KR20170048349A - Conductive adhesive sheet - Google Patents

Abstract

Wherein the adhesive pressure-sensitive adhesive sheet (X) is a conductive pressure-sensitive adhesive sheet having at least a pressure-sensitive adhesive layer (X) and a non-pressure-sensitive conductive layer (Y) Wherein the content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass based on 100 parts by mass of the adhesive resin (x1), and the non-adhesive conductive layer (Y) Wherein the conductive adhesive sheet is a layer comprising at least one conductive material selected from the group consisting of a conductive polymer, a carbon-based filler, and a metal oxide. The conductive pressure-sensitive adhesive sheet has good adhesion and excellent antistatic properties and conductivity.

Description

CONDUCTIVE ADHESIVE SHEET [0002]

The present invention relates to a conductive pressure-sensitive adhesive sheet.

BACKGROUND ART [0002] Conventionally, various kinds of joining such as an electronic shielding material of a container for housing electronic equipment such as a computer and a communication device, a grounding wire of an electric part and the like, and an ignition prevention material by a flame generated from static electricity such as triboelectricity, Sensitive adhesive sheet is used.

In the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer of the conductive pressure-sensitive adhesive sheet, a conductive material such as a copper powder, a silver powder, a metal powder such as a nickel powder and an aluminum powder is dispersed in a pressure-sensitive adhesive resin Is being used.

For example, Patent Document 1 discloses a conductive pressure-sensitive adhesive in which at least one of carbon nanotubes and carbon micro-coils is dispersed in a pressure-sensitive adhesive as a conductive material, and a conductive pressure-sensitive adhesive sheet using the conductive pressure-sensitive adhesive.

Japanese Patent Application Laid-Open No. 2001-172582

In order to improve the conductivity of the pressure-sensitive adhesive layer of the above-mentioned conductive pressure-sensitive adhesive sheet, it is necessary to form a large amount of a conductive material in the pressure-sensitive adhesive composition as a material for forming the pressure-sensitive adhesive layer, have.

However, when a large amount of a conductive material is mixed in the pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition tends to have poor adhesive force. On the other hand, if the content of the conductive material in the pressure-sensitive adhesive layer is reduced to increase the adhesive force, the conductivity of the pressure-sensitive adhesive layer is lowered.

The conductive pressure-sensitive adhesive sheet disclosed in Patent Document 1 is still insufficient in terms of improving both the adhesive strength and the conductivity.

An object of the present invention is to provide a conductive pressure-sensitive adhesive sheet having good adhesion and excellent antistatic properties and conductivity.

The present inventors have found that a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin and a carbon-based filler having a specific shape in a specific ratio, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a specific conductive material, And completed the present invention.

That is, the present invention provides the following [1] to [14].

[1] A conductive pressure-sensitive adhesive sheet having at least a pressure-sensitive adhesive layer (X) and a pressure-sensitive adhesive layer (Y)

Wherein the sticky conductive layer (X) is a layer formed from a sticky composition comprising a sticky resin (x1) and a carbon-based filler (x2) having an average aspect ratio of 1.5 or more,

The content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass based on 100 parts by mass of the adhesive resin (x1)

Wherein the non-tacky conductive layer (Y) is a layer containing at least one conductive material selected from the group consisting of a conductive polymer, a carbon-based filler and a metal oxide.

[2] The conductive pressure-sensitive adhesive sheet according to the above-mentioned [1], wherein the pressure-sensitive adhesive layer (X) alone has a surface resistivity (ρ _SX ) of 1.0 × 10 ² to 1.0 × 10 ¹⁰ Ω / square.

[3] The conductive pressure-sensitive adhesive sheet according to the above-mentioned [1] or [2], wherein the non-tacky conductive layer (Y) alone has a surface resistivity p _SY of 1.0 × 10 ^-2 to 1.0 × 10 ⁸ Ω / square.

[4] The conductive pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the carbon-based filler (x2) contained in the viscous composition is a carbon nanomaterial.

(5) The non-tacky conductive layer (Y) as described in the above [1], wherein the non-tacky conductive layer (Y) is a layer containing at least one conductive material selected from the group consisting of polythiophene, PEDOT-PSS, a carbon nanomaterial and ITO Sensitive adhesive sheet according to any one of [1] to [4].

[6] The conductive pressure-sensitive adhesive sheet according to any one of [1] to [5], wherein the conductive material contained in the non-tacky conductive layer (Y) has a density of 0.8 to 2.5 g / cm 3.

[7] The adhesive resin composition according to any one of [1] to [3], wherein the adhesive resin (x1) contained in the adhesive composition is at least one kind of adhesive resin selected from the group consisting of acrylic resin, urethane resin, polyisobutylene resin, styrene resin, polyester resin and polyolefin resin The conductive pressure-sensitive adhesive sheet according to any one of [1] to [6] above, further comprising:

[8] The conductive pressure-sensitive adhesive sheet according to any one of [1] to [7], wherein the sticky conductive layer (X) has a thickness (t _x ) of 1 to 1200 μm.

[9] The conductive pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein the thickness t _y of the non-tacky conductive layer Y is 0.01 to 200 μm.

[10] The conductive pressure-sensitive adhesive sheet according to any one of [1] to [9], wherein the substrate, the non-tacky conductive layer (Y) and the adhesive conductive layer (X) are laminated in this order.

[11] The conductive pressure-sensitive adhesive sheet according to the above-mentioned [10], which has a two-layered structure composed of a non-tacky conductive layer (Y) and a tacky conductive layer (X) on both surfaces of a substrate.

[12] The conductive pressure-sensitive adhesive sheet according to the above-mentioned [10] or [11], wherein the substrate is an insulating substrate having a surface resistivity of 1.0 × 10 ¹⁴ Ω / □ or more.

[13] The conductive film according to any one of [1] to [9], wherein the two-layered body constituted by the sticky conductive layer (X) and the non-adhesive conductive layer (Y) Adhesive sheet.

[14] A structure in which a three-layered body obtained by laminating a first adhesive layer (XI), a non-adhesive conductive layer (Y) and a second adhesive layer (X-II) in this order is sandwiched between two release sheets Sensitive adhesive sheet according to any one of the above [1] to [9].

INDUSTRIAL APPLICABILITY The conductive pressure-sensitive adhesive sheet of the present invention has good adhesion and excellent antistatic properties and conductivity.

Fig. 1 is a cross-sectional view of a conductive pressure-sensitive adhesive sheet having a substrate, which is a preferred embodiment of the conductive pressure-sensitive adhesive sheet of the present invention.
Fig. 2 is a cross-sectional view of a conductive pressure-sensitive adhesive sheet without a substrate, which is a preferred embodiment of the conductive pressure-sensitive adhesive sheet of the present invention.

In the present specification, the " mass average molecular weight (Mw) " is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC) and specifically measured based on the method described in the Examples.

In addition, for example, "(meth) acrylate" is used as a word indicating both "acrylate" and "methacrylate", and the same applies to other similar terms.

The "surface resistivity of the conductive pressure-sensitive adhesive sheet" means the surface resistivity measured from the surface side of the pressure-sensitive conductive layer (X) of the conductive pressure-sensitive adhesive sheet, unless otherwise specified.

In the present invention, the values of the surface resistivity and the volume resistivity of each layer are values measured in accordance with JIS K 7194, specifically, the values measured by the methods described in the examples.

[Conductive adhesive sheet]

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

By providing the non-tacky conductive layer (Y) in the conductive pressure-sensitive adhesive sheet of the present invention, the surface resistivity of the pressure-sensitive adhesive conductive layer (X) is greatly lowered and the antistatic property and the conductivity can be improved. As a result, since it is not necessary to contain a large amount of carbon-based filler in the viscous conductive layer (X), the conductive pressure sensitive adhesive sheet of the present invention has good adhesion.

In the present invention, the "sticky conductive layer (X)" and the "non-sticky conductive layer (Y)" are distinguished by the presence or absence of adhesiveness, and the presence or absence of stickiness depends on the peak of the probe tack Judge from the top value.

That is, in the present invention, if the value of the peak top of the probe tack with respect to the surface of the target conductive layer is 0.1 N or more, it is determined that the conductive layer has tackiness, and classified into "adhesive conductive layer (X) do.

Conversely, when the value of the peak top of the probe tack with respect to the surface of the conductive layer to be a target is less than 0.1 N, the conductive layer is determined to be non-tacky and is classified as " non-tacky conductive layer (Y) ".

The value of the peak top of the probe tip relative to the surface of the conductive layer to be a target is a value measured in accordance with JIS Z 0237 (1991), specifically, a value measured by the method described in the following Examples it means.

The conductive pressure sensitive adhesive sheet of the present invention is not particularly limited as long as it has at least the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), and may have other layers.

The conductive adhesive sheet of the present invention may have another layer provided between the adhesive conductive layer (X) and the non-adhesive conductive layer (Y), but the surface resistivity of the conductive adhesive sheet may be lowered, From the viewpoint of improving the barrier property and the conductivity, it is preferable that the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) are directly laminated.

Fig. 1 is a cross-sectional view of a conductive pressure-sensitive adhesive sheet having a substrate, which is a preferred embodiment of the conductive pressure-sensitive adhesive sheet of the present invention.

As the conductive pressure sensitive adhesive sheet of one form of the present invention, for example, a base material 13, a non-adhesive conductive layer (Y) 12 and a sticky conductive layer (X) 11 ) Are stacked in this order from the back side of the conductive adhesive sheet 1A. This conductive pressure-sensitive adhesive sheet 1A has a two-layered body 21 composed of a non-tacky conductive layer (Y) 12 and a tacky conductive layer (X) 11 on one side of a substrate.

1 (b), in which a release sheet 14 is further laminated on the adhesive conductive layer (X) 11, a conductive adhesive sheet 1B as shown in Fig. .

The conductive pressure-sensitive adhesive sheet according to one embodiment of the present invention may be applied to a pressure-sensitive adhesive sheet having a non-tacky conductive layer (Y) and a pressure-sensitive adhesive layer (X) (21a, 21b) formed of a conductive adhesive sheet.

That is, the conductive pressure-sensitive adhesive sheet 2A shown in Fig. 1 (c) has a first non-sticking conductive layer (YI) 12a and a first sticky conductive layer (XI) 11a And a second non-adhesive conductive layer (Y-II) 12b and a second adhesive conductive layer (X-II) (not shown) on the other side of the base material 13 And a second two-layered body 21b composed of the first and second laminated bodies 11a and 11b.

The conductive pressure-sensitive adhesive sheet 2B shown in Fig. 1 (d) is formed on the first pressure-sensitive adhesive layer 2A and the second pressure-sensitive adhesive layer 2B on the first pressure- II) 11b, respectively, and the release sheets 14a, 14b are further laminated.

2 is a cross-sectional view of a conductive pressure-sensitive adhesive sheet without a substrate, which is a preferred configuration of the conductive pressure-sensitive adhesive sheet of the present invention.

The conductive pressure-sensitive adhesive sheet of the present invention may be a conductive pressure-sensitive adhesive sheet without a substrate. Specifically, the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (X) And the conductive adhesive sheet 3 having a configuration in which the two-layered body 21 composed of the adhesive layer (Y) 12 is sandwiched between two release sheets 14a, 14b.

As the conductive adhesive sheet of the present invention, the first adhesive layer (XI) 11a, the non-adhesive conductive layer (Y) 12, and the second adhesive layer The electrically conductive pressure sensitive adhesive sheet 4 may have a configuration in which the three-layered body 22 in which the sticky conductive layers (X-II) 11b are laminated in this order is sandwiched between two release sheets 14a and 14b.

As a conductive adhesive sheet according to an embodiment of the present invention other than the above, a two-layered body composed of a sticky conductive layer (X) and a non-sticky conductive layer (Y) is adhered to one side of a release sheet having both- And a conductive pressure-sensitive adhesive sheet having a configuration in which the layer X is provided so as to be exposed so as to be wound in a roll form.

The first adhesive layer (X-I) 11a and the second adhesive layer (X-II) 11b may be formed of the same adhesive composition or may be formed of another adhesive composition.

Similarly, the first non-tacky conductive layer (YI) 12a and the second non-tacky conductive layer (Y-II) 12b may be layers formed of the same material or formed of different materials .

Hereinafter, the adhesive conductive layer (X), the non-adhesive conductive layer (Y), the substrate and the release sheet constituting the conductive pressure sensitive adhesive sheet of the present invention will be described.

In the present invention, the constitution of the first sticky conductive layer (XI) and the second sticky conductive layer (X-II) is the same as that of the sticky conductive layer (X) 2 non-tacky conductive layer (Y-II) is the same as that of the non-tacky conductive layer (Y).

[Tacky conductive layer (X)]

The adhesive conductive layer (X) of the conductive adhesive sheet of the present invention is a layer formed of a sticky resin (x1) and a sticky composition comprising a carbon-based filler (x2) having an average aspect ratio of 1.5 or more.

The adhesive conductive layer X has a tackiness (a peak top value of the above-described probe tack is at least 0.1 N), and also a conductivity (volume resistivity (ρ _VX ) of the layer alone is not more than 1.0 × 10 ⁸ Ω · cm) Layer.

The surface resistivity (rho _SX ) of the sticky conductive layer (X) alone is preferably in the range of 1.0 x 10 < ² > to 1.0 x ¹⁰ < ¹⁰ & , More preferably 1.0 x 10 ² to 1.0 x 10 ⁸ Ω / square, further preferably 1.0 × 10 ² to 1.0 × 10 ⁷ Ω / square, still more preferably 1.0 × 10 ² to 1.0 × 10 ⁶ Ω / □.

The volume resistivity (rho _VX ) of the sticky conductive layer (X) alone is preferably in the range of 1.0 x 10 < ⁰ > to 1.0 x 10 < ⁸ & , and more preferably 1.0 × 10 ⁰ to 1.0 × 10 ⁶ Ω · ㎝, more preferably from 1.0 × 10 ⁰ to 1.0 × 10 ⁵ Ω · ㎝, is still more preferably 1.0 × 10 ⁰ to 1.0 × 10 ⁴ Ω · Cm.

The thickness t _x of the viscous conductive layer X is appropriately adjusted in accordance with the use and the like, and is preferably 1 to 1200 μm, more preferably 2 to 600 μm, still more preferably 3 to 300 μm, Is 5 to 250 占 퐉, more preferably 10 to 200 占 퐉, still more preferably 15 to 150 占 퐉.

When the thickness (t _X ) is 1 탆 or more, a good adhesion force which does not depend on the kind of the adherend can be exhibited. On the other hand, if the thickness t _x is 1200 μm or less, the conductivity of the resulting electrically conductive pressure-sensitive adhesive sheet becomes good. Further, when the conductive adhesive sheet is formed into a rolled body, winding displacement caused by deformation of the viscous conductive layer (X) and adverse effects that the viscous conductive layer (X) is evacuated from the ends of the rolled body can be suppressed.

The adhesive composition which is a material for forming the adhesive conductive layer (X) contains a tacky resin (x1) and a carbon-based filler (x2) having an average aspect ratio of 1.5 or more. Depending on the type of the tacky resin (x1) , And general-purpose 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 which is a material for forming the adhesive and conductive layer (X) means a resin having a sticking property with a mass average molecular weight of 10,000 or more.

The mass average molecular weight (Mw) of the adhesive resin (x1) is preferably from 10,000 to 2,000,000, and more preferably from 20,000 to 150,000 from the viewpoint of improving the adhesive strength of the conductive pressure-sensitive 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 still more preferably 80.0% by mass to 80% by mass, with respect to the total amount (100% 99.5% by mass, and even more preferably 90.0% to 99.0% by mass.

As the adhesive resin (x1), an acrylic resin, a urethane resin, a polyisobutylene resin, a styrene resin, a polyester resin and a polyolefin resin are preferably used in order to improve the adhesive strength of the electrically conductive pressure sensitive adhesive sheet and to improve the antistatic property and the conductivity. Based resin and at least one adhesive resin selected from the group consisting of an acrylic resin, a urethane resin, a polyisobutylene resin, and a styrene resin, And more preferably at least one adhesive resin selected from the group consisting of an acrylic resin and a urethane resin.

(Acrylic resin)

Examples of the acrylic resin that can be used as the adhesive resin (x1) include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, a polymer having a structural unit derived from a (meth) acrylate having a cyclic structure , And the like.

The mass average molecular weight (Mw) of the acrylic resin is preferably 50,000 to 150,000, more preferably 150,000 to 1,300,000, still more preferably 2,500 to 1,100,000, still more preferably 350,000 to 900,000 .

(A1) derived from an alkyl (meth) acrylate (a1 ') having an alkyl group of 1 to 20 carbon atoms (hereinafter also referred to as "monomer (a1')") and a functional group- Is preferably an acrylic copolymer having a structural unit (a2) derived from a monomer (hereinafter also referred to as " monomer (a2 ') ").

The acrylic copolymer may have a structural unit (a3) derived from other monomer (a3 ') other than the monomers (a1') and (a2 ').

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

The number of carbon atoms of the alkyl group of the monomer (a1 ') is preferably from 1 to 12, more preferably from 4 to 8, and still more preferably from 4 to 6 from the viewpoint of improving the adhesive property.

Examples of the monomer (a1 ') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) (Meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

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

The content of the constituent unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, and still more preferably 70 to 99% by mass, relative to the total constituent units (100% 97% by mass, and even more preferably 80% by mass to 95% by mass.

Examples of the monomer (a2 ') include a hydroxy group-containing monomer, a carboxyl group-containing monomer, an epoxy group-containing monomer, an amino group-containing water monomer, a cyano group-containing monomer, a keto group-containing monomer and an alkoxysilyl group-

Among these monomers (a2 '), a carboxyl group-containing monomer is preferable.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, and (meth) acrylic acid is preferable.

The content of the structural unit (a2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 5 to 20% by mass, relative to the total structural units (100% 30% by mass, and even more preferably 7 to 20% by mass.

Examples of the monomer (a3 ') include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, vinyl acetate, acrylonitrile and styrene having a cyclic structure such as acrylate, dicyclopentenyloxyethyl (meth) acrylate and imide (meth) acrylate.

The content of the structural unit (a3) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass, relative to the total constituent units (100% By mass, more preferably from 0 to 5% by mass.

The above-mentioned monomers (a1 ') to (a3') may be used alone or in combination of two or more.

(Urethane resin)

The urethane resin that can be used as the adhesive resin (x1) is not particularly limited as long as it is a polymer having at least one of a urethane bond and an urea bond in the main chain and / or the side chain, and examples thereof include a polyisocyanate compound obtained by reacting a polyol and a polyisocyanate compound Based polymer (?) Obtained by subjecting a urethane-based prepolymer (?) Or the urethane prepolymer (?) To a chain extension reaction using a chain extender.

Among them, the urethane-based resin used in one embodiment of the present invention preferably contains a urethane-based polymer having a polyoxyalkylene skeleton.

The mass average molecular weight (Mw) of the urethane-based resin is preferably 10,000 to 200,000, more preferably 120,000 to 150,000, still more preferably 1,500 to 100,000, still more preferably 20,000 to 70,000 .

As the polyol to be a raw material of the urethane prepolymer (?), For example, polyol compounds such as alkylene diol, polyether type polyol, polyester type polyol and polycarbonate type polyol can be mentioned. But may be a bifunctional diol or a trifunctional triol.

Of these polyols, diols are preferable from the viewpoints of availability and reactivity.

Examples of the diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 1,7-heptanediol, , Alkylene glycols such as propylene glycol, diethylene glycol and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol, and polyoxyalkylene glycols such as polytetramethylene glycol. have. These diols may be used alone or in combination of two or more kinds.

Of these diols, when a reaction with a chain extender is further carried out, a glycol having a mass average molecular weight of 1,000 to 3,000 is preferable from the viewpoint of suppressing gelation in the reaction.

Examples of the polyisocyanate compound to be used as a raw material of the urethane prepolymer (?) Include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4- TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, Isocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxsilylene diisocyanate, 1,3-tetramethyl xylylene diisocyanate, .

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3 -Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (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'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) Hexane, and 1,4-bis (isocyanatomethyl) cyclohexane.

Further, the polyvalent isocyanate compound may be a modified product of a compound (polyisocyanate) selected from the above-mentioned aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate. Specifically, it may be a trimethylolpropane duct-type modified product of the compound, a buret-type modified product obtained by reacting the compound with water, and an isocyanurate-modified product containing an isocyanurate ring in the compound.

Among these polyisocyanate compounds, from the viewpoint of obtaining a urethane-based polymer having excellent tackiness, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6- At least one compound selected from the group consisting of 2,6-diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) , And from the viewpoint of weatherability, at least one selected from HMDI, IPDI and modified products thereof is more preferable.

The isocyanate group content (NCO%) in the urethane prepolymer (?) Is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass in terms of a value measured in accordance with JIS K 1603.

As the chain extender, a compound having at least two of a hydroxyl group and an amino group, or a compound having at least three of a hydroxyl group and an amino group is preferable.

The compound having at least one of hydroxyl and amino groups is preferably at least one compound selected from the group consisting of an aliphatic diol, an aliphatic diamine, an alkanolamine, a bisphenol, and an aromatic diamine.

Examples of the aliphatic diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 1,7- And alkylene glycols such as glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like.

The aliphatic diamines include, for example, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine and the like.

Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine, and the like.

As the bisphenol, for example, bisphenol A and the like can be mentioned.

Examples of the aromatic diamine include diphenylmethane diamine, tolylene diamine, xylylenediamine, and the like.

Examples of the compound having at least three of hydroxyl and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol, 1-amino-2,3-propanediol, 1 Amino alcohols such as methylamino-2,3-propanediol and N- (2-hydroxypropylethanolamine), ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine, and the like.

(Polyisobutylene-based resin)

The polyisobutylene resin (hereinafter also referred to as " PIB resin ") which can be used as the adhesive resin (x1) is a resin having a polyisobutylene skeleton in the main chain or side chain.

The mass average molecular weight (Mw) of the PIB resin is preferably 20,000 or more from the viewpoints of sufficiently obtaining the cohesive force of the obtained pressure sensitive adhesive composition, improving the adhesive strength of the pressure sensitive adhesive sheet and preventing contamination of the adherend, Is preferably from 30,000 to 1,000,000, more preferably from 50,000 to 800,000, and even more preferably from 70,000 to 600,000 from the viewpoints of wettability to the adherend and solubility in solvents.

Examples of the PIB resin include polyisobutylene, which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, And halogenated butyl rubbers in which these copolymers are subjected to bromination or chlorination.

When the PIB resin is a copolymer, the structural units derived from isobutylene are contained in the largest amount among all the structural units.

In the PIB resin used in one embodiment of the present invention, the content of the constituent unit derived from isobutylene is preferably 80 to 100 mass% with respect to the total constituent units (100 mass%) of the PIB resin, , More preferably 90 to 100 mass%, still more preferably 95 to 100 mass%, still more preferably 98 to 100 mass%.

These PIB 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 sticky conductive layer (X) to be formed, a composition derived from isobutylene, which has a dense molecular structure at the time of polymerization and does not have a polymerizable double bond in the main chain and side chains It is preferable to include a large number of units.

In the PIB resin used in one embodiment of the present invention, the content of the constituent unit derived from isobutylene in which the polymerizable double bond is absent in the main chain and the side chain is preferably 100% More preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, still more preferably 98 to 100% by mass with respect to the total mass (mass%).

When a PIB resin is used, it is preferable to use a combination of a PIB resin having a high mass average molecular weight and a PIB resin having a low mass average molecular weight.

More specifically, examples of the PIB resin used in an embodiment of the present invention include a PIB resin (p1) (hereinafter, also referred to as "PIB resin (p1)") having a mass average molecular weight of 270,000 to 600,000, (Hereinafter also referred to as " PIB resin (p2) ") having an average molecular weight of 50,000 to 250,000 is preferably used in combination.

The PIB resin (p1) having a high mass average molecular weight improves the durability and weatherability of the PSA layer (X) formed from the resulting PSA composition, and contributes to improving the adhesive strength.

The PIB resin (p2) having a low mass average molecular weight can be suitably used in conjunction with the PIB resin (p1) to appropriately plasticize the PIB resin (p1) Thereby improving the wettability to the complex, and improving the adhesive property, flexibility and the like.

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

From the above viewpoint, the mass average molecular weight (Mw) of the PIB resin (p2) is preferably from 50,000 to 250,000, more preferably from 80,000 to 230,000, still more preferably from 140,000 to 220,000 Preferably 180,000 to 21,000.

The content ratio of the PIB resin (p2) relative to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, further preferably 7 to 30 parts by mass , And even more preferably from 8 to 20 parts by mass.

When the content of the PIB resin (p2) is 5 parts by mass or more, the PIB resin (p1) can be sufficiently plasticized, the wettability of the formed sticky conductive layer (X) to the adherend is improved , And adhesion can also be improved.

On the other hand, when the content ratio of the PIB resin (p2) is 55 parts by mass or less, the adhesive strength, holding force and durability of the sticky conductive layer (X) to be formed can be improved.

(Styrene resin)

The styrene resin which can be used as the adhesive resin (x1) is a polymer having a constituent unit derived from styrene.

In the styrene-based resin used in one embodiment of the present invention, the content of the constituent unit derived from styrene is preferably 5 to 50 mass%, more preferably 5 to 50 mass% with respect to the total constituent units (100 mass% Preferably 10 to 40 mass%, and more preferably 15 to 35 mass%.

The mass average molecular weight (Mw) of the styrene type resin is preferably 10,000 to 400,000, more preferably 20,000 to 300,000, and still more preferably 25,000 to 20,000, in view of improving the adhesive force of the conductive pressure- Only.

The softening point of the styrene type resin is preferably from 80 to 200 占 폚, more preferably from 90 to 160 占 폚, still more preferably from 100 to 140 占 폚, even more preferably from 105 to 200 占 폚, from the viewpoint of improving the adhesive strength of the conductive pressure- Lt; 0 > C.

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

Examples of the styrene resin include styrene-butadiene-styrene triblock copolymer (hereinafter also referred to as "SBS"), styrene block (block) - (ethylene-co-butylene) (Hereinafter also referred to as " SEBS "), styrene-block- (ethylene-co-butylene) -block diblock copolymer (hereinafter also referred to as SEB), styrene-butadiene diblock copolymer, styrene- Block copolymers, styrene-isoprene-styrene triblock copolymers, styrene-block- (butadiene-co-isoprene) -block diblock copolymers, styrene-block- (butadiene-co-isoprene) And copolymers of carboxyl-modified products of these copolymers and aromatic vinyl compounds such as styrene and? -Methylstyrene.

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

Among these styrene resins, SBS, SEBS and SEB are preferable, and SBS and SEBS are more preferable.

When the styrene-based resin is a copolymer, the mode of copolymerization 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-based resin)

The polyester resin which can be used as the adhesive resin (x1) is a copolymer obtained by subjecting an acid component, a diol component or a polyol component to a polycondensation reaction, and the modified product of the copolymer is also included.

The polycondensation reaction is carried out by a general polyesterification reaction such as a direct esterification method, an ester exchange method and the like.

The form of the copolymerization 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.

Examples of the acid component include terephthalic acid, isophthalic acid, phthalic anhydride,? -Naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or their esters, pimelic acid, Aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid or esters thereof; And alicyclic dicarboxylic acids such as 1,4-cyclohexahydrophthalic anhydride and the like.

Examples of the diol component or the polyol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, Hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol Alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, aromatic glycols such as bisphenol A, and the like.

The polyester-series resin may be used alone or in combination of two or more.

(Polyolefin resin)

The polyolefin-based resin which can be used as the adhesive resin (x1) is a polymer having a constituent unit derived from an olefin compound such as ethylene or propylene.

Examples of the polyolefin resin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene, polypropylene, a copolymer of ethylene and propylene, a copolymer of ethylene and another? -Olefin, (Ethylene-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) of ethylene and other ethylenically unsaturated monomers and the like may be used as the copolymer of ethylene and other alpha -olefin. .

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

Examples of the? -Olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and 4-methyl-1-hexene.

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

Of these polyolefin-based resins, polypropylene-based resins containing constituent units derived from propylene such as polypropylene, a copolymer of ethylene and propylene, and a copolymer of propylene and another? -Olefin are preferable.

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

<Carbon-based filler (x2)>

The sticky composition as a material for forming the sticky conductive layer (X) includes a sticky resin (x1) and a carbon-based filler (x2) having an average aspect ratio of 1.5 or more.

If the average aspect ratio of the carbon-based filler (x2) is less than 1.5, the surface resistivity of the sticky conductive layer (X) to be formed tends to be high. Even if the conductive adhesive sheet is provided with the non-sticky conductive layer It is difficult to lower the resistivity, and the antistatic property and the conductivity are poor.

The average aspect ratio of the carbon-based filler (x2) is preferably from 2 to 10000, more preferably from 3 to 5000, and still more preferably from 3 to 5,000, from the viewpoint of lowering the surface resistivity of the formed adhesive conductive layer (X) More preferably from 4 to 1000, still more preferably from 5 to 500, still more preferably from 6 to 400, still more preferably from 10 to 300. [

In the present invention, the "aspect ratio" is the ratio of the length H of the long side to the length L of the short side of the target carbon-based filler, that is, the ratio of the length H of the long side / &Quot; The &quot; average aspect ratio &quot; is an average value of the &quot; aspect ratio &quot;

The length H of the longer side of the carbon-based filler (x2) means the length in the height direction (longitudinal direction) of the target carbon-based filler.

On the other hand, the length L of the short side of the carbon-based filler (x2) is a diameter or a long diameter when the cross section is a circle or an ellipse in a cross section orthogonal to the height direction (longitudinal direction) If the cross section is polygonal, it indicates 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 占 퐉, more preferably 0.05 to 1000 占 퐉, still more preferably 0.07 to 500 占 퐉, still more preferably 0.10 to 100 占 퐉 .

In the present invention, the average value of the lengths of the longer sides of arbitrarily selected 10 carbon-based fillers may be regarded as the value of the length (H) of the longer sides 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, still more preferably 5 to 100 nm More preferably 7 to 50 nm.

In the present invention, the average value of the lengths of short sides of arbitrarily selected ten carbon-based fillers may be regarded as the value of the length (L) of short sides of the carbon-based filler (x2).

Examples of the shape of the carbon-based filler (x2) include a columnar shape, a cylindrical shape, a weighted shape, a fiber shape, a shape of a plano-spherical shape (with a sphericity of usually 0.7 or less), and a combination thereof.

Among these shapes, at least one selected from a columnar carbon-based filler, a cylindrical carbon-based filler, and a fibrous carbon-based filler is preferable from the viewpoint of forming a sticky conductive layer (X) having good conductivity.

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

If the content of the carbon-based filler (x2) is less than 0.01 part by mass, the surface resistivity of the sticky conductive layer (X) to be formed tends to be high. Even if the conductive adhesive sheet is provided with the non-sticky conductive layer It is difficult to lower the surface resistivity, and the antistatic property and the conductivity are poor.

On the other hand, if the content of the carbon-based filler (x2) exceeds 15 parts by mass, the adhesion of the formed PSA layer X tends to be lowered.

The conductive pressure-sensitive adhesive sheet of the present invention exhibits excellent antistatic property and conductivity at least in the content of the carbon-based filler (x2) in the viscous conductive layer (X), so that it is necessary to add a large amount of the carbon- There is no.

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

Examples of the carbon-based filler (x2) include a carbon nano material, carbon black, ground carbon fiber, and graphite. The carbon-based filler (x2) , A carbon nanomaterial is preferable.

The carbon nanomaterial includes a material including a graphite sheet having a main structure of a six-membered ring structure. The carbon nanomaterial may contain an element other than carbon such as boron or nitrogen in the graphite structure, and the carbon nanomaterial may contain another substance Or may be a form in which the carbon nanomaterial is modified with another conductive material.

Examples of the carbon nanomaterial include carbon nanotubes (CNTs), carbon nanofibers, carbon nanofines, carbon nanocones, and fullerenes, and carbon nanotubes are preferable.

The carbon nanotube is a tubular carbon multi-sided body having a structure in which a graphite sheet (graphite) having a carbon six-membered ring structure as a main structure is closed in a cylindrical shape.

The carbon nanotubes include single-walled carbon nanotubes having a structure in which a single graphite sheet is closed in a cylindrical shape, double-walled carbon nanotubes having a structure in which two graphite sheets are closed in a cylindrical shape, and three- Layered carbon nanotubes having a multi-layered structure closed in a concentric tube form, and any two or more of them may be used in combination.

<Cross-linking agent>

The adhesive composition which is a material for forming the pressure-sensitive adhesive conductive layer (X) may further contain a crosslinking agent.

Particularly, in the case of using the acrylic resin (particularly, the acrylic copolymer having the above-mentioned constituent unit (a2)) as the adhesive resin (x1), from the viewpoint of improving the adhesive strength of the sticky conductive layer (X) , And a crosslinking agent.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelating crosslinking agent, an amine crosslinking agent and an amino resin crosslinking agent. These crosslinking agents may be used alone or in combination of two or more.

Of these, an isocyanate-based crosslinking agent is preferable from the viewpoint of improving the adhesive force of the conductive pressure-sensitive adhesive sheet.

Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane- Diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclo Hexyl methane-2,4'-diisocyanate, lysine isocyanate, and other polyisocyanate compounds.

The polyvalent isocyanate compound may be an isocyanurate type modified product comprising a trimethylolpropane adduct of the above compound, a buret-type modified product obtained by reacting with water, and an isocyanurate ring.

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 still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the adhesive resin (x1).

<Tackifier>

The pressure-sensitive adhesive composition as a material for forming the pressure-sensitive adhesive layer (X) may further contain a tackifier.

Particularly when the urethane resin, the PIB resin and the styrene resin are used as the adhesive resin (x1), from the viewpoint of improving the adhesive strength of the sticky conductive layer (X) to be formed, those containing the tackifier desirable.

The mass average molecular weight (Mw) of the tackifier is usually 10,000 or less and is distinguished from the above-mentioned tacky resin (x1).

The mass average molecular weight (Mw) of the tackifier is preferably from 400 to 4000, more preferably from 800 to 1,500, from the viewpoint of improving the adhesive strength of the sticking conductive layer (X) to be formed.

The softening point of the tackifier is preferably 110 占 폚 or higher, more preferably 110 to 180 占 폚, still more preferably 115 to 175 占 폚, still more preferably 120 to 170 占 폚.

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

Examples of the tackifier include rosin resins such as rosin resins, rosin phenol resins and ester compounds thereof; Hydrogenated rosin-based resins obtained by hydrogenating these rosin-based resins; Terpene resins such as terpene resins, aromatic modified terpene resins and terpene phenol resins; Hydrogenated terpene resins obtained by hydrogenating these terpene resins; A C5 petroleum resin obtained by copolymerizing a C5 oil (fraction) such as pentene, isoprene, piperine, and 1,3-pentadiene produced by pyrolysis of petroleum naphtha, and a hydrogenated petroleum resin of this C5 petroleum resin; A C9 type petroleum resin obtained by copolymerizing indene produced by pyrolysis of petroleum naphtha, a C9 oil such as vinyltoluene,? - or? -Methylstyrene, and a hydrogenated petroleum resin of this C9 petroleum resin; And the like.

In the present invention, the tackifier may be used alone or in combination of two or more kinds having different softening points or structures.

The content of the tackifier is preferably 1 to 200 parts by mass, more preferably 5 to 160 parts by mass, and still more preferably 10 to 120 parts by mass with respect to 100 parts by mass of the adhesive resin (x1).

When the adhesive resin (x1) comprises an acrylic resin, the content of the tackifier is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, More preferably 10 to 40 parts by mass.

When the viscous resin (x1) contains a urethane-based resin, the content of the tackifier is preferably 5 to 200 parts by mass, more preferably 40 to 160 parts by mass, further preferably 40 to 60 parts by mass, per 100 parts by mass of the urethane- Is from 80 to 120 parts by mass.

When the adhesive resin (x1) contains a PIB resin, the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, More preferably 15 to 40 parts by mass.

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

When the adhesive resin (x1) contains a polyester resin, the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass, per 100 parts by mass of the polyester resin More preferably 25 to 60 parts by mass.

When the adhesive resin (x1) contains a polyolefin-based resin, the content of the tackifier is preferably 5 to 100 parts by mass, more preferably 15 to 80 parts by mass, more preferably 15 to 80 parts by mass, per 100 parts by mass of the polyolefin- More preferably 25 to 60 parts by mass.

<Other additives>

The adhesive composition which is a material for forming the pressure-sensitive adhesive conductive layer (X) may contain a general-purpose additive which is generally used together with a pressure-sensitive adhesive resin, so long as the effect of the present invention is not impaired.

Examples of such a general purpose additive include ultraviolet absorbers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, curing agents, curing auxiliaries and catalysts.

When these general-purpose additives are blended, the blending amount of each of the general-purpose additives is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass, based on 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 which is the material for forming the sticky conductive layer (X) is preferably 20 mass% or more, more preferably 30 mass% %.

When a viscous resin (x1) containing an acrylic resin as a main component is used, the total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition is preferably 60 mass% More preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more.

(X1) containing a urethane resin as a main component, the total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition is preferably 35 mass% The content of the tackifier resin (x1), the carbon-based filler (x2) and the tackifier is preferably 70% by mass or more, more preferably 40% by mass or more, and still more preferably 45% Is 80 mass% or more, and more preferably 90 mass% or more.

(X1) containing a PIB resin as a main component, the total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition is preferably not less than 50 mass% , More preferably 60 mass% or more, and even more preferably 70 mass% or more, and the total content of the adhesive resin (x1), the carbon-based filler (x2) and the tackifier is preferably 70 mass% By mass is not less than 80% by mass, and more preferably not less than 90% by mass.

The total content of the adhesive resin (x1) and the carbon-based filler (x2) in the total amount (100 mass%) of the adhesive composition is preferably 20 mass% or more , More preferably not less than 25 mass%, and still more preferably not less than 30 mass%.

The expression &quot; adhesive resin (x1) containing ZZ-based resin as a main component &quot; means that the content of ZZ-based resin is the largest among the resins contained in adhesive resin (x1).

The content of the specific ZZ-based resin in the substrate is generally 50% by mass or more, preferably 65 to 100% by mass, more preferably 75 to 100% by mass, based on the total amount (100 mass%) of the adhesive resin By mass, more preferably 85 to 100% by mass.

&Lt; Method for forming the sticky conductive layer (X) >

The method for forming the sticky conductive layer (X) is not particularly limited and can be produced by a known method. For example, the following methods (X-1) and (X-2) can be mentioned.

Method (X-1): An organic solvent solution of the adhesive composition is prepared, and the solution is applied onto a release sheet described later by a known coating method to form a coating film, and the coating film is dried to form the adhesive conductive layer (X) &Lt; / RTI &gt;

Method (X-2): After the thermoplastic resin (x1) and the carbon-based filler (x2) are heated and kneaded to prepare a composite, the composite is molded into a sheet by a known molding method, A method for forming a conductive layer (X).

(Method (X-1))

The method (X-1) is a forming method suitable for the case of using an acrylic resin, a urethane resin, a PIB resin or the like as the viscous resin (x1).

Examples of the organic solvent to be used in the method (X-1) include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol , Dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and the like.

In these organic solvents, the organic solvent used in the synthesis of the adhesive resin (x1) may be used as it is.

In the method (X-1), the carbon-based filler (x2) is preferably blended with the adhesive resin (x1) in the form of a dispersion dispersed in a solvent.

Since the carbon-based filler (x2) can be mixed with the adhesive resin (x1) in a state of low viscosity by blending the carbon-based filler (x2) in the form of a dispersion, The surface resistivity and the volume resistivity of the sticky conductive layer (X) to be formed are liable to be lowered.

As the solvent used for preparing the dispersion of the carbon-based filler (x2), water or the above-mentioned organic solvent can be mentioned, and an organic solvent is preferable.

Examples of the method for producing the dispersion of the carbon-based filler (x2) include a method in which a carbon-based filler (x2) is added to a solvent and a vibration is generated for a predetermined time by ultrasonic waves or the like.

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

Examples of the method of applying the solution of the adhesive composition onto the release sheet in the method (X-1) include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll knife coating method, , A blade coating method, a die coating method, and a gravure coating method.

It is also preferable to apply a solution of the adhesive composition onto the release sheet to form a coating film, and then perform a drying treatment to remove the solvent contained in the coating film.

In the method (X-1), in order to improve the adhesive strength, the coated layer after the drying treatment is allowed to stand at an ambient temperature of, for example, 23 DEG C and 50% RH (relative humidity) It is preferable to sufficiently crosslink the inside of the coating layer.

(Method (X-2))

The method (X-2) is a forming method suitable for a case where a resin capable of enduring heating and kneading of a styrenic resin or the like is used as the adhesive resin (x1).

Examples of the heat kneading apparatus include a single screw extruder, a twin screw extruder, a roll mill, a Plastomill, a Banbury mixer, an intermix, and a pressurized kneader.

Examples of the method for molding the composite obtained by the heat kneading apparatus include a melt extrusion method, a calendering method, a compression molding method and the like, and a compression molding method is preferable.

As a concrete method of the compression molding method, the sheet-shaped adhesive conductive layer X can be formed by sandwiching the produced composite sheet between two release sheets and hot-pressing the sheet with the hot press machine or the like. Instead of the two release sheets, the adhesive conductive layer X on the sheet may be formed by sandwiching the substrate and the composite made of the release sheet.

[Non-tacky conductive layer (Y)]

A conductive pressure sensitive adhesive sheet is non-adhesive electrically conductive layer (Y) with the present invention is a layer of non-tacky (less than the value of the peak top of the above-described probe tack 0.1N), also the volume resistivity of the conductive sole (layer (ρ _VX) is 1.0 x 10 &lt; ⁸ &gt; OMEGA. Cm or less).

The surface resistivity rho _SY of the non-tacky conductive layer Y alone is preferably in the range of 1.0 x 10 ^-2 to 1.0 x 10 ⁸ Ω / square, more preferably in the range of 1.0 × 10 ^-2 to 1.0 × 10 ⁸ Ω / , Preferably 1.0 x 10 ^-2 to 1.0 x 10 ⁷ Ω / square, more preferably 1.0 × 10 ^-2 to 1.0 × 10 ⁶ Ω / square, and still more preferably 1.0 × 10 ^-2 to 1.0 × 10 ⁵ Ω / □, more preferably 1.0 × 10 ^-2 to 1.0 × 10 ⁴ Ω / □, even more preferably 1.0 × 10 ^-2 to 1.0 × 10 ³ Ω / □.

In one aspect of the present invention, from the viewpoint of effectively reducing the surface resistivity of the conductive pressure-sensitive adhesive sheet, the surface resistivity r _SY of the non-tacky conductive layer (Y) (? _SX ).

The volume resistivity (rho _VY ) of the non-tacky conductive layer (Y) alone is preferably 1.0 x 10 ^-4 to 1.0 x 10 ⁶ Ω · cm, more preferably 1.0 x 10 ^-4 to 1.0 x 10 ⁶ Ω · cm from the viewpoint of forming a conductive pressure- Preferably 1.0 × 10 ^-4 to 1.0 × 10 ⁴ Ω · cm, more preferably 1.0 × 10 ^-4 to 1.0 × 10 ³ Ω · cm, and further preferably 1.0 × 10 ^-4 to 1.0 × 10 ² Ω · cm. Cm, more preferably 1.0 x 10 ^-4 to 1.0 x 10 ¹ Ω · cm, even more preferably 1.0 × 10 ^-4 to 1.0 × 10 ⁰ Ω · cm.

In one aspect of the present invention, from the viewpoint of effectively lowering the surface resistivity of the conductive pressure-sensitive adhesive sheet, the volume resistivity (rho _VY ) of the non-tacky conductive layer (Y) (? _VX ).

The thickness t _y of the non-tacky conductive layer Y is appropriately adjusted in accordance with applications and the like, and is preferably 0.01 to 200 탆, more preferably 0.1 to 160 탆, still more preferably 0.5 to 130 탆 Preferably 1.0 to 100 mu m.

If the thickness (t _Y ) is 0.01 탆 or more, the surface resistivity of the non-tacky conductive layer (Y) can be effectively lowered.

On the other hand, if the thickness t _y is not more than 200 μm, winding displacement due to deformation of the non-tacky conductive layer (Y) when the conductive adhesive sheet is made into a winding body, We can suppress bad influence that we come out. Further, by reducing the total thickness of the conductive adhesive sheet, it is possible to obtain a conductive adhesive sheet which is easy to apply to small electronic apparatuses.

In the present invention, the non-tacky conductive layer (Y) is a layer containing at least one conductive material selected from the group consisting of a conductive polymer, a carbon-based filler, and a metal oxide.

Since the non-tacky conductive layer (Y) is a layer containing these specific conductive materials, the surface resistivity of the tacky conductive layer (X) can be remarkably reduced.

From the above viewpoint, the non-tacky conductive layer (Y) preferably contains at least one conductive material selected from the group consisting of polythiophene, PEDOT-PSS, carbon nanomaterial and ITO (indium tin oxide) , Polythiophene, PEDOT-PSS, and a carbon nanomaterial.

The density of the conductive material contained in the non-tacky conductive layer (Y) is preferably 0.8 to 2.5 g / cm 3, more preferably 0.8 to 2.0 g / cm 3, and still more preferably 0.8 To 1.7 g / cm &lt; 3 &gt;.

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

&Lt; Conductive polymer &

Examples of the conductive polymer include polythiophene, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)), polyaniline, polypyrrole, polyquinoxaline and the like.

Of these, polythiophene and PEDOT-PSS are preferred.

The non-tacky conductive layer (Y) containing a conductive polymer preferably contains a non-tacky resin together with the conductive polymer, and the non-tacky resin is preferably one selected from an acrylic resin, a urethane resin, a PIB resin, Or more of the non-tacky resin is preferable.

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

The method of forming the non-tacky conductive layer (Y) containing the conductive polymer is not particularly limited. For example, a method of preparing a solution of an organic solvent containing a conductive polymer, applying the solution to a substrate or a release sheet, To form a coating film, followed by drying to form the coating film.

The kind of the organic solvent used in the method and the method of applying the solution are the same as those described in the &quot; method (X-1) &quot;, which is the method of forming the adhesive conductive layer (X)

<Carbon-based filler>

Examples of the carbon-based filler include the same ones as the above-mentioned carbon-based filler (x2), and carbon nanomaterials are preferable.

The non-tacky conductive layer (Y) containing a carbon-based filler preferably contains a non-tacky resin together with the carbon-based filler, and the non-tacky resin is selected from an acrylic resin, a urethane resin, a PIB resin and a styrene resin Is preferably one or more non-tacky resins.

When the carbon-based filler is used as the conductive material, the content of the carbon-based filler is preferably 0.1 to 20 mass%, more preferably 0.5 (mass%) to the total amount (100 mass%) of the non-tacky conductive layer To 15 mass%, more preferably from 1.0 to 10 mass%, still more preferably from 2.0 to 7 mass%.

The method of forming the non-tacky conductive layer (Y) containing the carbon-based filler is not particularly limited. For example, a solution of a carbon-based filler and a solution of an organic solvent of a non-tacky resin are mixed, And then coating the solution on a substrate or a release sheet by a known coating method to form a coating film and drying the coating film.

Regarding the type of the organic solvent used in the method, the method of producing the dispersion of the carbon-based filler, and the method of applying the solution, the description of the "method (X-1)" which is the method of forming the adhesive conductive layer It is the same.

As a method of forming the non-tacky conductive layer (Y) containing a carbon-based filler, a carbon-based filler and a non-tacky resin are heated and kneaded to produce a composite, followed by molding the composite by a known molding method. Or the like.

The method of forming a heat kneader and a composite used in this method is the same as the description of "Method (X-2)" which is a method of forming the above-described sticky conductive layer (X).

<Metal oxide>

Examples of the metal oxide include ITO (indium tin oxide), ZnO (zinc oxide), IZO (zinc oxide indium), AZO (zinc oxide aluminum), GZO (zinc oxide zinc oxide), IGZO (indium gallium gallium oxide) Antimony), and the like.

Among them, ITO (indium tin oxide) is preferable.

When a metal oxide is used as the conductive material, the non-tacky conductive layer (Y) is preferably a layer containing only the metal oxide.

The non-adhesive conductive layer (Y) containing a metal oxide is preferably formed by vapor deposition on a substrate.

[materials]

The substrate used in the conductive pressure-sensitive adhesive sheet of the present invention is appropriately selected depending on the use of the conductive pressure-sensitive adhesive sheet, but may be an insulating substrate containing an insulating material, or may be a conductive substrate containing a conductive material such as metal.

In the present invention, an insulating base member refers to a substrate having a surface resistivity of 1.0 x 10 ¹⁴ ? /? Or more (preferably 1.0 x 10 ¹⁶ ? /? Or more).

Examples of the insulating substrate include various types of paper such as a top paper, an art paper, a coated paper, a gloss paper, or a laminate paper obtained by laminating a thermoplastic resin such as polyethylene to these paper bases; A porous material such as a nonwoven fabric; A plastic film or sheet including a polyolefin resin such as a polyethylene resin and a polypropylene resin, a polyester resin such as a polybutylene terephthalate resin and a polyethylene terephthalate resin, an acetate resin, an ABS resin, a polystyrene resin, a vinyl chloride resin and the like; A plastic film or sheet comprising a mixture of these resins; And a plastic film or sheet including a laminate of these plastic films or sheets.

The base material such as a plastic film or a sheet may be unstretched or may be stretched in a uniaxial or biaxial direction such as a longitudinal or transverse direction.

The insulating substrate (particularly, the plastic film or sheet) may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an anti-blocking agent, a colorant and the like.

Examples of the electrically conductive substrate include a film or sheet laminated with a metal foil or a metal foil with a resin forming the above-mentioned insulating substrate, a film or sheet obtained by performing the metal vapor deposition treatment on the surface of the above-mentioned insulating substrate, A film or sheet subjected to an antistatic treatment, a sheet formed by mesh-forming a metal wire, and the like.

Examples of the metal used for the conductive base material include aluminum, copper, silver and gold.

The thickness of the substrate is not particularly limited, but is preferably 10 to 250 占 퐉, more preferably 15 to 200 占 퐉, and still more preferably 20 to 150 占 퐉, from the viewpoint of ease of handling.

In the case where the substrate is a plastic film or a sheet, it is preferable to carry out surface treatment such as an oxidation method and a concavo-convex method on the surface of the substrate, if necessary, from the viewpoint of improving the adhesion between the substrate and the non-tacky conductive layer (Y).

The oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), a flame treatment, a hot air treatment, an ozone / ultraviolet ray irradiation treatment and the like. The unevenness method is not particularly limited, and examples thereof include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the kind of the substrate, but from the viewpoint of improving the adhesion with the non-tacky conductive layer (Y) and operability, the corona discharge treatment method is preferable. In addition, a primer treatment may be performed.

[Peeling sheet]

As the release sheet for use in the conductive pressure-sensitive adhesive sheet of the present invention, a release sheet having a double-side separation treatment or a single-side separation sheet or the like is used, and a release agent is coated on the release sheet .

Examples of the base material for the release sheet include a paper base such as a gloss paper, a coated paper and a top paper, a laminate paper obtained by laminating a thermoplastic resin such as polyethylene on the paper base material or a polyethylene terephthalate resin, a polybutylene terephthalate resin, Polyester resin films such as naphthalate resins, and plastic films such as polypropylene resins and polyolefin resin films such as polyethylene resins.

Examples of the releasing agent include a rubber-based elastomer such as a silicone resin, an olefin resin, an isoprene resin and a butadiene resin, a long chain alkyl resin, an alkyd resin, and a fluorine resin.

The thickness of the release sheet is not particularly limited, but is preferably 10 to 200 占 퐉, more preferably 25 to 150 占 퐉.

[Production method of conductive pressure-sensitive adhesive sheet, physical properties]

The conductive pressure-sensitive adhesive sheet of one form of the present invention can be produced by suitably bonding the adhesive conductive layer (X) and the non-adhesive conductive layer (Y) formed by the above-described forming method, and the substrate or the release sheet.

The value of the peak top of the probe tip relative to the surface of the adhesive conductive layer (X) of the conductive adhesive sheet of the present invention is preferably 0.1 N or more, more preferably 0.1 to 49 N, 49N, and even more preferably 1.0 to 49N.

Further, the value of the peak top of the probe tip means the value measured by the method described in the embodiment. The value of the peak top of the probe tack is a physical property value to be an index of tackiness of the electrically conductive pressure sensitive adhesive sheet, and the larger the value, the higher the adhesive force.

The surface resistivity p _S measured from the surface side of the adhesive conductive layer X of the conductive adhesive sheet of the present invention is preferably 9.0 x 10 ⁴ ? /? Or less, more preferably 1.0 x 10 ⁴ Ω / □ or less, more preferably 5.0 × 10 ³ Ω / □ or less, still more preferably 2.0 × 10 ³ Ω / □ or less.

The value of the &quot; surface resistivity measured from the surface side of the sticky conductive layer (X) of the conductive adhesive sheet &quot; is the value of the surface resistivity of the conductive adhesive layer the value of the surface resistivity measured from the surface side of the adhesive conductive adhesive layer (X) by the expression of the sheet, is different from a value of the "conductive adhesive layer (X) surface resistivity of the sole (ρ _SX)" described above.

Example

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

&Lt; Mass average molecular weight (Mw) >

The value measured in terms of standard polystyrene was measured using a gel permeation chromatograph device (manufactured by Toso Kabushiki Kaisha, product name "HLC-8020") under the following conditions.

(Measuring conditions)

Column: "TSK guard column HXL-H", "TSK gel GMHXL (× 2)" and "TSK gel G2000HXL" (all manufactured by Tosoh Corporation) are sequentially connected.

Column temperature: 40 ° C

· Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

<Aspect ratio of carbon-based filler, length of long sides and short sides>

10 particles of a randomly extracted carbon-based filler were observed using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, product name &quot; S-4700 &quot;) and the length of each long side and the length of the short side were measured , And the average value of the ten particles of the carbon-based filler was defined as the "long side length (H)" and the "short side length (L)" of the filler. In addition, the aspect ratio H / L was calculated from &quot; length H of long side / length L of short side &quot;.

<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 having a size of 10 mm x 10 mm was allowed to stand for 24 hours under an environment of 23 ° C and 50% RH (relative humidity), and then the surface of the layer to be measured of the test piece was exposed. Quot; PROBE TACK TESTER &quot;, manufactured by Rigaku Kogyo Kabushiki Kaisha), the probe tack value on the surface of the layer was measured.

The probe tack value was obtained by bringing a probe made of stainless steel having a diameter of 5 mm into contact with the surface of the layer to be measured at a contact load of 0.98 N / cm 2 for 1 second and then measuring the probe at a rate of 600 mm / The surface force of the layer was determined by the force required to form the layer.

Further, for the surface of the non-tacky conductive layer, the peak top of the probe tack value was measured. Further, for the surface of the sticky conductive layer (X) of the conductive pressure-sensitive adhesive sheet, the peak top and integral value of the probe tack value were measured.

Further, when the surface of the layer to be measured had no adhesiveness and the peak top of the probe tack value could not be measured, the value of the peak top was set to &quot; 0 (N) &quot;.

<Surface resistivity, volume resistivity>

Measured according to JIS K 7194.

Specifically, a test piece having a size of 20 mm x 40 mm was allowed to stand for 24 hours under an environment of 23 ° C and 50% RH (relative humidity), and then the surface of the layer to be measured of the test piece was exposed, (Manufactured by Mitsubishi Chemical Corporation, trade name "Loresta GP MCP-T610" manufactured by Kabushiki Kaisha), the surface resistivity and the volume resistivity were measured.

For the surface resistivity, the above measurement was carried out three times, and for the volume resistivity, the above measurement was performed five times. Tables 1 and 2 show the average value of the measured values obtained in the respective measurements.

The surface resistivity and the volume resistivity of the adhesive conductive layer (X) alone were measured by using a laminate in which only the adhesive conductive layer (X) was sandwiched between two release sheets as a test piece, and one of the release sheets And the values of these values were measured on the surface of the sticky conductive layer (X).

In the measurement of the surface resistivity and the volume resistivity of the non-tacky conductive layer alone, a substrate having a non-tacky conductive layer was used as a test piece, and the values of these values were measured on the surface of the non-tacky conductive layer of the test piece.

The measurement of the surface resistivity of the conductive pressure-sensitive adhesive sheet was carried out in the same manner as in Example 1 except that the conductive pressure-sensitive adhesive sheet in which the substrate, the non-tacky conductive layer, the sticky conductive layer (X) , The release sheet of the test piece was removed, and only the value of the surface resistivity was measured on the surface of the exposed sticky conductive layer (X).

Production Example 1

(Production of base material having non-tacky conductive layer (Y-1)

A solution of polythiophene (manufactured by Soken Chemical &amp; Chemical Co., Ltd.) on a polyethylene terephthalate (PET) film having a thickness of 50 탆 (manufactured by Toray Kabushiki Kaisha under the trade name of "Lumirror", surface resistivity: 1.18 × 10 ¹⁸ Ω / (Trade name &quot; Vera Sol IW-103 &quot;, manufactured by KABUSHIKI KAISHA) was applied so as to have a thickness of 2.4 mu m after drying to form a coating film and the coating film was dried to form a non-tacky conductive layer (Y- 1) was obtained.

Production Example 2

(Production of substrate having non-tacky conductive layer (Y-2)

(3,4-ethylenedioxythiophene) -poly (meth) acrylate was added to 100 parts by mass (solid content) of an acrylic water-soluble polymer (manufactured by Arakawa Chemical Industries, Ltd., trade name &quot; Tamanori G- 10 parts by mass (solid content ratio) of a dispersion of poly (styrene sulfonic acid) (PEDOT-PSS) (manufactured by Agfa, trade name "Orgacon S305") and 10 parts by mass of ethylene glycol.

Then, the above solution was coated on the same PET film as used in Production Example 1 to a thickness of 1.0 mu m after drying to form a coating film, and the coating film was dried to obtain a non-adhesive conductive layer (Y- 2) was obtained.

Production Example 3

(Production of substrate having non-stick conductive layer (Y-3)

10 mass parts of multilayer carbon nanotubes (CNT) (trade name &quot; NC7000 &quot;, the details of which will be described later) were added to 100 parts by mass (solid content) of a styrene resin (trade name: 1726M, (Solid content ratio) was added, and the mixture was kneaded at 100 ° C and 50 rpm using a heat kneader (product name "30C150" manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composite.

The compact was sandwiched between a PET film identical to that used in Production Example 1 and a 75 탆 thick release sheet (trade name: SP-PET751031, manufactured by LINTEC CORPORATION), and a hot press machine (Product name: &quot; SA-302 &quot;, manufactured by NOF Corporation) under the conditions of 130 캜 and 10 MPa for 10 minutes. After the hot pressing, the release sheet was removed to obtain a substrate having a non-tacky conductive layer (Y-3) containing 100.0 占 퐉 thick SEBS and CNT (10 parts by mass).

In Examples and Comparative Examples, a substrate having the following non-tacky conductive layer was used in addition to the substrate having the non-tacky conductive layer prepared in Production Examples 1 to 3 described above.

&Quot; Substrate having non-tacky conductive layer (YA) containing ITO &quot;, trade name &quot; ITO-polyethylene terephthalate &quot; (manufactured by Oike Kogyo K.K.). An ITO film having a thickness of 1.6 占 퐉 was deposited on one side of a 50 占 퐉 thick PET film (surface resistivity: 1.18 占¹⁸ ? /?).

&Quot; Substrate having non-tacky conductive layer (YB) containing copper &quot;, trade name &quot; NikaFlex &quot; (manufactured by Nikkan Kogyo Kabushiki Kaisha). A copper film having a thickness of 35.0 占 퐉 was bonded to one side of a 50 占 퐉 thick PET film (surface resistivity: 1.18 占¹⁸ ? /?) With an adhesive.

A substrate having a non-tacky conductive layer (YC) containing aluminum: "Metal Lumi # 50" (manufactured by TORAY FILM CORPORATION). An aluminum film having a thickness of 10.0 占 퐉 was deposited on one side of a 50 占 퐉 thick PET film (surface resistivity: 1.18 占¹⁸ ? /?).

The various properties of the non-tacky conductive layer of the substrate having the non-tacky conductive layer used in this example and the comparative example are shown in Table 1.

Examples 1 to 15 and Comparative Examples 1 to 8

(1) Formation of the sticky conductive layer (X)

A carbon-based filler (x2) having a type and a blending amount shown in Table 2 (solid content ratio relative to 100 parts by mass (solid content) of the adhesive resin) was added to ethyl acetate and vibration with ultrasonic waves (42 kHz, 125 W) was measured with an ultrasonic cleaner 1 hour, and a dispersion of a carbon-based filler (x2) having a solid content concentration of 0.5% by mass was prepared in advance.

Subsequently, a dispersion of the carbon-based filler (x2) was added to 100 parts by mass (solid content) of the adhesive resin (x1) of the kind shown in Table 2, and a crosslinking agent of a kind and a compounding amount (solid content ratio) An additional agent was added as needed. Then, the mixture was appropriately diluted with ethyl acetate and stirred until homogeneous to prepare a solution of the adhesive composition.

Then, the solution of the sticky composition prepared as described above was peeled off from the release-treated surface of a release sheet (trade name "SP-PET381031" manufactured by LINTEC CORPORATION, thickness: 38 mu m, surface-peeled polyethylene terephthalate film) To form a coating film, followed by drying to form a coating layer.

Subsequently, a release sheet of the same kind as that described above was separately laminated on the applied layer and allowed to stand for 14 hours under an environment of 23 DEG C and 50% RH (relative humidity), and then the applied layer was sufficiently crosslinked, Of the adhesive conductive layer (X) alone was sandwiched between two release sheets.

(2) Production of conductive pressure-sensitive adhesive sheet

In Examples 1 to 15 and Comparative Examples 7 to 8, the peelable sheet of one side of the layered product was removed to reveal the non-sticky property (X) of the substrate having the non-sticky conductive layer of the kind shown in Table 2 And the conductive layers were bonded to each other to produce a conductive pressure-sensitive adhesive sheet.

In Comparative Examples 1 to 6, the sticky conductive layer (X) exposed by removing one of the release sheets of the laminate and a PET film having a thickness of 50 탆 (manufactured by Toray Industries, Inc., trade name &quot; To prepare a conductive pressure-sensitive adhesive sheet.

Example 16

(1) Formation of the sticky conductive layer (X)

Layer carbon nanotube (CNT) (trade name: &quot; NC7000 &quot; manufactured by Nanosilan Co., Ltd.) was added to 100 parts by mass (solid content) of a styrene resin (trade name: "P-907Y" (Solid content ratio) shown in Table 2, and the mixture was heated at 100 占 폚, 100 占 폚, and 100 占 폚 using a heat kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "30C150" And kneaded under the conditions of 50 rpm to obtain a composite.

Then, the composite was sandwiched between two release sheets (trade name: SP-PET751031, manufactured by LINTEC CORPORATION, thickness: 75 μm), and hot press machine (manufactured by Tester Sanchung Kabushiki Kaisha, -302 &quot;) under the conditions of 130 캜 and 10 MPa for 10 minutes to obtain a laminate in which only the adhesive conductive layer (X) was sandwiched between two release sheets.

(2) Production of conductive pressure-sensitive adhesive sheet

A sticky conductive layer (X) containing a styrene type resin expressed by removing one of the release sheets of the laminate was bonded to a non-sticky conductive layer of a substrate having a non-sticky conductive layer (Y-2) Sheet.

The components of the adhesive composition used in the examples and comparative examples shown in Table 2 are as follows.

(Adhesive resin (x1))

BA / AA = 90.0 / 10.0 (parts by mass), Mw: 700,000, solid content concentration: 33.6 (parts by mass), "Acrylic resin": a methyl acetate solution of an acrylic polymer containing n-butyl acrylate mass%.

&Quot; Urethane resin &quot;: Lion Specialty Chemicals, trade name &quot; US-902A &quot;, urethane resin, Mw = 56,000.

(PIB resin): 90.9 parts by mass (solid content ratio) of a PIB resin having an Mw of 340,000 (trade name "Oponol B50" manufactured by BASF Corporation) and 100,000 Mw of a PIB resin (trade name "Opanol B30" ) 9.1 parts by mass (solid content ratio).

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

(Carbon-based filler (x2))

"NC7000": product name, manufactured by Nanosil Ltd., cylindrical multi-walled carbon nanotube, average aspect ratio (H / L): 150, length of long side (H): 1.5 μm, length of short side (L): 10 nm.

(H / L): 100, length of long side (H): 1.1 占 퐉, length of short side (L): 11 (trade name, manufactured by Ube Kosan Co., Nm.

(Crosslinking agent)

&Quot; Colonate L &quot;: trade name, manufactured by TOSOH CORPORATION, isocyanate crosslinking agent, solid concentration: 75% by mass.

(Tackifier)

&Quot; Alcon P-125 &quot;: trade name, manufactured by Arakawa Chemical Industries, Ltd., hydrogenated petroleum resin, softening point: 125 占 폚.

YS Polystar K125: trade name, manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resin, softening point: 125 占 폚.

(Other components)

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

Table 2 shows various physical properties measured on the basis of the above-mentioned method for the conductive pressure-sensitive adhesive sheet produced as described above.

Table 2 shows that the conductive pressure-sensitive adhesive sheets of Examples 1 to 16 have good adhesion and have a lower surface resistivity than the conductive pressure-sensitive adhesive sheets of Comparative Examples 1 to 8, and are excellent in antistatic property and conductivity .

INDUSTRIAL APPLICABILITY The conductive pressure-sensitive adhesive sheet of the present invention is excellent in antistatic property and conductivity because it has good adhesion and low surface resistivity.

Therefore, the conductive pressure-sensitive adhesive sheet of the present invention is capable of preventing ignition by a spark from static electricity such as a ground wire of an electromagnetic shielding material or an electric part of a container for housing electronic equipment such as a computer or a communication device, It is suitable as a joining member used for members such as ash.

1A, 1B, 2A, 2B, 3, 4: conductive adhesive sheet
11: sticky conductive layer (X)
11a: first adhesive layer (XI)
11b: Second adhesive layer (X-II)
12: Non-tacky conductive layer (Y)
12a: a first non-stick conductive layer (YI)
12b: second non-tacky conductive layer (Y-II)
13: substrate
14: Peeling sheet
21:
21a:
21b: second two-layered body
22: 3-layered

Claims (14)

Sensitive adhesive sheet having at least a sticky conductive layer (X) and a non-sticky conductive layer (Y)
Wherein the sticky conductive layer (X) is a layer formed from a sticky composition comprising a sticky resin (x1) and a carbon-based filler (x2) having an average aspect ratio of 1.5 or more,
The content of the carbon-based filler (x2) contained in the adhesive composition is 0.01 to 15 parts by mass based on 100 parts by mass of the adhesive resin (x1)
Wherein the non-tacky conductive layer (Y) is a layer containing at least one conductive material selected from the group consisting of a conductive polymer, a carbon-based filler and a metal oxide. The conductive pressure-sensitive adhesive sheet according to claim 1, wherein the PSA (X) alone has a surface resistivity (ρ _SX ) of 1.0 × 10 ² to 1.0 × 10 ¹⁰ Ω / square. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the non-tacky conductive layer (Y) alone has a surface resistivity (r _SY ) of 1.0 × 10 ^-2 to 1.0 × 10 ⁸ Ω / square. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the carbon-based filler (x2) contained in the adhesive composition is a carbon nanomaterial. The non-tacky conductive layer (Y) according to any one of claims 1 to 4, wherein the non-tacky conductive layer (Y) is at least one selected from the group consisting of polythiophene, PEDOT-PSS, a carbon nanomaterial, and ITO Wherein the conductive adhesive sheet is a layer containing a conductive material. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the conductive material contained in the non-tacky conductive layer (Y) has a density of 0.8 to 2.5 g / cm 3. The adhesive resin composition according to any one of claims 1 to 6, wherein the adhesive resin (x1) contained in the adhesive composition is an acrylic resin, a urethane resin, a polyisobutylene resin, a styrene resin, a polyester resin and a polyolefin resin And at least one tackifying resin selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the thickness t _x of the viscous conductive layer ( _X ) is 1 to 1200 μm. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein the thickness (t _Y ) of the non-tacky conductive layer ( _Y ) is 0.01 to 200 μm. 10. The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the substrate, the non-tacky conductive layer (Y) and the adhesive conductive layer (X) are laminated in this order. The conductive pressure-sensitive adhesive sheet according to claim 10, which has a two-layered structure composed of a non-tacky conductive layer (Y) and a viscous conductive layer (X) on both surfaces of a substrate. 12. The conductive pressure-sensitive adhesive sheet according to claim 10 or 11, wherein the substrate is an insulating substrate having a surface resistivity of 1.0 x 10 &lt; ¹⁴ &gt; The conductive pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the pressure-sensitive adhesive sheet (1) has a structure in which a two-layer structure composed of a pressure-sensitive adhesive conductive layer (X) . 10. The multilayer printed wiring board according to any one of claims 1 to 9, wherein a three-layer structure obtained by laminating the first adhesive layer (XI), the non-adhesive conductive layer (Y) and the second adhesive layer (X- Wherein the conductive adhesive sheet has a configuration sandwiched between two release sheets.

Images