five times as described above. In Tables 1 and 2, the average values of the measured values are described.

Furthermore, the surface resistivity and volume resistivity of the adhesive conductive layer (X) alone were measured, and the laminate obtained by sandwiching only the adhesive conductive layer (X) from two peeling sheets was used as a test piece, and the test piece was removed. On one side of the peeling sheet, the values of the exposed adhesive conductive layer (X) were measured.

In addition, the surface resistivity and volume resistivity of the non-adhesive conductive layer alone were measured. Using the substrate with the non-adhesive conductive layer as the test piece, the surface of the non-adhesive conductive layer of the test piece was measured. Of the value.

In addition, the measurement of the surface resistivity of the conductive adhesive sheet is based on the substrate, the non-adhesive conductive layer, and the adhesion prepared according to the examples and comparative examples. The conductive layer (X) and the peeling sheet, the conductive adhesive sheet laminated in this order is used as a test piece, the peeling sheet of the test piece is removed, and only the surface of the exposed adhesive conductive layer (X) is measured The value of surface resistivity.

Manufacturing Example 1 (Fabrication of substrate with non-adhesive conductive layer (Y-1))

Coated with a 50 μm thick polyethylene terephthalate (PET) film (made by Toray Industries, Ltd., trade name "Lumirror", surface resistivity: 1.18×10 ¹⁸ Ω/□) used as a substrate A solution of polythiophene (manufactured by Soken Chemical Co., Ltd. under the trade name "Verazol IW-103") was formed to form a coating film with a thickness of 2.4 μm after drying, and the coating film was dried to prepare Substrate for non-adhesive conductive layer (Y-1) of thiophene.

Manufacturing Example 2 (Fabrication of substrate with non-adhesive conductive layer (Y-2))

It contains 100 parts by mass (solid content) of poly(3,4-ethylidene dioxygen) relative to 100 parts by mass (solid content) of acrylic water-soluble polymer (Arakawa Chemical Industry Co., Ltd., trade name "Tamanori G-37", polyacrylic acid) A solution of 10 parts by mass (solid component ratio) of a dispersion liquid of thiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) (manufactured by Agfa, trade name "Orgacon S305") and 10 parts by mass of ethylene glycol.

Subsequently, the same article as used in Manufacturing Example 1 was coated on a PET film to form a coating film with a thickness of 1.0 μm after the above solution was dried, and the coating film was dried to obtain a PEDOT-PSS-containing coating. Non-adhesive conductive The substrate of layer (Y-2).

Manufacturing Example 3 (Fabrication of substrate with non-adhesive conductive layer (Y-3))

Multi-layer carbon nanotubes (CNT) (manufactured by Nanocyl, trade name "NC7000") are added to 100 parts by mass (solid content) of styrene resin (manufactured by Kraton, trade name "1726M", SEBS). Details are as follows: (Described later) 10 parts by mass (solid content ratio), using a heating kneading machine (manufactured by Toyo Seiki Co., Ltd., product name "30C150"), and kneading at 100°C and 50 rpm to obtain a composite.

Then, using the same PET film as that used in Production Example 1, the above-mentioned composite was sandwiched between a 75 μm-thick release sheet (manufactured by Linde Co., Ltd., trade name “SP-PET751031”), and a hot pressing machine ( Tester Industries Co., Ltd., product name "SA-302"), under the conditions of 130 ℃, 10MPa hot extrusion for 10 minutes. After hot extrusion, the peeling sheet was removed to prepare a substrate with a non-adhesive conductive layer (Y-3) containing SEBS and CNT (10 parts by mass) with a thickness of 100.0 μm.

Manufacturing Example 4 (Fabrication of substrate with non-adhesive conductive layer (Y-4))

With the exception of setting the amount of multi-layer carbon nanotubes to "4 parts by mass", the same method as in Manufacturing Example 3 was used to prepare non-adhesive materials containing SEBS and CNT (4 parts by mass) with a thickness of 100.0 μm. Base material of conductive layer (Y-4).

In the present examples and comparative examples, in addition to the non-adhesive conductive layer-attached substrates produced in the above Production Examples 1 to 4, the following non-adhesive conductive layer-attached substrates were also used.

. "Substrate with non-adhesive conductive layer (YA) formed of ITO": Trade name "ITO-polyethylene terephthalate" (made by Oike Industries Co., Ltd.). It is an ITO film with a thickness of 1.6 μm deposited on one side of a PET film (surface resistivity: 1.18×10 ¹⁸ Ω/□) with a thickness of 50 μm.

. "Substrate with non-adhesive conductive layer (YB) formed of copper": Trade name "NIKAFLEX" (manufactured by Nikkan Industries Co., Ltd.). It is used to bond a copper film with a thickness of 35.0 μm on one side of a PET film (surface resistivity: 1.18×10 ¹⁸ Ω/□) with a thickness of 50 μm using an adhesive.

. Substrate with a non-adhesive conductive layer (YC) formed of aluminum: trade name "Metalumy#50" (manufactured by Toray Film Processing Co., Ltd.. PET film with a thickness of 50 μm (surface resistivity: 1.18× 10 ¹⁸ Ω/□) On one side, an aluminum film with a thickness of 10.0 μm is deposited.

Various physical properties of the non-adhesive conductive layer of the substrate with a non-adhesive conductive layer used in the examples and comparative examples are shown in Table 1.

Examples 1 to 15, Comparative Examples 1 to 8 (1) Formation of adhesive conductive layer (X)

Add the carbon-based filler (x2) to ethyl acetate according to the types and addition amounts (solid content ratio relative to 100 parts by mass (solid content) of the adhesive resin) shown in Table 2 and use an ultrasonic cleaner to Ultrasonic wave (42kHz, 125W) was given vibration for 1 hour, and a dispersion of carbon-based filler (x2) with a solid content concentration of 0.5% by mass was prepared in advance.

Next, add the dispersion of the carbon-based filler (x2) to 100 parts by mass (solid content) of the adhesive resin (x1) shown in Table 2 and add the types and additions shown in Table 2 if necessary. Amount (solid content ratio) of crosslinking agent or adhesion-imparting agent. Subsequently, dilute moderately with ethyl acetate and stir until uniform to prepare a solution of the adhesive composition.

Then, apply the solution of the adhesive composition prepared by the above method to the peeling sheet (made by Linde Co., Ltd., trade name "SP- PET381031", thickness: 38 μm, polyethylene terephthalate film (polyethylene terephthalate film) whose surface has been subjected to silicone peeling treatment, to form a coating film, which was dried to form a coating layer.

Next, on this coating layer, a release sheet of the same type as above was laminated separately, and after allowing it to stand for 14 hours in an environment of 23°C and 50% RH (relative humidity), the coating layer was crosslinked. A laminate obtained by sandwiching the adhesive conductive layer (X) from the two peeling sheets with the thickness shown in Table 2 was prepared.

(2) Fabrication of conductive adhesive sheet

In Examples 1 to 15 and Comparative Examples 7 to 8, the adhesive conductive layer (X) exposed by removing the peeling sheet on one side of the above-mentioned laminate is the same as the type shown in Table 2 with a non-adhesive conductive layer The non-adhesive conductive layer is bonded to make a conductive adhesive sheet.

In Comparative Examples 1 to 6, the adhesive conductive layer (X) exposed by removing the release sheet on one side of the above-mentioned laminate, and a PET film with a thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror”) Laminate to make conductive adhesive sheet.

Example 16 (1) Formation of adhesive conductive layer (X)

For styrene-based resin (manufactured by Toyo ADL Co., Ltd., trade name "P-907Y", details will be described later) 100 parts by mass (solid content), multi-layers are added according to the addition amount (solid content ratio) shown in Table 2 Carbon Nanotube (CNT) (manufactured by Nanocyl Corporation, trade name "NC7000", details are as follows (Described later), using a heating and kneading machine (manufactured by Toyo Seiki Co., Ltd., product name "30C150"), kneading was performed under the conditions of 100°C and 50 rpm to obtain a composite.

Subsequently, the above compound was sandwiched between two peeling sheets (manufactured by Linde Co., Ltd., trade name "SP-PET751031, thickness: 75 μm), and a hot pressing machine (manufactured by Tester Industries Co., Ltd., product name "SA-" 302"), under the conditions of 130°C and 10MPa for 10 minutes of hot extrusion, a laminate obtained by sandwiching only the adhesive conductive layer (X) from two peeling sheets.

(2) Fabrication of conductive adhesive sheet

The non-adhesive conductive material containing the adhesive conductive layer (X) of the styrene resin exposed after removing the peeling sheet on one side of the laminate and the substrate with the non-adhesive conductive layer (Y-2) The layers are laminated to make a conductive adhesive sheet.

The details of each component in the adhesive composition used in the examples and comparative examples shown in Table 2 are shown below.

(Adhesive resin (x1))

. "Acrylic resin": methyl acetate solution of acrylic polymer formed by n-butyl acrylate (BA) and acrylic acid (AA), BA/AA=90.0/10.0 (parts by mass), Mw: 700,000, Solid component concentration: 33.6% by mass.

. "Carbamate Resin": LION SPECIALTY CHEMICALS Co., Ltd., trade name "US-902A", amine Carbamate resin, Mw=56,000.

. "PIB-based resin": 90.9 parts by mass (solid component ratio) of PIB-based resin (manufactured by BASF Corporation, trade name "Oppanol B50") of Mw340,000, and PIB-based resin (manufactured by BASF Corporation, trade name "Oppanol" of Mw200,000 B30") 9.1 parts by mass (solid content ratio) of mixed resin.

. "Styrene-based resin": a mixed resin containing Toyo ADL Co., Ltd., trade name "P-907Y", SEBS and SEB, total content of SEBS and SEB = 30% by mass, softening point = 112°C.

(Carbon filler (x2))

. "NC7000": trade name, manufactured by Nanocyl Corporation, cylindrical multilayer carbon nanotube, average aspect ratio (H/L): 150, length of long side (H): 1.5 μm, length of short side (L ): 10 nm.

. "AMC": trade name, manufactured by Ube Kosei Co., Ltd., cylindrical multilayer carbon nanotube, average aspect ratio (H/L): 100, length of long side (H): 1.1 μm, short side Length (L): 11nm.

(Crosslinking agent)

. "Coronate L": trade name, manufactured by Tosoh Corporation, isocyanate-based crosslinking agent, solid content concentration: 75% by mass.

(Adhesion-imparting agent)

. "Alcone P-125": trade name, manufactured by Arakawa Chemical Industry Co., Ltd., hydrogenated petroleum resin, softening point: 125°C.

. "YS Polystar K125": trade name, Yasuhara Chemical Co., Ltd. Co., Ltd., terpene phenol resin, softening point: 125℃.

(Other ingredients)

. A mixture of other components (adhesion-imparting agent, plasticizer, etc.) other than the (x1) component contained in "P-907Y" used as a styrene resin.

Examples 17~23

A commercially available double-sided adhesive tape (manufactured by Nissin EM Co., Ltd. under the trade name "conductive carbon double-sided tape 7311") and an adhesive layer containing an acrylic resin and carbon powder are held by two release sheets The adhesive layer of the conductive adhesive sheet composed of the clip is used as the adhesive conductive layer (X).

Remove the exposed adhesive layer (adhesive conductive layer (X)) from the release sheet on the side of the conductive double-sided tape of the above-mentioned commercially available product, and the non-adhesive conductive layer (Y -1) The substrate or the non-adhesive conductive layer of the substrate with a non-adhesive conductive layer (Y-4) is bonded to make a conductive adhesive sheet.

Comparative Example 9

The adhesive layer (adhesive conductive layer (X)) on the side of the conductive double-sided adhesive tape of the above-mentioned commercially available product exposed to a peeling sheet, and a PET film (manufactured by Toray Co., Ltd. under the trade name "Lumirror" with a thickness of 50 μm) ") Lamination to make a conductive adhesive sheet.

The various physical property values of the conductive adhesive sheet prepared in the above manner based on the above method are shown in Table 2 and Table 3.

It is known from Tables 2 and 3 that the conductive adhesive sheets of Examples 1 to 23, while having good adhesion, were compared with the conductive adhesive sheets of Comparative Examples 1 to 9 to confirm that the surface resistivity was lower , And has excellent antistatic properties and conductivity.

[Industrial utility]

The conductive adhesive sheet of the present invention has good adhesion and low surface resistivity, so it has excellent antistatic properties and conductivity.

Therefore, the conductive adhesive sheet of the present invention is suitable as, for example, an electromagnetic shielding material for a container for placing electronic equipment such as computers and communication equipment, a grounding wire for electrical parts, and even an anti-ignition material for sparks generated by static electricity such as friction and static electricity. The joint member used by the member.

1A, 1B, 2A, 2B ‧‧‧ conductive adhesive sheet

11‧‧‧Adhesive conductive layer (X)

11a‧‧‧The first adhesive conductive layer (X-I)

11b‧‧‧Second adhesive conductive layer (X-II)

12‧‧‧non-adhesive conductive layer (Y)

12a‧‧‧The first non-adhesive conductive layer (Y-I)

12b‧‧‧Second non-adhesive conductive layer (Y-II)

13‧‧‧ Base material

14‧‧‧Peeling flakes

14a, 14b ‧‧‧ peel sheet

21‧‧‧two-layer body

21a‧‧‧The first two-layer body

21b‧‧‧Second layer

Claims (16)

A conductive adhesive sheet, which is a conductive adhesive sheet having at least an adhesive conductive layer (X) and a non-adhesive conductive layer (Y), characterized in that the surface conductivity of the adhesive conductive layer (X) alone (ρ _SX ) is 1.0×10 ² ~1.0×10 ¹⁰ Ω/□, and the surface resistivity (ρ _SY ) of the non-adhesive conductive layer (Y) alone is 1.0×10 ^-2 ~1.0×10 ⁵ Ω/ □, and satisfy the formula (1): 0<log ₁₀ (ρ _SX /ρ _SY )≦6.0. The conductive adhesive sheet as described in claim 1, wherein the thickness (t _X ) of the adhesive conductive layer ( _X ) is 1 to 1200 μm. The conductive adhesive sheet according to claim 1 or 2, wherein the thickness (t _Y ) of the non-adhesive conductive layer ( _Y ) is 0.01 to 200 μm. The conductive adhesive sheet according to claim 1, wherein the adhesive conductive layer (X) is a layer formed of an adhesive composition containing an adhesive resin (x1) and a carbon-based filler (x2). The conductive adhesive sheet according to claim 4, wherein the adhesive resin (x1) contained in the adhesive composition contains acrylic resin, urethane resin, rubber resin, styrene More than one type of adhesive resin selected from the group consisting of resins, polyester resins, and polyolefin resins. The conductive adhesive sheet according to claim 4 or 5, wherein the average aspect ratio of the carbon-based filler (x2) contained in the adhesive composition is 1.5 or more. The conductive adhesive sheet according to claim 4 or 5, wherein the content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass relative to 100 parts by mass of the adhesive resin (x1) Copies. The conductive adhesive sheet according to claim 4 or 5, wherein the carbon-based filler (x2) contained in the adhesive composition is a carbon nanomaterial. The conductive adhesive sheet as described in claim 1 or 2, wherein the non-adhesive conductive layer (Y) is one or more selected from the group consisting of a conductive polymer, a carbon-based filler, and a metal oxide Of conductive material. The conductive adhesive sheet as described in claim 1 or 2, wherein the non-adhesive conductive layer (Y) is composed of polythiophene, PEDOT-PSS, carbon nanomaterials, and ITO (indium tin oxide) A layer of more than one selected conductive material. The conductive adhesive sheet according to claim 9, wherein the density of the conductive material contained in the non-adhesive conductive layer (Y) is 0.8 to 2.5 g/cm ³ . The conductive adhesive sheet as described in claim 1 or 2, which has a constitution in which a substrate, a non-adhesive conductive layer (Y), and an adhesive conductive layer (X) are laminated in this order. The conductive adhesive sheet according to claim 12 has two layers composed of a non-adhesive conductive layer (Y) and an adhesive conductive layer (X) on both sides of the substrate. The conductive adhesive sheet according to claim 12, wherein the substrate is an insulating substrate having a surface resistivity of 1.0×10 ¹⁴ Ω/□ or more. The conductive adhesive sheet as described in claim 1 or 2 is Yes, the two-layer body composed of the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) is sandwiched by two peeling sheets. The conductive adhesive sheet as described in claim 1 or 2, which is composed of a first adhesive conductive layer (XI), a non-adhesive conductive layer (Y), and a second adhesive conductive layer (X-II) The three-layered body laminated in sequence is sandwiched by two peeling sheets.

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